Investigation of Cold Fusion Phenomena in Deuterated Metals

INVESTIGATION OF COLD FUSION PHENOMENA IN DEUTERATED METALS

Final Report Volume I

Overview, Executive Summary Chemistry, Physics, Gas Reactions, Metallurgy

Sponsored by the State of Utah

Technical Information Series PB91175885 Foreword

The work presented in this Final Report of the National Cold Fusion Institute has been supported by the State of Utah. The advice and support of the Legislative Oversight Committee and the Fusion/Energy Advisory Council is gratefully acknowledged. Tribute is due to the dedication and hard work of all the Institute's employees, but special acknowledgement goes to Mrs. Angie Mitchell and Mr. Paul Woodward for their untiring efforts in assembling this document.

1-ii Table of Contents

Volume I

Page

Board of Trustees’ Preface 1-v

I. Overview and Executive Summary 1-1 F.G. Will

II. Chemistry

1. Tritium Analysis in Palladium with an Open System Analytic 1-65 Procedure K. Cedzynska, S.C. Barrowes, H.E. Bergeson, L.C. Knight and F.G. Will

2. Closed-System Analysis of Tritium in Palladium 1-80 K. Cedzynska and F.G. Will

3. Cold Fusion Studies in a High-pressure Sealed Cell 1-94 F.G. Will and M.-C. Yang

4. Tritium and Neutron Generation in Palladium Cathodes with 1-131 High Deuterium Loading F.G. Will, K. Cedzynska and D.C. Linton

111. Gas Reactions

1. Deuterium-Gas Phase Reactions on Palladium 1-151 J.R. Peterson

IV. Metallurgy

1. Calorimetric Measurements during Electrochemical Loading of 1-185 Deuterium in Palladium and Palladium Alloys Sivaraman Guruswamy, R.K. Rajamani, J. Li and M.E. Wadsworth

2. Excess Heat Estimation with the Kalman Filter 1-263 R.K. Rajamani and F. Bourgeois

3. Explosive Compaction of Electrode Materials and Metal 1-277 Deut erides Sivaraman Guruswamy, M. McCarter and M.E. Wadsworth

1 -iii 4. Measurement of D/Pd Ratio using Dilatometry and Factors 1-292 Influencing the Deuterium Loading Level Sivaraman Guruswamy, J. Li and N. Karattup

5. Ultrasonic Energy Effects on Palladium Electrodes in 1-310 Cold Fusion Cells L. Anderson and W. Tuntawaroon

V. Physics 1. Nuclear Measurements on Deuterium-Loaded Palladium 1-324 and Titanium H.E. Bergeson, S.C. Barrowes, K.C. Crawford, X.-M. Du, L. Knight, Y.-Q. Li, F. Lotfi, G. M. Sandquist, S.-X. Wang and J. West

Tables of Contents, Volumes II and Ill 1-388

Report of Legal Counsel 1-390

1-iv Board of Trustees' Preface

The March 1989 announcement by Pons and Fleischmann stimulated worldwide interest in the cold fusion phenomenon. In Utah the legislature appropriated $5 million to support cold fusion research and development. As cold fusion inquiries continue worldwide, this interim report has been written to document the scientific and legal work that has been funded by the Utah legislature.

More than 10% of the money provided was used by the University in its efforts to protect the intellectual property and patent rights. We think to have done anything less would have been irresponsible.

Was the State of Utah wise to have funded the work of the NCFl over the last two years? We think that as a venture capital investment it was prudent, and as an effort to protect and advance the state's interest in a property right, and in potential state economic development, it was a singular opportunity that should have been pursued.

The work has proven to be more complicated than was expected, as are almost all new ventures. Piecemeal work will continue at the University of Utah and elsewhere as funds are found. Patent protection will continue to be pursued in every way possible. No further funds will be requested from the state at this time.

When the science is fully understood, we predict there will be important new chapters written on the nature of new scientific claims, on the ownership and stewardship of intellectual property rights, and on the nature of regional and national economic competitiveness.

Respectfully submitted,

Ian Cumming, Chairman Board of Trustees, NCFl

Chase N. Peterson President University of Utah

1-v

Cold Fusion Overview and Executive Summary

by F.G. Will

1-1 Table of Contents

Page

I. Status of Cold Fusion 1-3

1. Political and Financial Status in the United States 1-3

2. Climate of Cold Fusion Abroad 1-4

3. Technical Status of Cold Fusion 1-5

a. Excess Heat 1-9

b. Nuclear By-products 1-10

c. Excess Heat and Nuclear By-products 1-13

d. Theoretical Aspects 1-15

e. Conclusions 1-16

f. References 1-17

g. Cold Fusion Review Articles 1-19

II. Executive Summary of National Cold Fusion Institute Work 1-20

111. Conclusions 1-28

IV. Cold Fusion Bibliography 1-29

1-2 1. Status of Cold Fusion

1. Political and Financial Climate in the United States

Recent strong findings in support of the reality of cold fusion, obtained at several Navy laboratories, Los Alamos National Laboratory, and the National Cold Fusion Institute, are giving rise to the hope that the perception of cold fusion in the scientific community and the public will be improving.

Presently, however, in spite of very encouraging scientific results obtained in cold fusion work, both in the United States and abroad, the political and financial climate in the U.S. remains generally negative. In public interview with the media in February, an official of the U.S. Department of Energy continued to express a negative attitude towards cold fusion, making it very difficult to obtain funding of cold fusion work from the Department of Energy until more significant positive evidence for cold fusion may change this environment. Other U.S. government agencies that had funded cold fusion work one year ago, have terminated or decreased their level of funding. However, the Electric Power Research Institute continues funding cold fusion work in the United States, and it is estimated that this Institute has appropriated approximately 1.5 million dollars in 1991 in support of cold fusion studies.

Several government laboratories are continuing their work on cold fusion, among them most notably are Los Alamos National Laboratories, The Naval Research Laboratory, The Naval Underwater Systems Command and The Naval Weapons Center. Significant positive results have been obtained in each of these laboratories. It is estimated that the rate of spending in these laboratories amounts to approximately $500,000 annually. At Universities, cold fusion efforts are continuing at Brigham Young University, Texas A&M University, Idaho State University, Colorado School of Mines, Arizona State University, The University of Tennessee, Massachusetts Institute of Technology, the University of Hawaii and a few others.

At the National Cold Fusion Institute, the University of Utah, the cold fusion effort in fiscal year 1991 has continued with about 15 technical personnel at an annual rate of expenditure of approximately $800,000.

All combined, it is estimated that the current rate of expenditures for cold fusion efforts nationally amounts to approximately four million dollars annually.

1-3 Corporate laboratories appear to be mostly in a holding pattern with respect to cold fusion work and are carefully monitoring advances made in cold fusion elsew here.

Based upon the good progress achieved in cold fusion work in the U.S. and abroad, it is predicted that cold fusion work in the U.S. will be expanded slowly and cautiously within the next year. It will be unavoidable that the weight of convincing scientific results will have a positive impact on the willingness of government funding agencies and corporations to invest more money in cold fusion work.

2. Climate of Cold Fusion Work Abroad

Japan continues its diverse involvement in cold fusion with what is most likely the largest effort anywhere. Reportedly, Japan now devotes 2% of its fusion budget to cold fusion studies. This would indicate that the number of groups and researchers involved in cold fusion work last year has increased. Last year, an estimated 200 researchers were involved in cold fusion studies in approximately 40 groups, mostly at universities.

Probably the second largest effort in cold fusion overseas is in Russia. The Soviet Academy of Science has given cold fusion a priority designation and work in over 20 institutions is now reportedly financed with $15 million Rubels for four years. The recent first Soviet National Conference on cold fusion that took place in Dubna, from March 22-26, 1991, bears witness to the increasing interest in cold fusion in Russia. The meeting was attended by over 100 scientists, and 60 papers were presented dealing exclusively with nuclear effects in deuterium-loaded solids.

An increasing number of groups appears to work on cold fusion in China. This involves at least 10 groups at different universities and at the Chinese Atomic Energy Center. Various Chinese cold fusion researchers have been participating in cold fusion conferences, such as the Provo-Utah Conference in October 1990. Also, Chinese scientists are performing cold fusion work on a Visiting Scientists basis at several universities in the U.S.

Cold fusion work is also continuing at the Bombay Atomic Research Center in India, although at a somewhat reduced level. Last year, approximately 40 researchers

1-4 were involved in cold fusion work in India, most of them at the Atomic Research Center in Bombay.

In Europe, it appears that Italy continues to have the largest cold fusion effort. Work is carried out at a number of universities across the country. The forthcoming Second International Cold Fusion Conference, a continuation of the First Cold Fusion Conference held in Salt Lake City in March 1990, will take place in Como, Italy from June 29 - July 4, 1991. This conference is expected to be attended by over 300 scientists with over 70 papers scheduled for presentation.

Work on a smaller scale continues in several other countries, among them, Argentina, Australia, Bulgaria, Canada, Germany, Isreal, Spain, Sweden and Taiwan.

3. Technical Status of Cold Fusion

Significant progress has been achieved in cold fusion, particularly in the area of nuclear phenomena. This is evident from the large number of papers published in the literature and from the fact that the two last major conferences on cold fusion, those in Provo, Utah and Dubna, Russia, have almost exclusively addressed nuclear phenomena rather than excess heat findings. Nevertheless, important excess heat findings have also been reported by several groups within the last year. Several of these new results were on excess heat, coupled with the generation of nuclear by- products.

An updated compilation of the groups that have reported to have found various manifestations of cold fusion is presented in Table 1. Over 100 groups from more than 12 countries have now reported on various types of evidence for the occurrence of nuclear reactions in deuterium-loaded metals or compounds. This includes evidence for excess heat, tritium, neutrons, x-rays or gamma rays, helium or charged particles. Results of this work have been presented in over 500 publications. A bibliography is given at the end of this Overview and Executive Summary.

Several review articles have also been published in the past year and are listed separately after the references of the Technical Status of Cold Fusion. In view of the existence of these review articles, only the highlight results obtained in cold fusion work will be addressed in the present overview.

1-5 Table 1

GROUPS REPORTING CO LD FUSION EVIDENCE

Investigators Institution System Heat 3H n Other Report Type*

Adams/Criddle U Ottawa, Canada Pd/LiOD xx 4 Adzic Case Western U Pd/LiOD xx 2 Alikin Perm State U, USSR Pd/D2 X 3 Alquasrni U Kiel, Germany Pd/Sol xx 4 Appleby Ctr. EI.Chem. Texas A&M Pd/LiOD X 2 Arata Kink U, Japan Pd/LiOD X 1 Bertin U Bologna, Italy Pd/LiOD X 1 Bockris TexasA&M U Pd/LiOD xx 182 Bose BARC, India Pd/D2 xx 1 Cai Chinese Acad Science X X 2 Cecil Colorado School Mines Ti, Pd/D2 Ions 2 Cedzynska NCFl/ U Utah Pd/D2S04 X X 3 Celani Frascati Res Ctr Ti, Pd/LiOD X Y 1 Chambers Naval Reserve Lab Ti/d t 1 Chene U Pans, France Pd/D2 X 1 Cherepin Metals Phys Inst, USSR Pd/D2 X He-3 3 Chernov Nuclear Phys Inst, USSR Pd/D2 X 4 Chien Inst. Nucl. Energy, Taiwan Pd/LiOD X 2 Claytor Los Alamos NL Pd/D2 X X 2 Dash Portland State U X 4 DeMana U Rome, Italy X X 4 DeNinno Frascati, Italy Ti/D2 X 1 Din, D.Z. Nuclear Energy Inst, China Pd/D2 X 2 Droege Batavia, Illinois Pd/LiOD X 2 Faler & Vegors Idaho State U TiD2 X 5,6 Fernandez U Madrid, Spain X Fukada Kyushu U, Japan X 4 Gam Matsushita, Japan MetalsID2, xx 8 LiOD Gao, G. T. Eng Phy Inst, China X 2 Golubnichi USSR Pd/LiOD xx 4 Gorodyetski Inst. El. Chern., USSR Ta,Ti,Zr/LiD X 4 Gou, Q. Q. Science & Tech Inst. Pd/LiOD X He-3 2 Chendu, China Gozzi U Rome, Italy Pd/Li0 D xxx 1 Granada Argentine Natl At.Energy Pd/LiOD X 2 Gu Pd/D2,d X 1 Gujovski Gorki, USSR Ti, Pd/LiOD xx 4 Hutchinson Oak Ridge NL Pd/LiOD X 2 lkegarni NFSI, Japan Pd/D2 x?x 5,6 lkezawa Chubu U, Japan Pd/D2 LiOD X? 3 lyengar BARC, India Ti/DZ X X X-rays 2 lyengar BARC, India Pd; Ti/LiOD xx 1

1-6 Investigators institution System Heat 3H n Other Report TvDe*

Jianyu China Inst. Atomic Energy X 4 Jones Brigham Young U Ti; Pd/LiOD X 1 Jordon U Rochester X Jorne Case Western U Pd/LiOD X 4 Kainthla Texas A&M U Pd/LiOD X 1 Karabut Sci. Ind. Assoc., USSR Pd/D2 x? X 4 Kazerashvili lnst Nuc Phys, Novosibirsk PD/LiOD X 4 Krishnan BARC, India Pd/Li0 D xx 1 Kuzmin Moscow State U xxx 3 Landau Case Western U X 4 Lewis Uppsala U, Sweden Pd/LiOD X X 1 Li Tsinghua U, China Pd/D2 y, Ions 2 Liaw U Hawaii Pd/LiD X He-4 2 Lin China Pd/D2 X 1 Lipson lnst Phys Chem, Moscow Ti/D20 X 4 Maeda KURRI, Japan Pd/D2 x? 4 Mathews lndira Gandhi Ctr, India Pd/Li0 D xx 4 Matsu moto Aoyamall, Japan Pd/D2S04 X 1 McBreen Brookhaven NL Pd/LiOD xx 4 Mclntyre NCFV UUtah Ti/D2 xx 3 McKubre SRI International Pd/LiOD X 2 Menlove Los Alamos NL Ti/D2 X 2 Mijrnura Tohoku U, Japan Pd/Li0 D X 6 Miles & Bush Naval Weapons Ctr Pd/LiOD X He-4 1,2 Milikan U C Santa Barbara Pd/LiOD X X 4 Miljanic Kidric Inst. Nuclear Sci., Pd/LiOD; X 1 Yugoslavia D2 Mizuno Hokkaido U, Japan Pd/LiOD X 1 Montgomery Weber State U X Nayar BARC, India xx Niimura Tohoku U Pd/Li0 D X 4 Noninski Sofia, Bulgaria Pd/LiOD X 1 Ohta U Tokyo, Japan Pd/Li0 D X 4 Okarnoto TIT, Japan Pd/Li0 D X 4 Oriani U Minnesota Pd/LiOD X 1 mama TAT U,Japan Pd/LiOD x? 4 Ozawa Hitachi, Japan Pd/D2 X 4 Perekrestenko Lebedev Phys. Inst., Pd/D2S04 X 4 Moscow Perfetti Raw Pd; Ti/LiOD X 1 Peterson NCFV UUtah Pd/D2 xx 3 Pons/Fleischmann NCFV U Utah Pd/Li0 D xx 1 Radhakrishnan BARC, India xx 1 Ragh ave n AT&T X 4 Raj BARC, India He 1 Riley NCFV U Utah Pd/LiOD xx 3 Romodanov USSR Nb,Ta,Y/D2 xx 4 Rout BARC, India X 1 Saini & Raye BARC, India Pd/Li0 D xx 3 Sakamoto Tokai U, Japan Pd/LiOD X 4 Sanchez U Madrid, Spain Pd; Ti/LiOD xx 1 Santhanam Tata Inst. India Pd/Li OD X 1 Sato Tokyo lnst Tech, Japan Pd/LiOD X 1 Schoessow U Florida Pd/LiOD xx 8 Sc hrei ber Stanford U Pd/LiOD X 2 Scott Oak Ridge NL Pd/Li0 D X X 1

1-7 investigators Institution System Heat 3H n Other Report TvDe*

Seeliger U Dresden, Germany Pd/LiOD X 1 Seminoz All-Union Inst, PD/D2, d X He 3 Monocrystals, USSR Shani Ben Gurion U, Israel Pd/D2 X 1 Shyam BARC, India X Sinha BARC, India Pd/LiOD X 1 Sona CISE Milan, Italy Pd/LiOD xx? 1 Storms & Talcott Los Alamos NL Pd/LiOD X 1 Szpak Naval Systems, San Diego Pd/PdCI2 xx X-rays? 1 Tachikawa Jaeri, Japan Pd/D2 x? 4 Takagi TIT, Japan Pd/LiOD X 4 Takahas hi Osaka U, Japan Pd/LiOD x?x 1 Taniguchi Osaka Rad. Inst, Japan Pd/LiOD X Ions 1 Tian, Z. W. Xiamen U, China Pd/LiOD X 2 Tsvyetkov SORUS, USSR Ti/D2 X 4 Tzumida Japan X 1 Venkateswaran BARC, India xx Wada Nagoya U, Japan Pd/D2 X 1 Wakaba yashi PRC, Japan Pd/LiOD x? 4 Wan Ching-Hwa U, Taiwan Pd/LiOD xx 5 Wang, D. L. Nucl Energy Inst, China X 2 Wanq, G. G. Nanjinq U, Nanjinq, China X X 2 Werth Englehard Industries X will & Yang NCFV U Utah Pd/D2S04 X X 3 Wolf Texas A&M U Pd; Ti/LiOD X 2 Xiong, R. H. SW Nucl Phys Inst, China X 2 Yagi Japan Ti/D2 X 1 Yamaguchi NlT Tokyo, Japan Pd/D2 X X 1 Yang, C. China xx 2 Y uk himchu k VNIIEP, USSR V/D2 X 4 Zahm X 1 Zelenskiy Kharkov Inst, USSR Ti; Pd/d X X 3He,t,p 3 Zhou, H. Y. Beijing Normal U, China xx 2 (no name) Belorussian U, USSR Pd/LiOD X 3 (no name) Karpov Inst, USSR X 3 (no name) Quinhua U, Beijing, China X X xory 2

TOTAL NUMBER OF GROUPS: 130 NUMBER OF COUNTRIES: 14

Key: 1= Refereed Journal Publication 2= Conference Proceedings 3= Non-refereed Report 4= Conference Presentation 5= Newspaper Article 6= Personal Communication 7= Submitted to Journal 8= PatenVPatent Application

1-8 Highlight results presented in this overview will be grouped into three major categories: a) Excess heat. b) Nuclear by-products. c) Excess heat coupled with nuclear by-products. d) Theoretical Aspects. e) Conclusions. a. Excess Heat

Fleischmann and Pons continue reporting excess heat findings, measured by isoperibolic calorimetry, carried out in double-walled, evacuated glass cells. In a paper published in July 1990 [l], they reported on continuous excess heat generation of 10 to 35% corresponding to more than 100 W/cmsPd. They also reported on rare heat bursts of up to 4000% excess power. The energy generated in these heat bursts is equivalent to between 5 and 50 megajoules/cm3 Pd. More recently, they have said to have identified a parameter that is the key to the reproducible generation of excess heat [2]. Reportedly, the generation of large excess heat events occurs after 9 to 10 days of electrolysis [3].

At the Provo-Utah meeting in October 1990, Liaw and Liebert [4]reported on the achievement of excess heat values up to 1500% in a molten salt eutectic, containing molten LiD at 380°C. Excess energy values of up to 5 megajoules were obtained in a 190 hour time span. No excess heat was observed in a LiH control cell.

McKubre [5] at Stanford Research International, sponsored by the Electric Power Research Institute, reports finding up to 10% excess heat which can be switched on and off on demand by raising and lowering the current into the electrochemical cell. Apparently, the heat -producing palladium electrodes had been preselected on the basis of whether high loading with deuterium had been achieved in electrochemical cells outside of the calorimeter. In spite of the fact that the excess heat attained is only lo%, the result is regarded as very significant due to its reproducibility and the high accuracy of the calorimetric technique employed. Furthermore, no excess heat is generated in light water control cells.

In an international patent application published in February 1991, Schoessow [6]claims up to 63% excess heat generation in electrochemical cells employing palladium, titanium and zirconium cathodes. Light water controls did not exhibit any excess heat, and heavy water cells that originally produced excess heat ceased to generate excess heat when large amounts of light water were added.

1-9 b. Nuclear By-products

A significant number of results has been obtained during the last year on the generation of nuclear by-products, in particular, neutrons and tritium, and to a lesser extent charged particles, helium and gamma radiation.

Neutrons

Jones [7] was the first to determine the energy of neutrons emitted during deuterium loading of palladium and titanium cathodes in electrolytic cells. He employed a fast neutron spectrometer to measure an energy of 2.5 MeV, showing the occurrence of deuterium fusion at room temperature. Shortly thereafter, DeNinno et al [8] detected neutron bursts up to 5,000 per second on titanium in deuterium gas. Since then, considerable refinement in instrumental techniques has occurred. This has led to significantly higher counting efficiencies and much reduced background.

Menlove [9] at Los Alamos National Laboratory conducted experiments on titanium filings in deuterium gas in an underground laboratory, employing 51 3He tubes, arranged in two concentric rings. This resulted in a counting efficiency of 44%. When performing the experiments in an underground laboratory, the coincidence neutron count background was only 0.03 counts per hour. Neutron events were counted in a time gate of 128 psec. When temperature-cycling the titanium between -190 and 25OC, neutron bursts of 200 -300 neutrons in the 128 psec time gate were observed. The most intense bursts occurred at -30°C. Superimposed on the neutron bursts was a rather continuous low-level neutron activity, amounting to three counts per minute.

Menlove's findings substantiated the earlier neutron results of DeNinno on deuterium-loaded titanium. A large number of other groups have in the meantime also confirmed these findings.

Takahashi [lo] at the University of Osaka, Japan, measured the energy spectrum of neutrons emitted during heavy water electrolysis, using palladium cathodes. The energy spectrum of the neutrons showed a peak at 2.5 MeV and a second broader peak at about 4.5 MeV. The neutron intensities were fairly low, amounting to 1.5 to 2 x above background. But, significantly, the neutron emissions were found to be time-related to the electrolysis conditions: The neutron intensity

1-10 increased when the current density was increased and vice versa. The energy maximum at 2.5 MeV is expected for d-d fusion. However, the maximum at 4.5 MeV cannot be readily reconciled with that reaction. Takahashi postulated a 3-body reaction namely, d-d-d. In quantum mechanical calculations, Takahashi was able to show that the probability for this reaction in a palladium lattice is about as high as for the d-d reaction. Other investigations have in the meantime substantiated the finding of a neutron energy maximum around 5 MeV.

Storms and Talcott [ll] made an extensive study of tritium production on Pd in heavy water electrolysis. They found tritium enhancement in 11 out of 53 cells at levels of 1.5 to 80 times the original concentration. The accumulation of tritium in the electrolyte with time of electrolysis was also determined. Tritium production was found to start within two to several days of starting the electrolysis and on cathodes having a D/Pd ratio as low as 0.7. However, the D/Pd ratios were determined by weighing and are likely to be too small, owing to D loss, especially at high loading ratios. Only one light water control cell was run which did not show any tritium enhancement.

In another extensive study of tritium generation during heavy water electrolysis involving titanium, palladium and palladium-silver alloys, researchers at the Bombay Atomic Research Center (BARC) have consistently found significant tritium enhancement in the electrolyte [12, 131. In 1 1 separate electrolytic experiments, they found cumulative tritium generation, in experiments run between 12 hours and 190 days, from 1 x 1010 to 1.7 x 1014 tritium atoms/cm2. The electrolytes in these experiments were mostly LiOD, but also NaOD and KOD.

Tritium and NeutronS

BARC also conducted an extensive study of simultaneous neutron and tritium generation [12, 141. In 10 separate experiments, performed on palladium, palladium- silver and titanium cathodes, they found total neutron yields from 1.3 x 1O4 to 3 x 106 neutron/cm* and tritium yields from 4 x 109 to 5 x 1013 tritium atoms/cm2 . The neutron to tritium ratio in these experiments amounted to between 1.2 x 10-9 and 10-3.

T. Gam0 et al [15] at Matsushita Electric Industrial Co., explored a large number of metals and alloys for their nuclear activity when loaded with deuterium either in electrolytes or in deuterium gas. On a TiZn2 cathode, they observed 2.45 MeV

1-11 neutrons at 10 x background and tritium enhancement in the electrolyte 5 x above the initial amount. Tritium enhancement up to 10 x background was found on ZrVo.5 Ni 1.5. When using the same alloy in pressurized deuterium gas, neutron bursts 1000 x background were observed for 1 minute. Likewise, tritium enhancements of about 4.5 times background were observed during heavy water electrolysis using Ti2 Ni cathodes.

Claytor et a1 [16] at Los Alamos National Laboratory performed studies in deuterium gas, employing a stack of alternating layers of palladium-silicon and of titanium and silicon. After applying pulsed high current densities to this solid state device, he found tritium enhancements of 3 sigma in 8 out of 30 such cells. He also found neutron bursts slightly above background, that is at up to 760 counts per hour as compared to a background of 712 counts per hour. The tritium to neutron ratio was also found to be significantly larger than 1, often of the order of 109 :l.

Recently, several groups at the National Cold Fusion Institute have found tritium and neutrons in both electrolytic and gas phase experiments on palladium as well as titanium. Cedzynska et a1 [17] developed a technique to reproducibly generate high D:Pd loading ratios and tritium, employing palladium cathodes in D2SO4 solutions. Tritium enhancements of up to 100 x background were observed in both electrolyte and palladium. Neutron generation was observed only on rare occasions, at rates from 4 to 12 counts in 300 to 400 psec. No tritium generation or neutron emissions of this type were observed on light water controls, equal in number to the heavy water cells. Peterson et. al [18] observed tritium enhancements of up to 120 x in palladium, loaded in D2 with the Wada technique. Neutron bursts up to 280 neutrons in 120 psec were observed in the same experiment. Mclntyre et al [19] found tritium in D2 gas- loaded titanium after temperature-cycling. Neutron emissions of 5 to 10 neutrons in 400 psec were observed in these experiments

Charaed Particles

Taniguchi [20] was the first to detect the emission of charged particles from thin Pd foils used in heavy water electrolysis. He employed a cell design in which one side of the Pd foil was exposed to the electrolyte and the other side was in contact with a silicon surface barrier detector. Charged particle emissions were observed in 6 out of 23 experiments conducted in D20 solutions, whereas none of 7 light water controls showed particle emissions. The maximum energy of the particles was 2.1 MeV. This

1-12 observed energy is consistent with 3 MeV protons originating in the palladium and being attenuated in the Pd; this is indicative of cold fusion, since 3 MeV protons would be generated in the tritium-proton branch of a d-d fusion reaction.

Cecil et al [21] at the Colorado School of Mines found evidence for charged particle emissions when conducting experiments on titanium in deuterium gas. The titanium foils were subjected to temperature cycling from -190 to 25°C and a d-c current density of 4Ncm2. He also used a silicon surface barrier detector to determine the energy spectrum of the emitted charged particles. Such particles where omitted in bursts at 25°C with one second to a few hours duration. The energies of the emitted particles were measured to be between 1 and 10 MeV. Cecil suggested that the charged particles were either tritons, 3He or 4He ions. Twelve out of 26 deuterated titanium samples showed such bursts, whereas none out of eight hydrogenated control samples showed bursts. Similar bursts have been observed on deuterated palladium foils.

c. Excess Heat and Nuclear By-products

Bockris et al. at Texas A&M University [22] found large amounts of tritium in both the electrolyte and the gas phase in conjunction with excess heat. The group conducted heavy water electrolysis, employing Pd cathodes. The excess heat generation amounted to values between 10 and 22% for over one month. Tritium accumulated in the electrolyte to values as high as 2 x 1014 tritium atoms. Similar peak values were measured in the gas phase after recombining the gas to water. More generally, however, values in the gas phase were between 3 and 7 x 1011 tritium atoms/cm*. Such values are very similar to the tritium findings at BARC [12].

Scott et al. [23], employing an accurate flow calorimeter cell, found the simultaneous occurrence of excess heat, neutrons and gamma radiation. The studies were conducted on Pd in LiOD. The excess power ranged from 5 to 10% for periods of up to 300 hours. In several cases, the neutron and gamma count rates increased slightly, in apparent correlation with the time periods of excess heat generation. While the increases of the count rates over background were small, the coincidence with induced excess power were seen as giving added credence to the results. Addition of light water to the electrolyte resulted in reduction of the excess power and decrease of the neutron and gamma signals to background levels.

1-13 Gozzi et ai. [24] at the University of Rome were able to associate neutron and tritium generation with excess heat production when charging a Pd cathode in LiOD solution. in a 4-minute period, in which the temperature rose from 36 to 150°C, 7 x 105 neutrons were emitted and excess tritium amounted to 2 x 1O1 atoms. The amount of tritium generated on this porous, high-surface area Pd is similar to the values found by Bockris et al. [22] and BARC [12] on smaller area electrodes but over longer times. The excess heat released in the 4-minute period amounted to 176 Joules (Wattseconds).

Szpak and Mosier-Boss [25] observed the generation of excess heat, concurrent with tritium generation and low-energy radiation, possibly soft x-rays. In their approach, they deposited Pd onto a Ni screen from a heavy water PdC12 solution. The Pd absorbed D while it was being deposited. Excess power amounted to between 10 and 40% and excess energy production was 2500 Joules. Tritium enhancement in the electrolyte amounted to a factor 10 over background. No excess heat or nuclear by-products were observed on a light water control cell.

Yamaguchi and Nishioka [26] at the National Telephone and Telegraph Laboratories in Tokyo, Japan found evidence for excess heat and nuclear by-product formation on palladium foils in deuterium gas. These researchers employed a solid state cell, comprised of a palladium foil with a gold film sputtered on one side and a manganese oxide film on the other side. They passed a current density of several A/cm* perpendicular to the face of the palladium foil. Temperature excursions of several hundred "C were observed, accompanied by the generation of products with mass three, most likely tritium or 3He. In one case out of 20 experiments, several large neutron bursts were observed in a 90-minute time period. Two of the bursts amounted to 106 neutronskec.

Will and Yang [27] observed excess power excursions and tritium generation on a Pd cathode in a high-pressure, sealed electrolytic cell under conditions of evolving no oxygen. The standard-type of anode had been replaced with a fuel cell-type deuterium oxidation electrode. Excess power of up to 20 and 33 o/o was observed in two time intervals of 36 and 26 hours, respectively. Excess energy amounted to approximately 500 Joules. The tritium content in "hot spots" of the Pd cathodes was 4 x 108 tritium atoms, compared to a maximum initial content of 5 x lo7.

1-14 Probably the most dramatic finding of excess heat accompanied by nuclear by- product formation was recently made by Miles at the Naval Weapons Center in collaboration with Bush at the University of Texas [28]. They found excess heat up to 27% during heavy water electrolysis using palladium cathodes and were the first to show helium in the off-gas in very approximate proportion to the excess heat generated. They collected the deuterium and oxygen gas, generated during electrolysis, in a sealed glass flask. After cryogenic absorption of these gases, the helium was detected in a mass spectrometer. 4He was observed at values up to 1000 times the detection limit of the mass spectrometer which amounted to 10'2 4He atoms. Light water control cells yielded no excess heat and no 4He. Likewise, no 3He was found in any of the experiments. d. Theoretical Aspects

A number of theoretical approaches have been advanced in an attempt to explain why fusion reactions might proceed in deuterium-loaded metals at ordinary temperatures. The principal challenge is to explain how the Coulomb barrier can be penetrated such as to raise the tunneling probability by some 50 to 60 orders of magnitude as compared to the barrier that inhibits d-d fusion in a D2 molecule.

G. Preparata [29] has recently reviewed existing theories of cold nuclear fusion. Hence, several of the theories will only be highlighted here.

Bush [30] has proposed a transmission resonance model which applies the well-known quantum mechanical result that a periodic set of potential barriers becomes transparent (may be penetrated) if the diffusing particles-"diffusons"- have certain well-defined wave lengths, that is, move with well-defined velocities. Recently, Bush has used his model to calculate excess heat and to predict optimal trigger points for excess heat generation.

Hagelstein [31] has developed a model involving electron capture by a deuteron, resulting in two off-shell neutrons and a neutrino. The neutrons then proceed to react with protons or deuterons, requiring no Coulomb barrier penetration. Neutron capture by a proton, yielding a deuteron, is favored lo4 times over capture by a deuteron, yielding a triton. The former reaction is exothermic, with the generated heat coupling to the metal lattice.

1-15 Rafelski et al. [32] proposed a model involving the interaction of yet undiscovered heavy negative particles with deuterium in the metal lattice. These particles are thought to be of ancient cosmic origin and cause a catalytic reaction similar to that of muon-catalyzed fusion which is well established.

Bressani et al. [33] and Preparata [34] applied superradiance theory to cold fusion phenomena in condensed matter. Their model involves the application of quantum electromagnetic field theory. The moving or oscillating charges, such as electrons, deuterons and palladium nuclei, have electromagnetic fields (plasmas) associated with them that provide for strong coupling. A central feature of the model is the coherent interaction of large numbers of charged particles. Coulomb barrier penetration is made possible by the presence of a sufficient electron density between two deuterons. Another factor 10’0 enhancement of the fusion probability is predicted from an interaction between loosely bound deuterons and the entire system of strongly bound deuterons contained in a coherency domain. This leads to the theoretical prediction that high fusion rates will exist only if the D:Pd loading ratio has attained a critical value just larger than one. Under these circumstances, the model predicts the generation of large amounts of excess heat (tens of W/cm3 Pd) by ultra-fast coupling of the fusion energy to the electron plasma. This process is predicted to vastl] enhance the 4He channel while suppressing the neutron and tritium channels. e. Conclusions

Cold fusion work continues in many countries with considerable pace n spite of the fact that the known funding level is fairly low. The degree of activity in cold fusion is evidenced by the attached bibliography which lists over 500 items. The occurrence of nuclear reactions in deuterium-loaded solids, such as palladium and titanium can no longer be reasonably denied. The generation of nuclear by-products, especially neutrons and tritium, has now been confirmed by a large number of groups worldwide. However, with the exception of one recent finding involving helium, the level of the nuclear by-products generated is smaller than the reported levels of excess heat by a factor of one million or more. If the observed heat is generated by deuterium fusion, then helium could still be the missing link that has not been pursued sufficiently by most groups. Other nuclear reactions may be involved, but then other nuclear by- products must be generated in sufficiently large quantities such as to correspond to the observed heat levels. The possibility that the excess heat is not of nuclear origin can

1-16 not presently be ruled out. Considerably more research is required to understand the phenomena involved and to explain the origin of the observed excess heat. This poses a significant challenge for both experimentalists and theoreticians.

The progress obtained in cold fusion work is impressive. Reproducibility of some of the phenomena appears to be in hand, enabling more systematic scientific work to be pursued.

f. References

1. M. Fleischmann, S. Pons, M.W. Anderson, L.J. Li and M. Hawkins, J. Electroanal. Chem. 287,293 (1990).

2. R. Adair, S. Bruckenstein, L. Hepler and D. Stein, Report of the Committee for the Review of the National Cold Fusion Institute, Dec. 1, 1990.

3. J.E. Bishop, Wall Street Journal, Feb. 7, 1991.

4. Y. Liaw, P.-L. Tao, P.-Turner and B.E. Liebert, submitted to J. Electroanal. Chem., March 1991.

5. M.C.H. McKubre, R.C. Rocha-Filho, S. Smedley, F. Tanzella, J. Chao, B. Chexal, T. Passel1 and J. Santucci, Proc. 1st Annual Conf. Cold Fusion, Salt Lake City, Utah, March 28-31, 1990, p. 20.

6. G. J. Schoessow, International Patent Appl. WO 91/02360, 21 Feb. 1991.

7. S. E. Jones, E. P.Palmer, J. B. Czirr, D.L. Decker, G. L. Jensen, J. M. Thorne, S. F. Taylor and J. Rafelski, Nature m,737 (1989).

8. A. DeNinno, A. Frattolillo, G. Lollobattista, L. Martinis, M. Martone, L. Mori, S. Podda and F. Scaramuzzi, II Nuovo Cimento 101A, 841 (1989).

9. H. 0. Menlove, M. A. Paciotti, T. N. Claytor, H. R. Maltrud, 0. M. Rivera, D. G. Tuggle and S. E. Jones, Proc. Conf. Anomalous Nuclear Effects in Deuterium/Solid Systems, Provo, Utah, Oct. 22-24, 1990.

1-17 10. A. Takahashi, T. Takeuchi, T. lida and M. Watanabe, J. Nucl. Science and Technol. 22,663 (1990).

11. E. Storms and C. Talcott, Fusion Technology u,680 (1990).

12. P. K. lyengar and M. Srinivasan, Proc. 1st Annual Conf. Cold Fusion, Salt Lake City, Utah, March 28-31, 1990, p. 62.

13. T. S. Murthy, T. S. lyengar, B. K. Sen and T. B. Joseph, Fusion Technology u, 71 (1990).

14. M. S. Krishnan, S. K. Malhotra, D. G. Gaonkar, M. Srinivasan, S. K. Sikka, A. Shyam, V. Chitra, T. S. lyengar and P. K. lyengar, Fusion Technology u,35 (1 990).

15. T. Gamo, J. Niikura, N. Taniguchi, K. Hatoh and K. Kinichi, European Patent Application 0 395 066, 26 April 1990.

16. T. N. Claytor, P. A. Seeger, R. V. Rohwer, D. G. Tuggle and W. R. Doty, Proc. Conf. Anomalous Nuclear Effects in Deuterium/Solid Systems, Provo, Utah, Oct. 22-24, 1990.

17. K. Cedzynska, F. G. Will, and D. C. Linton, Final Report, National Cold Fusion Institute, Vol.1, Technical Inform. Series PB91175885, June 1991.

18. J. Peterson, Final Report, NCFI, Vol. 1, Techn. Inf. Ser. PB91175885, June 1991.

19. J. D. E. Mclntyre, Final Report, NCFI, Vol. 1, Tech. Inf. Ser. PB91175885, June 1991.

20. R. Taniguchi, T. Yamamoto and S. Irie, Japan. J. App. Phys, a,L2021 (1989).

21. F. E. Cecil, H. Liu, D. Beddingfield and C. S. Galovich, Proc. Anomalous Nuclear Effects in Deuterium/Solid Systems, Provo, Utah, Oct 22-24, 1990.

22. J.O’M. Bockris, G. H. Lin and N. J. C. Packham, Fusion Technology u, 11 (1990).

1-18 23. C. D. Scott, J. E. Mrochek, T. C. Scott, G. E. Michaels, E. Newman and M. Petek, Fusion Technology a,103 (1990).

24. D. Gozzi, P. L. Cignini, L. Petrucci, M. Tomellini and G. DeMaria, II Nuovo Cimento 103q, 143 (1990).

25. S. Szpak and P. A. Mosier - Boss, J. Electroanal. Chen. m,255 (1991).

26. E. Yamaguchi and T. Nishioka, Japan. J. Appl. Phys. a,L 666 (1990).

27. F. G. Will and M.-C. Yang, Final Report, National Cold Fusion Institute, Vol. 1, Technical Inform. Series PB91175885, June 1991.

28. B. F. Bush, J. J. Lagowski, M. H. Miles and G. S. Ostrom, J. Electroanal. Chem. m,271 (1991).

29. G. Preparata, Final Report, National Cold Fusion institute, Vol. 3, Tech. Information Series PB91175885, June 1991.

30. R. T. Bush, Fusion Technology 19,313 (1991).

31. P. Hagelstein, Proc. 1st Annual Conf. Cold Fusion, Salt Lake City, Utah, March 28-31, 1990, p. 99.

32. J. Rafelski, M. Sawicki, M. Gajda and D. Harley, Fusion Technology u, 136 (1990).

33. T. Bressani, E. Del Giudice and G. Preparata, II Nuovo Cimento 1014, 845 (1989).

34. G. Preparata, Proc. 1st Annual Conf. Cold Fusion, Salt Lake City, Utah, March 28-31, 1990, p.91.

g. Recent Cold Fusion Reviews 1. J. O'M. Bockris, G. H. Lin and N. J. C. Packham, Fusion Technology 11 (1 990). 2. M. Srinivasan, Current Science, Apr. 25, 1991. 3. E. Storms, to appear in Fusion Technology 4. V. A. Tsarev and D. H. Worledge, submitted to Fusion Technology.

1-19 II. Executive Summary of National Cold Fusion Institute Effort

1. Introduction

The National Cold Fusion Institute was established in August 1989 with a State appropriation of $5 million dollars of which $4.5 million were earmarked for research and development and $0.5 million for patent and legal services. The forerunner of the Institute was the Cold Fusion Program, established in May 1989 under the direction of Hugo Rossi, who continued as Director of the Institute until December 1989. James Brophy served as Interim Director of the Institute from December 1989 - January 1990 until Fritz Will joined the Institute as Director in February 1990. The original research and development strategy of the Institute was based upon the hope that cold fusion phenomena could soon be exploited to build demonstration devices and engineering models. Thus, a broad-based interdisciplinary approach was initially taken, including efforts in all fields of interest to cold fusion work, that is, Electrochemistry, Metallurgy, Physics and Engineering. Strong emphasis was placed on increasing excess heat generation by devising an extensive parameter study, expected to culminate in building a heat demonstration device. The research strategy was reevaluated in the early summer of 1990, to address the following selected key scientific issues: 1) Increasing the understanding of cold fusion phenomena. 2) Developing an excellent analytical capability for analyzing tritium in palladium. 3) Expanding the study of loading of metals in deuterium gas. 4) Improving the neutron detection and developing charged particle detection capabilities. More specifically, emphasis was placed on identifying the factors influencing reproducibility and to explore possible methods to trigger and quench cold fusion phenomena. On the other hand, the budget for fiscal year 1991 made it necessary to de-emphasize the engineering effort and the visiting scie ntis ts/collabo rative program.

2. Organization of Final Report

The presentation of the technical results in this final report will be made in three volumes: Volume I - Introduction and Executive Summary, Chemistry, Gas Reactions, Metallurgy and Physics. Volume II - Engineering. Volume Ill - Theoretical and Collaborative Studies. The results of the Electrochemistry Group are anticipated to be presented in Volume IV, together with the results of a review of the calorimetric data, currently being undertaken.

1-20 3. Highlight Results Obtained at National Cold Fusion Institute

It is generally accepted that tritium generation comprises one of the most important manifestations for the occurrence of deuterium fusion. Following widely published claims of one group at Texas A&M University that tritium, found in cold fusion studies, results from contamination of the palladium and not from nuclear reactions, we decided to address this issue in depth and to develop a reliable analysis procedure. An open-system analytical procedure, essentially identical to that used by the Texas group, was first developed and shown to be subject to erroneous results unless extraordinary precautions were employed. We, therefore, developed a new closed-system analytical procedure for the analysis of tritium in palladium. This procedure has a sensitivity and accuracy of 5 x 107 tritium atoms and is not subject to the shortcomings of the open-system procedure. We have applied this new procedure to over 100 as-manufactured palladium wire sample of various lots and sizes from two different sources. We have found none of these samples to have any tritium contamination within a detection limit of 5 x lo7 tritium atoms. This closed-system procedure proved to be a key tool in our later successful demonstration of tritium generation in deuterium-loaded palladium and titanium.

In the past four months, we have successfully applied a continuous, reliable technique for the determination of the deuterium to palladium loading ratio, developed earlier by the Engineering Group. Application of this technique enabled us to develop, probably for the first time anywhere, a procedure to reproducibly attain D:Pd loading ratios of unity or slightly higher.

We were able to show that tritium could be generated reproducibly when loading ratios in the vicinity of one were achieved, whereas no tritium was found when the loading ratio was substantially smaller than one. Moreover, the tritium concentration in the electrolyte was found to increase linearly with time after a loading ratio close to one had been attained. These results were obtained in hermetically sealed cells in which the oxygen generated at the anode did not contact the palladium cathode. Tritium analysis was performed in the deuterium gas, the electrolyte and the electrode. Tritium enhancements in the electrolyte of up to 50 x and in the palladium of at least 10 times were observed. Light water control cells were always run in

1-21 electrical series with heavy water cells under identical conditions. None of the control cells ever showed tritium enhancements in the electrolyte or palladium cathode in spite of achieving loading ratios of one or slightly higher than one.

Several periods of neutron emissions were observed in these experiments. Neutron counting was done with an efficiency of about 2%, employing two 3He counters each at the D20 cell and the H20 control cell. On eight D20 cells, a total of five neutron events were monitored with 4 to 14 neutrons counted in a time interval of 400 psec. Although such events occurred very infrequently in the D20 cells, we regard their occurrence as significant, since none of these events occurred in an equal number of H20 control cells. Single, double or triple neutron counts were, further more, disregarded.

We have also developed a novel electrochemical cell, operating in high- pressure deuterium and featuring continuous and automatic determination of the D/Pd loading ratio as well as no oxygen evolution. With this cell, we have found a tritium content in hot spots of the Pd cathode, corresponding to 2.2 x 109 atoms/g Pd, whereas the maximum tritium contamination level in the Pd is 3 x 108 tritium atoms/g Pd. In this 12-day experiment in which we achieved loading ratios in excess of 0.84, two periods of excess power generation occurred. In the first time interval, lasting 36 hours, the excess power amounted to approximately 20%, whereas in the second time interval of 26 hours, the average excess power was 15%' with peak values as high as 33%. In other heavy water cells with D/Pd ratios smaller than .75, no excess heat and tritium were observed. Also, none of several light water controls showed tritium or excess heat. Nevertheless, we regard these findings as tentative, pending duplication of the excess heat and tritium results. b. Gas Reactions

In gas phase loading experiments of palladium with deuterium, employing the Wada-technique, we have found evidence for tritium generation in the palladium as well as neutron bursts. In this technique, two palladium electrodes are subjected to an electrical discharge, applying an a.c. voltage of typically 1 keV to activate the surface, followed by deuterium absorption. Neutron generation is monitored after the 10-20 minute electric discharge has been completed. Using one of NCFl's 3He neutron detection facilities with a collection efficiency of approximately 5%, six neutron generation events with between four and eight neutrons each were observed in a time

1-22 frame of less than 400 psec. Two more neutron events at 4.7 and 7.2 sigma levels were monitored in the early phases of the study with a germanium crystal gamma detector. These 8 neutron events were observed on a total 19 experiments conducted after the process conditions were under control. Several of the palladium electrodes showed definite tritium generation. The tritium distribution in the palladium electrode was usually highly non-uniform. In "hot spots" we observed tritium levels of up to 4 x 1010 atoms/g Pd. Before the experiment, the Pd did not contain tritium within our detection limit of 3 x 108 atoms/g Pd. The most successful experiment was carried out in collaboration with Jones at Brigham Young University. In a time period of 120 hours, four neutron bursts were observed with three of the bursts amounting to between 20-30 source neutrons in a 115 psec time gate and one burst amounting to 280 neutrons in the same time gate. Both of the palladium electrodes used in this experiment showed significant tritium levels of up to 1.5 x 1O1 atoms/g Pd.

In deuterium gas loading experiments on titanium powder, we have also observed significant tritium levels in the titanium and several neutron emission events. These experiments are similar to those originally carried out by the Frascati group in Italy. They involve deuterium loading of titanium, followed by temperature cycling between -190 and 25°C. We have found values up to 9 x 1010 tritium atoms/g Ti on samples that had been temperature-cycled. A deuterated titanium sample that was not temperature-cycled and a hydrogen control sample showed no tritium. Neutron generation was also observed in these experiments, with 4 to 9 neutrons counted in 400 psec with 5% counting efficiency. One, two and three-neutron events were not considered. Background measurements and an experiment performed on a hydrogen control never showed multiplicities of 4 or more neutrons. c. Metalluray

The dilatometer technique, measuring increases of the length of a palladium wire during loading with deuterium, was applied to determine the D/Pd and H/Pd loading ratio on Pd and Pd alloys. The effect on loading of various parameters, such as microstructure, hardness, surface condition, alloying, electrolyte composition and current density was investigated. Loading ratios between 0.7 and 0.93 were achieved and loading was found to change with applied cathodic overpotential. Addition of alloying elements reduced the maximum achievable loading ratio to less than 0.8. Microstructural studies indicate that at almost all practical current densities employed by different investigators, from a few hundred pA/cm2 to 600 mA/cm*, plastic

1-23 deformation of the palladium electrode occurs. The resulting dislocation density is likely to result in an overestimation of the D/Pd ratio. Extensive micro and macrocracking observed in palladium at high current densities or after extended charging times lowers the maximum loading that can be achieved. Diameter changes of the wire (on a percentage basis) are larger than changes of the length. Therefore, simultaneous measurement of the diametral and axial expansion would be required to accurately determine the D/Pd loading ratio. This was not undertaken in this study.

The effect of ultrasonic energy input to electrochemical cells containing palladium cathodes and D20 solutions was investigated. Cells which were subjected to ultrasonic energy always exhibited slightly higher temperatures and cell power than comparable cells without ultrasonic excitation, operated under otherwise identical conditions. Higher cell power persisted even in those cases where ultrasonic input was provided for only one hour each day. in several cases, excess power levels disappeared after a few days of cell operation. Stimulation of large excess power excursions what not observed.

Attempts were also undertaken to induce cold fusion events by explosive compaction of deuterated metals, alloys, as well as various deuterides. The compacted materials included Pd, Pd-Ti, PdDx, TiDx, Au-Pd-Pt, NiTi and metal matrix composites, such as TiAI-Sic. It was hoped that the unique compositions and microstructures, obtained by explosive compaction, might lead to cold fusion events. Slight enhancements in the tritium level, amounting to 20% above background were observed in several cases. In a single experiment involving TiD2, indication for low- level neutron generation was observed, but could not be reproduced in further experiments.

A mathematical technique - called the Kalman filter - was developed to enable on-line calculation of excess heat produced during heavy water electrolysis employing Pd (or other) cathodes. The method proved particularly useful owing to its capability to determine excess heat in the presence of electric noise and process disturbances. The method was applied successfully to analyze excess heat data of a large number of cells. The calculated values were in agreement with values using other approaches.

Extensive calorimetric measurements were performed on over 40 palladium cathodes in electrolytic cells, employing LiOD solutions. Large temperature

1-24 excursions were observed in experiments with an initial cell design having large heat losses. These results were later explained on the basis of intermittent gas recombination, resulting in thermal transients in the cells. Two later cell designs with lower heat losses did not exhibit such large temperature excursions, and no excess heat was demonstrated in any of these cells within the accuracy of the calorimetry, that is, 2-3%. Electrolyte boil-off during a time period of a few hours was observed on one cell. Heat balance calculations resulted in the finding that no excess heat had been generated in the cell either before or during the boil-off. d. Phvsics

The major thrust has been on building up and improving the nuclear by-product detection capabilities, collaborating with the other groups in detecting neutron generation, operating the liquid scintillation counter for tritium counting and making preparations for charged particle measurements in electrolytic-type and gas phase experiments. Initially, germanium single crystal counters and later helium-3 counters were used for neutron counting. This allowed neutron measurements with increased collection efficiency and in a time frame as short as of a few 1/1,000,000 of a second. Sophisticated electronics and event loggers were developed to make such measurements possible with a total of 12 helium-3 tubes. These neutron counting capabilities were successfully applied to detect small, but significant, neutron generation events in a variety of electrolytic and gas phase loading experiments, carried out , in particular, by the Chemistry and Gas Reactions Groups. Neutron generation events were observed (1) on palladium electrodes, highly loaded with deuterium in electrolytic solutions, (2) on palladium electrodes loaded in deuterium gas using the Wada-type of procedure and (3) on titanium powders, loaded in deuterium gas and then thermally cycled. Neutron generation events, that could not be ascribed to cosmic ray events, were detected in the form of 4 to 12 neutrons in a time frame as short as 100-400 psec. Such events were never observed on a large number of light water and hydrogen controls. Such high-multiplicity results are quite rare. To detect lower multiplicity events reliably, a low-background environment would be required. Plans were, therefore, developed to conduct future neutron measurements in an underground laboratory. This proved no longer possible within the remaining time and funding.

1-25 Flow calorimeter cells of various designs, employing internal or external gas recombination, were designed and applied successfully. Long-term electrolysis was carried out in (all but one case) D20 solutions of LiOD, using Pd cathodes. Tritium was found in 5 out of 9 cells. In 6 experiments, the Pd cathode was allowed to outgas in D20 for 8 days, after completion of the electrolysis; tritium was observed significantly above background in 3 of the 6 experiments. The level of tritium showed surprising uniformity, ranging for all 5 cells from approximately 1.7x I 010 to 2.1 x 1010 T atoms/cm2 of Pd cathode. These values are in the middle of the range of T findings at BARC in India, in experiments run for similar lengths of time. The values are also very similar to those found by the Chemistry Group at the NCFI. Evidence for excess heat was found in 3 of the 5 tritium-producing cells. No excess heat was found in the cells that had not produced tritium. One cell, in particular, showed excess power in a time interval of 13 days, with an average and peak excess power level of about 10% and 28%, respectively. The excess energy generated in these 13 days was more than 106 Joules.

Another significant achievement of the Engineering Group was the development of a feasible, continuous technique to determine the D/Pd loading ratio. This method was key to the later development by the Chemistry Group of a procedure to obtain reproducible D/Pd loading ratios in the vicinity of one, coupled with reproducible tritium generation. The D/Pd ratio is determined volumetrically, by measuring the decrease in the gas volume of a sealed electrochemical cell. The volume decrease is directly proportional to the deuterium absorbed by the Pd cathode. Loading ratios generally between 0.65 and 0.85 were obtained, with the lowest levels occurring in acid solutions. In most cases, prolonged electrolysis did not result in increased loading ratios above 0.85. However, on rare occasions and for unknown reasons, loading ratios of approximately one were achieved. f. Collaborative and Theoretical Stud’ies

Among the many contributions to the final report in this section, covering a wide range of subject matter, only a few will be highlighted here.

The accuracy of isoperibolic calorimetry was evaluated and was estimated to be the larger of 0.05 W or 5% of the total cell power.

1-26 Factors that may enhance the rates of cold fusion reactions are explored on the basis of existing experimental observations and theoretical considerations. The important question is addressed how to explain the large discrepancy between observed amounts of heat and the much smaller amounts calculated from the nuclear by-products that have been measured. The possible role of helium-4 is discussed in this connection. The likelihood for cold fusion to occur on the surface as compared to the interior of Pd (or other metals) is discussed, and it is concluded that attainment of uniform deuterium concentration in the metal as well as rate considerations favor reactions in the interior.

Self-consistent field level calculations were applied to evaluate the possibility of cold fusion in Pd. The calculations were aimed at finding a palladium-deuterium interaction which might give rise to an intermolecular potential sufficient to enable cold fusion at room temperature. This investigation, guided in part by chemical intuition, included a variety of singlet and triplet electronic states, anions and neutrals, with and without lattice deformations. No systems were found which gave a satisfactory modified intermolecular potential. For the arrangement of two deuteriums occupying the same octahedral hole it appears that the hypothesis that the electron density from the palladium lattice might screen the DD interaction is unlikely. This study suggests the opposite. Namely, the palladium-deuterium bonding interactions in the octahedral hole results in a buildup of electron density between the palladium and deuterium atoms and a subsequent depletion of density between deuteriums. For the systems studied it was predicted on the basis of self-consistent field theory, that simple DD fusion enhanced by lattice screening of deuterium atom interaction is not a likely mechanism.

Application of superradiance theory to cold fusion phenomena in condensed matter leads to conclusions opposite to those derived from application of self- consistent field theory. This theoretical model involves the application of quantum electromagnetic field theory. The moving or oscillating charges, such as electrons, deuterons and palladium nuclei, have electromagnetic fields (plasmas) associated with them that provide for strong coupling. A central feature of the model is the coherent interaction of large numbers of charged particles. Coulomb barrier penetration is made possible by the presence of a sufficient electron density between two deuterons. Another factor 10l0 enhancement of the fusion probability is predicted from an interaction between loosely bound deuterons and the entire system of strongly

1-27 bound deuterons contained in a coherency domain. This leads to the theoretical prediction that high fusion rates will exist only if the D:Pd loading ratio has attained a critical value just larger than one. Under these circumstances, the model predicts the generation of large amounts of excess heat (tens of W/cm3 Pd) by ultra-fast coupling of the fusion energy to the electron plasma. This process is predicted to vastly enhance the 4He channel while suppressing the neutron and tritium channels.

111. Conclusions

Convincing evidence now exists for the occurrence of nuclear reactions, at room temperature, in deuterium-loaded metals, such as palladium and titanium. The generation of tritium, neutrons, protons, helium-4 and gamma radiation provides evidence that deuterium-deuterium fusion comprises at least part of the nuclear reactions that occur. Other nuclear reactions, possibly involving as yet unknown nuclear particles, may well occur at the same time.

The fact that cold nuclear fusion occurs does not mean per se that the excess heat observed by many investigators originates from cold fusion or even from any nuclear reaction. Apart from the findings of a single group, the level of the various nuclear by-products, that have been measured, is approximately one million times smaller than required to explain the observed levels of excess heat. This poses an extraordinary challenge to both experimentalists and theoreticians.

Considerably more research is required to bring about an understanding of the phenomena involved. Only after such understanding is in hand can it be said with certainty what the origin of the nuclear reactions and the excess heat is, and only then does it appear feasible to discuss the potential technological implications.

The progress obtained in cold fusion work is impressive. Reproducibility of some of the phenomena appears to be in hand, enabling more systematic scientific work to be pursued.

1-28 IV. Cold Fusion Bibliography

1. NCFl Publications and Reports

1. Martin Fleischman n and Stan ley Pons. "Electrochemically lnduced Nuclear Fusion of Deuterium," J. Electroanal. Chem. 261,301 (1989). 2. Cheves Walling and Jack Simons. "Two lnnocent Chemists Look at Cold Fusion," Journal of Physical Chemistry s,4693 (June 1989). 3. S. Guruswamy, J. G. Byrne, J. Li, and M. E. Wadsworth."Metallurgical Aspects of

the Electrochemical Loading of Palladium with Deuterium, If Proceedings of NSF-EPRI Workshop on Cold Fusion in Washington D. C., (August 1989).

4. Gary M. Sandquist and Vern C. Rogers. "Isotopic Hydrogen Fusion in Metals," Fusion Technology 16,254 (September 1989). 5. Gary M. Sandquist, Vern C. Rogers, and Kirk Nielson. "Deuterium Concentration & Cold Fusion Rate Distributions In Palladium, "'Fusion Technology x,523 (December 1989).

6. M. Salamon, M. Wrenn, H. Bergeson, K. Crawford, W. Delaney, C. Henderson, Y. Li, J. Rusho, G. Sandquist, and S. Seltzer."Limits on the Emission of Neutrons, Gammas, Electrons and Protons from Pons/Fleischmann Electrolytic Cells," Nature 344, 401 (March 1990).

7. S. Pons and M. Fleischmann. "Calorimetry of the Palladium-Deuterium System," Proceedings of First Annual Cold Fusion Conference in Salt Lake City, Utah, 1 (March 1990).

8. S. Guruswamy and M. Wadsworth. "Metallurgical Aspects in Cold Fusion

Experiments, " Proceedings of First Annual Cold Fusion Conference in Salt Lake City, Utah, 314 (March 1990).

9. K. J. Bunch and R. W. Grow. "Electric Field Distribution of the Palladium Crystal Lattice," Proceedings of First Annual Cold Fusion Conference in Salt Lake City, Utah, 243 (March 1990).

10. Martin Fleischmann. An Overview of Cold fusion Phenomena," Proceedings of First Annual Cold Fusion Conference in Salt Lake City, Utah, 344 (March 1990).

11. Stanley Pons and Martin Fleischmann. "Calorimetric Measurements of the Pd/D System: Fact and Fiction," Fusion Technology YJ, 669 (July 1990).

12. Martin Fleischmann, Stanley Pons, Mark Anderson, Lian Jun Li, and Marvin

Hawkins. "Calorimetry of the Palladium-Deuterium-Heavy Water System, " J. Electroanal. Chem. 287,293 (1990).

1-29 13. Giuliano Preparata. "A New Look at Solid State Fractures, Particle Emission

and Cold' Nuclear Fusion, 'I International Progress Review on Anomalous Nuclear Effects in Deuterium/Solid Systems, Brigham Young University, Provo, Utah, October 1990. Submitted for publication.

14. Giuliano Preparata. "Theories of 'Cold' Nuclear Fusion: A Review, " NCFl Report, October 1990. Submitted for publication.

15. Gary Sandquist and Vern Rogers. "Enhancement of Cold Fusion Reaction Rates," Submitted in Journal of Fusion Energy, (January 1990).

16. Gary Sandquist and Vern Rogers. "Cold Fusion Reaction Products and Their Measurement, " Accepted by Journal of Fusion Energy, (January 1990).

17. K. J. Bunch and R. W. Grow. "Self-Consistent Field Calculations on Diatomic

Hydrogen in a Potential Well,If Submitted to Fusion Technology, (Septe m be r/Octo be r 1990).

18. Cheves Walling and Marvin Hawkins. "Temperature Dependence and Reproducibility of Cell Constants in FP Type Calorimetric Cells, '' NCFl Report, December 1990.

19. A. M. Riley, J. D. Seader, D. W. Pershing, C. Walling."An In-Situ Volumetric Method for Dynamically Measuring the Absorption of Deuterium in Palladium

During Electrolysis, 'I Submitted to J. Electrochem. Society, (1990).

20. A. M. Riley, R. M. Winter, J. D. Seader, and D. W. Pershing."Flow Calorimetry

and Related Experiments, I' NCFl Report-1, (May 1990).

21. A. M. Riley, John Cook, R. M. Winter, J. D. Seader, and D. W. Pershing. Seebeck Calorimetry," NCFl Report-2, (July 1990).

22. A. M. Riley, J. D. Seader, D. W. Pershing, A. Linton, and S. Shimizu. "Measurement of Absorption of Deuterium in Palladium During Electrolysis of Heavy Water," NCFl Report-3, (October 1990).

23. R. F. Boehm, Mark Case, Yi-Tung Chen, Xing Li, and Barry Lloyd."High Pressure Liquid Cell Development, '' NCFl Report, (September 1990).

24. A. M. Riley, J. D. Seader, D. W. Pershing, and J. Cook. "Heat Conduction Calorimeters for Nectrolysis of Heavy Water at Low Power Input, '' NCFl Report- 4, (October 1990).

25. A. M. Riley, J. D. Seader, D. W. Pershing, and J. Cook. "Development of An l lmproved Heat-Flow Calorimeter," NCFl Report-5, (October 1990).

26. A. M. Riley, J. D. Seader, D. W. Pershing, T. Williams, and A. Linton. " Determination of Critical Cold Fusion Parameters by Measuring Excess Tritium

from Small-Cell Necfrolysis Experiments, 'I NCFl Report-6, (October 1990).

1-30 27. A. M. Riley, J. D. Seader, and D. W. Pershing. "Search for Neutron Emission from Deuterated Palladium at Low Temperatures," NCFl Report-7, (October 1990).

28. Zhongqun Tian. "Project Report," NCFl Report, (January 1991). 29. K. Cedzynska, S. C. Barrowes, H. E. Bergeson, L. C. Knight, and F. G. Will. "Tritium Analysis In Palladium With An Open System Analytical Procedure," Submitted to Fusion Technology, (February 1991).

30. K. Cedzynska, S. C. Barrowes, H. E. Bergeson, L. C. Knight, J. R. Peterson, and F. G. Will. "Analysis of Palladium Samples For Tritium Contamination, " Abstracts of Papers of the Pittsburgh Conference, Abstract #349P, (March 1991). To be submitted for publication.

1-31 2. General Publications and Media Repo, ts -

"Electrochemically Induced Nuclear Fusion of Deuterium" by M. Fleischmann & Stanley Pons. March 11, 1989, rev. March 20, 1989. Paper. "Observation of Cold Nuclear Fusion in Condensed Matter," by S.E. Jones, et al. March 23, 1989. Paper. e "Cold (con) fusion", PatuE (30 March 1989): 364. "Fusion Breakthrough?", Sue(31 March 1989): 1661.

"SO you want to be a star", The Econo mist (1 April 1989): 75. "Fusion Claim Electrifies Scientists", Science News (1 April 1989): 196.

7) "Chemists Claim Lead To Fusion", Chemica1 Marketing wortex (3 April 1989): 7. "Nuclear Fusion: Utah findings raise hopes, doubts," Chemical b Endn dnaNe ws (3 April 1989): 4-6, "Star Power, Research Prompts Fusion Debate," Chr istian Science Mon itor (4 April 1989): 1. "A Fuss About Fusion", Chemical Week (5 April 1989) 14-15. "Scientists Angered by Refusal of 2 Chemists to-Give Details of Nuclear-Fusion Discovery," C=HHg iher Educat ion (5 April 1989): 1. 12) "Cold fusion caused frenzy but lacks confirmation", Nature (6 April 1989): 447. 13) "Fusion Follow-up: Confusion Abounds," Sc ience (7 April 1989): 27-29. 14) "Fusion Claims Multiply, Strengthen, " Sc ience News (8 April 1989): 212. 15) American Chemical Society. Abstracts of Papers. 197th ACS National Meeting. April 9-14, 1989. Abstract of S. Pons' paper.

1-32 "Platinum, palladium in fusion experiment," WernMiner, (10 April 1989): 3.

17) "Experiment in Fusion is Said to be Copied," New York T imes (10 April 1989); A13. "Cold Fusion: Race to claify Utah claims heats up," Chemical & E ns ineerina News (10 April 1989): 6-7.

19) "Electochemically induced nuclear fusion of deuterium," By M. Fleischmann €4 S. Pons . Journal Of the plectroanalyt ical Chemistry 261 (10 April 1989): 301-308. "7,000 Scientists Cheer Fusion-in-Jar Experimenter," Pew York Times (13 April 1989): A12. "Cold Fusion Patents Sought," New York Times (13 April 1989): A 12. "Disorderly publication," Nature (13 April 1989): 527-528). "Not-footed towards cold fusion," Nature (13 April): 537. "Prospect of achieving cold fusion tantalizes," Nature (13 April 1989): 529. "Scrutiny of Fusion Experiment Produces Few Believers Among Phupicists," New York Tima (16 April, 1989:

"A Triumph, Maybe For Small Science," Pew York Times (16 April 1989): "Trying to Tame H-Bomb Power," Time (17 April 1989): 72. "Cold Fusion: ACS session helps shed some light," Chemica1 & Enaineerina News (17 April 1989): 5-6.

29) "A Frenzy over Fusion in Hundreds of Labs," New York T imes (18 April 1989): 87.

30) "Other Laboratories Back Findings, Chemist Says," pew York TA(18 April 1989): 1.

31) "Italians Report Fusion in Experiment," New York Times (19 April 1989): 1.

32) "New Chemical Experiment Partly Confirm the Possibility of Achieving Fusion in a flask, but Skepticism continues,* The Chronicle of H iaher Educat ioq (19 April 1989): 1.

33) "Fusion Fever is on the Rise," Time (24 April 1989): 57. 34) "Table-Top Fusion Looks Less Like a Parlor Trick," Science b Technolosy (24 April 1989): 132.

1-33 35) "Confusion Continues Over Room.-Temperative Fusion," The Chronicle of Higher Education (26 April 1989): A8.

36) "The transmutation of hydrogen into helium," by Fritz Paneth b Kurt Peters. Chem ical Abs t r acta 21 (1927): 357-358

37) "The conversion of hydrogen into helium," by Fritz Raneth b Kurt Peters & Paul Gunther. Chemical Abstracts 21 (1927) : 1728-1729.

38) "Cold fusion in print," Nature (20 April 1989): 604. 39) "Scientific look at cold fusion inconclusive," Nature (20 April 1989): 605.

40) "Test-tube fusion experiment repeated," New Scientist (8 April 1989): 18-19. "Une fusion realisce en laboratoire? Un nucleaire de reve," Le Monde (24 March 1989): 1 b 29.

42) "The Utah Fusion Circus," Pew York Timu (Editorial) 30 April 1989. Sect 4, p. 24.

43) Feud frays edges of fusion hope," The Sunday Times (London) 9 April 1989. p. A17.

44) 'Cold fusion or fizzle?," The T imes (London) 20 April 1989. p. 32.

45) "Nuclear fusion search widens,' The Times (London) 24 April 1989, p.2.

46) "Fusion Confusion: New data, but skepticism persists," Chemical b Enaineerina News (24 April 1989): 4-5.

47) "Fusion in a Bottle: Miracle or Mistake? Bus iness Week (8 May 1989): 100-110.

48) "Cold Water", New Scientist (1 April 1989): 16. 49) "Claims for 'test-tube fusion' meet scepticism," &g Scientist (1 April 1989): 16. "The Race for Fusion," Newsweek (8 May 1989): 49-54.

Cold Water on Cold Fusion," New York Times (3 May 1989): A19. Fusion Claim Is Greeted With Scorn by Physicists," &y York Times (3 May 1989): 1 b A14. "Physicist Challenge Cold Fusion Claims,' New York Times (5 May 1989): 5B & B10.

1-34 54) "Stanley Pons Lays Claim To Tabletop Fusion - But Don't Sell Your Oil Stocks Just Yet," People (8 May 1989): 59-62

55) "Fusion experiments spark excitement," MininQ Enaineerinq (April 1989): 212.

"Cold Fusion: fact or fantasy?," Chemistry and Indust ry (17 April 1989): 234.

57) "Mines Nuclear Physicist Calls Fusion Breakthrough Genuine," Cal ifornia M inincr Jou rnaL (May 1989): 11-12. "Fusion Controversy", Chemica1 & Ensineerinu News (1 May 1989): 6-7.

59) "Utah's Fusion Fuels Heated Debate," The Sc ientisk (1 May 1989): 1, 2, 3, 8. "Fusion or Illusion?", Time (8 May 1989): 72-77. "How Cold Fusion Happened - Twice!," Science (28 April 1989) : 420-423. "Skepticism Grows Over Cold Fusion," Science 244 (21 April 1989): 284-285. "Fusion Confusion," Industry Week (1 May 1989): 59-60. "Fusion in a Jar: Recklessness b Brilliance," Pew York Times 9 May 1989, pp B5 b B10. "Putting the Heat on Cold Fusion," Time (15 May 1989): 63. "More than scepticism," pature (4 May 1989): 4. "Hopes for nuclear fusion continue to turn cool," Natura (27 April 1989): 691. "Science as spectator sport," Physics World (May 1989): 3. "U. of Utah Requests $ZS-Million From Congress for Room-Temperature Nuclear-Fusion Institute," T& Chronicle gf Hiaher Educat ion (3 May 1989): A6 7 A12.

70) "Physicists Say Claim of Room-Temperature Fusion by 2 Chemists Is a Widely Publicized Mistake," The Chronicle of Hicrher Education (10 May 1989): A4 & All.

71) "2 Defend Fusion Claim Before Peers," New York Times (10 May 1989): All. 72 "Cold Fusion or Confusion?," The New Americaq (22 May 1989): B1 & B2.

1-35 73) "Hatch goes to u.8 BYU to witness fusion work," Dm Pews (24 April 1983): Bl-B2.

74 1 "Alberta found chemist 'too fast on the draw'," The Globe & pail (11 May 1989): A:-A2.

75) '@Nuclear Con-fusion," Minina Journal (21 April 1989): 311.

76) "Chemists' meeting fans the flames of fusion debate," &VJ Scient ist (22 April 1989): 27.

77) "Utah Looks to Congress for Cold Fusion Cash," Sc ience (5 May 1989): 522-523.

78) "Dif-fusion: Beware the Ideas of March, " Science News (6 May 1989): 276.

79) "Fusion Donnybrook: Physicists assail Utah Claims," Chemical & Enaineerina News (8 May 1989): 466. "Putting the Heat on Cold Fusion," Time (15 May 1989): 63. "More than scepticism," Nature (4 May 1989): 4. "Y. physicist casts doubt on sustained fusion theory," Deseret News (19 May 1989): B1. "Fielding the Fussion Flak," The E vent (16-31 May, 1989) : 4. "u. must fuse team or lose to larger facility," Deseret News (18 May 1989): 81.

87) "Fusion Confusion is no Deterrent to Enterprising Utahns," Salt Lake Tribune (6 May 1989): Bl-2. "D.C. Postpones 2 U. Fusion Meetings," Salt La ke Tribune (5 May 1989): Bl-B2.

89) "Pons Says Alumnus Not Welcome to Speak at U." Salt Lake Tribune (20 May 1989): B1-2.

90) "Most Asked Questions About Fusion," Handout from Chase Petersen's presentation 5/18/89.

91) "Hope b hesitation on the fusion frontiers,* New Scientist (29 April 1989): 22-23.

92) "Physics community strikes back in depate over cold fusion," New Scientist (6 May 1989: 26. \ 93) "Of fusion, nobels & nobility," New Scientist (6 May 1989): 28-29. "Cold fusion: what's going On?," Nature (27 April 1989): 711-12

1-36 95) "What to say about cold fusion," Pature (27 April 1989): 701 .

96) *'Observation of cold nuclear fusion in condensed matter," by S. E. Jones. Nature (27 April 1989): 737-740.

97) "Mines physics professors will attempt to verify Utah's fusion experiment," The Mines Maua zine (May 1989): 3-4. "Views on nuclear fusion*, Chemical & EnQ ineerinu Ne ws 1s (May 1989): 2-3, 46. "Observation of cold nuclear fusion in condensed matter," by S. E. Jones, Nature (27 April 1989): 737-740.

100) "The Cold fusion family." Nature (27 April 1989): 705.

101) **Conferenceon Fusion Told of Failure," New York Times (24 May 1989): A12.

102) "Efforts abandoned in Japan", Nature (18 May 1989): 167. also

103) **Nonew fusion under the Sun," Nature (18 May 1989): 180.

104) "Problems with the gamma-ray spectrum in the Fleischmann et al. experiments," by R. Petrosso. Nature (18 May 1989): 183-185.

105) "Fusion in from the cold,?" PJature (18 May 1989): 185.

106) "Scientists Report Positive Results In Experiments With Cold Fusion," New York Times. (25 May 1989): All.

107) "Prospect of Commercial Gain From Unconfirmed Discovery Prompted Utah U. Officials to Skirt Usual Scientific Protocol," The Ch ronicle o f Hiaher Educat ion (17 May 1989): A5 & A8.

108) "2 Chemists Defend Room-Temperature Fusion From Growing Criticism of Other Scientists," The Chronicle oc Highex Educa t ion (17 May 1989): AS & A9.

109) "Hopes for Cold Fusion Diminish As Ranks of Disbelievers Swell," Chemical and EnaineerinQ News (22 May 1989): 8-20.

110) "Cold-Fusion Brouhaha Signals Shifts in the Way Science Proceeds," Chronicle of Hiuher Education (24 May 1989): Al. 111) "Solide Kerle" , Der Spieuel (3 April 1989): 266. 112) "The Implications of "Cold Fusion"," Journal of Chemical Education (May 1989): 361. 113) "Fusion gives energy to palladium markets," Enaineerinq & Mining Jou rnal (May 1989): 17.

1-37 114) "The Safest Ground for Fusion Critics Is to Wait b See," Salt Lake Triu (16 May 1989): B2. 115) "Cold fusion: Searching for hidden helium," Science Ne WS (20 May 1989): 311, 116) "Fusion Reaction," Science (26 May 1989): 904. 117) "The Confusion Profusion," Science (19 May 1989): 904. 118) "Cold Fusion: Bait & Switch?," Science (19 May 1989): 774. 119) "Cold fusion gathering is incentive to collaboration, "N- "N- (1 June 1989) v. 339, p. 325.

120) "Biological Cold Fusion," pature (1 June 1989), V. 339, p. 335. 121) "Cold fusion results still unexplained," Nature (1 June 1989)r V. 339, Pe 345. 122) "Fusion in 19471" Nature (1 June 1989), v. 339, p. 346. 123) "The 'Cold Fusion' Story Has Been an Object Lesson on Why Science Flourishes Only in the Open," Chronicle of Piaher pducatioq (June 13, 1989), p.44. 124) "Conflicting Cold Fusion Reports Deepen Mystery," Chemica1 5 Enaineerina News, June 5, 1989, pp. 16-18. 125) "Hardware Hacker. Try cold fusion for yourself" Radio -Electroniw (August 1989): 64-69, 85. 126) "Cold fusion doubts and controls," Patute (15 June 1989): 515 . 127) "The Vanity of scholar^,^ New York T imes (9 July 1989): E25. 128) "Britons Abandon "Cold" Quest," pew York T imes (20 June 1989): 12. 129) "Fusion Plan Iqnites Controversy at DOE," Sc ience (23 June 1989): 1434-1435.

130) "Cold Fusion Brouhaha Signals Shifts in the Way Science Proceeds," by C. Raymond. Chronicle of H iqher Educa t ion (24 May 1989): 1, AS. 131) "Science Newsfront. Fusion Fizzle?," Popular Science (August 1989): 8-12. 132) "Panel Rejects Fusion Claim, Urging No Federal Spending," yew York Times (13 July 1989): Al.

1-38 133) "Cold Fusion Couture," Scienca (7 July 1989): 31. 134) "Cold Fusion: How Close Can Deuterium Atoms Come Inside Palladium?," Ebysical Review Letters (3 July 1989): 59-61.

135) "Cold fusion results still unexplained," Nature (1 June 1989): 345. 136) "Cold fusion gathering is incentive to collaboration," Pature (1 June 1989): 325. 137) "Fusion in 19471," pature (1 June 1989): 346.

138) "Calculated fusion rates in isotopic hydrogen molecules, a Nature (29 June 1989): 690-691." 139) Measurement of gamma-rays from cold fusion," Nature (29 June 1989): 667-669. (Note: Pons' response to Petrasso's article "Problems with the gamma-ray spectrum ---.a See item #lo4 for the article. ) 140) "Muon catalyzed fusion," Fus ion Enqineerina and Des icln By C. Petitjean. 11 (July 1989): 255-264. 141) "Negotiations may result in collaboration with platinum firm to speed fusion work," Peseret News (June 8, 1989): 1.

142) "Us, G. E. near pact on solid-state fusion research," peseret News (26 June 1989): B5. 145) "On Cold Fusion, It Looks Like Utah Stands Alone," New York Times (16 July 1989): E5. 146) "Explanations of cold fusion," Nature (11 May 1989): 105. 147) "Cold Fusion: Still no certainty," Pature (11 May 1989): 84. 148) "Grim but not terminal," Chemistry & Industry (5 June 1989): 324-325. 149) "Double blow for cold nuclear fusion," Nature (22 June 1989): 567. 150) "Mystery of meteoritic fusion," Nature (22 June 1989): 588. 151) "Two Innocent Chemists Look at Cold Fusion," The Jou rnal Qf Physical Chemistry 93 (June 15, 1989): 4693-4697. (Note: Walling b Simons article) 152) "G.E., Utah agree to joint cold fusion effort," C & EN (10 July 1989): 5-60 153) "Examination of nuclear measurement condition in cold fusion experiments," Journal of Electroanalytical Chemistry 265 (23 June 1989): 355-360. 1-39 154) "Fusion cools down," Chemistry in Britain.. (July 1989): 691. 155) *S?arch for DD-Fusion Neutrons During Heavy Water Electrolysis," Electroch imica Acta 34 (July 1989) 991-993). 156) "Upper limits on neutron gamma-ray emission from cold fusion," Natura 340 (6 July 1989): 29-34. 157) "Evidence of Emission of Neutrons from a Titanium- Deuterium System, " wicalLetters 9 (1 June 1989): 327. 158) "Cold Fusion Confirmed," American Scient iSk (JUly-AuguSt 1989): 327.

159) "Big Brother, Ph. D. - Should scientists or bureaucrats form science's police force?,* Sc ientific American (Aug 1989): 128-16.

160) "End of cold fusion in sight," Nature 340 (6 July 1989): 15 . 161) "Unlucky break for the friends of cold fusion," Scienti& 1671 (1 July 1989): 16. 162) "Can solid-state effects enhance the cold-fusion rate?," Nature 340 (6 July 1989): 45-56. 163) "Federal panel advises no cold fusion funding," Chemical & Enaineerina Ne ws (17 July 1989): 8. 164) "Assessing the Future of Fusion," Vechan ical Enaineerinq pews (17 July 1989): 62-68. 165) "No new money from U.S. government?," Nature .340 (20 July 1989):174. 166) "A Brief History of Cold Fusion,* FAAS Obser vec (7 July 1989): C19. 167) "Despite Cold Water on 'Cold Fusion', Research Is Enjoying a Boom in Utah," flew York Times. (August 1, 1989): Cl9. 168) "If you read it First In Nature, It's Big and (Usually) True," Wall Street Jou rn a1 (15 May 1989): 1 b A8.

169) "Screening Corrections in Cold Deuterium Fusion Rates," Zeitschrift fur Physik A, Ato mic Nucle 233, No, 3 (1989): 317-18. 170) "Search for Nertuons from 'Cold Nuclear Fusion'," Zeitschrift fur Phvsik A0 Ftomic Nuclei 233 no. 3 (1989): 319-320. 171) "Search for Neutrons Production During Heavy Water Electrolysis on Palladium Electrodes," Zeitschrift fuc Physic &I Atomic Nuclei 233 no. 2 (1989): 321-322. 1-40 172) "Cold Fusion Still in State of Confusion," Science 245 (21 July 1989): 256. 173) "Into the Shadows,." r (3 July 1989): 399 . 174) "Quest for Fusion," mneerina & Sc ience (Calif . titute of Technology): Summer 1989. pp. 3-14.

175) "Search for cold fusion in palladium," Zeitschr ift fuc Phvsick (Condensed Matter). B. Vol. 76, 1-2 (1989): 1-2.

176) "Doubts grow as many attempts at cold fussion fail," Physics Todav (June 1989): 17-18).

177) "Sales pitching on the Hill," Physics World (June 1989): 5-6. 178) "Signs of 'Cold' Fusion Are Cited, Cautiously," New York Time% (June 27, 1989): B-8. 179) "Need Cold Fusion Information?," Library Hot1 ine (June 12, 1989): 4-5. 180) "Scientists claim nuclear fusion breakthrough," En- Worla (April 1989): 3. 181) "Hot or Cold?" Chemistry Industry (17 July 1989): 434. 182) "Search for the Proposed Cold Fusion of D in Pd." Modern Phvs ics Lette rs B 3 (1989): 753-760. 183) "Cold Fusion in Metals," Jou rnal of the Physical SOCiety gf Japan 58 (June 1989): 1869-1970. Article by Jun Xondo on Japanese experiment. 184) "Cold-Fusion Debunked?," PODUlar Mechan ics (July 1989): 29. 185) "A Critical analysis of electrochemical nuclear fusion experiments," J ou rna1 of Electroanalvtical Chernistrv 266 (1989): 437-450. A critique by G. Kreysa, G. Marx & W. Plieth 186) "The fusion rate of a confined deuteron pair," Jou rnal of Physics, Particle Physics 15 (1989): L157-L161. Article by W. N. Cottingham & D. A. Greenwood. 187) "Harwell freezes cold fusion," Chemistry in Britain (August 1989): 769. 188) "Cold Fusion Information & Misinformation," NSIT EmDloyee Newsletter. 189) "Will science ever recover from the cold fusion furor?," Resea rch & Development (July 1989): 33-39.

1-41 190) "Searches for low-temperature nvclear fusion of deuterium in palladium," Nature 340 (17 Aug. 1989): 525-530. 19 1) "Fusion rates of squsezed & screened hydrogenic nuclei," Phvs ical Review C (Aug. 1989): R 495-496. 192) "Muon Catalyzed fusion," Nuclear Instruments & Methods in sicalResearch 841 (July 1989): 419-25. 193) "Physicist deal cold fusion a theoretical blow," &y Scientist (29 July 1989): 29. 194) "Exact Upper Bound on Barier Penetration Probabilities in Many - Body systems: Application to "Cold Fusion", Physical Review Lette rs 63 (10 July 1989): 191-194.

195) "The Nuclear Fusion for the Reactions 2H(d;n)3He, 2H(d, pI3H0 3H(d,n)4He," I1 Nuovo Cimento 101(May 1989): 795-804.

19 6) "Emission of Neutrons as a Consequence of Titanium- Deuterium Interaction," I1 Nuovo C imentQ 101(May 1989) : 841-44 197) "First Steps Toward an Understanding of Cold Nuclear Fusion," I1 Nuovo Cimento 101 (May 1989): 845-849. 198) "Observations on the surface composition of palladium cathodes after D20 electrolysis in LiOD ~~lution~,~ Journal of the Electroanalvtical Chemi s t ry 267(1989): 351-57. 199) "Decoding of Thermal Data in Fleischmann and Pons Paper," Jou r nal of Nuclear Sc ience a nd Techno loay 26 (19894~1~): 729-32 200) "Cold Fusion in a dense electron gas; Le Journal de Phvsiaue 50 (Sept 1, 1989): 2307-2311. 201) "Search for cold nuclear fusion in palladium-deuteride," Zeitschrift fur Phvsik B 76(1989): 141-142. 202) "On the Observation of Charged Particles in Cold Fusion," Phvsica Sc rinta 40 (1989): 303-306.

203) "In-Situ X-Ray Diffraction of Palladium Cathodes in Electrolytic Cells," Solid St ate Co mmunications 71 (1989) : 805-807 204) "Conventional Sources of Fast Neutrons in "Cold Fusion" Experiments," Physics Lette rS B 228 (7 Sept 1989): 163-166. 205) "Theoretical Considerations on the Cold Nuclear Fusion in Condensed Matter," I1 Nuovo C imentQ 11 D (June 1989): 913-9190

1-42 206) "Fleischmann defends cold fusion," Chemistry in Britain (Sept 1989): 857.

207) "Electrochemically - Induced Solid-state Fusion," plat i nurq Veta 1s RevieM 33 (1989): 114-116, 208) "Measurement of the residual polarization of negative muons in gaseous deuterium at a pressure of 10 atm,' JEPT Lette rs 49 (May lo, 1989): 544-548. 209) "Cold fusion converts say British magazine not presenting full story," Deseret News Sept. 19-20, 1989; p. B5.

210) "Editorial: The Cold Fusion Debate," by R. D. Armstrong. Electrc hemica Acta 34 (Sept 1989): 1288. 211) "Prospects & Problems of Electochemically Induced Cold Nuclear Fusion," by J.W. Schultze et al. Ibid.: 1289-1313. 212) "Some Aspects of Thermal Energy Generation During the Electolysis of D20 Using A Palladium Cathode,' by R. D. Armstrong. Ibid.: 1319-1326. 213) "Sporadic Observation of the Fleischmann-Pcns Heat Effect," by R.C. Kinthla et al. Ibid.: 1314-1318. 214) "A Search for the Emission of X-Rays from Electrolylically Charged Palladium-Deuterium," by S.M. Bennington. Zbid. 1323-1326. 215) "Reactivation of a in muon-catalyzed fusion under p.lasma conditions," by M. Jandel. vsical Revi ey A 40 (1 Sept. 1989): 2799-2892. 216) "Fusion rates for hydrogen isotopic molecules,Df relevance for "cold fusion" by K. Szalewicz & J. De Morgan 111. Ibid.: 2824-2827. 217) "Investigation of Cold Fusion in Heavy Water," by S.H. Faller. Jou rnal of Rad ioana lytical a nd Nucleaf C hemi s t ry, Lette rS 137 (21 Aug 1989): 9-16. 218) "Considerations on Cold Nuclear Fusion in Palladium,' by C. Hargitai. Ibid.: 17022. 219) "Some Basic Electochemistry and the Cold Nuclear Fusion of Deuterium," by G. Horanyi. Ibid.: 23-28.

220) "Cold fusion, superconductivity," Letter to the editor by J. Rynasiewicz. Chemical & EnQineerinu News 18 Sept 1989. 221) "Cold comfort," Pew Scientist (29 July 1989): 67. 222) "A Possible Mechanism for Bulk Cold Fusion in Transition Metal Hydrides,": by C, Petri110 b F. Saccheth.. Europhvsics Lette rS 10 (1 Sept 1989): 15.

1-43 223) "A Thermodynamic Study of the Pd-Ti System," by N. Selhaoui, et al. Journal of the Less- Common Metals 154 (1989): 137-147. 224) "Cold fusion and brown dwarfs," letter to the editor of Nature by C. Sivaran & V. de Sabbata Patur.. 341 (7 Sept. 1989): 28. 225) "Deuterium nuclear fusion at room temperature: A pertinent inequality on barrier penetration," by G. Rosen. Journal of Chemical Phvsim 91 (Oct 1989): 4415-4416. 226) "Commentaire: Pourquoi les Experiences de Fusion Froide de Deuterium Sont-elles Si Difficiles a Peproduire?, " by Jan Augustynski . Chimig 43 (April 1989) : 99-100. 227) "Scenarios for Nuclear Fusion in Palladium-Deuterium Alloys at Ambient Temperature," by C. K. Jorgensen. Chimia 43 (May 1989): 142-143.

228) "Cold Fusion Confusion," by R. P. Crease and N. P. Samios. The New York Times Maaaz ina (Sept. 24, 1989) pp. 35-38 229) "The Secret life of cold fusion," The Econom ist (Sept. 30, 1989): 87-90. 230) "Tunneling Efficiency & the Problem of Cold Fusion," Czechoslovak Journal of Phvs ia B39 (1989): 793-795. By V. Capek. 231) "The fusion rate of a confined deuteron pair," by W. N. Cottingham & D. A. Greenwood. Journal of P hvsics G ; fluclear & Particle Physics 15 (Aug. 1989): L 157-L161.

1-44 232) "Cold nuclear fusion rates in condensed matter: a phenomenological analysis," by 2. Henis, et al. Journal gf Physics G ; N~uclear & Particle Phvs ics 15 (Oct. 1989): L219-L223.

233) "Cold nuclear fusion in metallic hydrogen and normal metals," by Chas J. Harowitz. Physical Re view c. 8 Nuclear Phvsia 40 (Oct. 1989); R1555-R1558. 234) "Search for neutrons from deuteriGm-deuterium nuclear reactions in electrochemically charged palladium," by M. M. Broer, et al. (ATLT Lab., N.J.). Physical Review C. 40 (OCt 1989): R 1559-Rl562. 235) "A search for evidence of cold fusion in the direct implantation of palladium and indium with deuterium," by J. J. G. Durocher, et al. Ca nadian Journal of Phvsics 67 (June 1989): 624-631. 236) "H2+02 recombination in non-isothermal, non-adiabatic electrochemical calorimetry of water electrolysis in an undivided cell," by V. J. Cunnane, et al. Journal of Electroanalytical Chemistry 269 (1989): 163-174

237) "Probing the Nature of Sticking in Muon Catalyzed Fusion with Lamionated Targets," by M. Jandel. Nucleal; Instruments & Methods in Physics Research A201 (Aug 20, 1989): 246-249. 238) "Virtual-State Internal Nuclear Fusion in Metal Lattices," by R. W. Bussard. Fusion Techno loav 16 (Sept. 1989): 231-236. 239) "On the Possibility of a Nuclear Mass-Energy Resonance in D + D Reactions at Low Energy," J. Rand McNally Jr. Fusion Technoloav 16 (Sept 1989): 237-239. 240) "Advanced Energy Conversion Methods for Cold Fusion," by Mark A. Prelas. Fus ion Techno loay 16 (Sept 1989): 240-242. 24 1) "On the Possibility of Deuteron Disintegration in Electrochemically Compressed D+ in a Palladium Cathode," by Magdi Ragheb b Geroge H. Miley. Fusion Tec hnoloav 16 (Sept. 1989(: 243-247. 242) "Preliminary Experimental Study on Cold Fusion Using Deuterium Gas and Deuterium Plasma in the presence of Palladium," by Albert G. Gu. Fusion Technoloav 16 (Sept. 1989): 248-250. 243) "A Novel Apparatus To Investigate the Possibility of Plasma- Assisted Cold Fusion," by D. N. Tuzic et al. Fusion Technoloav 16 (Sept. 1989): 245-259. 245) "Electrochemically Induced Deuterium - Tritium Fusion Power - Reactor - Preliminary Design of a Reactor System," by Y Oka, et al. Fusion Tech noloav 16 (Sept. 1989): 250-262. 1-45 246) "D20-Fueled Fusion Power Reactor Using Electrochemically Induced D-Dn, D-p, and Deuterium - Tritium Reactions - Preliminary Design of a Reactor System," by Y Oka et al. Fusion Techno loav 16 (Sept 1989): 263-267. 247) "Reactor Prospects of Muon-Catalyzed Fusion of Deuterium and Tritium Concentrated in Transition Metals," Fusion Technoloqy 16 (Sept 1989): 268-275. 248) "On a possible mechanism of cold nuclear fusion," by P. I. Golubnichi, et al. Akademiia Nauk S. S. R,, Pokladv 307 (1989): 99-101.

249) "Teller, Chu "Boost" Cold Fusion," by R. Pool Science (27 October 1989): 449. 250) "Heat Release from Deuterated Ti Fe or La Ni5 on Exposure to the Air," by M. Marinelli, et al. 11 Nuovo C imento 102A (Sept. 1989): 959-961. 251) "Nuclear Products Detection During Electrolysis of Heavy Water With Ti and Pt Electrodes," by C. Sanchez, et. al. Solid State Co mmunications 71 (Sept 1989): 1030-1043. 252) "Comment on "Cold Fusion: How Close Can Deuterium Atoms Come Inside Palladium,?" by P. K. Lam b Rici Yu. Phvsical Review Lettera 63 (23 Oct. 1989): 1895.

253) "Fusion-fact or fiction," The Chemical Enaineu (May 1989): 13. 254) "Effets thermiques associes a la decharge electrchimque de l'hydrogene et du deuterium sur palladium," by M. Chemala, et al. Comptes Rendus de L' Acade mie Des Sciences 309, Series 11, No. 10 (28 Sept. 1989): 987-993. 255) "The Fusion rate of a cinfined deuteron pair," by W. N. Cothingham b D. A. Greenwood. Journal of Physics si: Puclear b Particle Phvsia 15 (Aug. 1989): LlS7-Ll61. (Same as No. 231) 256) "DOE gives cold fusion a cold shoulder," Deseret News October 30, 1989: Bl-B2. 257) "Cold Nuclear Fusion: Viewpoints of Solid-state Physics," by G. Benedik and P. F. Bortignon. I1 NUOVO CimentQ 110 (August 1989): 1227-1235. 258) "Production of tritium from D20 electrolysis at a palladium cathode," by J. O'M. Bockris, et al. Journal of Electroanalytical Chemistry 270 (1989): 451-458. 259) "Cold Fusion keeps its head just above water," by I. Amato. Sc ience News 136 (October 28, 1989): 278.

1-46 260) "Despite reports, cold fusion isn't dead, Pons says," e#- r News (November 4, 1989): 81 & B2.

261) Despite Scorn, Some Scientists STill Seek Cold-Fusion clues,* by W. J. Broad. New York Times (Oct. 31, 1989): B5 & 88. 262) "Cold fusion in metals," by R. H. Parmenter & W. E. Lamb Jr. proceedina of the National Academy of Sciem 86 (Nov. 1989):8614-8617. 263) "Search for Energetic - Charged - Particle Emission from Deuterated Ti and Pd Foils," by P. B. Price, S. W. Barwick & W. T. Williams. Phvs ical Review Let te rs 63 (30 October 1989): 1926-1929. 264) "Evidence for a Background Neutron Enhanced Fusion in Deuterium Absorbed Palladium," by Gad Shani, et al. Solid State Communications 72 (1989): 53-57. 265) "Enhancement of Cold Fusion Rate by Electron Polarization in Palladium Deuterium Soldi," by S. Feng. Solid State Communicat ions 72 (1989): 205-209. .: 266) "Search For Cold-Fusion Events," by W. Hajdas, et al. Solid State Co fNWJ.i ication 72 (1989): 309-313. 267) "Fission in the Fusion Camp," Discovex 10 (December 1989): 32-42. 268) "Cold fusion anomalies more perplexing than ever," chemical & E naineer incI News 67 (November 6, 1989): 32-34. 269) "Search for cold fusion using x-ray detection," by J. D. FOX, et al. sical Review C 40 (November 1989): R1851-Rl853. 270) "Fusiomania," by E. J. Farkas. Chemistrv in Britain (November 1989): 1093. 271) "Noncommittal outcome," by D. Lindley. Nature 341 (26 October 1989): 679. 272) "Investigation on the Possibility of Cold Nuclear Fusion in Fe-Zr Amorphous Alloy," by E. Kuzmann et al. Journal of Radioanalytical Nuclea r Chemistrv, Letters 137 (1989): 243-250. 273) "Upper bounds on "cold fusion" in electrolytic cells," by D. E. Williams et al. Nature 242 (23 November 1989): 375-384 274) "How a Rectangular Potential in Schrodinger's Equation could explain some Experimental Results on Cold Nuclear Fusion," by Johann H. Schneider. Fusioq Technoloqy 16 (November 1989):377-378. 1-47 275) "Nuclear Reaction Products That Would Appear If Sub- stantial Cold Fusion Occurred,' by D. Vueller & L. Grisham. Fusion Technoloav 16 (November 1989): 379-382.

276) "A Study of "Cold Fusion" In Deuterated Titanium Subjected To High-Current Densities," by R. B. Campbell & L. J. Perkins. Fusion Technoloav 16 (November 1989): 383-387.

277) "High-Sensitikity Search For Neutrons During Electrochemical Reactions," by M. Butler et al. Fusion. Techno loav 16 (November 1989):388-390.

278) "Trials To Induce Neutron Emission From A Titanium- Deuterium System," by H. Werle, et al. Fusion Technoloay 16 (November 1989): 391-396. 279) "Search For Cold Fusion In High-pressure D2- Loaded Titanium and Palladium Metal and Deuteride,' J. E. Schirber. Fusion Technoloav 16 (November 1989): 397-400.

280) "The Selling of' Cold Fusion, " Scie'nce 245 (1 1989) : 1192. 281) "Search For Neutrons From A Titanium-Deuterium System," by H. W. Xamm, et al. Fusion Technoloav 16 (November 1989): 401-403. 282) "Negative Results and Positive Artifacts Observed in a Comprehensive Search for Neutrons From "Cold Fusion' Using a Multidetector System Located Underground," by R. J. Ewing et al. Fusion Technoloav 16 (November 1989): 404-407. 283) "Analysis of the Published Calorimetric Evidence for Electrochemical Fusion of Deuterium in Palladium," Science 246 (10 November 1989): 793-796. By N. Lewis et al. 284) "Neutron Limits form Gas-Loaded Ti-D Systems," Zeitsch rift fur Physik A 334 (1989): 357-358. 285) "On the Feasibility of cold Fusion," by A. T. Lee & T. M. Kalotas. Nuovo CimentQ 102 (October 1989): 1177-1180. 286) "A long-term calorimetric study of the electrohysis of D20 using palladium cube cathodes," by R. D. Armstrong, E. A. Charles, et al. Journal of Electroanalvtical chemistry 272 (November lo, 1989): 293-297. 287) "Enhancement of Nuclear Fusion in a Strongly Coupled Cold Plasma," by S. Y. Lo. Modern Physics Letters B 3 (1989): 1207-1211. 388) "An Attempt to Detect Fracto-Fusion During Microwave Irradiation of D20 Loaded Silica Gel," by K. Yoshihara et al. Journal o f Radioanalytical Nuclear C hemi s t rv, Letters 137 (1989) 333-339.

1-48 289) "Search for Energetic - Charged - Particle Emission from Deuterated Ti and Pd Foild," by W. T. Williams et al. Physical Review Letters 63 (30 October 1989): 1926-1929. 290) "Deuterium Concentration and Cold Fusion Rate Distributions In Palladoum," by Gary M. Sandquist et al. Fusion Techno loay 16 (Dec. 1989): 523-525. 291) "A Search For Anomalies In the Palladium - Deuterium System," by D. J. Gillespil et al. Fusim mhnoloay 16 (December 1989): 529-531.

292) "A Search For Neutrons In Single-phase Palladium - Deuterium," by A. C. Ehrilich. Fusion Technology 16 (December 1989): 529-531. 293) "Natloh" "Model For Cold Fusion," by T. Matsumoto. Fusion Technolow 16 (December 1989): 532-534. 294) "Deuterium molecule in the presence of electronic charge concentrations: Implications for cold fusion," by A. B. Hassam & A. N. Dharamsi. Physical Review A 40 (1 December 1989): 6689-6691. 295) "Detection of Delium-3 and tritium produced as a result of ion plasma saturateion of litanium by deuterium," by A. A. Kosyachkov, et al. Soviet Physics8 49 (25 June 1989) : 744-746. 296) "Cold Fusion: Effects of Possible Narrow Nuclear Re~onance,~by A. A. Shihab - Eldin, et al. Modern Phvsia Letters B 3 (1989): 965-959. 297) "Sitting on the fence," by D. Lindley. Nature 342 (21/28 December 1989): Review of the book "Cold Fusion: The Making of a Scientific Controversy," by F. D. Peat. 298) "Electrochemical Measurements on Palladium Cathodes in LiOD/D2O Solutions related to the Cold Fusion Experiments :8 by J. Augusttynski, et al. China 43 (1989): 355-357. 299) "Search for Emission of Neutrons from a Palladium- Deuterium System," by F. Botter, et al. Physics Letters 232 (14 Dec. 1989):536-538. 300) "Tritium in cold fusion," by A. J. Leffler. Chem ical & EnQineerina News (18 Dec. 1989):2. 301) "Improving the accuracy of the calculation of fusion rates of sticking fractions in muon-catalyzed fusion," by J. D. Morgan 111. Physical Review 9 40 (15 Dec. 1989): 6857-6862. 302) "Fusion in a Flask: Expert DOE Panel Throws Cold Water on Utah 'Discovery'," by Irwin Goodwin. Physics Today (Dec . 1989): 43-45. 1-49 303) "An old-fashioned lone-song", Nature 342 (7 Dec. 1989): 606. 304) "In Hot Water Over Cold Fusion," By R. Pool. Science 246 (15 Dec. 1989): 1384,

305) "Despite report, cold fusion isn't dead, Pons says," Deseret Ne Ws (NOV. 4, 1989): E1 & B2.

306) "Despite Scorn, Some Scientists Still Seek Cold Fusion Clues," by W. J. Broad. The New York Tima (October 3 1 , 1989): B5 b B8.

307) "DOE gives cold fusion a cold shoulder," by Lee Davidson, Deseret News (30 Oct. 1989): B1 & B2. 308) "Scientists are fuming over cold fusion," Research & Development (Dec. 1989): 5.

309) "Clandestine NSF Panel Warms To Cold Fusion" The Sc ientist (13 Nov. 1989): BS. 310) "2 Chemists fuse culinary talent," by A. W. Allen. Deseret News (22 Dec. 1989): BS. 311) "Detection of Charged Particles Emitted by Electrolytically Induced Cold Nuclear Fusion," R. Taniguchi, et al. JaDanses Journal of Amlied Phvsia 28 (November 1989): L-2021-L2023. 312) "Laser-Induced "Semicold" Fusion," by Christoph Steinert. Fusion Techno loay 17 (Jan. 1990): 206-208). 313) "Cold Fusion," Nature 343 (4 Jan. 1990): 6. 314) "Unsteady Diffusion Reaction of Electrochemically Produced Deuterium in Palladium Rod," by Jacob Jorne. Journal of the E lectrochemical SOCiety 137 (Jan. 1990): 369-370. 315) "Search for protons from the *H(d,p)3H reaction in an electrolytic cell with Pd-Pt electrodes," by K. E. Rehm, et al. Physical Review C 4l(Jan. 1990): 47-49. 316) "Energy balance of D20 electroysis with a palladium cathode," by J, Balej and J. Divisek. Parts I and 11. Journal of Electroanalvtical Chemistry 278 (1989): 85-117. 317) "On the Possibilities of "Cold Enhancement" of Nuclear Fusion," by V. Goldanskii and F. Dalidchik. Physical Letters B 234 (18 Jan. 1990): 465-468. 318) "Cold Fusion as the Subject of a Final Exam in Honors General Chemistry," by N. Porile Journal of Chemical Educat ion (Nov. 1989): 932-933.

1-50 319) "Scenario for Cold Fusion by Free Quark Catalysis," by G. L. Shaw et al. 61 Nuovo CimentQ 102A (Nov. 1989): 1441-1447.

320) "Biases in cold fusion data," by S. Freedman and Daniel Krakauer. EJature 343 (22 Feb. 1990): 703-704.

321) "An Approach to the Cold Fusion through Hydrogen Isotopes Analysis by the Heavy Ion Rutherford Scattering," M. Yanokura, et al. memist ry Letters No. 12 (1989): 2197-2200, 322) "A Mechanism for Neutron Emission from Deuterium Trapped in Metals," by S. Segree, et al. EuroDhvs ics betters 11 (1990):201-202. 323) "Peut-on Faire du Solei1 en Bouteille," Le Fiuaro (16 Dec. 1989): 16. 324) "Theory of Screening-Enhanced D-D Fusion in Metals," by S.N. Voidya b Y.S. Mayya. Japanese Jou rnal of ADPlieQ Physics 28 (Dec. 1989): L2258-L2260. 325) "Experimental investigation of thermal and radiation effects induced by deuterium discharge at the palladium electrode," by M. Chemla, et al. Journal of Blectroana lytical C hemist ry 277 (1990): 93-103. 326) "On the Interactions between Hydrogen and Palladium," by M. Springborg. EUrODhySiCS Letters 11 (15 February 1990): 325-330. 327) "Examination of Cathodically Charged Palladium Electrodes For Excess Heat, Neutron Emission, or Tritium Production," by H. Wiesmann. Fusion Techno ioav 17 (March 1990): 350-354. 328) "An Analysis of Cold and Lukewarm Fusion," M. Rabinowitz b D.H. Worledge. Fusion Technoloay 17 (March 1990): 344-349. 329) "On Cold Fusion," by B. Spinrad. Fusion Technoloav 17 (March 1990): 343. 330) "Stability of Atomic and Diatomic Hydrogen in FCC Palladium," by Su-Huai Wei and Alex Zunger. Solid State Communications 73 (February 1990): 327-330. 331) "On the possibility of nuclear transformation in chemical reactions," R.K. Maziton (In Russian), Uademiia Nauk S.S.S. R. Dokladp 307 (1989): 1158-1160. 332) Foreign patents filed for cold fussion," by Jo Ann Jacobsen-Wells. Deseret News (March 20-21, 1990): 2 B.

1-51 333) "Heat over cold fusion will linger," by Hugo Rossi. Peseret News (March 22-23, 1990): A 23. 334) @@ColdFusion, Part IV," Metals Week (March 268 1990): 3. 335) "The role of combined electron-deuteron screening in d-d fusion in metals," by S.N. Vaidya and Y.S. Mayya. Pramang 33 (2 AUg. 1989): L343-L346.

336) "Stability of Atomic and Diatomic Hydrogen in FCC Palladium," by Su-Huai Wei and Alex Zunger. Solid State Commun ications 73 (1990): 327-330. 337) "Cold-Fusion meet at U. will include severe critics, " Deseret News (March 19-20, 1990): Bl-B2. 338) "On the Feasibility of Nuclear Fusion in F.C.C. Metals," by S. Feyita. Physics St atus So lid6 B 156 (Nov. 1989): K17-K21. 339) @*A theory of cold nuclear fusion in deuterium-loaded palladium," by S.K. Ghosh et al. Pramana 33 (Aug. 1989): L339-L342. 340) "Electrochemical fusion: a mechanism speculation," by G.H. Lin et al. (J.O'M. Brockris). Journal of Elect roanalvtical Chemistrv 280 (1990): 207-211.

341) "Tritium production during the cathodic discharge of deuterium on palladium," J. Chene and A.M. Brass. Jou rnal of E lectroanalvtical Chemistry 280 (1990): 199-205. 342) "Nuclear reactions from Lattice Collapse On A Cold Fusion Model," by E. Tabet & A. Tenenbaum. Phvsics T,etters 4 144 (12 march 1990): 301-305. 343) "Search for cold fusion in palladium-deuterium and titanium-deuterium," by G. Badurek et al. Perntechn ik 54 (1989) : 178-182. 344) "Upper limit on cold fusion in thin palladium films," G.P. Chambers, et al. Phvsical Review B 41 (15 March 1990): 5388-5391. 345) "Our Calorimetric Measurements of the Pd/D System: Fast and Fact and Fiction," by Stanley Pons and Martin Fleischmann. Paper submitted to the Journal of Fusion Technology. 346) "Limits on the Emission of Neutrons, Gammas, Electrons, and Protons from Pons/Fleischmann Electrolytic Cells," by M.H. Salamon, H.E. Bergeson et al. Paper submitted to Nature Magazine.

1-52 347) "Limits on the emission of neutrons, Grays, electrons and protons from Pons/Fleischmann electrolytic cells," by M.H. Salamon, H.E. Bergeson et al. Nature 344 (29 March 1990): 401-4050

348) "Farewell (not fond) to cold fusion," Editorial. Nature 344 (29March 1990): 365,

349) "The Embarrassment of cold fusion," by D. Lindley. Nature 344 (29March 1990): 375-376.

350) "State is assured fusion investment will pay off," Pese ret flews (March 24, 1990): B1 b B6. 351) "Scientists converge on S.L. in fusion quest," Deseret NewS (29 March 1990): A1 b A2. 352) "Scientist Defends 'Cold Fusion' Work," New York Times (30 March 1990): A9. 353) "Press should separate facts, opinion," by M. Fleischmann and S. Pons. Deseret News (28-29 March 1990): A9. 354) "Two at ISU lab say they've produced cold fusion," by Jo Ann Jacobsen-Wells. Deseret Ne ws (April 4, 1990): B 3,

355) "Attorneys have a patent interest in monitoring new fusion tests," by Jo Ann Jacobsen-Wells. Deseret News (15 January 1990): B1 & B2. 356) "Fusion Confusion Offers Window on Utah's Psyche," by Rick Atkinson. Washinaton Post (23 March 1990): A3. 357) "Estimate of nuclear fusion rates, arising from a molecular-dynamics model of Pd DX," by J. W. Halley b J. L. Valle's. Physical Re view 41 (15 March 1990): 6072-6075. 358) "Nuclear Reactions From Lattice Collapse In A Cold Fusion Model," by E. Tabet b A. Tenenbaum. Physics Lette rs A 144 (12 March 1990): 301-305. 359) "Fusion Rates For Deuterium In Titanium Clusters," by K. Sohlberg and K. Szalewicz. Physics Lette rs A 144 (12 March 1990): 365-370, 360) "On the possibility of nuclear fusion by the electrolysis of heavy water," by C.K. Mathews et al. Indian Jou rnal oc Technolocly 27 (May 1989): 229-231. 361) "Cold Fusion Rates In Titanium Foils," by J. P. Briand b G. Ban et al. Physics Lette rs 9 145 (9 April 1990): 187-191.

1-53 362) "Thermal Neutron Measurements on Electrolytic Cells with Deuterated Palladium Cathodes Subjected to a Pulsed Current," by J. R. Granada, et al. Journal of Nucleat, Science-ad Technology 27 (March 1990): 222-22'9. 363) "Evidences for Associated Heat Generation and Nuclear Products Release in Palladium Heavy-Water Electr~lysis,~ by D. Gozzi et al. In Nu0vo Cim- 103 A (Jan. 1990): 143-162 364) "Isotope heat effect in reactions involving hydrogen evolution on palladium catalyst particles," by 0.1. Lomovsky et al. Proceedinqs of the Indian Academy of Science 102 (April 1990): 173-176.

365) "Palladium Metallurgy and Cold Fusion: Some Remarks," by L.E. Murr. Sc ripta Metal -1uraica et Materialig 24 (1990) : 783-786. 366) "Plasma and Surface Tension Model for Explaining the Surface Effect of Treitium Generation at Cold Fusion," by H. Hora et al. I1 Nuono cimento 12D (March 1990): 393-399. 367) "Tritium separation effects during heavy water electrolysis: implications for reported observations of cold fusion," by D.A. Corrigan b E.W. Schneider. Journal 9f Electroanalvtical Chemistry 281 (26 March 1990): 305-312. 368) "Experimental investigations of the electrolysis of D20 using palladium cathodes and platinum anodes," by L.L. Zahm et al. Journal of Electroanalytical Chemistry 281 (26 March 1990): 313-321. 369) "World Flash On Cold Fusion, No.4" by T. Braun. Journal of Radioana lvtical a nd Nuclear Chemis t ry Letters 144 (1990): 323-326. 370) "Fusion Reastions During Low Energy Deuterium Implantation Into Titanium," by J. Roth et ale fluclear Fusion 30 (1990): 411-446. 371) "World Flash On Cold Fusion, No. 3," by T. Braun. Jopurnal of Radioanalytical and Puc lear Chemistry Letters 144 (1990) : 161-164

372) "High Temperature Superconductivity and Cold Fusion," by Mario Rabinowitz. Podern Phvsics Letters B 4 (1990) : 233-247. 373) "Production of tritium from D20 electrolysis at a palladium cathode," by N.J.C. Packham et al. Journal of. Electroanalytical Chemistry 270 (1989): 451-458. 374) "Electrochemical incorporation of lithium into palladium from aprotic electrolytes," by F. Dalard, et al. Jouranl of Electroanalytical Chemistry 270 (1989): 445-450.

1-54 375) "Search for the Neutron Production in Niobium Deuteride," by F. Demanins, et al. Solid State Co mmunications 71 (1989): 559-561, 376) "Titanium fracture yields neutrons?," by B.V. Derjaguin, et al. Nature 341 (12 Oct. 1989): 492. 377) "Utah keeps embers of cold fusion aglow," New sc ientist 127 (7 April 1990): 25. 378) "Cold Fusion: Wanted Dead and Alive," I. Amato. Science News 137 (7April 1990): 212. 379) " Magazine's cold fusion confusion has sparks flying," by Jo Ann Jacobsen-Wells. Dese ret News (7 April 1953\: B1.

380) "Still crazy, after a year?," The Economist (31 March 1990) : 82.

1-55 381 ) "Cold-Fusion meet at U. will include severe critics," Desert News (March 19, 1990): B1-2.

382) "Hawaiian research fuels new hope for fusion," Desert New (July 25, 1990): B1.

383) "Limits on neutron emission from "cold fusion" in metal hydrides," by B. Balke, et al. Phvsical Review C 42 (July ,1990): 30-37.

384) "Upper limits to fusion rates of isotopic hydrogen molecules in Pd," by M. A. Alberg, et al. Phvsical Review C 41 (June, 1990): 2544-2547.

385) "Surface and electrochemical characterization of Pd Cathodes after prolonged charging in Li OD + D20 solutions," by M. Ulmann, et ai. Jour nal of Electroanalvtical Chemistry 286 (25 June 1990): 257-264.

386) "Comment on "Cold Fusion in Condensed Matter: Is a theoretical Description in Terms of Usual Solid State Physics Possible?" by V. C. Sahni. Modern PhvsiE Letters B 4 (1990): 497-498.

387) "Upper limit for neutron emission from cold d-t fusion," by J. R. Southon, et al. Phvsical Review C 41 (May 1990): R1899-R1900.

388) "Surface-controlled deuterium-palladium interactions," by W. R. Wampler & P. M. Richards. Phvsical Review B 41 (1 5 April ,1990): 7483-7490.

389) "Cold Fusion at Texas A & MI" by D. M. Anderson & J. 0. Bockris. Science 249 (3 August ,1990): 463-465.

390) "A Sensitive Multi-Detector Neutron Counter Used to Monitor "Cold Fusion" Experiments in an Underground Laboratory; Negative Results and Positive Artifacts," by R. I. Ewing et al. I. E. E. E. Transactions on Nuclear Science 37 (June, 1990): 1165-1 170.

391) "World Flash On Cold Fusion, No. 6," by T. Brown. Jou rnal of Radioanalvtical ulear Chemistry, Letters 145 (1 990): 245-248.

392) "Search for charged-particle emission from deuterated palladium foils," by K. D. Schilling et ai. Zeitschrift fin PhysikA 336 (1990): 1-4.

393) "Coulomb-Assisted Cold Fusion In Solids," by M. Danos. Fusion Technolow 17 (May, 1990): 484-489.

394) "Cold Fusion Observed With Ordinary Water," by T. Matsumoto. Fusion Technoloav 17 (May, 1990) 490-492.

395) "Cold Fusion In A Confining Phase Of Quantum Electrodynamics," by M. Jandel. Fusion Technolow 17 (May, 1990): 493-499.

1-56 396) "On Fusion/Fission Chain Reactions In The Fleischmann-Pons "Cold Fusion" Experiment," by S. Anghaie et al. Fusion Technoloav 17 (May, 1990): 500- 506.

397) "Cross Section For Cold Deuterium-Deuterium Fusion," by Y. Kim. Fusion Technology_ 17 (May, 1990): 507-508.

398) "Neutron Measurements on Electrolytic Cells (Pd-DzO) Performed under Very Low Background Conditions," by J. R. Granada et al. Jou rnal of Nuclear Science & Technoloa~27(April 1990): 379-381.

399) "Absorption of electrolytic hydrogen & deuterium by Pd: the effect of cyanide absorption," by J. McBreen. Journal of Flectroanwcal Che mistrv 287 (25 July 1990): 279-291.

400) "Calorimetry of the palladium-deuterium-heavy water system," M. Fleischmann, S. Pons, et al. Jou rnal of Electroanalvtical Chemistry 287 (25 July 1990): 293-348.

401 ) "Solid-state Fusion" Effects," by D.T. Thompson. Platinum Metal Review 34 (July, 1990): 136-141.

402) "Cold" Fusion caused by a Weak "On-Off Effect" by Y. Arata & Yue-Chang Zhang. Proceedinas of the Japan Acade mv Se ries B 66 (February 1990): 33- 36.

403) "On Electrochemical Tritium Production," by G. H. Lin, J. O'M. Bockris, et al. International Journal of Hvdroaen Enerav 15 (No. 8): 537-550.

404) "Real Time Deuterium Loading Investigation in Palladium Using Neutron, Diffraction," by R. Mukhopadhyay, et al. Solid St& Co m municatio n 75 (JUlyll990): 359-362.

405) "Limits on Neutron Emission following Deuterium Absorption into Palladium & Titanium," by D. Aberdom, et al. Physical Review Letters 65 (3 September 1990): 1196-1199.

406) "An Attempt To Replicate Cold Fusion Claims," by S. Miljanic, et ai. Fusion Technoloav 18 (September 1990): 340-346.

407) "Relaxation Toward Equilibrium in Plasmon-Enhanced Fusion," by M. Baldo, et al. 18 (September, 1990): 347-350.

408)' "Heat Flow Calorimeter With A Personal-Comwter-Based Data Acauisition System," by 0. A. Velev and R.C. Kainthlo. Fusion Technoloav 18 (September 1990): 351 -355.

1-57 409) "Observation of New Particles Emitted During Cold Fusion," by T. Matsumoto. Fusion Tec hnologlL 18 (September, 1990): 356-360.

41 0) "Calorimetric Measurements of the Palladium/Deuterium System: Fact & Fiction," by S. Pons and M. Fleischmann. Fusion Technoloav 17 (July 1990): 669-679.

41 1) "Electrolytic Tritium Production," by E. Storms & C. Talcott. Fusion Technology 17 (July, 1990): 680-695.

41 2) "Enhanced Fusion Induced By Affiliated Muons," by du T. Van Der Merwe. Fusion TechnoloqlL17 (July, 1990): 696-698

41 3) "The Behavior of Electrochemical Cell Resistance A Possible Application To Cold Fusion Experiments," K. A. Ritley, et al. Fusion TechnoloaL17 (July,l990): 699-703.

41 4) "Theoretical and Experimental Studies on the Cold Nuclear Fusion Phenomena," by M. Abdel Harith, et al. Fusion Technolow17 (July, 1990): 704-709.

41 5) "Bloch-Symmetric Fusion in Pd Dx," by T. A. Chubb and S. R. Chubb. Fusion Technoloav- 17 (July,l990): 71 0-712.

41 6) "Preliminary Tests on Tritium and Neutrons in Cold Nuclear Fusion Within Palladium Cathodes," by P. G. Sona, et al. Fusion Technology_ 17 (July, 1990): 71 3-71 7.

41 7) "Further Measurements on Electrolytic Cold Fusion With D2 0 and Palladium at Gran Sasso Laboratory," by F. Celani, et al.Fusion Technoloav 17 (July, 1990): 71 8-724.

41 8) "Corroborating Evidence for "Cold" Fusion Reaction, by Y. Arata and Y. Zhang. Proceedinas- of the Jarsan Academv 66 (June, 1990): 110-115.

41 9 "Numerical Calculation on Deuterium Absorption in Palladium Under High Pressure D2 Gas at Low Temperatures," by K. Nakamura, G. Maizza, & M. Kitajima. Solid State Com munications 75 (September 1990): 1019-1 021.

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467) "Cold fusion archive opens its doors," announcement of The Cornell Cold Fusion Archive at Cornell University's Olin Library (607) 255-3530, Attn. Elaine Engst. Chemical & Enaineerina News (August 6, 1990): 22.

468) "Telling a Detective Story on Cold Fusion in a Jar," by W. Goodman. New Yo rk Times (January 4, 1991): B4.

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1-64 Tritium Analysis In Palladium With An

Open System Analytical Procedure

K. Cedzynska

S. C. Barrowes

H. E. Bergeson

L. C. Knight

F. G. Will

1-65 Table of Contents

Page

Abstract 1-67

Introduction 1-67

Experimental 1-60

1. Apparatus 1-68

2. Calibration of Liquid Scintillation Counter 1-69

3. Materials and Reagents 1-70

4. Analytical Procedures 1-71

Results 1-72

Discussion 1-73

Conclusions 1-74

Acknowledgeme nts 1-74

References 1-75

1-66 Abstract

In 45 palladium samples, produced by three different manufacturers in various lots and sizes, we found no evidence for tritium contamination. Within the maximum error of our experiments, that is 3 DPM/ml, the palladium samples gave tritium counts identical to the background of 26 DPM/ml. The major factors leading to possible errors in applying this technique are discussed. Falsely high readings may be caused by c he mi I u mi nesce nce , photo lu mi nesce nce , colored so Iu t io ns , and chemical reactions. But such false high readings were not obtained when automatic quench control and other standard precautions were employed. On the other hand, falsely low readings can result from the escape of dissolved tritium gas. Closed system analytical procedures are, therefore, preferred.

Introduction

"Cold Fusion" (1,2) has been reported to take place when a metal lattice, usually Pd or Ti, is highly loaded with deuterium. Whether the loading is accomplished by electrolytic action or by D2 gas pressure, many groups have then looked for evidences of nuclear processes, such as the generation of neutrons (3), gamma rays, x-rays, or isotopes of hydrogen or helium not initially present (43). Much attention has focused on measuring tritium since (1) its radioactive decay affords highly accurate determination by scintillation counting techniques and (2) its presence, if reliably found well above background, would demonstrate the occurrence of nuclear reactions in the deuterium-loaded metal.

Tritium analysis of electrolyte samples has been done at many laboratories (6) involved in cold fusion experiments. Recently, a few groups have checked for tritium contamination in Pd cathodes before usage (7-9). For a proper assessment of excess tritium production in an electrolytic cell, tritium levels in the as-received D20 and Pd must be analyzed beforehand.

In the work of lyengar et al. (7) and Bockris et al. (5), tritium analysis was performed on electrolyte samples by liquid scintillation counting (LSC). lyengar et al. (7) measured tritium in the palladium samples before and after electrolysis. Their Pd cathodes were degassed at 680" K, and the released gas was passed through an

1-67 assembly of palladium catalyst and copper oxide for conversion to water. The recombined water was quantitatively collected and counted for tritium.

Before their cathodes were prepared, palladium samples were collected and analyzed for tritium content. The palladium was first dissolved in aqua regia, followed by dilution and neutralization to prepare suitable stock solutions. Samples of the stock solutions were counted for tritium with LSC. Tritium counts were taken several times over a period of one week and showed no evidence for tritium contamination in any of the palladium samples analyzed.

Yanakura et at. (8) have analyzed for tritium and helium-3 in palladium cathodes by means of heavy ion Rutherford back-scattering, while degassing the Pd cathodes at 680" K in vacuum. They reported detecting neither tritium nor helium-3 in palladium electrodes after electrolysis.

Wolf (9) also analyzed for tritium in palladium samples, dissolved in aqua regia. He found tritium contamination in both "virgin" palladium wires and in wires used as cathodes in heavy water electrolysis. This was widely interpreted to mean that tritium found in "cold fusion" experiments by other groups as well might be due to tritium contamination of palladium rather than to nuclear reactions.

Such conclusions appear premature and underscore the necessity of carefully determining the initial and final tritium contents both of the electrolyte and of the cathode materials which are used.

Because of the significance of the tritium issue, we have applied essentially the same "open-system" analytical procedure, as used by Wolf (9), to a large number of as-manufactured palladium samples from three different suppliers. The objective of this study was to explore this particular analytical procedure with respect to both its promises and limitations. The results of the study are presented in this paper.

Experimental

1. Apparatus

Tritium measurements were performed by liquid scintillation counting (LSC), using a Beckman LS 5000 TD system.

1-68 The Beckman system employs two photomultiplier tubes, counting events only when scintillation light reaches the two tubes simultaneously. This coincidence requirement eliminates most spurious events occurring in only one tube, such as thermionic electrons in the photomultiplier tube, chemiluminescence photons and photoluminescence photons. About five cm of lead shielding reduces the cosmic-ray gam ma backg ro un d .

Each 1 ml solution sample was added to 10 ml of scintillation cocktail (Pseudocumene/Xylene from Beckman) and allowed to stand in a dark place for several hours before counting. This time was usually sufficient to minimize c he mi lu mi ne sce nce and photo Iu mi nesce nce contributions .

Several successive counting cycles were performed on the solutionkocktail mixtures to enable comparison of results and form statistical averages.

PH adjustments of solution samples, when necessary, were made using a pH meter made by Cole-Parmer Instrument Company. Centrifuging of the solutions was performed with a Sargent Centrifuge, Model...

2. Calibration of Liquid Scintillation Counter

The Beckman automatically does a calibration on each sample, because counting efficiency depends strongly on the amount of chemical quenching (reduced scintillation efficiency due to chemical quenching in the samples) and color quenching (absorption of light by colors in the sample). A radioactive source (Cs-137) is placed near the sample and light pulses, owing to Compton-scattered electrons, are recorded. The efficiency is computed by comparing the measured energy of the Compton edge while irradiating the sample to the Compton edge while irradiating a standard. The measured counts per minute (CPM) for the sample are then divided by this efficiency to calculate the actual decays per minute (DPM).

A feature called automatic quench compensation (AQC) adjusts the window of detected pulse heights. This reduces background by rejecting counts too large to have come from tritium decay after adjusting for the amount of quenching. If the AQC feature is not used, these large counts are included as legitimate counts. In darkly colored samples, the artificially large counts result in very exaggerated DPM values,

1-69 due to the division by very low efficiency values (10). One must therefore use the AQC feature for consistent results.

Another caution concerns the random coincidence monitor (RCM) value for each sample run. This is an estimate of the percentage of the counts which does not originate from tritium but from chance coincidence of single pulses from the two photomultiplier tubes. When RCM is over a few percent (more than 5%), the measured tritium concentration should be considered unreliable.

Single pulses (pulses from only one photomultiplier tube) come from c he mi lu mi nescence, photo Iu mi nescence, and from therm ionic electrons in side the tube. As their rate R goes up, the number of chance coincidences grows as R2. Thus it is important to reduce these as much as possible, to get reliable readings. The first two can be reduced by storing samples in the dark 24 hours before counting. Chemiluminescence also depends on sample pH. Low thermionic emission is achieved by making certain that the laboratory is kept at a controlled cool temperature.

To verify that the present window settings were correct for tritium, we analyzed the energy spectrum of tritium standard samples.

3. Materials and Reagents

The following types of palladium samples were analyzed for tritium:

1. 1 mm and 2 mm diameter Pd wires from Hoover & Strong Inc. (HS) of Richmond, Virginia.

2. 1 mm and 6.25 mm diameter Pd wires from Aesar/Johnson Matthey, (JM) of Royston, England.

3. 1 mm and 3 mm diameter Pd wires made by Hoover Strong, from J. O'M Bockris at Texas A&M University.

4. 4 mm diameter Pd wires from Metalor Co. (M).

5. 2.35 mm diameter Pd wire prepared by the metallurgy group at NCFl from 1 mm thick plate (JM).

1-70 The aqua regia solution was prepared by mixing 82 ml of concentrated HCI and 18 ml of concentrated HNO3 (the amounts recommended for palladium in Inorganic and Theoretical Chemistry, p. 595),using concentrated stock solutions (Mallinckrodt, AR grade). The concentrated and diluted solutions of NaOH were prepared from NaOH pellets (Mallinckrodt, AR grade).

4. Analytical Procedures

Palladium samples for tritium contamination measurements were not identified to the experimenters until the analyses had been performed; they were only known by sample numbers. Samples were prepared by two different procedures:

1. Pd samples (0.04 - 0.10 g) were dissolved in 1 or 2 ml of aqua regia in closed polypropylene containers. After two hours the solutions were neutralized with concentrated NaOH to pH 7 in an ice bath, to prevent excessive heating of the neutralized sample and reduce possible loss of dissolved gases, such as T2 and TH. 1 ml of each sample was adjusted to a pH level between 2 and 3 (with a pH- meter), using a dilute solution of HCI and quantitatively diluting to 5 ml in a volumetric flask. One ml of this solution was added to 10 ml of cocktail, which was then subjected to tritium counting. The cocktail solution mixture was placed in closed containers that were tightly wrapped with Teflon@ tape.

2. Pd samples (0.04 - 0.07g) were dissolved in 1 or 2 ml of aqua regia solution in closed polypropylene containers as above. After two hours, the solutions were neutralized and adjusted to pH 13 with concentrated NaOH. The amount of NaOH added was determined by acymetric titration of the aqua regia solution. The solutions, along with any precipitates formed, were moved quantitatively to closed polypropylene centrifuge tubes and centrifuged for 5 minutes. After separating the precipitate from the solution, the pH of the latter was measured. Two separate samples of this solution (1 ml each) were taken; one was neutralized to pH 7 and the other adjusted to pH 2-3. The volumes of the samples, their color and pH were noted. The two solutions were then added to 10 ml cocktail, each of which was then subjected to tritium counting.

In spite of all reasonable precautions taken to minimize exposure of the solutions to the environment, both procedures must be regarded as "open-system'' procedures. Escape of dissolved gases, such as tritium, as well as the absorption of

1-71 contaminants present in the environment by the solutions is unavoidable during transfer between vessels, pH measurement, etc.

Results

To check the efficiency of tritium counting, the tritium activity of standard solutions with known tritium concentrations was determined. Palladium chloride was also added to the standard solutions to simulate the same color as solution samples containing dissolved palladium metal. The results, plotted in Figure 1, show a linear dependency of tritium counts (DPM/ml values) on the activity of added tritium (pCi x 106), as expected.

Table 1 lists results for solution samples with pH 2 to 3 prepared by procedure 1. Each result in Table 1 is an average of tritium determinations on at least two Pd samples. When the samples were measured within a day after preparation, the more acidic solutions, (which had lighter color than those at pH 7) gave readings with higher efficiencies, and, hence, higher reliability.

When these same samples were neutralized to pH 7, they became darker, resulting in more color quenching. In some samples, a small amount of precipitate was observed which also reduced the count rate.

Table 2 shows results of tritium analysis for Pd samples prepared by procedure 2, adjusted to neutral and acidic pH levels (7 and 2-3, respectively). Values shown are averages from at least two runs. Note that the efficiencies at pH 2-3 are slightly higher than the values in Table 1 at the same pH. This reflects the beneficial, but not dramatic effect of centrifuging.

The color of the same samples at pH 7 is also darker than at pH 2 to 3, causing lower efficiencies, longer counting times, and more uncertain results.

In general, however, results from both procedures are comparable and neither procedure shows any tritium contamination in the investigated samples.

Table 3 shows a summary of the results for tritium analysis in 45 as- manufactured palladium samples using either procedure. The average number of tritium counts was found to be 25.9 DPM/ml with a standard deviation of 1.3. Also shown in the table is the background resulting from the cocktail alone. The value of 26

1-72 DPM/ml is the average of results obtained on 14 samples, with a standard deviation of 0.8. Further background measurements were performed on mixtures of the cocktail and neutralized aqua regia, and the same background result was obtained.

Discussion

Neither of the two open-system analytical procedures was good enough to get colorless samples, owing to the amphoteric nature of Pd. The second procedure, with the separation of palladium as palladate hydroxide, Pd (0H)z and Pd(OH)4, does not allow the complete precipitation of Pd because of the amphoteric behavior of Pd (OH)4. The latter dissolves in strong acid (HCI and HNO3) to give a Pd+Z ion, and, although insoluble in dilute NaOH, it dissolves in concentrated NaOH (pH=l3) to give palladate ions, PdO3-2. The best pH level to precipitate and separate most of the palladium is pH=l1-12. Even in this case some of the palladium reacts with CI- ions to give (PdC14)-2 complexes, which are very soluble in water.

Because none of these solutions is colorless, color-quenching and lower counting efficiency result. In some cases, falsely high count rates have been observed.

We also found that some of the samples gave extremely high tritium counts (up to several thousand DPM/ml) when left for a few days as a mixture of scintillation cocktail and acidic buffer. These artificially high tritium counts are possibly due to impurities in the palladium. Analysis by emission spectroscopy (SPECTRA COMPANY, San Diego) of these specific samples of palladium yielded metal contaminations at the 1 to 10 ppm level. These metal contaminations are: Cu, Ir, Pt, Rh and Ag.

Extra caution must, therefore, be applied before claiming tritium counts in colored samples because of the chances of making errors, such as originating from color, chemical quenching and possibly impurities in the palladium. When analyzing colored samples, care must be taken that the LSC system is calibrated to give accurate background counting rates for samples of colored, deionized water. With the Beckrnan system, use of the automatic quench compensation feature (variable energy window) is essential to obtain accurate results.

1-73 Conclusions

By applying the open-system analytical procedure, used earlier by Wolf (9), we find no evidence for tritium contamination in 45 Pd samples, manufactured by three different suppliers, in various lots and sizes. These 45 samples gave an overall tritium count average of 25.9 k 1.3 DPM/ml, as compared to a background count of 26 f 0.8 DPM/ml. None of the 45 Pd samples analyzed (Table 3) showed tritium contents exceeding background by more than 3 DPM per ml of solution at the 99% confidence level. In terms of the tritium to palladium atom ratio, this ratio was less than 5 x lO-l3 in all cases.

Unfortunately, in evaluating the applicability of the present analytical procedure for reliable tritium determinations, we find the open-system technique to be subject to (1) sometimes artificially high count rates--due to color effects in the solution and, possibly, metal contaminants in the palladium--, but also (2) occasionally artificially low count rates--due to possible loss of gaseous tritium during the various steps involved in the open-system procedure.

While our results do not show tritium contamination in 45 Pd samples, they do not disprove possible spot contamination found elsewhere on rare occasions. Based upon a knowledge of the procedures involved in the fabrication of Pd, such contamination is unlikely to be present in the as-manufactured metal. It is much more likely that tritium contamination is introduced through improper handling of the metal or improper analytical procedures. If tritium analysis is done on representative samples as a reasonable precaution, the use of reliable techniques should be mandatory. Only then can definitive statements be made that tritium, found in such experiments, originated from nuclear reactions in the metal. A reliable technique to achieve such analysis has been developed and will be described in the near future.

Acknowledgements

The funding of this work by the State of Utah is gratefully acknowledged as is the furnishing of several of the palladium samples by Dr. S. Guruswamy.

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3. S. E. Serge, S. Atzemi, S. Briguglio, F. Romanelli, "A Mechanism For Neutron Emission From Deuterium Trapped In Metals," Europhys Lett. 11 (3), 201 (1990).

4. R. C. Kainthala, 0. Volev, G. H. Lin, N. J. C. Packham, M. Szklarszyk, J. Wass, J. O'M. Bockris. "Eight Chemical Explanations Of The Fleischmann-Pons Effect," Electrochem. Acta 35(g), 1200 (1 988).

5. N. J .C. Packham, K. L. Wolf, J. C. Wass, R. C. Kainthla, J. O'M. Bockris, "Production Of Tritium From D20 Electrolysis At A Palladium Cathode," submitted for publication.

6. Proceedings of the 1st Annual Conference on Cold Fusion, Utah (1990).

7. T. S. Murthy, T. S. lyengar, B. K. Sen, and T. B. Joseph, "Tritium Analysis Of Samples Obtained From Various Electrolysis Experiments At Barc," Fusion Technology, u,71 (1990).

8. M. Yanakura, M. Minami, S. Yamagata, S. Nakabayashi, M. Aratani, A. Kira, I. Tanihata, "An Approach To The Cold Fusion Through Hydrogen Isotopes Analysis By The Heavy Ion Rutherford Scattering," Chemistry Letters, 21 97 (1 989).

9. K. L. Wolf, "Cold Fusion And Hot Tritium," transcript of talk given August 11, 1990, at Stanford University; Quoted in Science 8 (1 990).

10. D. L. Horrocks, "Application's Of Liquid Scintillation Counting," New York: Academic Press, p. 253, (1 974).

1-75 TABLE 1

Tritium Analysis of Pd Using no Centrifuging (Procedure 1)

Pd Sample Efficiency DPM/ml (W &!X!x Diameter (mm)

Hoover & Strong 2 35.8 25.8 Hoover & Strong* 1 38.8 25.0 Hoover & Strong* 3 32.3 25.8 Johnson Matthey 2.35 39.2 24.0 Johnson Matthey 6.25 34.5 25.8 Metalor 4 34.9 25.2

Backg ro u nd 49.8 25.4

Pd samples obtained from J. O'M Bockris.

1-76 TABLE 2

Tritium Analysis of Palladium Samples From Different Sources, After Precipitation and Centrifuging (Procedure 2)

Pd Sample Solution pH = 7 Solution pH = 2-3

Source Diameter o/o EFF DPM %EFF PPM (mm>

Hoover & Strong 2.00 26.7 26.4 38.3 26.0 Hoover & Strong 2.00 27.6 25.3 36.7 26.0 Hoover & Strong 1.oo 48.2 27.0 48.3 25.3 Hoover & Strong 1 .oo 47.5 26.8* 48.3 26.1 Johnson Matthey 6.25 16.3 26.9 30.6 28.1 Johnson Matthey 6.25 15.0 ** 24.0 25.6 Johnson Matthey 2.35 33.9 26.9 36.1 28.2 Johnson Matthey 2.35 32.5 24.2 40.2 25.6 Johnson Matthey 1 .oo 40.6 25.2 41.2 24.9 Johnson Matthey 1.oo 35.9 24.4 38.5 24.0

Backg ro u nd 50.2 26.2

* One reading on this sample (57 DPM) was rejected due to inconsistency with other runs.

** No useful reading was obtained for this sample because chemilumenescence was excessive on each run (RCM much greater than 5%).

1-77 TABLE 3

Tritium Analysis in Palladium

PALLADIUM CHARACTERISTICS OF TRITIUM STANDARD MANUFACTU RER JPES AVERAGE PFVIATION Wire No. of No. of DPM/ml Diameter Cuttings Samples (mm>

Hoover & Strong 2.0 26.0 1 .o Hoover & Strong 1.o 25.9 1.2 Hoover & Strong 1 .o 24.8 Hoover & Strong 3.0 26.2 Johnson Matthey 1.o 24.5 1.9 Johnson Matthey 2.35 25.7 1.8 Johnson Matthey 6.25 27.7 1.2 Metalor Co. 4.0 26.2 1.2

Total 45 25.9 1.3

Background - Scintillation Liquid 14 26.0 0.8

1-78 70

\ E e

4 n 40

20 0 x 10-6 pCi added as T

Fig. 1. CALIBRATION CURVE FOR H20 WITH KNOWN TRITIUM CONTENTS (PdC12 ADDED FOR COLOR SIMULATION) Closed-System Analysis of Tritium

in Palladium

by K. Cedzynska F. G. Will

1-80 Table of Contents

Page

Abstract 1-82

Introduction 1-82

Ex pe ri mental 1-83

Materials and Reagents 1-83

Apparatus 1-84

Wet-C hemical Procedure 1-84

Scintillation Counting 1-85

Verification of Procedure 1-86

Results and Discussion 1-86

Conclusions 1-88

Acknowledge me nts 1-88

References 1-88

1-81 Abstract

We have developed a closed-system procedure for the analysis of tritium in palladium which has a sensitivity and accuracy of 5x107 tritium atoms, corresponding to one tritium atom per 1013 palladium atoms for a typical 0.lg palladium sample. The technique involves palladium dissolution in acid, distillation of the tritiated water and catalytic oxidation of tritium gas to tritiated water, followed by liquid scintillation counting. This technique is not subject to false tritium findings from a variety of chemical factors or environmental influences which may affect the results of open- system analytical procedures. We have applied the closed-system procedure to nearly 100 as-manufactured palladium wire samples of various lots and sizes from two different sources. None of these samples show any tritium contamination within our detection limit of 5x107 tritium atoms. By comparison, others, employing an open- system procedure, have reported tritium contamination in as-manufactured palladium 10,000 times larger than our values.

Introduction

The question of whether or not tritium found in palladium, employed in "cold fusion" experiments, has actually been generated by nuclear reactions occurring in the deuterium-loaded palladium or was already present as a contaminant in the palladium is central to the reality of cold fusion.

There appear to be only few groups that have recently reported on the analysis of tritium in palladium. M. Yanakura et al. (1) described an analytical method using heavy ion Rutherford back-scattering while degassing the Pd cathodes at 680°K in vacuum. 0. Matsumoto et at. (2) monitored the beta radiation from Pd, immersed in a liquid scintillator. These authors also employed a temperature-programmed desorption technique, coupled with mass spectrometry. T.S. Murthy et al (3) employed degassing of the palladium at 680°K and catalytic oxidation of the released tritium over heated copper oxide, followed by scintillation counting. K. Wolf (4) employed a method of dissolving palladium in acid, followed by alkaline precipitation, centrifuging and scintillation counting of the resulting solution.

In a previous paper (5),we described the results of tritium analysis in palladium, employing an open-system analytical procedure, essentially identical to that used earlier by Wolf (4). While we found no evidence for tritium contamination in 45

1-82 palladium samples, we concluded that this technique cannot be expected to yield reliable results. We found that falsely high tritium counts may be caused by a number of factors; also, an open-system technique is subject to possible contamination from the environment. On the other hand, falsely low tritium readings can result from the escape of tritium gas, formed during the acid digestion of the palladium.

We have, therefore, developed a closed-system procedure which involves dissolving the palladium in acid, distilling the water and catalytically oxidizing the released tritium gas to water, followed by scintillation counting. Thus, the counting is performed on a clear solution, thereby eliminating the possibility of false tritium counts due to color, precipitated particles and chemical reactions. Since the procedure is performed in a closed system, gases and vapors cannot escape, nor is the procedure subject to contamination from the environment.

The objective of this paper is to describe the analytical technique and present the results of analyzing nearly 100 palladium samples of various diameters and cuttings from two manufacturers for possible tritium contamination. Although the manufacturing process of palladium wires and foils makes it highly unlikely that there would be tritium contamination, we decided to address this issue in depth in view of widely and prematurely publicized statements (4,6) that tritium found in "cold fusion" studies results from contamination and not from nuclear reactions in the palladium.

Experimental

Materials and Reagents

The following as-manufactured palladium samples were analyzed for their tritium content :

1. 1, 2 and 4mm diameter Pd wires of purity 99.5% from Hoover & Strong (Richmond, Virginia); four different batches of 2mm wires were used.

2. 0.5 and 1mm diameter Pd wires of purity 99.995% from Aesar/Johnson Matthey (Royston, England); two different batches of 1mm wires were used.

3. lmm diameter Pd wire of purity 99.5% made by Hoover & Strong, supplied by J. O'M Bockris at Texas A & M University.

1-83 Fuel cell grade Pt catalyst on Ag-plated Ni screen (ESN), made by E-Tek, Inc., was used as a recombination catalyst.

The aqua regia solution was prepared by mixing 82 ml of concentrated HCI and 18 ml of concentrated HNO3 (the amounts recommended for palladium in lnorganic and Theoretical Chemistry, p,. 595), using concentrated stock solutions (Mallinckrodt, AR grade). The concentrated and diluted solutions of NaOH were prepared from NaOH pellets (Mallinckrodt, AR grade).

Apparatus

A closed system for the distillation apparatus was assembled from KONTES (Vineland, New Jersey) microscale glassware and polypropylene/PTFE connections. The apparatus is shown in Figure 1. It comprises the following: (A) A distillation flask which contains 1 to 1.5 ml aqua regia and the 20 to 200 mg Pd to be digested. (B) A standard water-cooled condensor. (C) A glass tube leading from the condensor to the bottom of the receiving flask; the glass tube is surrounded by a glass envelope, sealed at the top, but open to the receiving flask. The envelope contains Pt catalyst on two pieces of Ag-plated Ni screen of 1 to 2 cm2 area each. (D) A receiving flask, containing 1 ml of a 5% aqueous H202 solution.

Tritium measurements were performed by liquid scintillation counting (LSC), using a Beckman LS 5000 TD system, as described in our previous paper (5).

Wet-Chemi cal Procedure

The Pd sample (20-200 mg) was placed in the distillation flask, 1 ml H202 solution injected into the receiving flask and, using a syringe and septum, 1 to 1.5 ml of aqua regia solution was injected into the distillation flask to dissolve the Pd. The system was then hermetically sealed. After the Pd was dissolved (approximately 2 hours), the solutions in the flask were neutralized with concentrated NaOH and heated in a mantle to approximately 110°C until all the water from the flask was distilled. Then 1 ml of deionized water was added to the flask and distilled again until only dry residue remained. Tritium, occluded by the Pd, is released into the aqua regia during dissolution of the Pd as gas or is oxidized to T20 or THO. The T2 gas recombines on the catalyst to form T20, and the T20 and THO vapors are condensed to the liquid

1-84 state. This procedure allows us to collect the entire amount of T, occluded by the Pd, in the receiving flask.

The reactions occurring during the distillationhecombination process are as follows.

1. In the distillation flask:

3 Pd + 4 NO3 -+ 16 H+ + 18 CI --+ 3 [PdC16]2- +4NO +8H2O (1a) - 3 Pd + 2 NO3 + 8H+ +12CI A 3[PdC14]2- + 2N0 + 4H20 (1 b)

T(Pd) + 02(~0l.) TO2 (24

T2(Pd) -+T2(sol) -+ T2 (gas) (2c)

2. On the Pt catalyst:

T2 + 1/2 02+ T20

TH + 1/2 02-+ THO

3. In the receiving flask:

2N0 + 3H202 + 2 HNO3 + 2H20 (5)

Following completion of the distillation, the receiving flask was heated to 60°C for 30 minutes to expel any dissolved T2 gas for recombination with 02 on the Pt catalyst. The distillation flask was then removed from the condensor and the condensor and catalyst rinsed with deionized water to wash any tritiated water from these parts into the receiving flask. The contents of the flask were diluted to precisely 5 mi in a volumetric flask. One ml of this dilute nitric acid solution was added to 10ml of scintillation cocktail (pseudo cumene/xylene from Beckman), which was then subjected to tritium counting in the Beckman system.

Sci n til iat ion Counting

The Beckman was calibrated, employing a procedure described in an earlier paper (5). To verify that the window settings were correct for tritium, we verified that

1-85 the Liquid Scintillation Counter measured and displayed the correct energy spectrum for tritium. Such a spectrum is shown in Figure 2 for a tritium standard, supplied by Beckman with the instrument.

Verification of Procedure

To verify the correctness and linearity of tritium counting, the tritium activity of standard solutions with known tritium concentrations was determined. The results are plotted in Figure 3 and show a linear dependency of the tritium counts (DPM/ml values) on the activity of added tritium (pCi x 10-6), as required.

To establish the efficiency of T20 transfer from the distillation to the receiving flask, a known amount of T20 was added to the aqua regia, a distillation carried out and tritium counting performed, maintaining the identical procedure as in later actual analyses. We obtained 98% distillation efficiency, referred to the T.

In a second control experiment, the catalytic recombination of gas with 02was verified. For this purpose, a 0.1 molar aqueous NaOH solution was tritiated by adding various known amounts of T20. A glass cell, containing this solution and two Pt electrodes was connected to the distillation apparatus, taking the place of the distillation flask. Constant current electrolysis was performed for various lengths of time, the evolving H2 and T2 recombined to H20 and T20, collected in the receiving flask and analyzed for tritium in the Beckman scintillation counter. Figure 4 shows a linear dependency of the tritium counts in the recombinate on the electrical charge passed through the electrolytic cell. This establishes that the catalyst converts T gas to T20 or THO as expected.

Results and Discussion

The results of tritium analysis on 90 as-manufactured palladium samples and 30 background samples are presented in Table 1. The tritium background of the 30 scintillation liquid samples was determined as 27.1 f 1.1 DPM/ml, and the overall tritium count average of the 90 palladium samples was 27.2 f 1.1 DPM/ml, identical to back-ground. Thus, none of the 90 Pd samples. was found to contain any tritium contamination, in spite of the fact that they were cut from ten different batches of Pd

These measurements have now been extended to over 130 Pd samples, and the same results have been obtained on all of these.

1-86 wire of various diameters, supplied by two different manufactures. For each Pd sample, the DPM/ml values shown are averages from at least three measurements.

The sensitivity and accuracy of tritium determination, employing the closed- system analytical procedure is _+ 1 DPM/ml, equivalent to 9.28~106tritium atoms per ml. For our 5 ml solution volume and for a typical 0.lg Pd sample, this corresponds to a detection limit of 5x107 tritium atoms or approximately 1 tritium atom per 10'3 Pd atoms.

Table 1

Tritium Analysis in Palladium

PALLADI UM CHARACTERISTICS OF TRITIUM STANDARD MANUFACTURER SAMPLES AVE RAG E DEV IATlON

Wire No. of No. Of DPM/mI Diameter Cuttings Samples (mm)

Hoover & Strong 1 8 14 26.9 1 .o Hoover & Strong 2 7 12 27.4 1.4 Hoover & Strong 2 7 12 27.5 0.4 Hoover & Strong 2 8 12 26.8 0.8 Hoover & Strong 2 1 2 27.4 Hoover & Strong 4 7 12 27.7 1.2 Hoover & Strong' 1 1 2 27.7 Johnson Matthey 0.5 3 6 27.8 1 .o Johnson Matthey 1 4 7 26.8 0.7 Johnson Matthey 1 6 11 26.9 1.5

Total 90 27.2 1.1

Background - Sci nt i llatio n Liquid 30 27.1 1.1

Obtained from Texas A & M University

1-87 Conclusions

We have developed a closed-system analytical technique for the analysis of tritium in palladium which features high reliability and accuracy. This technique employs a distillation and catalytic gas recombination procedure which leads to the quantitative determination of the tritium content of palladium with an accuracy and sensitivity of 5x107 T atoms. Application of this technique to 90 palladium wire samples of various lots and sizes, manufactured by two different suppliers, yields no tritium contamination in any of these samples.

While our results do evidently not exclude the possibility of rare spot contamination of Pd with tritium, such contamination is exceedingly unlikely both in view of our results and the details of the Pd manufacturing process.

The closed-system analytical procedure, described here, is not affected by the shortcomings of open-system techniques, such as falsely low or high tritium readings. Application of the closed-system procedure for tritium analysis of Pd prior to use in "cold fusion" studies is advisable to ascertain that there is no possibility for tritium contamination.

Acknowledgements

The authors gratefully acknowledge the assistance of Y. Zhang, B. Nkamsi and X. Du in carrying out the analysis, the receipt of palladium samples from Drs. J. O'M. Bockris and S. Guruswamy as well as the financial support from the State of Utah.

References

1. M. Yanakura, M. Minami, S. Yamagata, S. Nakabayashi, M. Aratani, A. Kira, I. Tanihata, "An Approach To The Cold Fusion Through Hydrogen Isotopes Analysis By the Heavy Ion Rutherford Scattering," Chemistry Letters, 21 97 (1 989).

2. 0. Matsumoto, K. Kimura, Y. Saito, H. Uyama and T. Yaita, "Detection of Tritium in Cathode Materials after the electrolysis of D2S04-D20 Solution", Denki Kagaku, a 471 (1990)

1-88 3. T.S. Murthy, T.S. lyengar, B.K. Sen, and T.B. Joseph, "Tritium Analysis of Samples Obtained From Various Electrolysis Experiments At BARC," Fusion Technology, u,71 (1990).

4. K.L. Wolf, "Cold Fusion And Hot Tritium, I' transcript of talk given August 11 , 1990, at Stanford University.

5. K. Cedzynska, S. C. Barrowes, H.. E. Bergeson, L. C. Knight and F. G. Will, "Tritium Analysis in Palladium With an Open-System Analytical Procedure" to appear in "Fusion Technology", Aug. 1991.

6. R. Pool, "Wolf: My Tritium was an Impurity", Science, 248, 1301 ; 15 June 1990

1-89 A’

Figure 1 : Distillation apparatus for analysis of tritium in palladium with distillation flask A, condensor B, catalyst C, receiving flask D.

1-90 0 . 1 0 I I I I I Aw

r ~~ I 0 r' rn

c 0 E 2

)r I el a, I c z w I

0 c3 .Irl

L . I I . I ..I 0 0 0 0 0 c3 0 0 0 Q c) ln If) N rl

1-91 60

20 0 2 4 6 8 10 12 14 16 18 20

Tritium Addition to H20 (x 10-6 pCi)

Figure 3: Calibration curve for H20 with known tritium contents.

1-92 300

200

0 0 100

0 0 2000 4000 6000 8000 10000 12000

Electrical Charge (As)

Figure 4: Dependency of tritium counts on electrical charge when electrolyzing a tritiated NaOH solution.

1-93 Cold Fusion Studies In A High-pressure Sealed Cell

by Fritz G. Will

Ming-Chang Yang

1-94 Table of Contents

Page

Abstract 1-96

1. Introduction 1-96

2. Technical Approach 1-97

3. Experimental 1-98

Cell I Design 1-98

Cell II Design 1-98

Determination of Loading Ratio 1-99

4. Results and Discussion 1-100

Hydrogen Loading 1-100

Deuterium Loading 1-102

Effect of Repeated Deuterium Loading and Unloading 1-103

Long-Term Deuterium Loading 1-103

Apparent Excess Heat Generation 1-104

Tritium Generation in Palladium 1-105

5. Conclusions 1-105

Acknowledgements 1-106

References 1-106

Figures 1-107 Abstract

A novel electrochemical cell has been designed and employed in a high- pressure sealed vessel, featuring continuous and automatic loading ratio determination, fast temperature response and no oxygen evolution. This cell design avoids several of the difficulties encountered in standard cell designs. Maximum deuterium to palladium loading ratios of up to .84 and .93 were obtained for deuterium and hydrogen, respectively. The cell design allows power measurements with a sensitivity of .56 milliwatts, corresponding to a temperature sensitivity of .02OC. In one long-term experiment, we have found small, but definite, tritium generation in the Pd electrode and anomalous temperature excursions that are, very tentatively, interpreted as excess power excursions of up to 30 per cent.

1. Introduction

Since Fleischmann, Pons and Hawkins [I] reported their observation of large amounts of excess heat during the electrolysis of heavy water with a Pd cathode, numerous laboratories around the world have attempted to reproduce their results.. The approach used in most laboratories employs: 1) a single compartment cell, housing both electrodes; 2) a rather large volume of aqueous electrolyte, that is, 50 to 200 cm3; 3) a not hermetically sealed cell; 4) Pt, Ni or steel as the anode, and 5) Pd wire or rod as the cathode. Such a system has several disadvantages: First, the cell usually has a large heat capacity and hence gives slow response to temperature changes. Second, electrolysis of heavy water produces oxygen which may recombine with D on the Pd cathode. This reaction may lower the surface activity of deuterium and interfere with D occlusion. Also, the cell voltage, required to electrolyze water is large, thereby generating large amounts of undesirable waste heat which makes it more difficult to determine excess heat. Third, the anode may dissolve into the electrolyte. The dissolved metal ions will then deposit on the Pd cathode, and thus change the rate of D absorption. Fourth, the pressure usually is 1 atm. Such a low pressure leads to less D-loading of Pd and requires long initiation time to reach the minimum D/Pd ratio for the fusion process [2]. Fifth, while several techniques can be employed to measure the D/Pd ratio, it is difficult to have a continuous, automatic and accurate readout of the D:Pd loading ratio with most of these techniques. Based on the above background, the objective of this project was to establish another approach to cold fusion studies, avoiding several of the shortcomings which arise in the more standard approaches.

2. Technical Approach

In our cell design, a hermetically sealed cell was employed which contained pressurized deuterium. Oxygen evolution was eliminated by using deuterium gas diffusion electrodes as anodes. With a controlled applied potential or current, deuterium ions are produced on the anode from deuterium gas and no oxygen is evolved, as shown in Figure 1. This results in significantly lower cell voltage and less waste heat. Deuterium ions are transported to the cathode through a solid polymer electrolyte or thin battery separator saturated with electrolyte. The deuterium ions are subsequently reduced to atomic D on the separator or solid polymer electrolyte1Pd interface, followed by diffusion of D atoms into the Pd lattice. The reaction on the anode is

The reaction on the cathode is

The overall reaction becomes

The last reaction has a smaller equilibrium potential than electrolysis of water by 1.22 volts. Therefore, this approach requires smaller applied potentials and power inputs which is favorable for calorimetric measurements. Furthermore, due to the small cell size, the proposed cell has low heat capacity and affords fast temperature measurement response which is particularly important in detecting fast temperature excursions of the Pd cathode due to possible nuclear events in the Pd.

A major advantage of our cell design is the continuous, automatic and accurate determination of the DIPt loading ratio: The decrease of the D2 gas pressure, which is measured continuously, is directly proportional to the amount of D occluded by the Pd. 3. Experimental

Cell I Design

Figure 2 shows a schematic of the cell with a typical size of 1.3 cm x 1.3 cm x 0.3 cm. The cell uses one Pd foil as the cathode in the center and two Pt fuel cell electrodes as anodes on both sides of the cathode. Between the cathode and anodes is placed a piece of polypropylene battery separator, type FS 2106 from Freudenberg Company. For a variation of this cell geometry, a Pd wire of 1 or 2 mm diameter was wrapped with battery separator material, followed by a cylindrical fuel cell anode and another layer of separator material.

The cell was installed in a stainless steel high-pressure vessel', as shown in Figure 3. This vessel was submerged in a controlled temperature water bath, Model 2095 SIN from Forma Scientific. Typically, the water bath was kept at 23.8 + O.l°C. Two pressure transducers, PX931-100GV and PX425-100 AV from Omega Engineering, Inc., were used to measure the D2 pressure, which afforded a continuous calculation for D:Pd loading ratio. A PAR TM Model 173 Potentiostatl Galvanostat, coupled with a Model 179 Digital Coulometer, was used to control the potential or current, respectively. Temperatures of the cell and water bath were measured with thermistors of type SP6OBT103M1 from Thermornetrics, Inc.. The data were collected and stored in a Macintosh IIX computer through a WB-AA1-M2 & WB-FA1-M2 Data Acquisition and Control System with an Omegabench~usoftware program from Omega Engineering, Inc.

The Pd foils and wires used in the experiments were obtained from Johnson Matthey with purity of 99.9%. The D2 gas was from Cryogenic Rare Gas Company with minimum purity of 99.99%.

Cell ll Design

Figure 4 shows the schematic of the second cell design with a typical size of 1.5 cm x 2.0 cm x 0.2 cm. Two Pt fuel cell electrodes are bonded onto two pieces of Nafion membrane, which are in contact with the two surfaces of the Pd foil cathode. This sandwich-type arrangement may avoid the leakage of deuterium from the Pd

The high-pressure vessels used in this study were designed and built by Prof. Robert F. Boehm and Mr. Marc Case of the Mechanical Engineering Department of the University of Utah.

1-98 cathode. More importantly, after full loading has been achieved, independent control of the applied potential on the two anodes can be such as to load deuterium on one side of the cathode, while suddenly producing out-diffusion of deuterium on the other side by inverting the potential on that side. On each side, a smaller rectangular Pt electrode serves as a reference electrode and is surrounded on three sides by a larger Pt anode, as shown in Figure 5.

Figure 6 shows the schematic of the pressure vessel with a cell installed. The insulating shell and plug, made of polyurethane, are used to minimize the heat loss through the pressure vessel which is submerged in a thermostated bath for excess heat measurement. Inside the insulating shell and plug is an aluminum inner shell to provide an isothermal environment for the uniform heat flux from the inner shell to the outer pressure vessel. A Teflon cup is used for holding heavy water to humidify the deuterium gas and hence to saturate the Nafion membrane with heavy water. Two high-power resistors will be installed inside the aluminum shell for heat calibration. All of the electrical and thermistor lead wires go through the insulating plug and connect to the electrical feed-through device at the top of the pressure vessel.

Cell II design was actually not used in electrochemical experiments. The porous insulator was found to absorb deuterium, thus interfering with the D/Pd loading ratio determination. Teflon parts were ordered to eliminate this problem. But the parts arrived too late to still be used in experiments.

Determination of Loading Ratio

In the above two types of cell, the calculation of the D:Pd (or H:Pd) loading ratio from the measured D2 (or H2) pressure in the pressure vessel was based on the ideal gas equation. The number of moles of consumed DZ(or H2), which diffuses as D (H) atoms into the Pd lattice, is

where Po and P are the initial pressure and the pressure at the measuring time, V is the total volume of the vessel and the gas lines, T the temperature and R the universal gas constant.

1-99 Therefore, the loading ratio is

The volume, V, was measured by using a glass vessel, whose volume, Vg, was determined by calibrating with water. These two vessels were connected with a valve. Before the valve was opened, the stainless steel vessel was evacuated and the glass vessel was filled with D2 whose pressure, P,, was measured with a pressure transducer. After the valve was opened, the equilibrium pressure, Pf,was measured. The volume V was calculated as P v = (#-1) v,

The total electrical charge, Q, passing through the cell, was occasionally also used to double-check the loading ratio. The number of moles of D atoms, n,, occluded by the cathode, if there is no D2 evolution, is Q nD=r (7) where F is the Faraday constant.

The loading ratio then becomes

The charge was measured with the digital coulometer and also calculated by integrating the current with respect to time, employing the Data Acquisition System.

4. Results and Discussion

Hydrogen Loading

After the Pd cathode was wrapped with a battery separator and sandwiched between the two Pt fuel cell electrodes, the cell was pre-soaked in electrolyte. After installation of the cell in the high pressure vessel, the open circuit voltage of the cell was about -100mV (Pd electrode with respect to Pt electrode). After the vessel was

1-100 evacuated and filled with H2 or D2 at 50 psia, the open circuit voltage changed to about 70mV (Pd electrode with respect to Pt electrode). The resistance of the electrolyte in the battery separator was measured to be 2-4 ohms, using a 4284A Precision LCR Meter from Hewlett Packard Company.

After D2 or H2 were admitted to the pressure vessel, the pressure decreased due to occlusion of D2 or H2 by the Pd foil on open circuit. In one experiment, the cell potential was applied immediately after the desired H2 pressure was obtained. Figure 7 shows the pressure of H2 when 0 mV, with respect to the Pt electrode, was applied to the Pd foil of 0.5mm thickness. Simultaneous to the pressure decrease, the current density decreased from 25 mA/cm2 to 0.05mA/cm2 in 210 minutes, at which time the pressure became constant. The loading ratios calculated from both pressure and electrical charge are shown in figure 8. The calculation from the observed pressure decrease gives a higher loading ratio than that calculated from the charge. After 210 minutes, the loading ratio is approximately 0.9 as determined from the pressure and 0.6 as determined from the charge. The differences between these two methods of calculating the loading ratio are believed to be a result of a significant amount of H being occluded by the Pd cathode directly from the H2 gas phase. In addition, the pressure decrease reflects the amount of H loaded electrochemically. Therefore, the calculation from the electrical charge, corresponding only to the electrochemically loaded part, results in too low a value for the loading ratio. With further charging at a cell potential of 50 mV, with the Pd electrode at -50mV versus the Pt anode, the loading ratio calculated from the pressure increased by only 0.04 to a value of 0.93 where it remained constant. At the same time, the current also reached a constant value of 24.1 mA (or 12 mA/cm*). However, the loading ratio calculated from the charge continued to increase at a rate of 0.145 per hour. Clearly at this time, all the electrical charge was going into the generation of molecular H2 at the cathode and simultaneous oxidation (consumption) of H2 at the same rate on the Pt anodes. These reactions result in no further pressure changes or increase in the loading ratio.

When discharging with a constant potential of 52 mV between the Pd electrode and the Pt electrode, the pressure increased in the first 100 minutes and then remained essentially constant at about 29.5 PSlG as shown in figure 9. The current became constant at 1.3 mA (or 0.65 mA/cm*)about 200 minutes after discharging had started. The loading ratios calculated from the pressure increase and the electrical charge, respectively, are shown in figure 10. The loading ratio calculated from the

1-101 pressure increase attains a constant value of 0.78 after 100 minutes. However, the loading ratio calculated from the electrical charge continues decreasing at a rate of 0.0096 per hour. The reason for this discrepancy is that all of the electrical charge, after the pressure had reached a constant value, was used to oxidize (consume) the H2 on the Pd at the same rate that it was generated at the two Pt electrodes. Furthermore, in the first 50 minutes, the deloading rate, calculated from the pressure increase, was larger than that calculated from the charge. This difference is probably due to some chemical recombination of H atoms, resulting in H2 generation and hence pressure increase. In addition, the electrochemical cell reaction leads to a pressure increase. In contrast, the electrical charge reflects only the electrochemical reaction and not the chemical recombination reaction.

These results establish that coulometry (measuring charge) is not an acceptable technique to determine loading ratios when employing our cell design.

Deuterium Loading

Similar experiments as with H2 were carried out with D2. Figures 11 and 12 show the D2 pressure decrease and the D:Pd loading ratio, respectively, when loading a 1 mm thick Pd foil with D. In the first 75 minutes, the Pd wire was exposed to D2 gas with no cell potential applied. During this time, the pressure decreases from 48.8 to 47.9 PSIA, reflecting absorption of D directly from the gas phase. This results in a loading ratio D:Pd = 0.06. When applying a cell potential of 0.5V (Pd negative), the pressure decreases to a plateau value of 36.3 PI, corresponding to a loading ratio of 0.83.

Figures 13 and 14 show the pressure and loading ratio, respectively, during subsequent discharge or unloading, followed by a second charging or loading event. At 50 minutes, in the graph, the cell voltage was inverted, such as to make the Pd electrode 0.5 V positive with respect to the Pt electrode. At 175 minutes, the cell voltage was increased to 1V to effect faster discharge. At 350 minutes, the loading ratio had decreased to 0.49. Inverting the cell voltage, making the Pd 0.4 V negative with respect to the Pt, led to a decrease in the pressure to essentially the starting value at t = 0, corresponding to a loading ratio of 0.83. Thus, unloading followed by a second loading event did not result in increased loading.

1-102 No neutron emissions were observed during loading and unloading, and tritium analysis of the electrolyte and the Pd electrode, after completing the experiment, did not reveal any enhancement of the tritium level above background.

Effect of Repeated Deuterium Loading and Unloading

Figure 15 and 16 show results of an experiment which includes four charging and three discharging periods, on a Pd foil cathode with a thickness of 1 mm. Before the second discharging period, the experiment was performed under potentiostatic conditions. The other periods were performed at constant current with potentials limited such that no 02was evolved. Four consecutive charge/discharge cycles led to only a small increase in the loading ratio. The small increase of the loading ratio in the first, second and fourth charging periods were the result of higher applied potentials. The cell temperature was measured by contacting the cell with a thermistor bead. Transient temperature excursions could be detected with a precision of 0.02"C and a response time of a few seconds. Such temperature excursions could be indicative of excess heat generation. Figure 17 shows temperature excursions only when the magnitude or the direction of the voltage or current are changed. Such changes are expected from changes of the input power to the cell and changes of the loading ratio owing to the exothermic character of D absorption or endothermic character of D desorption. They are not the result of cold fusion events.

Long-Term Deuterium Loading

A Pd wire cathode of 2 mm diameter and 1.8 cm length was charged for 12 days with two discharge-charge cycles performed from 6970 to 7290 minutes and from 12,775 to 12,881 minutes. The pressure changes occurring in this cell during the long-term charging and two discharge-charge cycles are shown in Figure 18. The D/Pd ratio, calculated from the pressure changes is plotted in Figure 19. Loading ratios up to .84 are obtained during this long-term charging. These were the highest loading ratios obtained in any of our high-pressure cell experiments. Long-term charging in this experiment was performed with constant applied potential of various magnitudes. However, the initial charge as well as the two discharge-charge cycles were carried out with constant applied current. Figure 20 shows the cell potential (Pd electrode vs Pt electrode) as a function of time. As evident from Figure 20, six constant voltage regimes were employed, namely (a) -.35V from 0 to 1138 minutes; (b) -.5V

1-103 from 1138 to 5642 minutes; (c) -.6V from 5642 to 6970 minutes; (d) -.55V from 7290 to 8524 minutes; (e) -.6V from 8524 to 12,775 minutes and (f) -.6V from 12,881 to 16,939 minutes. The current density as a function of time is plotted in Figure 21. Whenever a cathodic potential of increasing magnitude is applied, as evident from Figure 20, the current first increases dramatically and then decays exponentially to a new steady- state value. The two large excursions in the positive direction correspond to constant current discharge periods. The constant discharge currents have magnitudes of 30, 20, 10, and 5 mA/cm2.

The electrical input power, as calculated by multiplying the voltages and currents of figures 20 and 21 at any given time, is plotted in Figure 22. During periods of applied constant voltage, the exponential decay of the power mimics the exponential decay of the current. Figure 23 shows the temperature of the cell as a function of time. It should be noted that the entire ordinate spans a temperature range of only 1.2"C. Also, the sensitivity of the temperature measurement is .02OC, equivalent to the size of the square symbols in Figure 23. It is seen that the temperature tracks the input power quite well during the first 10,000 minutes. The temperature also tracks the sudden increases in input power, reflecting the fast response of our temperature measurement which is of the order of a few minutes.

Apparent Excess Heat Generation

The steep temperature excursions that appear as a consequence of changing the input power to the cell can be used to derive a calibration curve between electric input power and temperature change of the cell. Such a curve is plotted in Figure 24. A rather good straight-line relationship is obtained. The straight line has a slope of 0.035°C/mW/cm* and extrapolates through the origin, as required. Since the temperature sensitivity is k O.O2OC, the power sensitivity of our cell is 0.56mW.

The calibration curve allows us to calculate the cell power output which can then be compared to the measured electrical power input taken from Figure 22. This has been done in Figure 25 for the time interval of particular interest, namely, from 8000 to 17,000 minutes. We note that the power output exceeds the power input in two clearly visible time intervals, namely, from 10,500 to 12,775 minutes and from 14,200 to 16,939 minutes. The apparent excess power excursions go to highest values of 13 mW as compared to an electrical power input of lOmW, thus amounting to excess power values of up to 30%. The apparent energy generated in the two time

1-104 intervals amounts to approximately 300 Joules. It should be emphasized that (1) these are the results of a single experiment at this time, (2) the temperature excursions are very small, (3) there was only one thermistor measuring the temperature and (4) light water control cells have not been run, yet, for comparison. Therefore, We present the observed temperature and power anomalies as tentative observations that require considerable verification.

Tritium Generation in Palladium

The Pd cathode used in this long-term experiment was analyzed for its tritium content, employing the closed-system analytical procedure developed by K. Cedzynska et al [3] which had been demonstrated to give very reliable results as compared to open-system analytical procedures [4]. The Pd electrode, loaded with deuterium, had a weight of 0.71g and dimensions of 1.8cm x .2cm diameter. Two pieces of Pd, amounting to a total weight of 0.26 g were cut from the Pd electrode and analyzed individually for their tritium contents. One piece was cut from near the center of the electrode and showed 3.8 x 108 tritium atoms, equivalent to 2.7 x 109 atoms/g Pd. The second piece, cut from the end of the Pd electrode, showed no tritium. This agrees with the findings of several other groups at the NCFI, namely, that the ends of the Pd electrodes generally do not exhibit tritium content.

The actual tritium counts (DPM/ml) were corrected for the background of the scintillation cocktail alone, namely, 27.2 k 1.1 DPM/ml and adjusted for the 5 ml of solution in which the tritium, contained in the Pd, were collected. This results in the number of T atoms quoted. Careful tritium analysis conducted on over 90 samples of as-received Pd, including Pd samples cut from the same wire spool as the Pd cathode, yielded no tritium in fresh Pd within the limits of detection, that is, 5 x lo7T atoms or 5 x lo8 T atoms/g Pd. (3). This allows the conclusion that the tritium found in the Pd cathode has been generated by nuclear reactions in the Pd.

5. Conclusions

A high-pressure, sealed cell with continuous automatic loading ratio determination was applied to cold fusion investigations. D2 and H2 were successfully loaded into Pd foils employing fuel cell anodes and electrolyte-wetted battery separators. In this new technique, oxygen evolution and anode dissolution were avoided. The maximum loading ratio was up to 0.84 with D2 and 0.93 with H2. In our

1-105 cell design, the loading of H2 and D2 into Pd proceeds by a combination of gas phase process and electrochemical charging process.

Among the four experiments conducted on high-pressure deuterium cells, we have detected evidence for very low-level nuclear reactions only in the one cell that was operated over a long period of time, namely 12 days. In this experiment, we attained loading ratios D/Pd of 0.83 and small but definite tritium generation in the Pd electrode. As compared to a maximum tritium contamination level of 5 x 10' tritium atoms in fresh Pd, we find 1.4 x 109 tritium atoms in the Pd cathode after the 12-day experiment. We have also detected anomalous temperature excursions which are very tentatively assigned to excess power generation of levels up to 30 %. We emphasize the tentative nature of the excess power finding pending a more detailed study of these effects.

Acknowledgments

The authors gratefully acknowledge the design of the high-pressure vessel by Dr. Robert Boehm and Mark Case, the tritium analysis by Dr. Cedzynska, Yuan Zhang and Xuanming Du, as well as the financial support of the State of Utah.

References

1. M. Fleischmann, S. Pons, and M. Hawkins, "Electrochemically Induced Nuclear Fusion of Deuterium", J. Electroanal. Chem. 261, 301 (1989).

2. B. A. Dasannacharya, and K. R. Roa, Part C in BARC Studies in Cold Fusion, Edited by P. K. lyengar and M. Srinivasan, Bhabha Atomic Research Centre, Bombay, India (December 1989).

3. K. Cedzynska and F.G. Will, "Closed-System Analysis of Tritium in Palladium", to be published in Fusion Technology.

4. K. Cedzynska, S.C. Barrowes, H.E. Bergeson, L.C. Knight and F.G. Will, "Tritium Analysis in Palladium with an Open-System Analytical Procedure", to appear in Fusion Technology, Aug. 1991.

1-106 t e- I

I- - D2

Typical cell: 1 1.3cm x 1.3 cm x 0.3cm 1 -

Pt fuel cell electrode \IPt fuel cell electrode Battery separator

Pd Cathode 2~++2e-d2D Pt Anode D2 &2e-+ 2D'

Overall reaction D2- 20

Figure 1. Electrochemical Cell I and Reactions

1-107 Pt fuel cell electrodes

Pd cathode

Battery separator (Top view)

Battery separator

(Side view)

Figure 2. Schematic of Cell I

1-108 Potential, current and temperature measurements Stainless steel

* *, ,.-- fl:

I 11

I ,Cell Thermistor - -Y Glass cup

Tef1 on surporter / Stainless steel ’pressure vessel

Figure 3. Pressure Vessel and Cell I Schematic

1-109 PI

Naflon membrane

Pt Anode L Pd Cathode Pt Anode 2

Figure 4. Electrochemical Cell II and Reactions

Pt lead wires

Pt reference electrode

Pt fuel cell anode

Pd Cathode

/Nafion membrane

Figure 5. Frontal View of Electrochemical Cell II

1-110 Potential, current and temperature measurements

TT+ Vacuum

Teflon cell holder \ Cell 1

Tellon cup -

Figure 6. Pressure Vessel and Cell II Schematic

1-111 34

- p wu

28 I I 0 100 200 3 D

Tim. (mln)

Figure 7. Relationship between hydrogen Pressure and time of charging at 0 mV on Pd cathode with respect to Pt anode.

1-112 1.o

0.8

0.6 from charge U - P ~ from I pressure 0.4

0.2

0.0 0 100 200 300

The (mln)

Figure 8. Relationship between loading ratio and time of charging at 0 mV on Pd cathode with respect to Pt anode.

1-113 0 200 400 600 800 1 oc

tlme (mln) Figure 9. Relationship between hydrogen pressure and time of discharging at 52 mV on Pd anode with respect to Pt cathode.

1-1 14 from * charge from -pressure

Figure 10. Relationship between loading ratio and time of discharging at 52 mV on Pd anode with respect to Pt cathode. tlme (mln) Figure 1I. Pressure versus time when loading 1 mm thick Pd foil with deuterium. time (min) Figure 12. D:Pd loading ratio versus time when loading 1 mm Pd foil with deuterium. the (mln) Figure 13. Pressure versus time during deuterium unloading and subsequent loading of 1 mm Pd foil previously loaded as shown in Figure 11. 1 .o

0.8

0.6 0 - 0.. Y D:Pd 0 0.4

0.2

0.0 0 200 400 600 800 1000

time (min)

Figure 14. D:Pd loading ratio versus time when unloading and loading I mm Pd foil previously loaded as shown in Figure 13.

1-119 tlmo (mln) Figure 15. Pressure versus time during repeated loading and unloading 1 mm Pd foil with deuterium.

1-120 - D:Pd

0 1000 2000 3000 4000 5000 6000

time (mln)

Figure 16. D:Pd loading ratio versus time when repeatedly charging and discharging Irnrn Pd foil.

1-121 20 rn

- temp (cell)

I I I 1 I 0 1000 2000 3000 4000 5000 6000

tlme (mln)

Figure 17. Cell temperature versus time when repeatedly loading and unloading Imm Pd foil of Figure 16 with deuterium.

1-122 52

h (D -cn 46 n Y P (psia) Y n

40 I 0 10000 20000

tlme (mln) Figurel8. Pressure versus time during long-term charging of 2 mm Pd wire with deuterium. Pressure spikes at 7,000 and 12,800 minutes represent deuterium u nload i ng/loadi ng cycles. 0.8

0.6

U n.. I D:Pd n

0.4

0 10000 20000

time (min) Figure 19. D:Pd loading ratio of 2 mm Pd wire during long-term loading. Spikes at 7,000 and 12,800 mintues represent unloading/loading cycles. 1

Y E (Volts, Pd-Pt)

-1 ! I 0 10000 20000

time (min) Figure 20. Cell voltage versus time during long-term charging of 2 mrn Pd wire with deuterium, using various applied voltages. Spikes at 7,000 and 12,800 minUtes represent con st ant cur rent dischargekh arge cycles. A (Y a

I (mNcm"2)

-60 ! I 0

time (min)

Figure 21. Cell current versus time corresponding to cell voltage of Figure 20. 40 -

30 *

20 Y Power (mW)

o! I 0 10000 20000

tlme (mln) Fiaure 22. Electrical input power versus time, determined from cell voltage and cell Y current of Figures 20 and 21. 25.0

24.8

24.6

24.4 Y temp. of cell

24.2

24.0

L 23.8 3 I 0 10000 20000

tlme (min) Figure 23. Measured cell temperature versus time during long-term deuterium loading of same 2 mm Pd electrode. Temperature spikes at 7,000 and 12,800 minutes are caused by dischargelcharge cycles. 0.8

n 0 Y0

0.6

0.4

0.2

0.0 0 10 20 30

cell power difference (mW) Figure 24. Calibration curve, representing cell temperature as function of electrical input power for cell with 2 mm Pd wire. 40

FE Y 20 :L 0 -n

of I I I I 8000 10000 12000 14000 16000 18000

time (mln) Figure 25. Measured electrical power input (from Figure 22) compared to cell power output, determined from measured cell temperature (Figure23) during deuterium loading of 2 mm Pd wire. Tritium and Neutron Generation in Palladium Cathodes

With High Deuterium Loading

by F. G. Will

K. Cedzynska

D. C. Linton

1-131 Table of Contents

Page

Ab st ract 1-133

Introduction 1-133

Ex pe ri me nt al 1-134

Cell Design 1-134

Materials and Reagents 1-135

Instrumental Setup 1-136

Ex pe ri mental Proced u re 1-137

Results and Discussion 1-138

Deuterium to Palladium Loading Ratio 1-138

Trit iurn Gene ration 1-138

Neutron Generation 1-141

Excess Power Generation 1-142

Conclusions 1-143

Acknowledgements 1-143

Ref e re nces 1-144

Figures 1-146

1-132 Abstract

Tritium generation in palladium cathodes, highly loaded with deuterium during electrolysis of deuterated sulfuric acid is described. Tritium generation has been observed on four out of four such highly loaded cathodes. No tritium has been observed in four ordinary sulfuric acid control cells operated simultaneously. Total tritium analysis is performed on all cells before and after each experiment. Evidence is also presented for neutron generation from all four D2SO4 cells. A single anomalous heat excursion in one of the cells is mentioned as a tentative result.

lntrod uction

Since Fleischmann and Pons first reported on cold nuclear fusion in cells containing palladium cathodes and heavy water electrolyte [l], many groups have confirmed the occurrence of nuclear reactions in deuterium-loaded metals by identifying some of the nuclear by-products formed. In particular, a large number of groups has reported evidence for neutrons [2-71 and tritium [8-131. While neutrons have generally been detected at only very low levels, tritium generation has been reported at lo7 to lo9 higher levels. Unfortunately, these findings are not generally reproducible or predictable, which has made systematic research of cold fusion phenomena most difficult. Furthermore, doubts have been voiced [14] whether tritium found in palladium cathodes, employed in heavy water electrolysis, has been generated by "cold fusion" reactions or whether it was present in the palladium as a contaminant before any experiments were conducted. Such doubts have not been confirmed in recent analyses of large numbers of as-manufactured palladium samples with two different methods [15,16].

The present study reports on the reproducible generation of significant levels of tritium, in both Pd cathode and electrolyte, as well as on low levels of neutrons. Reproducibility of tritium generation has been achieved by developing a method to reproducibly attain deuterium to palladium loading ratios near and sometimes slightly higher than unity. A hermetically sealed cell design with internal gas recombination is employed, and the tritium content of the electrolyte, the Pd and the gas above the electrolyte is determined prior to and after an experiment. Therefore, any increase in tritium content can only originate from nuclear phenomena occurring during the experiment. A light water control cell is always run in electrical series to every D20

1-133 cell under essentially identical conditions. This procedure always allows for direct comparison of any tritium, neutron or excess heat generation in the D20 cell and the H20 control cell.

Experimental

Cell Design

In contrast to most cell designs used in cold fusion studies, the cell used in our electrolytic experiments employs a fritted (porous) glass cylinder to separate the Pd cathode from the Pt anode, thus avoiding 02gas evolved on the anode to come into contact with the Pd. Furthermore the cell is hermetically sealed, employs a catalyst to recombine D2 and 02, and has provisions to continuously measure the D:Pd loading ratio.

Figure 1 shows a schematic drawing of the cell which features a 2.5 cm diameter x 3.0 cm long cylindrical tube of fritted glass to separate the cathodic compartment from the anodic compartment. The anode and cathode are arranged coaxially. The fritted glass tube has holes of 200 microns mean diameter. This two- compartment cell prevents contact of the oxygen with the Pd. The palladium electrode (2.0 mm diameter wire) is placed at the center of the fritted glass tube which in turn is surrounded by a 0.1 mm thick Pt foil cylinder(anode) to provide uniform current distribution. The various parts are kept in position at the bottom of the cell with a Teflon holder, which has channels to equalize the electrolyte levels in the two compartments. Both the anodic and cathodic compartments have two fittings each for gas inlet and outlet. The anodic and cathodic compartments are connected by an exterior loop so that the gases can recombine on a platinum catalyst placed above the anolyte. The electrolyte volume in the cell is approximately 38 cm3>whereas the total gas volume is approximately 300 cm3.

A simple water-filled manometer, comprised of two burets which are connected at their lower ends with flexible tubing, serves to determine volume changes in the gas volume above the electrolyte. This technique, developed earlier by the NCFl Engineering Group [17], allows reliable measurement of the D:Pd loading ratio during electrolysis.

To determine possible temperature excursions, produced by cold fusion reactions, two calibrated thermistors were used. One of these was employed to

1-134 measure the cathode temperature. It was enclosed in a glass capillary and bonded to the cathode with thermally conductive epoxy. For better heat conduction, the thermistor was embedded in thermal joint compound inside of the capillary glass tube. The second thermistor was employed to measure the temperature in the anode compartment. It was positioned as close as possible to the Pt foil.

Materials and Reagents

To avoid problems of glass dissolution and plating of glass components on the Pd cathode, as encountered in LiOD solutions, our experiments were carried out in 0.5 M H2SO4 for the light water control cells and 0.5 M D2SO4 for the heavy water cells. The heavy water (99.9%) was purchased from Cambridge Isotopes Laboratories Ltd. and had a typical tritium content of 36 dpm/ml). The D2SO4 solution was made by diluting conc. D2SO4 (98%; Aldrich Chem. Comp. Inc.) with D20 and the H2SO4 solution by diluting conc. H2SO4 (96%; Baker Analyzed Reagent) with H20. In one experiment, Li2SO4 (solid 99.99% from Aldrich Chem. Corp. Inc.) was added to the acids. Deuterium gas was 99.99% pure (lot UN1954 from Cryogenic Rare Gas Comp. or from Liquid Air Comp.), hydrogen gas 96% (US Welding Comp.) and oxygen gas 99.9% (Liquid Air Comp.). Palladium wire of 2 mm diameter was obtained from Aesar (Johnson Matthey) and was of 99.99% purity.

Platinum foil for the anode (0.1 mm thick; 99.98% pure) was obtained from Johnson Matthey. The anode was platinized by electrodepositing platinum black in PtC12 solution.

As a recombination catalyst, a piece of fuel cell grade catalyst on Ag-plated Ni screen (ESN) electrode (E-TEK Inc.) was used.

Deuterium gas was purchased from Air Products & Chemicals Inc. and Alphagaz-Liquid Air Corp. Both suppliers use heavy water electrolysis to produce D2 gas, and both purchase the heavy water from the same source, Ontario Hydro (Canada). It can be assumed that any tritium contamination in the D2 gas originates from this heavy water and therefore should be similar for both gas suppliers. The level of tritium contamination in the D2 gas is given as less than 5 nCi/liter gas.

Since an accurate value of the tritium contamination level was not supplied, a tritium analysis procedure for D2 gas was developed and applied in our laboratory [18]. The recombination reaction of D2 with 02gas on a catalyst surface was used to

1-135 obtain aliquots of heavy water for analysis. A gas-tight vessel was connected to a gas buret to measure the volume of D2 gas recombined. An evacuated vessel containing a 12 cm2 piece of catalyst was filled with the D2 gas. Oxygen was injected with a syringe through a septum and the deuterium displacement was measured. The recombined heavy water was rinsed out with distilled water and analyzed for tritium in a Beckman LS5000 TD Liquid Scintillation Counter. The tritium content was found to be 0.13 to 0.14 nCi/liter of D2 in good agreement with values obtained by Dr. Claytor at Los Alamos National Laboratory on a D2 tank provided to him by the NCFl

Instrumental Setup

All experiments were performed with an identical light water control cell run in electrical series to the heavy water cell. The two cells were contained in two separate water baths of type EX-510D from NESLAB Inst. Inc., which controlled the temperature to f 0.1"C. The following data were measuredkollected with the instrumentation as indicated:

Applied current for electrolysis: Keithley 228A Current Source or EG&G Potentiostat /Galvanostat.

Potential: Keithley 179 Multimeters and Yokogawa HR 230 Hybrid Recorder.

Potential of cathode vs reference electrode (where applicable) Keithley 179 Multimeters and HR 2300 Hybrid Recorder.

Temperatures of the cathode and anode: Thermistors (+ 0.02OC) of type SP6OBT 103M1 from Thermornetrics, Inc.; stored in a Maclntosh 11X computer with an OmegabenchTMsoftware program from Omega Engineering, Inc.

Gas volume measurements were made with a water manometer to an accuracy of f 0.1 ml; air temperature and air pressure were monitored with an accuracy of k0.1"C and kO.1 mm Hg, respectively.

Neutron detection was performed with 3He tubes. Two tubes each were used to monitor the light and heavy water cell, respectively. They were installed and positioned at a distance of 7 cm from the electrolysis cells in the water baths. To prevent cross talk between the 3He tubes for the light and heavy water cells,

1-136 they were spaced lm apart and separated by a layer of borate-impregnated paraffin bricks. Neutron data were recorded with an IBM computer system.

Experimental Procedure

Before each experiment, the tritium contents of the electrolyte, representative pieces of the Pd and the De fill gas were determined. Our closed-system analytical procedure for analyzing the tritium content in Pd has been described in detail elsewhere [16]. The Beckman LS5000 TD was employed for tritium counting.

The electrolytic cells were evacuated and then refilled with D2 and H2 gas of ambient pressure. This assured proper and immediate functioning of the internal gas recombination catalyst. When starting the electrolysis, which was always conducted with the same current flowing through both the D2 and H2 cells, essentially no D2 or H2 gas is generated on the Pd. The 02 gas, generated on the Pt anodes, recombines with the prefilled D2 or H2 to form water. The amount of D2 or H2, consumed by reaction with the 02, is precisely equivalent to the number of D or H atoms absorbed by the Pd. Hence, the decrease in the gas volumes in the cells is a precise measure for the D/Pd and H/Pd loading ratio, respectively. The gas volume stops changing when full loading is attained. Gas volume determinations were always done with the manometer levels equalized, such as to maintain ambient pressure in the cell. The volume changes measured were reduced to standard pressure and temperature. We estimate that the overall error in our loading ratio determinations is +5%.

The cells were always maintained in a vacuum-tight condition. Leak checks were performed periodically by pressurizing the cells slightly. This was done by adjusting the position of the movable buret of the manometer and establishing that the level of the water column did not change with time.

After completing an experiment, which generally lasted for about one week, the electrolyte, Pd electrode and gas were analyzed again for tritium and compared to the tritium amounts present before the experiment.

Since we analyze for all the tritium in the cell before and after an experiment and since the cell is sealed during the experiment, any increase in tritium level can only result from tritium generation in the experiment itself. Considerations regarding deuterium-tritium partitioning between gas, electrolyte and Pd are therefore eliminated.

1-137 Results and Discussion

Deuterium to Palladium Loading Ratio

Typical results of our loading ratio measurements as a function of time are presented in Figures 2a and 2b. Similar results were obtained in three other experiments. The electrolytic deuterium loading experiment was performed for 12 days. At the start of applying an electrolytic current, the loading ratio already had a finite value which for the deuterium cell was 0.68 and for the hydrogen cell 0.75. Figures 2a and 2b show only a small fraction of the large number of data points taken during these 12 days. Both curves show a continuous rise in the loading ratio to values of about 0.95. The loading ratio in the deuterium cell appears to continue increasing whereas the HIPd appears to be saturating. Actually, the tendency to saturate is observed in most cases. The procedure applied to obtain the loading curves in Figures 2a and 2b will be described elsewhere.

Tritium Generation

The electrolyte, palladium and gas above the electrolyte in each D2 cell were analyzed for their tritium contents before and after each experiment. In the H2 cells, only electrolyte and Pd were analyzed. Table 1 summarizes the tritium analysis results for all four experiments. We have found in experiments to be reported elsewhere, that tritium is generated predominantly at loading ratios in excess of 0.85. Table 1 lists in the first horizontal column the times at which this loading ratio is attained in the four experiments. The table also gives the maximum loading ratios that were achieved in the four experiments, comprising four D2 cells and four H2 cells. It is noted that the loading ratios lie between 0.95 and 1.15, with an experimental uncertainty of f 0.05. Tritium was not detected in any of the four H2 control cells. On the other hand, significant tritium enhancements are found in all four D2 cells, in particular, in the electrolyte and in the palladium. The total amount of tritium contained in the gas phase is relatively small. But an increase in this small tritium level in the gas phase was observed in two cases. The total amount of tritium generated in these four sealed cells is surprisingly uniform, from a low value of 7 x 1010 to a high value of 2.1 x 10l1 T atoms. As the palladium cathode area in all four cells was approximately 2cm2, the number of T atoms generated in the four cells is also in a relatively tight band, from 4.3 x 1010 to 1.1 x 1011 T atoms/cm2. These

1-138 values are in good agreement with the values obtained by several research groups at the Bhabha Atomic Research Center in Bombay, India. Their values run from a low of 5 x 109 to a high value of 1.7 x 1014 T atomskm2. Predominantly, however, their values are in the range from 1010 to 1011 T atoms/cm2. These experiments were run for comparable lengths of time as our experiments.

The average tritium generation rate in our experiments varies from 5.8 x 1O4 to 2.0 x lo5 T atoms/cm%ec. In calculating this rate, the time prior to attaining loading ratio of 0.85 was not counted, as we have evidence for little or no tritium generation at loading ratios smaller than 0.85. We have calculated a tritium "enhancement factor" which expresses the ratio of the total tritium present in the cell after the experiment to the total tritium present before the experiment. Three of the four cells show enhancement factors from 31 to 52. The fourth cell has an enhancement factor of only 1.7, owing to the fact that in this cell a new batch of heavy water was inadvertently used with a tritium contamination level 30-40 times larger than the normal tritium content of the heavy water we have used. Strikingly, none of the four H2 control cells showed any detectable tritium in the electrolyte, or the palladium cathodes after the experiment.

Since we are employing hermetically sealed cells in these experiments, and since we analyze for total tritium content before and after the test, we can only come to the conclusion that the tritium that we find at the end of the experiments has been generated in or on the palladium cathodes during heavy water electrolysis.

The tritium analysis of the palladium cathodes was carried out by analyzing several small pieces cut from the entire electrode. The four samples for analysis were cut one each from the two ends and two from near the center of the cathode. The only exception was the palladium cathode used in experiment three in which the entire electrode was cut into four pieces. The tritium distributions in the four Pd cathodes are shown in Figure 3 in T atoms/g Pd. Significantly, in the three experiments where the ends of the palladium wires were analyzed separately from the center sections, comparatively much less tritium is found in the ends of the wires as compared to the center. The 8 pieces near the center of the 4 electrodes show a surprisingly tight band of values namely, from 1.2 x 1010 to 8.9 x 10lo T atoms/g Pd. It appears that the ends of the Pd wires either did not charge as efficiently as the center regions or that tritium escaped from the ends more readily.

1-139 Table 1

Tritium Analysis of Electrolyte, Pd and Gas

Exper. # 1 2 3 4

Time at 163.8 169.7 144.4 161.3

LR > 0.85 [h] bso4 H2S04 Electrolyte +Li2SO4 +Li2SO4

Loading Ratio 0.99 1.030 Atom Fraction

#T atoms Before 3.8 xi09 ND Electrol. After 1.9 xiol ND

#T atoms Before ND ND in Pd After 1.7 xiol0 ND

#T atoms Before 1.8~10~ NM Gas After 1.8 x108 NM

#T atoms Before 4.0 xi09 ND Total After 2.1 xioll ND

T Generated 2.1 x10” ND [# atoms]

Enhancement 52.5 ND Fador

/ T Generated 1.1 x101’ ND [# atoms/cm2]

T Generate Rate 2.0 x105 ND [# atoms/cm2/S]

= Batch of D20 with high T content ND = Not Detected NM= Not Measured LR = D/Pd or H/Pd Loading Ratio

1-140 It should be noted that the detection limit of our analytical procedure is 5 x lo8 T atoms/g Pd. Therefore, the tritium levels that we find in the Pd after electrolysis are up to 178 times larger than the maximum possible contamination level before electrolysis. In previous analysis of over 100 as-manufactured palladium samples from the same supplier as the present palladium cathodes, we have found no evidence for tritium contamination within the detection levels of our procedure. Therefore, we conclude that the tritium found in the palladium cathodes has been generated by nuclear phenomena occurring in the deuterium loaded palladium.

Two experimental observations made in this study indicate that the tritium was generated in the interior of the palladium rather than at its surface: 1) Tritium generation appears to be related to the D/Pd loading ratio; this would not be the case if tritium generation were a surface phenomenon. 2) Tritium is evidently emerging from the palladium during the analytical procedure which involves dissolution of the palladium of aqua regia; if the tritium were adsorbed on the surface of the palladium, it would be very unlikely that it would survive several minutes of exposure to air during the cutting procedure and the transfer into the analytical system.

Neutron Generation

Neutron measurements on the electrolytic cells were carried out during the entire period of experimentation, that is for two months. Two 3He counters each were positioned next to the D2and H2 cell, respectively. Details of the neutron counting technique involving sophisticated electronics and event loggers will be described elsewhere. The detectors were capable of detecting neutron emissions in a time gate as small as 8 psec. In the present paper, we will not address single and double neutron events. We will only be concerned with events involving three or more neutrons, counted in less than 1 millisecond. We have consistently found significantly larger numbers of triple events in the D2 cells than in the H2 cells. The results of the neutron counting are presented in Table 2. It is seen that the number of triples monitored on the four D2 cells is consistently between a factor of 2.0 and 2.6 higher than in the H2 cells. In the entire two month period of observation, the total number of triples is 51 for the four D2 cells and 22 for the four H2 cells.

1-141 Furthermore, we find the occurrence of two quadruple neutron events in the D2 cells and one quadruple in the H2 cells. Figure 4 shows the two quadruple neutron events monitored in experiments 1 and 3. It is seen that the first event consists of 4 neutrons counted in 320 psec whereas in experiment #3 the 4 neutrons are counted in 120 psec. While the number of neutron events involving triplets and quadruplets detected in our experiments is quite small, we regard their consistently more frequent occurrence in the D2 cells as compared to the H2 controls as significant. Conducting the neutron detection in an underground laboratory would significantly reduce the background and lead to firmer conclusions.

Table 2

Triple and Quadruple Neutron Counts in D2SO4 (D) and H2SO4 (H) Cells

Experiment # 1 2 3 4

Electrolyte DH DH DH DH # Triples 13 5 14 7 13 5 11 5 #Quadruples 1 0 00 10 01

Excess Power Generation

Figures 5a and 5b show the electrical input power into the cell and the temperature of the Pd cathode and Pt anode as a function of time for the D2 cell whose D/Pd ratio is shown in Figure 2a. The curves shown in Figure 5a and 5b relate to the time interval from 15,430 to 16,030 minutes. Figure 5 a conveys that the electrical input power to the cell increases steadily with time. From Figure 5b it can be seen that the temperature of the platinum anode stays constant at 26.84"C during the entire time period of 600 minutes. However, the temperature of the Pd cathode shows a relatively constant value of 26.7"C only in the first 370 minutes of the time period shown. The relatively sudden temperature excursion of the Pd cathode from 26.7"C to 27.7"C followed by less elevated temperatures in the subsequent 70 minutes represents an increase in temperature which can not be explained on the basis of the smoothly rising electrical input power. On the basis of a temperature- power input calibration performed on the cell, the temperature excursion in Figure 5b

1-142 corresponds to an excess power excursion with a peak value in excess of low, representing a 187 times increase over the electrical input power. The excess energy produced during this power excursion amounts to approximately 5 x lo4 Joules. Operation of the thermistor was verified as correct after the conclusion of the experiment. However, the cell is not set up to do precise calorimetry and these results should be regarded as approximate and tentative.

Conclusions

We have applied a novel procedure to attain D/Pd ratios in the vicinity of 1. When such high loading ratios are obtained, we have observed tritium generation on four out of four D2 cells, whereas none of the four H2 control cells shows any evidence for tritium generation. As we performed total tritium analysis on electrolyte, electrode and gas before and after each experiment, and as the cells are hermetically sealed, we conclude that the tritium can only have been generated by nuclear phenomena in the deuterium-loaded palladium during the experiment.

The total tritium enhancement amounts to factors as high as 50. The total amount of tritium generated is between 4.3 x 1010 and 1.1 x 1011 T atoms/cm2in typically 7 days. this corresponds to an average tritium generation rate from 5.8 x 104 to 2.0 x 105 T atoms/cm2/sec. Neutron generation has also been observed in these experiments. However, the levels are fairly small, amounting on very rare occasions to 4 neutrons counted in a time frame of less than 320 psec. In one of the four D2 cells studied, we have found evidence for a temperature excursion lasting approximately 70 minutes with excess power values in excess of 1OW and an excess energy generation of approximately 5.1 O4 Joules. Since this represents a single event in 4 experiments during two months, we regard this excess heat result as very tentative. The levels of tritium observed could only explain excess power levels of the order of 10-7 W.

Acknowledgements

We would like to acknowledge the help of X. Du, J. Yuan, 6.Nkamsi and J. Peterson in the tritium analysis and S. Barrowes, H. Bergeson and J. West in the neutron measurements. We are also indebted to T. Claytor of Los Alamos National Laboratory for tritium analysis of D2 gas. This study was made possible through the financial support from the State of Utah.

1-143 References

1. M. Fleischmann, S. Pons, and M. Hawkins. J. Electroanal.. Chem. 261,301 (1 989).

2. S. E. Jones, E. P. Palmer, J. B. Czirr, D. L. Decker, G. L. Jensin, J. M. Thorne, S. F. Taylor, J. Rafelski. Nature a,737 (1989).

3. A. DeNinno, A. Frattolillo, G. Lollobattista, L. Martinis, M. Martone, L. Mori, S. Podda and F. Scaramuzzi, II Nuovo Cimento 101A, 841 (1989).

4. H. 0. Menlove, M. A. Paciotti, T. N. Claytor, H. R. Maltrud, 0. M. Rivera, D. G. Tuggle and S. E. Jones, Proc. Conf. Anomalous Nuclear Effects in Deuterium/Solid Systems, Provo, Utah, Oct. 22-24, 1990.

5. A. Takahashi, T. Takeuchi, T. lida and M. Watanabe, J. Nucl. Science and Technol. a,663 (1990).

6. D. Gozzi, P. L. Cignini, L. Petrucci, M. Tomellini and G. DeMaria, II Nuovo Cimento 103A, 143 (1990).

7. C. D. Scott, J. E. Mrochek, T. C. Scott, G. E. Michaels, E. Newman and M. Petek, Fusion Technology 18,103 (1990).

8. E. Storms and C. Talcott, Fusion Technology u,680 (1990).

9. P. K. lyengar and M. Srinivasan, Proc. 1st Annual Conf. Cold Fusion, Salt Lake City, Utah, March 28-31, 1990, p. 62.

10. T. S. Murthy, T. S. lyengar, B. K. Sen and T. B. Joseph, Fusion Technology 18, 71 (1990).

11. M. S. Krishnan, S. K. Malhotra, D. G. Gaonkar, M. Srinivasan, S. K. Sikka, A. Shyam, V. Chitra, T. S. lyengar and P. K. lyengar, Fusion Technology u,35 (1 990).

12. T. Gamo, J. Niikura, N. Taniguchi, K. Hatoh and K. Kinichi, European Patent Application 0 395 066, 26 April 1990.

1-144 13. T. N. Claytor, P. A. Seeger, R. V. Rohwer, D. G. Tuggle and W. R. Doty, Proc. Conf. Anomalous Nuclear Effects in Deuterium/Solid Systems, Provo, Utah, OCt. 22-24, 1990.

14. K. L. Wolf, "Cold Fusion and Hot Tritium," transcript of talk given August 11, 1990 at Stanford University; R. Pool, "Wolf: My Tritium was an Impurity," Science, 248, 1301; 15 June, 1990.

15. K. Cedzynska, S. C. Barrowes, H. E. Bergeson, L. C. Knight, F. G. Will, Fusion Technology. Submitted for publication (August 1991).

16. K. Cedzynska and F. G. Will, Final Report, National Cold Fusion Institute, Vol. 1, Technical Inform. Series PB91175885, June 1991; to be submitted to Fusion Tech no logy.

17. A. M. Riley, J. D. Seader, D. W. Pershing, A. Linton, S. Shimuzu. NCFl Final Report (1991); submitted to J. Electrochem. SOC.

18. J. Peterson and K. Cedzynska, National Cold Fusion Institute, unpublished work.

1-145 Sampling Port with septum 1

and ients 1

TWO COMPARTMENT CELL DESIGN

Figure 1. Schematic Drawing of Electrolytic Cell

1-146 0 -c a5

0.6 0 10000 20000

Time (min)

0.7 -

0.6 I

Time (mln)

Figure 2. D/Pd and H/Pd Loading Ratio as a Function of time for 2 mm Pd Wire of Experiment #2. Only Fraction of Data Points Shown. Details Omitted.

1-147 Exp. '1 Exp. "2 Exp. *3 Exp. '4 tri tium tritium tritium t ri ti urn atomdg Pd atoms/g Pd ..:: . atoms/g Pd atoms/g Pd 7.. 1.6~1O1 ND 1 .ixi 09

4.4~10' 1.2x1010 8.9~10'

6.7~1O1 4.7~1O1 6.4~1O1

l.lxlO10 ND

Figure 3. Tritium distribution in Pd cathodes after D20 electrolysis. ND = not detected; detection limit is 5x108 tritium at o ms/g .

1-148 V a, 4 c 3 0 u 2 v) S 0 L 4 3 a, Z I b 1 I I

I I I I I I I I- 0 I I I I I I I 0 100 200 300

-0 a, 4 S 3 0 u 2 v) c 0 L & 3 a, Z b 1

0 I I I I I I I I I I I 0 100 200 300 L Time [psec]

Figure 4. Neutron count data for D2 cells in experiments 1 and 3.

1-149 f E Y n

0 100 200 300 400 500 600 700

Time (min)

L. .-

27.6 -

h 27.4 - 0, ?! Y D/Pt c.3 27.2 - 2 , D/Pd Q) - : +0) 27.0 - I

26.8

f- 257 Hours into experiment I 1 I I I I 0 100 200 300 400 500 600 700

Time Min. Figure 5. (a) Electrical Power Input of D2SO4 Cell in Experiment #2. (b) Observed Tempurature - Time Curve of Pd Cathode and Pt Anode. 1-150 Deuterium-Gas Phase Reactions on Palladium

by John R. Peterson

1-151 Table of Contents

Page

Abstract 1-153

I. Introduction 1-153

II. Experimental 1-155

A. Vacuum and Gas Lines 1-155 B. Reaction Vessel Design 1-155 C. Electrode Design and Preparation 1-157

D. Nuclear Product Detection 1-157

111. Results and Discussion 1-158

A. Early Results 1-158

B. Tritium Results 1-160

C. Tritium and Neutrons 1-161

D. Elect rode Pre-Treatment 1-162

E. Electrode Surface Analysis 1-164

F. Gas Analysis 1-164

IV. Conclusions 1-165

Acknowledgements 1-165

Appendix I 1-166

Figures 1-170

1-152 Abstract

An attempt was made to produce anomalous nuclear events in gas phase deuterium loaded palladium. Stimulation was achieved by applying a high voltage a.c. potential across two Pd electrodes. In some cases electrode cleaning was performed by using a similar high voltage discharge under vacuum. In others, electrode pre-treatments of aqua regia etch or electrolytic palladization were performed.

Of twenty valid experiments with palladium, nine or ten exhibited elevated levels of neutrons and/or tritium, representing a success rate of about 50%. These experiments and possible explanations will be discussed.

I. Introduction

For the first six months of the existence of the National Cold Fusion Institute, most research dealt with systems similar to the original Pons-Fleischmann experiment (1) in the sense of being electrolytic in nature. What this means is a beast wrought with complications: Solid-liquid interface and double layer charge and species complexities; multilayer boundary diffusional problems; electrolyte composition variations. The result is a system with more variables than the ideal. During this same period, a paper appeared (2) in which a novel gas phase system was utilized which seemed to support the notion of cold fusion by way of detecting neutrons produced in a high voltage discharge of deuterium loaded palladium. At this point, it was decided to pursue this avenue at NCFl since it seemed to be in a much simpler form.

The gist of this method involves first performing a gas phase loading of deuterium (or hydrogen in the blank experiment) in a sample of palladium metal. Under normal conditions of pressure and temperature, maximum loading attainable is for a deuterium-to-palladium atom ratio of D/Pd = 0.6. At that point there occurs an alpha to beta phase transition of the Pd metal, and no further deuterium can enter. Deuterium atoms are believed to occupy octahedral sites of the palladium atoms, though full occupation does not occur.

Upon maximum loading, a high voltage discharge is performed on the electrodes, and following this, nuclear reaction products are sought after. In the Wada experiment, neutron bursts were detected following high voltage activation, but two main problems existed, both concerning the type of detector used. These researchers

1-153 used a system in which three reaction vessels surrounded a single BF3 neutron detector, the arrangement being to increase the neutron density. This type of detector is extremely sensitive to EMI, electromagnetic interference, and the most dramatic neutron burst seen by Wada occurred during the high voltage discharge, a time during which extreme levels of spurious EM noise would be present. Following HV discharge, Wada detected low levels of above-background neutrons appearing anywhere from 20 to 100 hours later.

In addition to a sensitivity to EMI, this type of detector has many problems with spurious microphonics, and reproducibility and statistics become an insurmountable task.

In the seventeen months since the start of the NCFl gas phase project its evolution has been one of trial and error: The number of errors has been a trial for the researchers. As is now well known by most cold fusion workers the reproducibility of positive results seems more to do with luck, rather than by good science. The most predictable thing, aside from the low probability of getting "good" results from an experiment, is the increased likelihood of positive results just as one is preparing to "throw in the towel." In April of 1990 a series of three experiments all showed evidence for statistically-above-background levels of neutrons following activation (approximately four hours after, in all three cases). In September of the same year, after seeing rn definite signs of nuclear products following the April results, an experiment yielded dramatic evidence for unevenly distributed levels of tritium in the used electrodes. This experiment showed no neutrons, however, and it was the first time tritium analysis had been performed. Finally in December of that year, definite neutron bursts were seen while using the fine detection facilities of Dr. Steven Jones at Brigham Young University, and subsequent tritium analysis demonstrated the same high but uneven levels of tritium.

Many questions posed at the start of this project are yet unanswered, and the number of questions has risen during the course of the work. As the life of the Institute ebbs away (less and less slowly) the realization of one's being at the point of having a definite course of action, now that a one year-plus period of exploratory work is complete, leads to strong feelings of futility.There is little doubt now, that Cold Fusion does exist, and there is little doubt that some of the gas phase experiments done here at NCFI have shown clear evidence of some kind of "anomalous nuclear events" occurring in deuterium loaded palladium, yet there is no time to explore these further,

1-154 and there is no point in planning what to do next. All that remains is to explain what & been done, and to encourage other researchers to continue the hunt for this elusive creature, and offer suggestions (possibly helpful ones, yet) to those with enough courage and foresight to carry on this important work.

II. Experimental

Much of the time spent on this project involved the development and continued modification of the equipment used, with the goal being the optimization of the system with respect to producing and detecting cold fusion. This section will therefore be subdivided into the following four parts: Vacuum and gas lines, reaction vessel design, electrode design and preparation, and nuclear product detection.

A. Vacuum and Gas Lines

A four port glass manifold with cold trap was connected to a high capacity two- stage mechanical pump (Edwards Model 5). This system was capable of quickly achieving a vacuum better than 10-3 torr as measured by a Pirani vacuum gauge (Edwards Model PRHl OK with Model 1005 controller). Unfortunately, accurate measurements of D2 and H2 gases were difficult with this gauge, although as a measure of vacuum quality it sufficed. AI1 four manifold ports closed with O-ring teflon stopcocks (Kontes, 5mm) and one of these was connected to a second manifold in 0.25 in. copper tubing and brass connections (Swagelock). On this manifold were compound dial gauge and connections to various gas supplies and finally a flexible stainless steel tube ending in a quick-release connection (Cajon Ultratorre) to which the reaction vessel was attached.

Deuterium (Air Products research grade) and hydrogen gases were introduced via two-stage regulators directly from the cylinders as supplied. Argon was passed through drying and oxygen scavenging columns (5A molecular sieve and activated copper on alumina, respectively) before use.

B. Reaction Vessel Design

In following along the lines of the Wada-type experiment, the reaction vessel used had to have the following properties: Two vacuum feed through ports capable of transmitting high voltage currents into the vessel; have a shape compatible with various neutron detectors; and have inlets for both vacuum/gas lines and pressure

1-155 measurement devices. Commercial three-necked flasks were originally used for convenience, with the side necks for the electrodes and the central neck for gadgauge connections. It was soon found that rubber stoppers, as in the Wada system, were insufficient to insure vacuum and pressure maintenance, and so ground glass joints connecting to nylon Swagelock fittings were employed. In Figure 1. can be seen the final version of the Three-neck vessel design used. The vessel was 250 ml. and the high voltage connection consisted of 0.25 in. copper rods, in the ends of which were attached the palladium (or other metal) electrodes, with nylon Swagelock reducing unions creating the gas-tight fitting.

This type of vessel was eventually abandoned for two main reasons. First, the number of joints increased the possibility of leaks and therefore limited the maximum pressures. Secondly, changes in neutron detector configuration determined the need for a reaction vessel of narrower diameter (3.5 in.) with all connections fitting this size. Figure 2. shows this second generation design in which no ground-glass connections are necessary. The resulting design also meant that the electrodes were now parallel, resulting ion a more uniform discharge envelope around the electrodes. Pressures up to 3 atm. were then regularly used, resulting in more rapid loading and the possibility of remaining above ambient pressure throughout the experiment.

Vessel pressure measurements were first made using a compound dial gauge connected, along with the gas/vacuum inlet, to the central neck. Eventually this gauge was replaced with a diaphragm pressure transducer (Omega Model Px236) whose output was displayed on a chart recorder then stored on computer by means of a data acquisition system (Keithley Model 500) which also took values of several thermocouples placed near and in contact with various locations on the reaction vessel.

High voltage discharges were achieved by using a 15,000 volt AC transformer (Frankformer Model 15030P) with a variable transformer connecting it to line. This allowed the high voltage to be controlled. The AC voltage across a series of resistors (5000 ohm) was continuously measured on an isolated voltmeter which allowed for the AC current running through the vessel to be monitored. Typical currents of 10 mA were found during discharge, although this varied tremendously depending upon the the actual discharge, be it glow or arc. System noise due to these discharges were a source of problem, both for the neutron detection and the pressure/thermocouple data acquisition systems. By proper shielding these problems were eventually overcome.

1-156 C. Electrode Design and Preparation

In general, 3 to 5cm lengths of 2.0mm palladium (Johnson-Matthey or Hoover and Strong) were used. These samples were pre-treated in one of several ways in order to encourage loading of the deuterium gas. The typical procedure included rough sanding, rubbing with a paste of alumina powder in de-ionized water, water rinse and acetone rinse, and final drying in air. The samples were then weighed and quickly placed in the vessel which was immediately evacuated to prevent any oxidation of the outer layer.

Later experiments, including the dramatic results achieved at Brigham Young University, were performed with the electrodes in the form of 3 foot lengths of 0.5mm wire (Hoover and Strong) which were coiled (usually around a narrow diameter alumina rod). This material did not lend itself to the above pre-treatment, and so a method utilizing aqua regia etching of 0.5 to 5.0 minutes followed by water and acetone rinses.

A third pre-treatment method involved performing an electrolytic pailadization technique using a solution of 0.05M PdCI,, 2M LiCl and 0.1M DCI in D20 and having platinum as the counter electrode. These palladizations were run at 20 mA/cm* for 1 or 2 minutes. The increase in surface area greatly enhanced the loading rates, as will be discussed below.

D. Nuclear Product Detection

The two types of nuclear reaction products searched for (and, occasionally, detected) were neutrons and tritium. In early experiments neutron capture gamma rays, with their characteristic energy signature were, sought by immersing the vessel in a water bath in contact with a purified germanium detector. Later on a system with 3He detector tubes was developed, allowing for the direct measurement of neutrons. These system are described in the report of the Physics Group.

Tritium content of the used Pd electrodes was not attempted until K. Cedzynska of this Institute developed the method of closed system tritium analysis. This is described in the report of the Surface Chemistry. Results of both neutron and tritium detection will be described below.

1-157 111. Results And Discussion

Progress in these gas phase reaction has not followed an orderly and conventional path, and so deciding the proper format for the presentation of these results has come with some difficulty. An overall chronological approach will be taken in which early experiments demonstrating production of neutrons will first be described. These will follow with mid-period results involving tritium measurements, and lastly then by more recent experiments in which both neutrons and tritium were detected. A description of electrode pre-treatment variations, electrode surface analysis and deuterium gas analysis will conclude this section.

A. Early Results

The first successful system utilized was a 3-neck vessel (See Figure 1.) which was immersed in a plastic tub of water 18 x 18 in. with a depth of 9 in. In contact with this tub was a purified Ge gamma ray detector, capable of discriminating between those produced by a naturally occurring Bismuth isotope at 2.205 MeV, and those caused by the capture of neutrons by protons in water, the later having an energy of 2.224 MeV. Usually data was acquired for at least 48 hours with no vessel present, and these background data was compared to data acquired with an experiment in place.

In a typical experiment, the palladium electrodes were prepared, weighed, and mounted on the copper contacts. The vessel was then evacuated and allowed to continue until a minimum pressure was achieved. A high voltage discharge was then performed while still under vacuum in order to further clean the electrodes. The system was cooled, a partial pressure (usually 0.1 atm) of D2 gas was introduced, and a second discharge performed. The vessel was again evacuated and allowed to cool. At this point the vessel was charged to its working pressure of D2 and placed in the detector. Upon reaching maximum loading of deuterium (as measured via the pressure drop) a final activation was performed. Figure 3. demonstrates the temperature-pressure evolution in a typical experiment. In this case, a later experiment is shown for which automated data acquisition was used. The temperature curve is for a thermocouple attached to the exterior vessel wall, and the two preloading activations, as well as the final loaded activation can been seen as temperature excursions which go as high as 70 C. The actual electrode temperatures

1-1 58 are much higher, in fact for the vacuum discharge high enough for the electrodes to reach a dull orange glow. The pressure drop follows an exponential decay to a final value well above ambient (app. 0.85 atm), and from the difference a final loading ratio D/Pd=O .65 was calculated.

In March and April of 1990 three such experiments were performed, each of which showed evidence of neutron production. In Figure 4. can be seen the integrated counts/channel over the 28.5 hour period following the final activation for the second of these experiments, GPLlO. The part of the gamma spectrum presented includes both the Bismuth peak as well as neutron-capture peak, and data are also shown for the 123 hours before the vessel was in place, normalized to the 28.5 hour experiment. It can clearly be seen that the count rate under the neutron capture peak is higher during the experiment as compared to the background period whereas, in fact, the bismuth peak values are reversed. Furthermore, the increase in the neutron capture peak yields an integrated value of 7.2 standard deviations above background. By comparing to a calibrated neutron source, it was determined that the measured count excess was a result of 1.3 x 106 source neutrons over the 28.5 hour experiment. As the rate was still above background at the end of the experiment, this is clearly a lower limit. In later experiments the need to continue these studies over several days and even weeks became more and more clear.

The third of these experiments was performed with two reaction vessels in the water bath, with twice the mass of palladium. The comparable gamma spectra can be seen in Figure 5. The integrated sigma value was 4.7, substantially less than for the previous experiment, in spite of having doubling the potential source of neutrons. It is obvious that the anomalous behavior was at a reduced level in both vessels or occurring only one.

Current knowledge of these neutron bursts suggests durations on the order of mseconds, and so long-term integration of data as shown above will clearly lead to a loss of short-term information. Integration of the 2.224 Mev shows, when examined hour by hour, a general rise from the background average with dramatic peaks far in excess of three standard deviations. In two of the three experiments the rise in neutron rate begins three to five hours following activation and in the third, three to four hours

after activation. Instantaneously with the onset of the final activation there is a sharp , rise of pressure which signifies a partial loss of the loaded deuterium. This rise

1-159 continues more slowly as the temperature increases, and following activation drops in a similar fashion to the temperature drop.

Replication of these experiments faced serious difficulties for a number of reasons, the first being that the neutron detection system was immediately modified (see below). Slight variations in the palladium pre-treatment had occurred in the each of the three also. Since no direct measurement of the electrode temperature change during each of the activations was made, it is not known what effect this had. It is known that during the vacuum activation enough of a temperature increase occurs that the electrodes often begin to glow a dullish orange, indicating a minimum temperature of 550 C. The net result is an in-situ annealing taking place, and if lattice defects play a key role in cold fusion, this annealing might have an effect. In latter experiments, at least, a continuous monitoring of the actual AC current during activation took place, and so the local electrode heating could be controlled carefully.

B. Tritium Results

Upon completion of the above experiments, dramatic modification of the detection system took place. These changes included a move to a different part of the Institute building, a change of the water bath tank, and an "improvement" of the shielding for cosmic rays. A double-walled house of both lead and boric acid- saturated paraffin were employed, the former to stop cosmic rays and the latter to then absorb the resulting spallation neutrons. Unfortunately, it is now clear that boric acid was also acting efficiently to absorb part of our source neutrons. Whether a result of the new shielding or simply because the experiments were no longer generating neutrons is not known: The only certainty is that no positive neutron events were seen following the three "successfu I" experiments.

By August it was clear that a different method for neutron detection must be employed, one that had no gamma ray sensitivity. A system using 3He tubes was built, along with the requisite electronics. Experiments were performed while the development was underway, and following one of these (during which no neutrons were detected) small portions of the electrodes were subjected to a closed system method for tritium analysis. The results can be seen in Figure 6 for one of the two electrodes, the other of which showed I~Qtritium above background levels. The startling fact that excess tritium was detected is far outweighed by the non-uniform location of the tritium, which seemed to arise in "hot spots", and only in one of the two

1-160 electrodes, each cut from the same length of stock metal, each subjected to the same environment of the experiment.

This result caused renewed enthusiasm in the search for this elusive phenomenon. Whereas less and less confidence in the early experiments was the only product of several months work, one could now feel sure of those results, and the search could continue. This experiment showing residual tritium was a typical one using 2mm x 3cm palladium electrodes which were, for the first time, subjected to a a pre-treatment 5-minute etching in aqua regia. Such an etching tends to dramatically slow the uptake of deuterium into the metal: After 36 hours, the deuterium to palladium ratio was still only 0.46. Nonetheless, a final activation was performed, and the tritium result was positive. This was the first indication that a high loading ratio is not a necessary requirement.

C. Tritium and Neutrons

By the Fall of 1990 the need to effectively detect both neutrons and tritium was very clear. Since the closed system tritium method had proved itself to be both accurate and sensitive, it was the problem of neutrons that was addressed. Such a system had yet to be developed at NCFl for a number of reasons, mainly because of the high background levels present and the aforementioned sensitivity to electromagnetic noise. For this reason, an offer of Dr. Steven Jones was gratefully accepted, and a series of experiments were performed in his laboratory at Brigham Young University.

The Jones detector was comprised of eight 3He tubes in a well shielded housing in a basement laboratory. The system had an efficiency of 34%, and suitable electronics for the determination of neutron bursts. Of three experiments performed in this detector, two showed definite neutron bursts arising from the experimental vessel. Of those two, the second produced the largest neutron burst Dr. Jones has seen in his detector.

The total neutron counts for this experiment, GPL32, can be seen in Figure 7. Included can be seen the key events during the experiment, among these several bursts, each taking place within 128 usec. Ninety-one hours following the final activation there can be seen a burst large enough to register in the 90-minute totals.

1-161 This burst represented 280 source neutrons, much too large to be caused by cosmic rays.

Tritium analysis was performed on several sections of the used electrodes, and these results can be seen in Figure 8. Clearly visible are the unevenly distributed tritium "hot spots" similar to those found in GPL21. In addition to the Disintegrations Per Minute Per ml (DPM/ml) values, the above-background radioactivities normalized to sample mass are shown. The hottest of these, the .2089g section of electrode one, showed a tritium level of 2 x1Ou tritons. Subsequent analysis of tritium levels in the stock deuterium gas (see below) showed that these levels are far too high to be accounted for by tritium already present.

This experiment was one in which electrodes of 0.5mm x 3ft. were employed, and once again a 5-minute pre-treatment aqua regia etch was performed. In this case, loading hindrance was such that at the time of final activation the D/Pd ratio was only 0.3, and after 3 more days (at the time of the most dramatic burst) had still only reached 0.45. Clearly, then, high loading is aa requirement for cold fusion.

D. Electrode Pre-Treatment

As previously mentioned, the experiments exhibiting anomalous nuclear behavior had been subjected to a pre-treatment involving an etching in aqua regia. Originally utilized in an attempt to improve the loading ability of the surface, these 5- minute etches in fact had the opposite effect of slowing down the uptake of deuterium. With this in mind, a series of experiments in which the electrodes were aqua regia etched for 0.5, 1.0, 2.0 and 3.0 minutes. As expected, loading times increased with increased etch time. Figures 9 and 10 show neutron bursts which occurred following activation of an experiment in which the palladium electrodes had been subjected to a 2-minute aqua regia etch. This treatment resulted in a maximum loading ratio of only 0.38, yet these two bursts were observed at 29 and 56 hours after the final activation. The first of these involved five neutrons appearing within 100 psec and the second, four neutrons within 500 psec. These intervals are such to exclude the possibility of naturally occurring background incidents, and, considering the low efficiency of our detector each represent several hundred source neutrons.

In Figure 11 can be seen the one burst recorded in an experiment for which the electrodes had been subjected to a one minute aqua regia etch. A full loading of 0.69

1-162 had been achieved, and this one burst of eight neutrons within 300 psec was detected 68 hours after the final activation. Again, several hundred source neutrons are estimated.

By contrast, the aqua regia etching is not a necessary requirement for such bursts to occur. Figure 12 demonstrated a five neutron burst detected 70 hours following the final activation of a system for which the only electrode pre-treatment was a rough sanding which resulted in deep scratches. A final loading ratio of 0.65 resulted, and the observed burst occurred within 100 psec. Unfortunately, no tritium was detected in any of these three experiments. Unfortunately, further experiments using a 5-minute etch were also unsuccessful.

One explanation for the observed effect of etching might concern the adsorption of chlorine into the metal surface. As adsorption is thus hindered, so might also be the desorption during activation: This "crowding" of energized deuterons near the surface might enhance crack formation and defect sites, improving the chance for intense field formation to occur. Scanning Electron Microscopy of a section of a GPL32 electrode, for which a 5-minute etch was employed shows deep channels scored into the electrode. These channels are not present for shorter etching times (see below).

Several gas phase experiments were performed using electrodes of various shapes that had, in contrast to aqua regia etching, been subjected to electrolytic palladization. The finished prepared electrodes had a layer of palladium black which greatly increased the surface area: A typical loading time of 24 hours was reduced by this method to under one hour. Again, unfortunately, none of these experiments demonstrated neutron or tritium, though an interesting sidelight resulted:

Following an experiment sections of each electrode were cut and tritium analysis was performed. The remaining sections were taped onto a sheet of paper, allowing their original positions to be maintained. Occasionally it is found that certain electrode sections heat up, enough that the transparent tape is melted and the paper is burned where there was contact with the section. This is easily explained, since palladium black is a good D2/02 recombination catalyst. The loaded deuterium is rapidly recombined with ambient oxygen, thus speeding up the desorption process. What is curious is that when this electrode heating occurs, it is always on only one of the electrode sections, as if, possibly, loading is a non-uniform process, and thus the concentration of deuterons in the metal lattice is highly non-uniform.

1-163 E. Electrode Surface Analysis

Sections of electrodes from several experiments were analyzed using a scanning electron microscope and x-ray surface analysis. In Figures 13 and 14 can be seen micrographs of electrodes from GPL32 and GPL39, respectively, the former having exhibited dramatic neutron and tritium results. Deep channels can clearly be seen, whereas in the latter a 1-minute etch was enough only to cause a crystalline appearance. Experiment GPL39 showed no neutron or tritium enhancement.

Figure 15 shows electron micrographs of an electrode section from experiment GPL40 in which a 2-minute, 20 A/cm2 palladization had been performed. A crystalline appearance, similar to the unsuccessful experiment above, can be seen. Experiment GPL40 showed no enhancement of neutrons or tritium. Micrographs of experiment GPL21, the earlier successful one, showed very little channel scoring although high tritium levels were found.

At the time of this SEM analysis, elemental x-ray surface analysis was also performed. Surprisingly, chlorine was found in the surface, even in the aqua regia etched successful experiments. In fact, the only substance found besides palladium was carbon, and this was only in unused pieces of the metal. This suggests that the electrode preparation, whether etching, roughing palladization or vacuum discharge, is very efficient in cleansing the metal surface.

F. Gas Analysis

A question that has continuously arisen in these studies is whether or not selective concentration of residual background tritium coming from the stock deuterium gas could account for these elevated levels found. An efficient means of measure these levels was used in which the gas was recombined (using a commercial catalyst) and the resulting water was analyzed. Several sets of analyte ranging from 0.1 to 0.39 water were collected and measured, and good agreement were obtained with an average activity of 0.138 nCi/L @STP. At this low concentration, even if all of the tritium present in the 0.5L reaction vessel had concentrated in a 0.2g section of one electrode, the resulting analysis could not produce the >750 DPM/mI activity found in our "hottest" sample from the experiment that produced such dramatic neutron bursts in the BYU laboratory.

1-164 \v. Conclusions

The tritium and neutron results obtained in this Study show that anoma\OUS nuclear reactions do Occur when deuterium is loaded into palladium ftWn deuterium gas. The problem was, and still is, the irreproducibility of the effects. AS in many other laboratories around the world, the success rate achieved in this study is approximately one out of two.

Neutron bursts have been recorded following high voltage discharge of deuterium loaded-palladium electrodes. The most dramatic of thest were recorded using the high-quality facilities of Dr. Steven Jones at Brigham Young University. Four neutron bursts were observed in a time span of 80 hours. The most intense burst consisted of 280 source neutrons in the gate of 128 psec.

"Hot Spots" of tritium in used electrodes, far in excess to be accounted for in terms of contamination have been found using a highly sensitive and accurate "closed- system" analytical method, developed by Dr. Krystyna Cedzynska at the NCFI. The largest amount of tritium was found near the center of one of the electrodes which had produced the 280-neutron bust. A tritium concentration equivalent to 4.5 nCi/gPd or 9.3 x 109 tritium atoms/g Pd was found. This compares to a maximum possible tritium contamination level of the Pd of 5 x 108 atomslg Pd.

The two most dramatic sets of results occurred in palladium that had been subjected to five-minute etchings in aqua regia. The effects of this etching on loading times was evident, however no chlorine was found during elemental surface analysis.

Acknowledgements

The cooperation and encouragement of Dr. F. G. Will is gratefully accepted. Much of this work would not have been possible without the participation of Dr. K. Cedzynska. Thanks is given to Mr. Hans Morrow of the University of Utah's Chemistry Department for his glass blowing artistry, and also to Dr. M. E. Wadsworth and the Metallurgy group as well as to Dr. H. E. Bergeson and the Physics group.

Lastly, a special appreciation is given to Dr. S. E. Jones of Physics Department at Brigham Young University for his generous cooperation and expertise.

1-165 Appendix 1. A Summary of Gas Phase Loading Experiments

Exp. # Date Description Detection 1 1-20-90 J- M 2.3mm, 2.467g no capture gamma (ncg)

2 1-24 II If 2.34079

3 2-5 I1 I, D/Pdmax= 0.49 (3 days, starting at ambient)

4 2-13 J-M 2.3mm, 3.04269 vacuum annealed, 1030' 30 min.

5 2-19 J-M 2.3mm, 3.9294g ncg First exp. w/ground glass side joints (center neck still whubber stopper)

6 2-27 H&S I, 2.0mm, 2.95929 ncg Only 1 hr. of detection after final activ.

7 3-2 Cu blank Activation, 1.25 hr. dectedion on 3/5/90

8 3-6 H&S I, 2.9096g ncg D/Pdmax= 0.49 (6 days, including repress. twice to initial 1 atm value) Neutrons seen above 3 sigma, about 4 hrs. after activation.

9 3-8 Cu blank Activation, 2 hr. dectection on 3-13

10 3-19 H&S 11, 3.1057g ncg D/Pdmax= 0.55 (8 days, 1 recharge to 1.1 atm. Neutrons above 3 sigma seen after about 4 hrs.

11 3-20 Cu blank Activation, dectection on 3-28-90

12a 4-1 7 H&S II, 3.0031g ncg 12b 4-1 8 ,I ,I 2.9952 These two sets (in two vessels) were activated and observed si mu It an eously . Neutrons well above 3 sigma were seen about 4 hrs. following activation.

1-166 13 4-30 H&S I, 4.01049, 1050 C annealed D/Pdmax= 0.6 (14 days, PO= 1.2 atm) Vessel transferred to rm. 55 for dectection. Final activation on 5-18-90

14 5- 1-90 H&S II, 4.0209g D/Pdmax = 0 .55 (15 days, 1.2 atm start)

15 5-9 J-M Vanadium, 1.9033g After 3 weeks, little uptake (however 4 weeks later, apparent uptake)

16 5-25 Cu blank 24 hr. background, started 5-30 Final activation 5-31, 10:50

17 5-31 H&S II, 3.1272g, D/Pdmax = 0.44 (10 days, 1.15 atm start) Final activation 6-1 1, 1O:ll

18 6-9 H&S II, 2.70509 Rough emery, acetone ultrasound D/Pdmax = 0.63 (5 days, 1.3 atm start) Final activation 6-15, 10:22 Reactivation 6-20, 15:07

19 6-21 H&S II, 3.91949 Possible leak, vessel repressurized several times. Final activation 6-27, 17:32 Reactivated 6-28, 1455

20 7-3 H&S 11, 3.70869 (after restart) ncg D/Pdmax = 0.55 (6 days, 1.3 atm start) Final activation 7-19, 14:27

21 9-6 H&S II, 2.9200g He-3 5 min Aqua Regia (AR) etch D/Pdmax= 0.5 (2 days, 2.1 atm start) T analysis performed on 4 pieces, 97.5 DPM seen on one e Iect rode.

22 9-1 4 Ti 15-3, 0.4396g He-3 Rapid loading occured (within 20 min. to ~2.0D/Ti, after 2.5 hrs.). Not in detector at time. T analysis no good.

23 10-1 H&S I!, 2.45089 He-3 5 min AR etch, H20 wash, dried. D/Pdmax = 0.67 (1 day, 1.9 atrn start) Final activation 10-3, 15:30, aquis. cont. until 10-8-90

1-167 24 10-9 Ti 15-3, 0.77769 No uptake observed, even after 24 hrs.

25 10-25 Ti 15-3, 0.5272g No uptake seen, even after repeating vacuum discharge.

26 11-1 H&S I, 2.79279, roughed, AR etch Vessel inverted Final activation 1 1-5, 1 1 :23-11:33 Next file P65H0771 Repeat activation 1 1-7, 12:32-12-40 Next file P65H0819

27 11-13 H&S I, 3.0172g, sanded, alumina paste, H20 rinsed, dried. Taken to BYU dectector 11-14 Final activation 11-1 5, 14:30, several 1 min cycles of on-off c.t. +4857 Repeat activation 11-1 6, 15:45, c.t. +94101 28 11-20 J-M Grade 1, 6.26369, each 0.25mmx5m. In 3-neck flask, wound on alumina sleeves. D/Pd = 0.69 (35.5 hrs., PO= 1.69 atm) Final activation 11-22, 22:40-22:48

29 11-26 H&S 111, 3.79219, roughed, H20, acetone rinsed. TO BYU 11-27, 15141 (Ct 15141 155) D/Pd = 0.63 (23.5 hrs., Po = 1.76 atm Final activation 11-28 11 :35 (ct 70980) Repeat activation 11-29 15:30, (ct 83865) 30 11-29 H&S Ill, 3.51 789, 3-neck flask Terminated during final activation due to vessel cracking (arcing occured heavily). 31 12-14 H&S 111, 3.1 771g, 3-neck flask D/Pd = 0.67 (21 hrs., PO= 1.89 atm) Final activation 12-18 9:15 P65H1392

32 12-20 H&S 0.5mm, 4.28759, 5 min AR etch H20, acetone rinse. Coiled wires hung from insultated Cu rods. In BYU dectector 12-21 12:15 (ct 91850) 33 1-9-91 H&S 0.5mm, 1.7991g, 8 min AR etch No final activation - - test for D2 T contamination. 34 H&S OSmm, 2.91809, 5 min etch to repeat GPL32. Problems with arcing, computer crashing, restarts. Activation 1-25, 1O:OO (D/Pdmax= 0.26, after 72 h)

1-168 35 1-30 H&S Ill, 4.37389, filed, AR etched (maybe 2 min). D/Pdmax = 0.38, problem with vacuum line leak.

36 2-12 H&S Ill, 3.8108g, PV IV. Electrodes deeply scratched, nothing else. 0.65 loading in 20 hrs. (Po = 2.1 atm) Final activation 2-14 1O:lO

37 2-22 H&S IV, 4.54799, 20 sec AR etch, H20, acetone rinses. Vac discharge at 0.02 atm D2. D/Pdmax = 0.7 (after 10 hrs, Po = 1.99 atm) T analysis started 3-1 1-91, 1 week after end.

38 3-4 H&S IV, 4.50909, 1 min fresh AR etch, H20, acetone rinses. D/Pdmax = 0.69 (after 21 hrs., Po = 1.56 atm). Elogger system now has 4 tubes. D2 gas recombination performed.

39 3-18 H&S IV, 4.56769, 1 min AR etch, H20 rinse. D/Pdmax = 0.73 (after 20 hrs., Po = 1.92 atm) Final activation 3-20 9:39 No excess tritium found.

40 3-24 H&S IV, 4.46009 palladized (20 A/cm2) D/Pdmax = 0.61 (after 45 min., Po = 1.86 atm) Final activation 3-25 13:33 No excess tritium found.

41 3-27 H&S I, 3.7909, palladized (300 A/cm2) D/Pdmax = 0.76 (after 20 hrs., Po = 1.94 atm) Final activation 3-31 10:26

42 4-1 1 H&S V, 3.10829, roughed, alumina paste, etc. In 3-neck flask D/Pdmax = undetermined (slight leak present ) No discharge (detached electrode)

43 4-30 H&S IV, 4.454g, palladized D/Pdmax= 0.62 (after 70 rnin., PO= 1.84 atm) Three 2 min. activations, 5-7 Four 1 min. activations All tritium samples at background.

1-169 nn to vacuum I 4

Swagelock

Figure 1. Early Gas Phase Reaction Vessel

1-170 m

Vacuum ++---

T A Pressure Transducer

High Voltage

p It Palladum Rod

Figure 2. Parallel Electrode Reaction Vessel

1-171 Gas Phase Loading Exp. 37 Started 2-25-91, 9:51 2.5- I200

1.5

1 ......

b1 .$,....a 0.5 1: I. 1 '; I ..,J i

0 I I 0 5 10 15 20 25 30 Time, hours

Pressure ...... Vessel Temperature

Figure 3. Typical Gas Reaction Pressure and Temperature Evolution

1-172 GPLIO: 28.5 Hr data begun 3-28-91 12:21 123 Hr Background 180

......

21 a0 21 90 2200 221 0 2220 2230 2240 2: 50 Energy (keV)

______-_Bkg Nrmlzd to 28 H -28,s-H data

Figure 4. Gamma Spectrum From Experiment GPLI 0

1-173 GPL12: 20 Hr dat begun 4-23-91 1550 48 Hr Background begun 4-21, 11 :48

vv I A

......

--...... -......

I 1 I I I I 21 80 21 90 2200 221 0 2220 2230 2240 2 50 Energy (keV)

______Bkg Nrmlzd to 20 h - 20-h Data I I

Figure 5. Gamma Spectrum from Experiment GPLI 2

1-174 DPM/ml nCi/g

0.108g 29.8 057

0.080 97.5 2.01

28.6 a67 0.051 29.3 034 0.14.9 0.108 29.8 .603 0.030 80.5 4.05

Figure 6. Tritium Levels from Experiment GPL21

1-175 GPL32 Totals and Bursts 0.5mm x 1 .Om coiled Pd electrodes

700- S L + + -200 = 600- + ++ +#*A+ ++ .-E .-c +++*** ++ 4++&*ih++ *++++&-&+ + #ee<-v) 500- +*+ ++++ + -150 + 400- -c t t -100 Vwrrl 300- Hgh 3 h m 200- Dotoctw VOltU. #Khug, -50 c 100- 0- +e 0- 0- 3 a 0 I I I I I I I I I I I I I I oz

I + ~ota~count 0 Burst Intensity I

Figure 7. Neutron Totals and Bursts from Experiment GPL32

1-176 ,.___---- 27.3 DPM 0.05821 ; 0 nWg __ _.--

- --I I------3 49.9 DPM ,---- 55.4 DFM 0.102 j 0.30 ncvg 0.157 \ 3 1 0.24nCVg ___ - --- I------723.2 DPM 64.4 DFM 0.209 j ;;I ;;I 4.5 nCi/g 0.3 nCi/g 42.1 DPM 37.0- 0.15 nCi/g 0.12 nci/g

27.0 DPM 0 nCl/g

.------I ; j 89.5DPM 0.137 i 3, -___-___--j 0.6nCiIg

Electrode 1 Electrode 2

Figure 8. Tritium Levels from Experiment GPL32

1-177 GPL35 Neutron Burst 1 2/6 14:54, 29 hrs. after activ.

Figure 9. First mSec Neutron Burst from Experiment GPL35

1-178 GPL35 Neutron Burst 2.

Time, usec.

Figure 10. Second mSec Neutron Burst from Experiment GPL35

1-179 GPL38 Neutron Burst 3/11/91 2:33 68 hrs. following activation

Time, usee.

Figure 11. mSec Neutron Burst from Experiment GPL38

1-180 GPL36 Neutron Burst 2/17 14:32 70 hrs. following activation

Time, usec.

Figure 12. mSec Neutron Burst from Experiment GPL36

1-181 GPL32 5 min aquaregia etch

xi 00

XI 000

Figure 13. Electron Micrographs of Experiment GPL32 Electrode

1-182 x1000

Figure 14. Electron Micrographs of Experiment GPL39 Electrode

1-183

- .- - GPL40 Electrolytic palI ad izati oi

X30

X400

Fig ire 15. Electron Micrographs of Experiment GPL40 Electrode

1-184 Calorimetric Measurements During Electrochemical Loading of Deuterium In Palladium and Palladium Alloys

Sivaraman Guruswamy

Raj K. Rajamani

Jun Li

Milton E. Wadsworth

1-185 Table of Contents

Page

Abstract 1-187 1. Introduction 1-187 2. Cell Design, Operation and Results 1-188 2.1 Single Wall HHT-A Cells 1-188 2.1.1 Cell Configuration, HHT-A Cells 1-188 2.1.2 Temperature Excursions Observed in HHT-A Cells 1-194 2.1.3 Analysis of Heat Bursts Observed in HHT-A Cells -201 2.2 Single Wall HHT-B Cells -207 2.2.1 Cell Configuration, HHT-B Cells -207 2.2.2 Operating Results -207 2.3 Double Wall MHT-A Cells 1-212 2.3.1 Cell Configuration, MHT-A Cells 1-212 2.3.2 Calibration Curves and Operating Data 1-212 2.4 Double Wall MHT-B Cells 1-215 2.4.1 Cell Configuration, MHT-B Cells 1-215 2.4.2 Calibration Curves and Operating Data 1-215 2.5 Fleischmann-Pons (FP LHT) Type Cells 1-219 2.5.1 Determination of the Heat Transfer Coefficient 1-219 2.5.2 Electrolysis Experiments 1-225 3. Nuclear Product Monitoring 1-234 4. Discussion and Conclusions 1-234 4.1 Loading Level 1-235 4.2 Metallurgical Parameters 1-235 4.3 Special Operating Conditions 1-236 4.4 Summary of Cell Results 1-236 5. Acknowledgeme nt s 1-238 Appendix I. Summary of Experiments and Cell Operating Conditions 1-239 Appendix 11. Operating Conditions and Results for Small Glass 1- 251 and Teflon Cells

1-186 Abstract

The results of over 40 separate experiments on the electrochemical loading of palladium cathodes with deuterium are summarized. Extensive calorimetric measurements were made for these electrochemical cells. These results cover an 18 month period during which time a variety of parameters were considered. Initially, experiments were carried out using single wall quartz cells with high heat transfer (HHT) constants suitable for resolution of rapid thermal changes. Large temperature increases were observed on several occasions. Cell design was subsequently changed to double walled cells to increase cell sensitivity for detection of medium to low level heat transfer (MHT). Some of the key variables investigated were electrode preparation procedures, electrode composition, electrolyte composition, cell operating temperatures, cathode poisoning, current pulsing and introduction of transient conditions. The HHT cells had cell constants in the range of 2.5-5 watts/"C. Except for two of the early temperature excursion events in HHT cells, all heat bursts were explainable on the basis of intermittent recombination behavior resulting in thermal transients. The double walled cells had cell constants between 0.5-0.7 watts/"C. Excess heat below approximately 5% would be within experimental error for these cells. No evidence of excess heat above the level of 300 mW at 6-10 watt input levels were observed. A third series of tests were run on Fleischmann-Pons (FP) low heat transfer (LHT) cells having cell constants in the range of 6x10-10 WK-4 (0.1-0.2 WK-1 in the temperature range of interest, if heat transfer is assumed to vary linearly with cell temperature). Data were analyzed using a Kalman Filter Analytical Method. One cell experienced "boil off" of the electrolyte. A light water cell, operated in series with the heavy water cell, did not experience the "boil off event". Analysis of the thermal behavior of these FP cells is presented. The rapid heat excursion with "boil off" can be explained solely on the basis of the heat balance. The radiation heat transfer coefficient was measured separately in a FP light water cell. Apparent excess heat below 2 or 3 percent can be explained on the basis of cell chemistry, for example partial recombination. All tests results using FP cells were within the 1 to 2 percent range in these experiments. Therefore, excess heat generation in FP cells was not verified. 1. Introduction

High hydrogen gas fugacities or gas pressures at the cathode surfaces during aqueous electrolysis is not new to electrochemists or metallurgists. The idea of Pons and Fleischmann that such electrochemically imposed pressures can be utilized to

1-187 create conditions for fusion in the metal lattice was quite revolutionary. The apparent simplicity of the experiment, coupled with an appreciation that the physics of the metal lattice is still far from fully understood, resulted in multiple international research efforts to replicate and provide explanations for their observations. Excited by the prospects of cold fusion and the key role metallurgists may play in this technology, a program was initiated to determine metallurgical changes, structural integrity of the electrodes and possible alternate metals and alloys. The experimental program consisted of electrolytic loading, gas phase loading, thermal cycling of deuterated samples, explosive loading of deuterides as well as preparation and analysis of electrode material. While most attention was focused on Pd and its alloys, limited experimental work was performed on Ti, Zr and related alloys. In this report, the results of electrolytic cell experiments dealing with calorimetric measurements on three different types of cells are described. The cells were all based on Newton's Law of cooling and the cell thermal output was estimated from the differences in temperature between the cell electrolyte and external water bath. The three types of electrolytic cells used in calorimetric studies were: (i) high heat transfer (HHT) single-walled cells, with cell constants from 2.5-5 wattdoc; (ii) medium heat transfer (MHT) double-walled cells, with cell constants of 0.5-0.8 watts/"C; and (iii) low heat transfer (LHT) Fleischmann- Pons' type cells, with cell constants of less than 0.2 watts/"C. The thermal relaxation times varied from about 90 seconds for the HHT cells to about 10 minutes for LHT cells. The first category of cells were intended to measure large excess heat or heat excursions while the later refined cells could detect low level excess heat. Experiments performed in each of these cell configurations are described in the following sections. Effects of changing the electrode composition, heat treatment, surface preparation, electrolyte composition, addition of alloying elements to palladium on the excess heat or tritium generation were monitored.

2. Cell Design, Operating Conditions And Results

2.1 Single Wall HHT-A Cells

These cells had cell constants in the range of 2.5-3.5 W/"C. and the experiments were completed during the period April 1989 to August 1990.

2.1.1 Cell Configuration, HHT-A Cells: The first set of cells (Figure 1) consisted of a single-wall quartz tube, approximately 40 mm in diameter, 2 mm in wall thickness and 8 inches in length. In these cells, 4-mm diameter x 10 cm long Pd rod

1-188 Palladium Cathode Contact

.-c Gas Outlet #I Type T tinurn Wire Leads Leads Gas Outlet X 2 -

,Ground Glass Joint

Outer Glass Tube for Gas Collect ion /Glass Rod Spacer for Pt Anode Winding

Inner Glass Tube to Support Cathode - -E lec t roly te Leve I

Thermocouple in Thin Walled Glass Tube /Palladium Cathode

-Pt Anode Winding

Porous Teflon Plug - 'Spacer between Anode k40mm- and Cathode

Figure 1. Electrolytic cell configuration 1

1-189 centrally located cathodes were used. The anodes consisted of Pt or nickel wire, mesh, or sheet supported by a glass rod cage anodes surrounding the cathode. Electrochemical gases were allowed to exit freely to the external atmosphere. External or internal catalytic recombination was not employed in this set of cells. LiOD electrolyte (0.1 molar) was prepared by the slow addition of (Aesar) Li powder into low activity D20 (Cambridge Isotopes Laboratories). Initially, the temperature, voltage and current measurements were made manually but were subsequently automated using a Keithly 500 data acquisition system. The cells were run in constant current mode except for a few initial runs as indicated in Table 1, Appendix I. Hewlett Packard and KEPCO Power Supplies were used to maintain constant current to within ItO.l%. A single, type T copperkonstanton thermocouple was used to monitor the cell temperature. It was placed in a thin-walled glass tube located near the longitudinal central section of the cell but outside of the platinum anode winding. The temperatures inside the cell and in the bath were measured and used to develop the calibration curves to evaluate the power output level. Thermal calibration was done by performing electrolysis at different power levels as well as by using an internal heater. Figure 2 illustrates the steady state temperature of the cells at different input power levels. Figure 3 illustrates a typical calibration curve where temperature difference between cell electrolyte and the bath is plotted against input power. The rapid thermal response of this cell is shown in Figure 4.

Cell temperatures were measured at a single location. At the time, this assumed adequate because vigorous stirring by evolving gas bubbles resulted in fairly uniform temperatures. Off gases were vented to a hood. In some tests there was provision to collect D2 through the central annular tube using a Nafion membrane separator and 02 through a valved tube in the glass top. However, in most of the experiments, no attempt was made to separate the gases. D20 additions were made at regular intervals.

To determine the extent of stirring, fluid/gas bubble velocity measurements were made within the cell under typical operating condition at a current of 1A. Laser Doppler measurements of bubble velocities in the cell demonstrated excellent stirring, resulting in a temperature distribution within kO.5"C over the length of the cell. The greatest deviation was near the bottom one cm. of the cell where poor mixing occu rred.

1-190 Calibration Curve for Cell #2

Temperature at middle

a, L -+3 Temperature at bottom U L a, CT E a, I-

Bath temperature Bath temperature away from cell near cell

Figure 2. Cell Temperature-Time profile at power input levels of 10-50 Watts. w- u t z ttw tt E

SUVM ‘LndNI XIMOd

1-192 50

Temperature at middle

40 LQ) emperature at top -+3 U L 2 0 I 2 a E erature at bottom 0 I- I- 30

20 0 Time (sec)

Figure 4. Cooling cuwes for cell configuration 1 from 42°C to room temperature Lithium concentration, electrolyte conductivity and pH were monitored periodically. The Li concentration was measured using DCP analysis. The Li concentration and the cell conductivity were found to decrease gradually over a period of two weeks resulting in a gradual increase in voltage. Li loss was presumed to occur by the formation of Li carbonate deposits observed within the cell and to a small extent by reaction with the cathode.

Several experiments were performed using 6 cells of this type over a 6 month period. Table 1, Appendix I summarizes the results from experiments conducted with these cells. Cathode metals tested were 99.9+% purity palladium from Johnson and Matthey, 99.99+% palladium from Metalor, titanium from Johnson and Matthey and nuclear-grade zirconium from Western Zirconium (Westinghouse). However, most of the attention was focused on Pd. The experimental variables included: the form of the platinum anode, anode to cathode surface area, anode to cathode distance, separation of deuterium and oxygen using a Nafion 117 cation membrane, preloading of deuterium under high-pressure deuterium gas, annealing at 600°C and 900°C, surface treatment by acid etching and Pd black deposition (in PdC12-LiCI-D20 solutions) and the use of a Pd anode.

2.1 -2. Temperature Excursions Observed in HHT-A Cells: Over an extended period of time, several temperature excursions above the normal operating temperature of the cell, were observed. All of the cells in which temperature excursions were observed had Pd cathodes. Some of these experienced mild to strong explosions. Temperature excursions associated with some of these events were dismissed as being due to deuterium/oxygen recombination. During the third week of May, 1989 a large temperature excursion of about 12°C was observed in cell 3, Figure 5. The cell temperature rise lasted about 90 minutes. The temperature-time profiles showed a similar pattern to an earlier temperature excursion in the same cell during a previous run (Figure 6). This particular cell was operating at constant current mode at a current setting of 0.95 amperes during the heat excursion shown in Figure 5. The voltage was recorded continuously while the current was manually recorded. The temperature excursion was interrupted by the addition of make up D20. Assuming a temperature distribution of kO.5"C and a low limit calibration value of 2.5 watts/"C for the cell constant (a low bound value typical of this set of cells), the estimated power output was calculated to be about 38 watts and the excess energy generated during this event about 220 KJ. However, there is concern that the voltage

1-194 QO* n cv v) a U Ea 0 -w 0 v 'i cv .-C - BL a I n .8 S 0 0- C .-0 E 2 W 7 .. $? . a .-E .. I-

r z 8 a . v)

1-195 nln

C n c BL 0- a EB

0 0 0 0 0 d (D In * r) cv P

1-196 drop observed is smaller than expected to match the large rise in cell temperature. This observation is discussed in detail below.

During the burst shown in Figure 6, the cell was operated in a constant voltage mode and the voltage and current readings were manually recorded. Explosive popping of the cell interrupted the large heat burst and dislodged the electrodes. The cell was reassembled immediately and the cell temperature remained at a level well above the normal values corresponding to the gross power input to the cell (about 9.6 watts). Thermal calibration curves for nearly identical cells were in the range of 2.5-3.5 W/"C. Assuming a temperature distribution of f0.5"C and a cell constant of 2.5 W/"C, estimated power output would be around 70 watts during the 40 minute excursion followed by about 22 watts output during the following 30 hours. The power input was less than 10 watts. The excess heat generated during this event would be around 1 MJ. No credit was taken for the dissociation of D20 (1.54 V current). This level of energy output could not be explained by simply burning all the deuterium stored in the Pd cathode. The heat of solution of deuterium in palladium, or the heat of formation of PdDx would be much smaller. Since only one thermocouple was used, it was not possible to eliminate completely the possibility that strong thermal transients occurred, promoted by sporadic recombination events, during the apparent excess heat excursion.

To check the possibility of storing energy in the solution in the form of peroxide solution analyses were performed. Analysis of electrolyte samples from all the operating cells showed peroxide concentration was less than 10-4 moles/cm3 as expected from the instability of peroxide under high cathodic over-voltage conditions. The tritium level in the electrolyte after electrochemical degassing of the electrode, for the cell had the 90 minute heat burst, were checked by 3 different laboratories. The level of tritium was found to have increased by a factor of 3-4 over the starting solution. The same electrode (JM 2, Johnson Matthey, 99.95% Pd) was used in the above tests where the two heat bursts were observed. The heat treatment involved annealing at 600°C in an ultra high purity argon atmosphere.

Figures 7 and 8 show two consecutive bursts in the same cell using a high purity Pd rod, (Electrode #5, from Metalor, USA). Figures 9a & 9b illustrate two other temperature excursions observed under constant current conditions.

1-197 QO

n S *- E W .-E" I-

1-198 n .-c .-C E W .-E I- I-

0 00

1-199 32

20 0 400 800 1200 1600 2000 2400 Time (min)

W> l1 Q) m 0 2i 10 >0 U .-Q) 9E a Q 25__ 0 250 500 750 1000 1250 1500 1750 2000 Time (min)

Figure 9. Some of the other temperature excursions obsetved in the first set of cells

1-200 2.1.3. Analysis of Heat Bursts Observed in HHT-A Cells (Figures 5, 6 and 7): In the past year, no large heat bursts were observed in more than 30 cells in which the cell sensitivity had been improved (as discussed in later sections) and multiple temperature sensors have been used. Changes in electrode material, electrolyte used or operating conditions have resulted in the disappearance of these heat bursts.

There is the possibility that the early recorded temperature excursions may be due to localized high temperatures in the vicinity of the thermocouple resulting from spontaneous D2/02 recombination events. It seems likely that changes in the flow pattern within the cell may result after initiation of burning (recombination) in the top section of the cell on the surface of the exposed surface of the cathode. Flow patterns were determined with a Laser Doppler anemometer (Figure 10) under uniform operating conditions, during which time no recombination occurred.

To simulate localized high temperatures, resulting from recombination in the top section of the cell, resistive heat sources of different geometries were placed near the top section of the cell electrode. The temperature changes in different sections of the cell were monitored. Different geometries tested were:

(i) Cylindrical coil heater 5 cm in length placed around the cathode.

(ii) Cylindrical coil heater with a diameter of 4 mm and length of 1 cm placed centrally; (a) just above and (b) just below the electrolyte level.

Power input to the coil varied from 1 watt to 46 watts and the temperature distribution was measured with and without air bubbling to simulate gas evolution at the cathode. These indicated that with gas bubbling, even at 46 watt level heat input, temperature variation was less than about 5°C in the axial direction. Figure lla shows temperature versus time in seconds at the top, middle and bottom sections of the cell during a power input of 46 watts using heater coil arrangement (i). The temperature in the top and middle were within 1°C of each other and the temperature in the bottom section was about 5°C less resulting from poor stirring and larger heat removal through the bottom face of the glass vessel. Figure llb shows the temperatures in different sections of the cell with a power input of 26 watts using coil configuration (iib). The top and middle section thermocouples follow each other

1-201 aEcTRoty= b LEVEL 41PEDESTAL

/GLASS ROD /

I..... I..... 1 PEDESTAL

Figure 10. Gas bubble velocity profile measured using Laser Doppler technique.

1-202 45

0u 35

Power Input: 46 W Coil Config. : i

45:

40 3 Gas Bubbler On Gas Bubbler Off

20 : 3 Power Input: 26 W I Coil Config. : ii b

1-203 closely but on stopping the gas bubbling, the temperature variation was as high as 25°C.

In another set of experiments, the effect of radiative heat transfer to the thermocouple from a burning hydrogen flame in the vicinity of a thermocouple, immersed in the electrolyte, was investigated. The results are shown in Figure 12. No appreciable increase in temperature was observed as long as the thermocouple was immersed in the electrolyte.

It is possible that all of these tests may not have reproduced the temperature distribution and flow patterns in the cell during the temperature excursions observed. A condition may have resulted in which simultaneous loading (electrochemically) and unloading (recombination) of the cathode occurred. If the flow of bubbles was seriously interrupted, large temperature gradients could result.

As noted earlier, the voltage drop observed in Figure 5 is small compared to the drop expected from the increase in temperature of the electrolyte. Figure 13 illustrates that the voltage drop with increased electrolyte temperature was around 0.19 V/"C while the heat burst. While changes in the conditions at the interface may account for a smaller the measured drop was about 0.2 V for a temperature increase of more than 12°C during than expected voltage drop, high temperatures over a small section of the cell with the remainder of the cell at a much lower temperature also could result in such a a voltage profile. The total current passing through the cell was held constant and the presence of hot and cold regions would therefore result in a fraction of the current passing through the hot region. This would lead to high current density in the section of the electrode at a higher temperature. This non uniform current flow pattern would complicate the estimation of both the temperature distribution and the variation in cell voltage for theoretical considerations. Also the large variation in cell temperature sensed by the thermocouple suggests the presence of temperature transients in the cell. Also the initial drop in temperature observed on many of these temperatures and a small initial increase observed prior to the heat burst &em again to arise from the transient fluid flow conditions that bring in warm or cold packets of fluid past the thermocouple. The above arguments based on temperature transients can explain most of the bursts observed. One exception appears to be the burst illustrated in Figure 7.

1-204 Flame Effect on Thermocouples H2 flame, 6-12-90 a: Bare thermocouple b: In 3mm water-filled glass tube c: TC 'immersed 2cm in 3cm water-filled tube

0 0 lIIIIII1 11111l111~111111111~1lll1llIl/llllilll1~111111111~ Q.60 2.60 4.00 6.00 8.00 10.00 12.00 Distance, cm

Figure 12. Effect of H, flame in the vicinity of a type T thermocouple.

1-205 9.20 I

9.10 ?lrlllliilil~l~,~lllI,,, IIIIIIIIIIrl 1,,,~,',',11,,,,,,11 111',111,, I,I,,,# 29.00 29.50 30.00 30.50 31.00 31.50 32.00 32.50 33.00 33.50

TEMPERATURE, OC

Figure 13. Cell voltage in cell 1 as a function of cell temperature.

1-206 The temperature excursion illustrated in Figure 7, though much smaller in magnitude than previous bursts, is accompanied by a voltage drop (about 0.4 V for 2 degree rise) comparable to that anticipated from Figure 13 (0.19V/1 degree rise). This suggests that the temperature of the cell is fairly uniform and the measured temperature is representative of the entire cell despite the use of a single thermocouple measurement. If there had been no abrupt change in the cell constant, the excess power generated would be about 5 watts and the total excess energy generated during this period would be around 54,000 J which would be quite significant. Of all the temperature excursions observed this result appears to be the most consistent and difficult to explain away.

2.2 Single Wall HHT-B Cells

2.2.1. Cell Configuration, HHT-B Cells. (Cell Constant 5 watts/"C): This configuration (Figure 14) also had a single quartz wall cell placed in a stirred constant temperature Neslab bath maintained within 0.01 "C of the set temperature. The cell temperature was measured using three Type T thermocouples in the top, middle and bottom section of the cell electrolyte region. InternaVexternal recombination of deuterium and oxygen from the electrolysis was done using a PrototekR catalyst on a nickel screen mesh. The temperatures inside the cell and the temperature of the bath in conjunction with calibration curves are used to measure the power output level (Figure 15). The cell constants for these cells were about 5 W/"C and the thermal relaxation constants were about 90 seconds. The Neslab bath temperature can be varied from -20 to +50 "C. Each bath accommodated 4 cells. D20 addition was made either continuously using syringe pumps or manually at regular intervals. The cells were all operated in a constant current mode. The cell operation was automated both in D20 addition and data recording. Temperature, voltage, current and other signals were sampled every 10 seconds and recorded every 1 minute. When sudden changes in cell operating conditions were sensed, recording then occurred every 10 seconds.

2.2.2 Operating Results: Figure 16 shows the operating cell data for HHT-B Cell 9. Each point corresponds to an average temperature and power input data for a period during which the cell was operated at a given current level. Figure 17 includes operating data when cell currents were changed frequently (every 12 or 24 hours) to introduce transients. After one of these current level changes from (1 A to 2 A), the temperature of the cell was about 1.8"C (about 7.6 excess watts) above the expected

1-207 Gas Outlet TC i :3 Continuous Metered "D20 Addition with 1 Syringe Pump

c I I c C P c U C c A. I I Electrolyte Level 4

4 Tef Ion Anode Cage A- I Support (top) I -Top Thermocouple Middle Thermocouple Gloss Rod in Thin Walled Quartz Tube Platinum Anode Gauze/Winding

Gloss Tube for Water Bottom Thermocouple Addit ion Polladium Co thode Teflon Anode Cage - Rod Support (bottom)

Figure 14. Electrolytic cell configuration 2

1-208 30i

TEMPERATURE DIFFERENCE, OC

Figure 15. Cell calibration cuwe for cell HHT-B-9 TEMPERATURE DIFFERENCE, OC

Figure 16. Cell operation data for cell HHT-B-9 TEMPERATURE DIFFERENCE, OC

Figure 17. Cell operation data for cell HHT-B-9 showing possible excess heat generation value suggesting excess power production during this period. No excess tritium was seen in this cell. The results were analyzed by scientists at General Electric Company. Their analysis concluded that the experimental results fell within the error range dictated by the small temperature variations within the operating cell. Their analysis did not support excess heat generation.

During this phase of experimentation, procedures were dominated by the perception that long term loading and high current densities were required to achieve a required D/Pd ratio above a critical value; namely, D/Pd ratio >1. Electrodes were used for extensive periods of time and at high current densities. Frequent changes in current densities, always maintaining current densities above 100 mA/cm2, were made during later phase of cell operation to check if the excess heat release may be associated with transient effects. With microscopic evidence of extensive microcracking and plastic deformation during loading, attempts to minimize these effects were made by generating extremely low surface pressures initially, followed by progressive increases in current density at appropriate intervals. Microcracks in the near surface can reduce effective current density as well as introduce differences in surface D pressures from one region to another, resulting in a lower loading ration.

2.3 Double Wall MHT-A Cells

2.3.1 Cell Configuration, MHT-A Cells: In this configuration an intermediate water jacket between the cell and bath was used to decrease the heat transfer and increase cell sensitivity. The MHT-B cell below is identical except the water jacket was replaced with an acrylic jacket. When operating the MHT-A cell, the level of the fluid in the annular jacket was maintained at the same level as that of the cell electrolyte. Continuous D20 addition to the cell was made using syringe pumps. The cell constant of about 1.4 W/"C was maintained for over a period of two months, and the cell thermal response, though nonlinear, was highly reproducible.

2.3.2 Calibration Curves and Operating Data (MHT-A Cells): Figures 18 and 19 show calibration curves and operational data for one of these cells (MHT-B cells 9 and 23). Four of these cells were operated over a period of 4 months. Current level changes, low temperature annealing of electrode, Pd black coating on the cathode, low pH and As poisoning of the cathode were the variables tested during this period. Appendix I, Table 3 lists experiments carried out in these cells.

1-212 w

TEMPERATURE DIFFERENCE, OC

Figure 18. Cell calibration and operation data for cell MHT-A-9. TEMPERATURE DIFFERENCE, OC

Figure 19. Cell calibration and operation data for cell MHT-A-23. The calibration curve is nonlinear because of a larger component of convective heat transfer in the effective cell constant. With increasing temperature difference between the cell and the bath, this contribution becomes larger.

2.4 Double Wall MHT-B Cells

2.4.1 Cell Configuration, MHT-B Cells: To eliminate the nonlinearity, the intermediate water jacket was replaced by an acrylic jacket (see Figure 20) to improve sensitivity and to obtain a linear temperature response. The tight-fitting acrylic jacket tube with a wall thickness of 3 mm reduced the effective heat transfer coefficient into the range of 0.5-0.8 watts/"C. The cell relaxation time constant was about 5 minutes. The temperature variation within the cell was reduced to about 0.25"C. This sets the limit of detection of excess heat output at 250-400 mW. The lower cell constant results in an increased cell temperature for a given current density level. Using a lower operating bath temperature of 5 or 10°C and smaller electrodes served to offset this increase to a large extent.

2.4.2 Calibration Curves and Operating Data (MHT-B Cells): Most of these cells were started up in the first week of March, 1990. Calibrations of these cells were done on a continual basis. Calibration curves for two of these cells are shown in Figures 21 and 22. These cells had a relaxation time of less than 10 minutes. Table 4, Appendix I, lists the experiments carried out in these cells. The initial loading was done at extremely low current densities sufficient to iniate D loading of the Pd rod. The current density and overvoltage conditions required were determined in a separate dilatometry experiment. The initial current density was less than about 8 mA/cm2 and after a few days raised to 25 mA/cm2 and to 60 mA/cm2 and then to about 400 mA/cm2- No excess heat effects were observed. Bath temperature, and therefore the cell temperature, were lower during the first phase of operation of these cells. No effect of low cell temperature on excess heat generation was observed. Subsequently, the bath temperature was raised to 22°C for additional experiments.

The effects of the addition of noble elements such as Cu and Ag as well as reactive metals such as Ce and Li to Pd were tested. Electrodes from 3 different sources, as well as in-house prepared Pd electrodes, were used. The effects of small and extremely large grain size (mm range), obtained by low and high temperature annealing, and cold working were evaluated. In none of these cases was there any clear evidence of excess heat generation above the detectability limits of these cells.

1-215 D20 Inlet 1 TC1, 0 TC2

E Iec t roly te Top Level

Quartz Cell Tube

Internal Callbration , 01s Support Rods Heator

Teflon Bottom \ Glass Support PT Anode Wire Cago

Tof Ion Bottom Support

Figure 20. Electrolytic cell configuration MHT-B

1-216 28.00

/- n 3 -24.00 / L al 3 2 20.00 + 3 (1 +J 16.00 3

Figuie 21. Cell calibration curve for cell MHT-6-45 9.00

8.00

7.00

6.00

5.00

4.00

3.00 t

2.00

1 1 .oo ~"""'ll~ll~lll111~l~"lilii~ilillllll~lllllllll~lllli1111~11111,11111,111111111,1111 I I I I I I I 1'1 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00

TEMPERATURE DIFFERENCE, OC

Figure 22. Cell operation data for cell MHT-B-55. Figures 23, 24 and 25 present operational data on three cells operated with bath temperatures of 5,lO and 22°C. Each data point refers to the ratio of power input to the temperature difference averaged over a 24 hour period. During each of these periods, no unusual excess heat events were observed. Variations observed in this ratio of power input to temperature difference were very small over extended periods of time. The observed variations in this ratio set the detectability limit for excess heat generation above +2%. The temperature variations were within f 0.25"C and the cell constants are in the range of 0.5-0.8 W/"C. This sets the lower limit of detection at about 250-400 mW at power input levels of 6-10 watts.

2.5 Fieischmann-Pons (FP LHT) Type Cells

To detect low level excess heat production, it was decided to switch over to FP cells which have high sensitivity, are relatively inexpensive, and have been well characterized by Professors Pons and Fleischmann. In September, 1990, Drs. Pons and Fleischmann provided two of their prototype cells to the Metallurgy Group for testing. The principal characteristic of these cells are: a vacuum jacket around the cell and a silver coating that covers the cell from the top leaving open about 5 cm at the bottom. A set of calibration experiment and two sets of electrolysis experiments were carried out. In each set of electrolysis experiment a pair of cells, one using light water and the other with heavy water, were run under otherwise identical conditions.

2.5.1 Determination of the Heat Transfer Coefficient (FP LHT Cells): The purpose of the calibration experiment was to determine the radiation heat transfer coefficient which is so critical in the evaluation of excess heat. The electrolysis experiments were run in pairs to observe temperature differences between the cells, hopefully leading to conclusions about heat effects based on observed temperature differences. The internal details of the cell can be found in Pons and Fleischmann's reports.

In both the electrolysis and calibration experiments, the cells were started with 60 cc of LiOD or LiOH. The cell temperature was measured using a thermistor calibrated to 0.001"C accuracy and the recorded temperatures (via the data acquisition system) are accurate to 0.01"C. A Hitek potentiostat was the source of constant current. The cell voltage was measured by a Keithley 199 Scanner. Every 300 seconds, the data acquisition/personal computer system recorded current, voltage, cell temperature and bath temperature. Every twenty-four hours the cells

1-219 .*

t ..

&ISLLVM ‘LV / LndNI IIBMOd

1-220 . .. t

t .t 0. t . t t it t t t

t 0 .r * t t. *. t t

t t t

0 t .t t t t t 0. . .t

0 0 0 0 O0 03 co d- cv 0 0 0 o 0 0 3oIS.L.LVM 'LV / LLndNI EIMOd

1-221 *I ***+*I**** * ********* **

20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00

TIME, DAYS

Figure 25. Cell operation data for cell MHT-B-55, 22°C operation. were replenished with 3 cc D20 or H20. Both cells contained a 4-mm diameter and 25-mm long palladium cathode and platinum wire anode.

Hereafter the radiation heat transfer coefficient will be referred to as the radiation coefficient. The radiation coefficient is only an overall heat transfer coefficient because this term approximates the heat loss both by convection and radiation. However, the value of this coefficient very much determines the excess heat generation (see Kalman Filter Report, R. K. Rajamani). Since the determination of the radiation coefficient is for computing excess heat generation, this coefficient should be determined in an experiment where these is no possibility of excess heat. Hence, light water electrolysis was chosen for this purpose. However, it is possible simultaneously to estimate the radiation coefficient and excess heat from a D20 experiment data set, but the interpretation of radiation coefficient always leaves unanswered questions. The use of light water assures that excess heat production is zero and hence the estimated value of the radiation coefficient is unique.

A cell was filled with 4.533 gm-moles of LiOH and the normal electrolysis procedure was followed. Initially, the current input was set at 0.55 amperes and the cell was monitored for an additional 28 hours.

A description of the Pons and Fleischmann model of the electrolysis process is included in the Kalman Filter Report (R. K. Rajamani). This model contains thermodynamic constants and the radiation coefficient. If these constants are known, the model can accurately predict the temperature evolution of the cell with time. Since the thermodynamic constants are readily available, the model can be forced to match the observed temperature - time profile by searching for the value of the radiation coefficient that produces the best match. In other words, the sum of squares of the difference between experimental and model predicted cell temperature is minimized by searching over possible values of the radiation coefficient,

minimize (over Kr)

The minimization was done over two hour periods of the data set. Table 2.5.1 lists the radiation coefficients determined in this study.

Caution should be exercised in using the numerical value of the radiation coefficient. The heat within the cell is carried by natural convection currents to the

1-223 Table 2.5.1. Radiation Coefficients Determined from tight Water Cell Data

Time Mid-period Current Radiation interval temperature amperes coefficient seconds oc W K-' 0 - 6899 67.0 0.55 5.55 x 10-'O 6899 - 13,799 71 .O 0.55 5.60 x 10" 13,799 - 20,699 71.9 0.55 5.58 x lo-'' 20,699 - 27,599 72.3 0.55 5.60 x 10'" 27,599 - 34,499 72.7 0.55 5.58 x 10" 34,499 - 41,399 73.4 0.55 5.59 x 10-'O 41,399 - 46,199 74.1 0.55 5.59 x 10'O (clock reset to zero here) 0 - 6,899 62.5 0.4 5.53 x 10"O 6899 - 13,799 60.0 0.4 5.57 x 1o1O 13,799 - 20,699 58.8 0.4 5.55 x 10'O 20,699 - 27,599 58.5 0.4 5.55 x 10'O 27,599 - 34,499 58.4 0.4 5.54 x 10'O 34,499 - 41,399 58.4 0.4 5.53 x 10-'O 41,399 - 48,299 58.4 0.4 5.53 x 10'O 48,299 - 55,199 58.6 0.4 5.53 x 10'O 55,199 - 62,099 59.2 0.4 5.52 x 10-l' 62,099 - 68,999 60.1 0.4 5.50 x 10'' 68,999 - 75,899 62.5 0.4 5.48 x 10'' 75,899 - 82,799 64.4 0.4 5.48 x 10-'O 82,799 - 89,699 67.0 0.4 5.46 x 10'' 89,699 - 96,599 68.8 0.4 5.46 x 10'"

1-224 wall, the wall in turn transmits heat by conduction to the outer surface of the wall, then by radiation heat reaches the outer jacket wall. After this conduction path, heat is dissipated into the bath water both by convection and radiation. In the model, all of these paths of heat transfer is represented by the term,

Heat Loss to the Bath = Kr which implies that this term is an empirical approximation. In view of this fact, the radiation coefficient would depend on the nature of the temperature excursions within the cell. Yet, the validity of the calorimetry depends on this constant. Many more experiments of this nature are needed to gain complete confidence about this coefficient, but time did not permit this to be pursued further.

2.5.2 Electrolysis Experiments (FP LHT Cells): The purpose of these experiments was to see if there is any significant difference in cell temperature due to excess enalhalpy generation in the cell. For this study, a pair of cells, one with D20 and the other with H20, were run in series under identical conditions. The light water cell is not expected otherwise to produce any heat at all and if the running temperature of the D20 - cell is higher than the H20 - cell, it is solely due to excess heat generated in the D20 - cell. There are other factors that can mitigate this expectation; nevertheless, as a first approximation, a temperature difference would be expected. The first pair of experiments was done at 0.4 ampere current following the normal experimental procedure. Daily recordings of key variables are shown in Figures 26 through 29.

There is a difference of 2OC between the two cells most of the time which indicates that in terms of cell energetics the D20-cell behavior is similar to that of H20- cell, so it was concluded that there was no significant heat production in the D20-cell. This was further confirmed by Kalman Filter Analysis presented in Fig. 30. Using a radiation coefficient of 5.84 x 1O-lo WK-4 the excess enlhalpy generation was close to 0%. There was a general consensus that the radiation coefficient is 5.84 x 10-10 rather than the value of 5.55 x 10-lo measured in the calibration experiment. Hence, the higher value was used. The use of 5.55 x 1O-lo would have resulted in negative heat generation. The same figure shows a 13% heat generation when the radiation coefficient is set at 6.86 x 10-10 WK-4. This shows how much the results of calorimetry depend on the value of the radiation coefficient.

1-225 Te m perature ...-..-..-..- Voltage

I I I I 1 I 1 I 0 100000 200000 300000 400000 Time (sec) Figure 26. Temperature and cell voltage recorded during the 1-5 day period for the D20cell. [Cell current 0.4 A, bath temp. 30°C] I 1 1 I 1 I I I 07;

0 oc m Temperature ...- .- _..- Voltage

8 t

’Q) 0 0 -+J >0 - Q) 6 0

1 I 1 I 1 I 1 I 5 0 100000 200000 300000 400000 Time (sec)

Figure 28. Temperature and cell voltage recorded during the 1-5 day period for the H20cell. [Cell ourrent 0.4 A, bath temp. 30°C] Temperot u re .----Voltage -- r .. % c

20 ’ 1 1 1 1 I 1 0 100000 200000 300000 400000 Time (sec) Rgure 29. Temperature and cell voltage recorded during 6-10 day period for the H20cell. [Cell current 0.4 A, bath temp. 30°C] 1.o

0.8

0.6

0.4

13%

------* 0%

-0.6 '

-0.8

. 1 a . 1 1 1 . a -1.0 I I I I I I a 1 I J 4 0 2 4 6 0 10 12 14 16 18 20 22

Figure 30. Kalman filter analysis of D,O cell data. [Cell current 0.4 A, bath temp. 3o0C] The second experimental - pair was run at 0.5 amperes. The cell temperature - time history of the D20-cell was quite unusual. It was expected that the cell would level off somewhere in the 60-70°C range, but the temperature continued to rise rapidly. As seen in Fig. 31, the cell reached 80°C in 6 hours and after the seventh hour the cell entered boiling conditions. The cell temperature was 90°C+ during the last six hours. Actually, the cell content was boiling and the recorded temperature was at 90°C due to a calibration limit imposed in the data acquisition program. What is even more interesting is the recordings of the cell voltage. In the first 6 hour period it was about 10 volts; then, it increased to 24 volts in the next four hours. In the last 2 hours, it went as high as 80 volts. Conversely, throughout the 12 hour period, the LiOH cell ran at 64°C and 10 volts.

In view of this drastic difference in cell temperature between the D20-cell and the H20-cel1, it is tempting to conclude that there was substantial excess heat production in the D20-cell; but this is not the case. Unfortunately, the Kalman Filter Analysis cannot be used under these extreme transient conditions. The model of the cell includes only evaporation terms, i.e., a term for D20 vapor saturated at the temperature of the cell, leaving with D2 and 02 gases, but not a boiling mass transfer term. In other words the model cannot quite predict the amount of LiOD liquid in the cell correctly. Therefore it was necessary to do an approximate analysis of this data. In this analysis the energy input was balanced with energy required to evaporate all of the LiOD and the energy lost by radiation. Even though the liquid level kept dropping in the cell during the 12 hour period, it was assumed that radiation occurred at the cell temperature through the entire area of the cell to the bath. Table 2.5.2 describes the calcu lat io ns.

This analysis assumes no recombination. If as much as 27% recombination had occurred, the calculated excess enthalpy would be zero. Also, the calculated excess enthalpy is sensitive to the radiation cell constant used. For example, if 6.8 x 10-lo WK-4 is used, then the energy dissipated would be 275,877 joules and the calculated excess enthalpy would be approximately 13.5%. Therefore a 17.2% increase in the radiation coefficient will change the calculated excess enthalpy by a factor of 5.6 fold.

Local heat generation in the cell is another matter that should be explored. In all of the analysis reported here, it was assumed that there are no temperature gradients across the cell. In other words, heat is generated within the Pd-electrode

1-231 Tempera ture .----Voltage

-8

n 0 60 W 0 L 3 -c, 0 L Q) 50 A Q wr;J E lu Q) I- - 4 Q) 40 0 3

I 1 I I 1 I I 30 1 I iI:, 0 10000 20000 30000 40000 50000 60060 Time (sec) figure 31. Temperature and cell voltage recorded during 12 hours of D,O cell operation. [Cell current 0.5.A, bath temp. 30°C] Table 2.5.2 Approximate Heat Balance for D,O-cell (inputs indicated as positive and outputs indicated as negative terms)

Energy input during 12 hours 400,561 joules (voltage x current x time) Energy dissipated in -33,360 decomposition of LiOD (1.5 x current x time) Energy required to raise LiOD 15,751 temperature from 3OoC to boiling temperature (mass x specific heat x temperature difference) Energy required to convert LiOD 125,019 liquid to vapor (mass x latent heat of evaporation) Energy dissipated by radiation 235,307 (5.8 x x ($cell - $bath) x time Excess enlhalpy generation 8,876 (2%)

1-233 and due to this the temperature of the electrode increases uniformly everywhere. However, heat generation in a localized spot would set up convection currents and the thermistor would register the temperature of these currents. If it registers the hotter temperature, say due to its location in the cell, then the actual excess energy would be much less than calculated values. The gas bubbles in the cell produces good mixing, and so to a good approximation the cell temperature is uniform everywhere.

3. Nuclear Product Monitoring

Tritium in recombined and cell electrolyte were periodically monitored in all the cells. On two occasions, factors of 3-4 enhancement in the tritium level were found associated with two of the observed heat bursts. However, these are not considered significant due to the pitfalls associated with T monitoring. Occasionally, some of the cells were monitored for gamma rays and X-rays using Ge, SiLi, and Nal detectors. No evidence of nuclear product generation was obtained during the time monitoring was performed.

The nuclear monitoring capabilities of the Physics Group at NCFI included (a) A 4" x 8" diameter sodium iodide crystal with associated electronics providing a sensitivity for the measurements of all gamma rays with energies in the range 0.5 MeV to 25 MeV, (b) a HP Ge detector with associated power supplies, amplifiers and multichannel analyzer, providing high resolution measurements of gamma rays in the range of 5 keV to 10 MeV (this system complements the sodium iodide detector, having a lower efficiency and a higher resolution), (c) A Si(Li) detector with the capability of measuring x-rays with energies between 1 keV and 60 keV and (d) A neutron spectrometer with large-area cosmic-ray veto counters to make low-level neutron studies possible. A Beckman scintillation unit capable of automatic measurement of several hundred samples per day were used for routine tritium monitoring of the cells. Nuclear products were never detected conclusively or reproducibly as a result of repeated attempts to measure such products during the multitude of electrolysis experiments conducted in this study.

4. Discussion and Conclusions

Parameters that were considered potentially important for generation of excess heat were: (i) the D/Pd ratio, (ii) current density and the rate of loading, (iii) electrode purity/composition, (iv) electrode microstructure, (v) temperature, (vi) electrolyte purity

1-234 and (vii) voltage and thermal transients during loading. Over 40 experiments were carried out in the three types of cells described earlier. The parameters listed above were examined in part in each of the three cells. Since some runs were extended for weeks and in some cases months, it was not possible to consider all variables in each type of cell. In the FP LHT cells, only a Johnson Matthey proprietary Pd alloy was used in an as-received condition.

4.1 Loading level

Loading of D to a level where all tetrahedral sites are occupied was initially considered a prerequisite to initiate fusion of D atoms. Loading therefore was carried out in the final loading stages at high current densities. Also, in some experiments the surface area of the Pd electrode surface was increased by the deposition of Pd black to facilitate loading. No apparent beneficial effect was observed. There was uncertainty in the time required to fully load the material because of the lack of information on diffusion coefficients in a highly loaded electrode. Estimates based on diffusion coefficients in a-Pd and t3-PdDo.7 (in the range 10-7 to 10-5 cm2/sec) suggested that loading times should be less than 4-5 days for a typical rod diameter of 4 mm. In the absence of clear knowledge about the diffusion coefficients at high concentrations of D in Pd, uninterrupted long term loading was carried out. In-situ measurement of dimensional changes in the electrode during loading with current densities greater than 100 mNcm2 in 0.1 molar LiOD indicated that loading of a 4 mm rod was complete in about 3-4 days. The loading ratio (D/Pd ratio) achieved during these experiments were between 0.8 to 0.98. A maximum value of 0.98 was observed for two experiments involving a Pd-5%Li alloy. Loading ratios in excess of 1 were never attained.

4.2 Metallurgical Parameters

The role of the structure of the Pd in catalyzing the proposed fusion reaction was not clear. Possibilities that fusion of D-D may occur at some or all of the lattice defect sites such as vacancies, impurities, dislocations and grain boundaries were considered. Grain size was varied from about 40pm to several hundred pm by annealing at 600°C to 1250°C. Differences between cold worked and annealed electrodes were explored. It is important to note that even an annealed electrode is heavily deformed during loading of D in Pd and therefore has a very high dislocation density. Deformation observed after loading was significant, even though loading was

1-235 done at extremely low current densities. Gradual loading of the Pd rod, initially at low current density and then at increasingly higher current densities, was followed as a standard procedure to minimize deformation during the loading process. No excess heat effects were observed following the above treatments.

During handling and treatment, care was taken to remove H, N, C and 0, all of which compete with D for the octahedral sites of the Pd lattice. This was achieved by remelting the Pd, annealing under high vacuum conditions and keeping the electrodes under UHP argon cover prior to use. Palladium for three different sources, Johnson and Matthey, Metalor and Hoover & Strong were utilized. The Hoover & Strong is essentially recycled Pd, Johnson & Matthey Pd is primarily of South African origin while Metalor Pd is of Russian origin. The impurity type and levels and processing conditions were expected to be different. Limited experiments were performed to determine the effect of alloying with Ag (25 atomic%), Cu (10 ab/,) and deuteride formers such as Li (-5 a% and 500 ppm levels) and Cerium. These studies failed to demonstrate any correlation between electrode metallurgy and excess heat generation.

4.3 Special Operating Conditions

In addition to the standard operating conditions outlined earlier, special modes of operation were introduced. Examples are the introduction of voltage and temperature transients, pulsed current (2 minute cycles), use of Li2SO4 electrolyte and low bath temperatures. These biases were all experimented with so as to initiate excess heat events. No excess heat was observed in the limited number of experiments done on several different materials. The large number of variables involved make it difficult for make a definitive statement on the influence of each of the variables introduced on cell operation. Particularly is this true in the absence of the excess heat phenomenon.

4.4 Summary of Cell Results

Except for the thermal characteristics of the cells, the electrochemical conditions for D loading were similar in the three types of cells examined in this study. Evidence for possible excess heat generation was in the form of large temperature excursions observed during an early phase of experimentation in single wall cells. These cells were characterized by high heat transfer coefficients and rapid thermal response.

1-236 Inherent in this design was the possible formation of thermal transients throughout the cell. With the exception two results (in the same cell), the large heat excursions could be attributed to the presence of thermal transients within the cell during operation. During subsequent operation of these cells and other more sensitive and refined cells, there were no indications of excess heat generation above the sensitivity limits of the cells used.

Large scale temperature excursions that were observed in the first type of cells were most of the time accompanied by or associated with D2-02 recombination explosions. The exposed electrode surface near the top of the electrode and exposed Pt lead wires could catalyze the recombination reactions intermittently. The effect of these recombination reactions on the temperature distribution in the cell and therefore excess heat measurements need yet to be looked into in greater detail. Exposed electrode surfaces, above the electrolyte in some of these tests, may have acted as sites for leakage of the D charged into the submerged regions of the electrode. We cannot eliminate the possibility of recombination of this D2 with 02 on a continual basis or intermittently during observed heat bursts. It was found that the electrolyte balance during operation indicated negligible recombination; however, no such measurements were made during the heat excursions themselves. The steady state power output from the recombination reaction would be about 1.5 watts (about 15-20% of the power input) and the temperature increase in the bulk of the electrolyte would be a fraction of a degree if the temperature distribution was uniform. However, under extreme conditions, it is likely that this may result in a high temperature region in the top section of cell electrolyte, that might be sensed differentially by the thermocouple.

Separate experiments were carried out to evaluate the effect of differential temperature regions within the cell. In these experiments as much as 26 watts was input using a small heater coil in the top section of the electrolyte. This was done while gas bubbles, simulating actual operation, were introduced into the bottom of the cell. Under these conditions, only a few degree difference in temperature of different sections of the cell as long as forced convection by gas bubbling was present. With no gas bubbling, the temperature sensed at the top of the cell varied by as much as 25°C from the bottom of the cell. Therefore, if the recombination event materially influences bubble generation, large thermal gradients may result.

An indication of uniformity or nonuniformity of the cell temperature during a heat burst may be obtained from the cell voltage change associated with the increasing cell

1-237 temperature. The total cell voltage consists of voltages across the cathode/electrolyte interface, through the electrolyte and across the electrolyte/anode interface. The voltage change with temperature is expected to be mainly due to changes in electrolyte resistance with temperature. Therefore, cell voltage should drop to known values dependent upon the electrolyte temperature. The heat excursion illustrated in Figure 7 is self consistent in this regard and the amount of excess heat released is more than that can be explained by recombination of all D stored in the cathode. We have no explanation as yet for this heat burst. There was no evidences of generation of nuclear products.

In case of PF cells, the limited work performed in this study indicates that the cell excess heat estimation is very sensitive to heat transfer coefficients used and therefore requires an extensive calibration data base. The heat transfer coefficients determined during these experiments suggest at best a nominally small excess heat output. Thermal analysis of the experiment in which cell electrolyte rapidly boiled off is difficult because of the lack of information on the amount of liquid remaining at different times during the boiling event. The cell constants can change drastically. Approximate analysis indicates, at best, a small excess heat in the range of 2% in that experiment.

5. Acknowledgements

Many graduate students and faculty have contributed to this work in particular Prof. J. G. Byrne, Dr. John Peterson, llesh Shah, H. Hwang, Narendran Karattup, Jose Hevia and Jim Nolan and their contribution is gratefully acknowledged. We are thankful to Dr. John Morrey at Battelle Northwest Laboratories, for the help with surface analytical work. We also are thankful to the Physics Group at NCFl for their help with nuclear radi at io n mo nito ri ng.

1-238 APPENDIX I: Summary of Experiments and Cell Operating Conditions

1-239 TABLE 1. Summary of experiments performed in cells of type HHT-A

Exp. Cell Electrode Electrode Current Voltage Duration Observations No. No. Anode Cathode Treatment Density

1. 1 Pt Wire Pd cathode JM1 Machined and annealed 1.5A*-3.OA 8.0-7.0 V 4/10-5/1/89 *looking for abrupt winding 4 mm x 10 cm 900"Cl lHr, UHP Argon 0.1 M LDD (V control) changes in cell/bath Au Contact Leads *Naphion diaphragm used ini- temperature. PYREX CELL BODY tially but removed as I was Excess heat measure- low(0.25 A); Make up was ments using a large dewar partially 0.1 M IiOD. Manual VI I and T measurements. 2. 1 Pt wire Pd Cathode JM1 Heated to 275'C. 2 Hrs 0.6A-0.8A 6.0-10.0 V 5/6-6/25/89 *Current Interruption winding 3mm\4mmx8cm in Vacuum; Constant I Mode test on 5/21/89; 7 mts Machined to 3 3 min. in aqua regla; Effect of transients mm dia over a Pd Mack deposit using power interrupt and I from 4 cm length PdCI,/NaCI in D,O Manual V & I measurements 0-2.5 A 2 r;, P 3. 2 PtRh PdCathode JM2 Machlneto4mmlAnneal 1.e1 .6-1.0A 7.4-7.75 v 4/26-5/1/89 *Cell top wkh cathode blown 0 4mmx 9 cm 600°C ltir.. Made anodic Tubular Nafion membrane out of the cell and bath on Pd lead? + 25OmV, then cathodic-250 between anode and cathode 5/1/89 due to D,-O,recombl mV in PdCI,/D,O soln. -nation detonation. Naflon membrane showed effects of heating Manual V&l measurement. *Cell restarted after reassembly & about 8 hours after cell had stopped

4 2 Pt-Rh 1.3 A 7.4 v 5/1-5/5/89 *Mild cell explosion on 5/2/89. No damage. Reconnected. Manual V&l measurement. *Temperature burst of 25' lasting 40 minutes observed on 5/2/89 after restart.

5 2 Pt-Rh rn Above electrode abraded 0.9-1.2A 7.7-9.9v 5/7-6/2/89 *Analysis for peroxMe in & Pd lead in alumina, cleaned Manual V&l moasurement. electrolyte on 5/20/89 was negatfve. *Temperature excursion from 31 to 47 and maintained at 42" C for 90 minutes on 5/21 /90. Cell electrolyte Tritlum was 34 X BG.

6 2 Pt wire Titanium Polished, Pickled, O.G.09 A 6.3-1OV (7/4-9/30/89) *Int. 8/25/89 winding 2mmxlO cm washed, abraded UOD + PdCI,

7 Old3 Ptsheet MetalorPD6 Electrodedeaned 1.4-2.85-1.2A 8-7.6-4.3V 4/26-5/5/89 8.5~3cm 4mmx 9cm Precharge D In D, Constant Voltage 8cm of cathode gas 11OPsl,125'C, 1Hr; 1.OA 4.3v 5/5-5/7/89 In sdn. Cool to RT;80"C,lWpsl, Const. I mode from 5/5/89 2 Hrs.;Cod to RT; Transfer to cell under Ar

8 2(01d 3) Pt Sheet Metalor PD6 Electrode from above apt. 1.14.80 A 8.8-9.9V 5/86/12/8!3 *Cell Calibration on 6/12/89; 10-50W A 8.5x3crn 4rnmx9cm Degassed 2OO"C, 3 Hrs., Const. I mode r;, vacuum(MP);Ar, D, purge;D, Current dec. due lnc. In V cell exploded at 50W P lOOpsI, cooling Heater Input A gas slow to 70"C, hdd for 15 Hrs. Pd lead spot welded

9 4 Pt sheet Zirconium Pdished; taken anodic 0.8-1 .OA 7.94-9.6V (5/9-12/21/89) cylinder 4mmxlO cm before charging 0.1 M UOD 5/9-7/9/89

10 4 Pt Foll sameasabove 0.88-1.2 A 9.0-10.0 V 7/98/25/89 *(lnt./move) we 0.1 M UOD+ 8/25-10/5/89 New Cell Top 0.04g PdCI,/lOOCC

11 4 Pt sheet sameasabove Zr electrode 1.05-1.1 A 6.06.7 V 10/8-11/3/89 Qge polished;Pd depostt 0.1 M UOD+ New Cell Top

1.0-3.OA 6.0-1 4.5V 11 /3-12/21/89

Current stepped Up/Down every 24 hours Reverse current for outgassing 12/21 /89 8 hours. 12 3/5 Pt wire Metalor Pd3 As received 0.8 A 7.4 V 19 Hrs. 4/26-5/4/89 *Mild Cell explosion 1' dia immersed length Const. I control coil 8 ern 1.0 A 8.0-7.4 V *Electrode exfdhtion along the rod axis

13 3/5 s 3M)'C lHr;275'C PHrs, 0.69A-1.3A 6.6-9.93V 5/4-6/23/89 *Power failure on 5/12/89 UHP Argon. (early morning) *cell renumbered 5 5/17/89- peroxide analysis was negative

14 5 PtAnode Electrode pdlshed wtth 0.95-1 .lA 8.8-1O.OV 6/23-8/25/89 Glass/teflon alumina, deaned and 8/25-10/4/89 wle and reused

15 8 Ptwlre Pd rod, JM32 900*Vacuumanneal2Hr 1.OA 7.3-8.6V 6/29-8/11/89. 2 wlnding 4 mm x 8.5 crn OIgas phase loading: 0-1 M uoo Machined to 110 ps1;20OoC lHr;l25'C Auto feed D,O Pr;, 3 ru mm dia over a 2Hrs;80*C 6Hrs;cod to RT 4 cm length and maintained for 72 Hrs at 110 psi and RT.

16 8 8 8 1.04.0 A 7.1 -22V 8/11-11 /4/89 *Cell currents changed every 24 hours (1-1 62- 2.5-5A)

17 6(C4/B6) R Wire Metalor Pd4 Aqua regla 3 mts, Wash 0.2A3.10A 1.7-8V V,=-2.3 4/29-5/23/89 *Current changes 4 mm x 8 cm HCI 3 mts;Anodic at t 250mv between 0.2-1.2 A In PdCI,/UCI/O,O solution Const V mode 111 5/6/89 3 Electrode Cell and then taken cathodk Then Const. I mode *VERY POWERFUL Calomel Ref. electrode -250mV at lmV/sec EXPLOSION ON 5/23/89 T=45'C,I = 3.1 A Reassemble & restart in 1 hour

18 6 Pd sheet Metalor Pd4 rn 2.1-1.26A 9.5-1OV. 5/23-6/26/89 1.4-0.9 A 9.69-8.6V (At 1 .5A,VC,,, = 6.05). TABLE 2. Summary of experiments performed in cells of type HHT-6.

Exp. Cell Electrode Electrode Current Voltage Duration Observations No No Anode Cathode Treatment Density

1. 7 Ptmesh JM33Pd M/c to 4mm d& and polished; 1.0 A 6.4 V 6/278/11 22 mm dia 4mmx 9cm aqua reg&,l Hr;O.3pm alumina 0.1 M UOD 9 cm long polish; 600"C,vacuum,l Hr;4Hr Auto Feed from 7/4 cool to s0o"C; introduce Ar+ l.6A 8.8 V 8/11-8/24 trace oxygen 10 mts;cool in Ar; 1.0-2.5A 8/24-9/24 *Current changed every D, gas 110 psi, 200-12540°C 24 hours to levels in the -RT. Transfer under Ar to cell range Of 1-1.5-2.0-2.5 Cell stopped. Electrode D/Pd 3.5 mts after stopplng > 0.78(gravlmetric)

27 I W +900°C GHrs,H,,Zr getter; 1-2A 6.5-1OV 9/27-11 /6/89 *Current changes 1-1.5- 2 Cool to RT;500"C UHP Ar,Zr 0.1 M UOD r;, getter; PdCI,/UCI solution, P P 10 mts, -250mV cathodic. Add -1.8 M D2S04 *Voltage Increased from 10.7- 1 ml on 10/18/89 14.9N at 2A current. Add 1.8 M DZSO, 0.5 ml on 10/19/89 *Voltage decresed to 13.9

Add 1.8M D,S04 *Voltage dropped to 9.35 at 2A7 W I 2.5 ml with 0.013 gm As

3 9 Ptwlre PdrodJM1 Electrode from cell 1; 1.OA -2.0 6.0- V 6/25-11 /3/89 *Current cycling from 1- winding 3rnm/4mx&m Cleaned In HNO,; alumlna Autcbfeed of D,O from 1.5-2A starting 9-12-89 Machined to 3mm powder polish 7/5/89 Cell temp was 2°C above dh over a 4 cm anticipated value length indicative of possible NEW CEU ASSEBMLY,3Thermocouples Manual V & I measurement excess heat at steady state on 9/13/89 after current was increased from 1 to 2A 4 8 Ptwlre Pd JM32 Electrode from previous 0.9A 8.8V 919-1 0/5/89 run was used as is

5 8 Pt wire Pd JM32 Electrode from previous 1.03.OA 6.5-15.N 10/5-12-21/89 *Current changes every run was abraded with 24 hours to levels alumina powder, deaned between 1 and 3 A. and plated with Pd Mack

65 Alumina powder polish 1-2.75A 6.6-16.5V 1014-1 1/23 *Current level changes Pd Black deposit 1-2.5 A.

7 10 Pt wire Metalor PD5 As receked 1-1.3A 6.5-7.8V 711 1-9/9/89 4 mm x 9.5cm Internal Pt on Teflon cataiyst/Auto D20feed. 1-2.5A 919-9/27/89 *Current level changes 1-2.5A

A 8 10 Ni wire PD5 electrode Anneal at 900"C,6Hrs; 1A 7.7 v 9/27-10/28/89 *Bubbler exploded during b As above 500°C 2Hrs Internal recombination calibration. P m Pd leads Pt on teflon catalyst

1-1 S-2A 10128-1 1/10/89 *After 1 1 /8/89, continuous increase in V and decrease in I due to Ni disintegration

10 * - 0.18A 11 112-1 2/16/89 *Degassing

10 1.0 A 1 1116-1 2/5/89 -0.1- -2.OA 12/5/89 8 Hrs *Cell shut down TABLE 3. Summary of experiments performed in cells of type MHT-A

Exp. Cell Electrode Electrode Current Voltage Duration Observations No No Anode Cathode Treatment Density

1 9 Pt wlre Pd Cathode JM1 Electrode from cellsl&dd9 1.0 A 4.0 A 6.6-9.9V 11 /34/11/89 Current cycling from winding 3mm/4mmx8cm alumina powder @Ish Auto-feed of D,O from 13A Machined to 3mm rinse In water 7/5/89 dh over a 4 cm length

2 22 Pt mesh Hoover&Strong 6OO'C Anneal 0.5A 4.5v 11 /20-12/4/89 lOxfjcm Pd 2mmx8.2cm Pd black coating In 0.1 M UOD 0.5 mm Pd lead PdCI,/LCl sdn. AUTO D,O feed tll 12/11

0.6-3A 12/4-1/6/90 Current level change 1.0 A 1/6-1/22/90 1.0-3.0 A 1/22-2/16/90 1.0 A 2/16-3/10/90

3 23 Pt mesh Pd Electrode Cleaned wtth alumina, 0.5A 4.5v 11/23-11/24/69 lOx5cm from dd cell 5 Rinse, Pd Mack coating 0.1 M UOD 0.5 mm Pd lead In PdCi,/W=I sdn. AUTO D,O feed till 12/11 1.0 A 5.2V 1/24-12/4/89 0.6-5.OA 12/44 /5/90 Current level changes 1.0 A 1/5-1/22/90 1.0-5.OA 1/22-1/27/90 Current level changes 1.0 A 1/27-2/14/90 1.0-1.6A 2/14-2/15/90 Current level changes 1.0 A 2/153/17/90

47 W 8 +5OO'C 1 Hr, Zr gettered 1.OA 5.4v 11 /8-12/11/89 On 11 /13,14 current UHP Ar, repeated flushing same solutlon(pH= 1.71) changes between 1.0-1.5 at 200,400,500"C during as above with As -1.75-2.5-3.0 A heating and coding Pda, t ua, -250 mv, io mts 57 1,1.25,2.5,3,5A 12/11 -2/28/89 1/4/89:Noise heard from cell 7. Intermittent sparks/flame at the top of the electrode above the electrolyte. I = 3 A. Cell explosion on 1/5/89. Reassembied and restarted.

Cell 7 in ultrasonic bath for 10 minutes. Bubble patterns changed to slender column of bubbles near the cathode; Cell put back in the bath; No unusual cell temperature changes.

1.lA 212813110/89 Bath Temp. 10°C TABLE 4. Summary of experiments performed in cells of type MHT-B.

Exp. Cell Electrode Electrode Current Voltage Duration Observations No No. Anode Cathode Treatment

BATH TEMPERATURE 5. l0"G

1 40 Pt wire Old Metallor As Received 17-600 mA 3.2-6.9V 3/10-/90 *Overvoltage measured cage 4mmx50mm 0.3 M U2S04 *No excess heat observed

2 41 Ptwire Fusion Grade As Received 17-600 mA 3.36.4V 3/11-7/9/ . cage 8mmxl2.5mm 0.1 M UOD

3 42 Pt wire Fusion Gade As Remelted 15-600 mA 3.3-6.4V 3/11 -7/9/90 cage 8mmx12.5mm 0.1 M UOD

4 43 Ptwire Old JM1 - 15-35 mA 3.27-6.4V 3/11-/O 8

A cage 4mmx40mm 0.1 M UOD r;, 00P BATH TEMPERATURE 25"(;

5 44 Ptwlre Old Metallor As Received 17-600 mA 3.2-6.9V 3/lO-/W *Overvoltage measured cage 4mmx50mm 0.1 M UOD *No excess heat observed

BATH TEMPERATURE 10°C

6 7 Pt wire Electrode JM33 Electrode from 0.55-2.2A 3/10-5/10/90 clipped In half expt 2.2 used Bath Temp 10°C 4 cm piece reused as Is. (30 mt Delay) 7 45 Ptwire JM34 As Received 17400 mA 3.3-6.4V 3/18-6/11/90 cage 6.25mWOmm 0.5 M U,SO, *Shut down for Raj/Bourgois' work /KF

8 46 Ptwire Fusion Grade Annealed 15-600 mA 3.3-6.4V 3/18-/90 cage 8mmxl2.3mm 0.3 M U2S04

9 47 Pt wire Fusion Grade As Received 1535 mA 3.27-6.4V 3/21-/90 . cage 8 mmxl2.5mm 0.3 M Li2SO4 BATH TEMPERATURE 5 'G

10 48 Pt wire NITi(0NR) As Recelved 40-14OmA 3.8-6.6/16 5/186/12/90 *Overvdtage measured cage 1x8x12mm 0.3 M U2S04 No excess heat observed

NiTl (new electrode) 40-140mA 3.95-5.5/5.8 6/19-7/25/90

11 49 Pt wire JM Electrode Annealed 40400mA 4.1 6- 5/27-7/23/90 S cage 2.8x5x17.5mm 1250 c 0.3 M U2S04

12 50 Pt wire HOOVER&STRONG Annealed 40 -6OOmA 4.1-27-6.4 5/27-7/23/90 . cage 2x35mm 1250 "C 0.3 M Li2SO4

13 51 Ptwire METALOR Annealed 40 mA-35 mA 4.1-6.4 5/27-/90 . cage 2x20mm 1250°C 0.3 M US04 BATH TEMPERATURE 5 and 22 "C

A rn I 14 52 Pt wire JM wire drawn 600 'C Anneal 17 mA-GoomA 3.38.5 7/16-7/30/90 Iu P cage 2.35x30mm 0.3 M US04 CD 15 53 Ptwire Metalor 600 'C Anneal 17 mA-GoomA 3.3-6.5 7/16-9/21/90 rn cage 4mmxlOmm 0.3 M US04

16 54 Pt wlre Hoover&Strong 600% Anneal 17 mA35 mA 3.3-6.4 7/16-9/22/90 . cage 2mmx35mm 0.3 M US04 BATH TEMPERATURE 22 'G

17 55 Metallor Pd As Received 17 mA-6OOmA 3.2-6.87 7/23-9/19/90 Overvoltage measured 4mmx 19.25mm 0.3 M US04 No excess heat observed

18 56 PdSa%U As melted 17 mA-6OOmA 3.3-6.5 7/23-9/19/90 2.8x5x17.5mm 0.3 M US04

19 57 Pd remelted As Remelted 15 mA-GoOmA 3.3-6.4 8/1-9/18/90 2.2x2.8x18.45mm 0.3 M U2S04

20 58 Pd-Sa%LI As Melted 15 mA-35 mA 3.3-6.4 8/3-9/21/90 2x2x18.35mm 0.3 M Li2SO4 BATH TEMPERATURE 5 "C

21 59 Pt Wire Pd Remelted As Remelted 17-520 mA 3.3-24.2 8/343/17/90 No excess heat observed cage 2.3~2.38~17.1mm

BATH TEMPERATURE 22 "G 22 62 Pt Wire Ti-15-3 ALLOY As Received 17-88 mA 3.243.8 8/7-9/21/90 %le 2x1.9x32mm 23 64 Pt Wire Pd Remelted As Remelted 42 mA 3.3-24.17 8/18-9/21/90 No excess heat observed cage Same as Electrode of cell 52

24 66 Pt wire Pd-25a% Ag As Received 17 mA-GoomA 3.18-6.9 7/23-9/19/90 Overvoltage measured cage 4mmx 19.25mm 0.3 M US04 No excess heat observed

2 r;, 25 67 Pt wire Pd-1Oa%Ce As melted 17 mA4OOmA 3.276.4 7/23-9/19/90 ul 2.8x5x17.5mm 0.3 M US04 0 mge 26 68 Ptwire Pd-lOa%Cu As Remelted 15 mA-GoomA 3.27-6.4 8/1-9/18/90 -€le 2.2x2.8x18.45mm 0.3 M US04

27 69 Ptwire Pd-Sa%U As Melted 15 mA-35 mA 3.27-6.4 8/3-9/21/90 -ge 2~2~18.35mm 0.3 M US04 APPENDIX II: Operating Conditions and Results for Small Glass and Teflon Cells

Eight small teflon-walled cells were originally set up for T monitoring (Table V). Except for cell 17, which showed a threefold enhancement of T during a temperature excursion in early September, no other cell had showed any significant increase in T level. These cells used 0.5-mm wires and 2 or 2.35 mm dia. Pd rods were used as cathodes at the axis of a cylindrical Pt mesh. The current densities used in the 2 or 2.35 mm Pd cathode cells were between 60 to 400 mA/cm2; whereas, the Pd wire cells had a current density of 1100 mA/cm*. When it was decided to shut down these cells in late November, these cells were subjected to large transients in temperature as well as current density. On cell 17, a low energy X-ray peak was observed around 4 KeV. While trying to reproduce this effect in other cells, the SiLi detector window was damaged. The experiments were resumed in early February. Low energy X-ray signals were again detected. The Physics Group is still trying to identify the source of these signals. Two sets of cells designed to minimize X-ray absorption were built. The first set had an outer Pd wire winding and interior Pt wire anode mesh. The Pd cathode wire was close to the teflon wall (Table VI). In the second set, thin Pd (100 micron thick) and Pt sheet electrodes close to the thin polypropylene tube wall were used (Table VII). This design allows shorter charging times, difference in current density in the inner and outer surface of Pd cathode, and less X-ray absorption in the electrolyte and cell wall. While some unexplained peaks in the low energy region have been observed on different occasions, the source of these signals has not yet been identified. In the next set of experiments, the above two cell configurations were modified to have a thin 10 mil thick mylar wall. While no large signals were observed, the data still needs to be analyzed in detail by the Physics Group.

1-251 TABLE V. Summary of experiments performed small cell made of glass/teflon.

Exp. Cell Anode Cathode Cathode Electrolyte Current Duration Comments Treatment

1 011 NI Sheet Pd Wire As Recehred 0.1M UOD 33 mA 7/10-7/12/89 No changes In cell Perforated 0.5~35mm (Cold worked) 15 cc 66mA 7/12-7/13/89 temperature observed Pt Leads 150 mA 7/13-7/31/89 100 mA 7/31 8/25/89 Cell shutdown Cell in a Small insulated Dewar

j**Cells 11-1 8 here are referred as 11-13.16-20 in Lab. Note boo kl 2. 11-1 Ni Mesh Pd wire As received 0.1 M UOO 6omA 9/16-10/2/89 0.5 mmx 50 mm 15 ml

3 12-1 Ni Mesh Aldrlch Pd Wire 600°C Anneal 0.5~7.5 cm 4 Hrs;Alumina --L pol1sh;Pd deposlt r;> VI In PdCIJUCI R) soln. at -250mV

4 13-1 NI Mesh Aldrich Pd Wire 9/22-10/2/89 0.5~7.5 cm

5 14-1 Ni Mesh JM Wire drawn 600°C Anneal 0.1M WD 22omA 9/ 16- 1 0/2/89 2.35 x 49mm 4 Hrs; Alumina 15 cc Pd lead wire polish;Pd deph (0.3 mm) in PdCI,/UCI soln. at -250mV

6 15-1 Ni Mesh JM wire drawn rn 2.35 x 50 mm Pd lead wire (0.3 mm)

7 16-1 NI Mesh Hoover&Strong As Recehred Pd, 2x48.5mm Pd lead wire (0.3 mm) 8 17-1 Ni Mesh Hoover&Strong 600°C Anneal Pd, 2x48.5mm 4 Hrs;Alumina Pd lead wire polish;Pd deposlt (0.3 mm) in PdC12/UCI soh. at -250 mV . . . 9 18-1 NI Mesh Hoover&Strong W Pd, 2x48.5mm Pd lead wire (0.3 mm)

10 11-2A Niwire Hoover&Strong W 220 mA 10/4-10/14/89 Pd, 2x48.5mm 400-34 mA 10/14-10/26/89 Degradation of Ni w1re;lnc. Pd lead wire in V & dec. in I; Replace (0.3 mm) with Pt anode anode wire

11-28 Pt wire . W 400mA 10-26-11 /7/89

800/400mA 11/7-11/29/89 cell shut down Day/Night

11 12-2 Ni wire JM wire drawn 600°C Anneal O.lM WD 220mA 10/4-10/14/89 2.35 x 49mm 4 Hrs; Alumina Pd lead wire polish;Pd deposlt 400-160mA 10/14-10/26/90 Degradation of NI anode (0.3 mm) in PdC12/UCI Inc. in V & Dec. in I sdn. at -250mV; Electrode from expt.5, clean; redeposit Pd

12-28 Pt Mesh W . . 400mA 10/27-11/7/89 800/400mA 11 /7-11/30/89 12 13-2 Ni Mesh JM wire drawn Electrode from 220 mA 10/4-10/7/89 Disintegaration of Ni anode 2.35 x 50 rnm expt.6; Clean & Pd lead wire redeposit Pd (0.3 rnrn)

Pt Foil- Electrode cleaned; 220 mA 10/7-10/14/89 Perforated Redeposit with Pd 300-400mA 10/14-11/7/89 0.3 cc of D,S in UOD soh added, No effect

800/4OOmA 11/7-11/28/89 Change to Teflon Cell D/N

13 14-2 NI Mesh Hoover&Strong Electrode from 22omA 10/4-10/10/89 Disintegartion of NI anode Pd, 2x48.5rnrn expt. 7; Clean Pd lead wire redeposit Pd (0.3 mrn)

14-28 Pt wire a 220 mA 10/10-10/14/89 0.5 mm 4oomA 10/14-11/7/89 800/400 mA 1 1/7-11/30/89 Change to Teflon Cell

14 15-2 Ni Mesh Hoover&Strong Electrode from 22omA 10/4-10/10/89 Pd, 2x48.5mm expt. 8;Uean; Pd lead wire redeposit Pd (0.3 mm)

15-28 Pt wire 22omA 10/10-10/14/89

4oomA 10/14-11/7/89 sOo/400 mA 1 1/7-12/1/89 D/N

15 16-2 Ni Mesh Pd wire As recehred 0.1M UOD 60 mA 10/4-10/12/89 0.5mmx50rnm New electrode 15 mi 250 mA 10/12-10/14/89 4OOmA 10/14-10/15/89 mmA 10/15-10/18/89 Electrode became red hot during transfer. Quenched Immediately. 16-28 Pt mesh 8 8 8oomA 10/1&12/22/89 0.3 cc D2S In UOD soh.

Small vdtage a/=.drop. Cells 16-18 inserted in a 28 mm on 11/1/89

12/7/89- Current varied from 0.8-1.7A, T varied from 60-90°C. Monitor for X-rays with SIU and Ge detectors

12/15/89- Current varied from 0.8-2.4 A, T varied from 60-boiling. Monitor for X-rays using SIU and Ge detectors

2 Change to teflon cell b VI VI 16 17-2 Ni Mesh Aldrich Pd wire 600°C Anneal 8 6omA 10/2-10/12/89 0.5~7.5 cm 4 Hrs;Alumina 250 mA 10/12-10/13/89 polish;Pd deposit 400-500 mA 10/13-10/15/89 in PdCI,/UCI mmA 10/15-10/25/89 ,Temperature excursion on soln. at -250mV 10/25/89 evenlng. Cell electrolyte forced out of the cell 81 Ni anode degraded

17-28 Pt Mesh 8 8oomA 10/26-12/18/89 Thermal/current cycling on 12/7/89. X-ray in the low energy range ?

12/15/89- Current varied from 0.8-3.1 A, T varied from 60-90°C. Monitored for X-rays using SIU and Ge detectors. 17 18-2 NiMesh Alddch Pd wire 600°C Anneal 0.5mrnx7.5cm 4 Hrs:alumina polish

16-28 Pt Mesh Theml/Current cycling on 12/7/89. Signal In the low energy (-4KeV) range? TEFLON CELLS (Internal recombination catalvst: TemD. excursion and T monitorinq)

18 113 Ptwire JM wire drawn 900°C H2 Redn. 0.1 M UOD 800 mA 11/123/1/89 On 2/5/89, All Cells Moved 6 Hrs;SOO"C Ar to Lab 35;2/18/90 cell 2Hrs; Alumina Polish. Current (8003500 mA) cycling on 3/1/89. SIU detector used for low energy X-ray monitoring

19 12-2 Ptwire JM wire drawn 600°C Anneal 0.1M UOD 800 mA 11/30/8!3-3/1/90 2/28/90 cell explosion 2.35 x 49mm 4 Hrs; Alumina Pd lead wire po1ish;Pd deposit (0.3 mm) in PdU2/UCI Thermal(30-1OO°C)& soin. at -250mV; current (8003500 mA) cycling on 3/1/89. Electrode from SiU detector used for 2 expt. 11; clean; Low energy X-ray r;, monitoring. VI redeposit Pd 4 20 13-2 Pt wire JM wire drawn 600°C Anneal 0.1M LDD 800 mA 11/28/893/1/90 2.35 x 49mm 4 Hrs; Alumina Pd lead wire pdish;Pd deposit (0.3 mm) In PdC12/UCI sdn. at -250mV; Electrode from expt 12

21 14-2 Pt wire Hoover&Strong s0o"C Anneal 0.1 M UOD 800 mA 11 /30/89-3/1/90 2mmx5cm 4 Hrs; Alumina Pd lead wire polish;Pd deposit (0.3 mm) in PdU2/UCI soln. at -250mV; On 3/1/90 temperature Electrode from cycling(30-100°C) and expt. 13 current cycllng(800- 350($1A); SiU detector used to onitor low energy X-ray emission 22 15-2 Pt wire Hoover&Strong 600°C Anneal 0.1 M UOD 800 mA 12/1/893/1/90 2/21 /W-Current cycling 2mmx5cm 4 Hrs; Alumlna 1-2.1 A; Monitored for Pd lead wire pdish;Pd deposit X-ray Signals With SIU (0.3 mm) in PdCI,/UCI detector soin. at -250mV; Electrode from 2/28/90Current cycling expt 14 0.8-2.1A;Monitored for X-ray signals with SIU detector

23 16-2 Pt Mesh Aldrich Pd wire As received 0.1 M UOD 800 mA 12/12/89-2/28/90 2/15/90- Current cycling O.5mmx5cm Electrode from 1-2.2 A; Monitored for X-ray expt. 15 slgnals with SIU detector

2/21 /W-Current cyding 0.8-2A;Monitored for X-ray signals with SIU detector

24 17-2 Pt Mesh Aldrich Pd wlre 600°C Anneal 0.1 M UOD 800 mA 12/18/89-2/28/90 2/15/90- Current cydlng 2 lb 0.5mm x 5cm 4 Hrs; Alumlna 0.8-2.5 A;5088"C;Monitored v1 pdish;Pd deposit for X-ray Signals wlth SIU (x, in P~CI,/UCI detector soh. at -250mV; 2/28/90-Current cydlng Electrode from 0.8-2.7A;Monitored for X-ray expt. 16. signals with SIU detector

25 18-2 Pt Mesh Aldrich Pd wire 600°C Anneal O.lM WD 800 mA 12/18/89-2/28/90 On 12/29/89 cell exploded 0.5mm x 5cm 4 Hrs; Alumlna 4 cm out of 5cm Immersed pdish;Electrode length disappeared. from expt.17 Black resMue In the cell bottom. Lead wire section reused.

2/14/90- Thermal/current cycling 1-2.5A; 5048°C; SIU Detector for monitoring X-ray signal

2/28/90- Current cycling 0.8-2A;Monitored for X-ray signals with SiLl detector Table VI. Summary of experiments performed small teflon cells with Pd cathode coil near cell wall.

Nafion 417 membrane, Pd near outslde wall, Pt winding on Inner glass rod support

Exp.# cell# Anode Cathode Electrolyte Current Duration

1 24 Pt wire Pd wire 0.1 M UOD 17 mA 316-3/8/90 0.5mmx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 200 mA 4130-5/3/90 mmA 5/3-5/7/90 4oomA 5/7-5/11/90

2 25 Pt wire Pd wire 0.1 M UOD 17 mA 3/64/8190 0.5mmx30cm 24 mA 3/84/20/90 100mA 4/204/30/90 200 mA 4/30-5/3/90 300 mA 5/3-5/7/90 400- 5/7-5/25/90 u1 CD 3 26 Pt wire Pd wire 0.1 M UOD 17 mA ~/6-3/8/90 0.5mmx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 2oomA 4130-5/3/90 3oomA 513-5/7/90 4oomA 5/7-6/3/90

4 27 Pt wire Pd wire 0.1 M UOD 17 mA 3/64/8190 0.5mmx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 mmA 4130-5/3/90 3oomA 513-5/7/90 4oomA 5/7-6/18/90

5 28 Pt wire Pd wire 0.1 M UOH 17 mA 3/63/8/90 0.5mmx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 200 mA 4/30-5/3/90 300 mA 5/3-5/7/90 4oomA 5/7-6/7/90 6 29 Pt wire Pd wire 0.1 M UOH 17 mA 3/63/8/90 0.5mrnx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 200 mA 4130-5/3/90 300 mA 5/3-5/7/90 4oomA 5/7-5/28/90

7 30 Pt wire Pd wire 0.1 M UOH 17 mA 3/63/8/90 0.5mmx30cm 24 mA 3/8-4/20/90 100 mA 4/204/30/90 200 mA 4130-5/3/90 300 mA 5/3-5/7/90 4oomA 517-5121190

8 31 R wire Pd wire 0.1 M UOH 17 mA 3/63/8/90 0.5mmx30cm 24 mA 3/84/20/90 100 mA 4/204/30/90 2oomA 4/306/3/90 3oomA 5/3-5/7/90 4oomA 5/7-5/14/90 Table VII. Polpropylene centrifube tube cells with Pt mesh anode and Pd foil cathode.

Exp.# Cell# Anode Cathode Cathode Electrolyte Current Transients Duration Treatment

1 32 PtMesh Pd foil Annealed 600°C 0.1 M UOD 0.1-1.0 A 3/74/19/90 1OOpm 4xl5mm

2 33 Pt Mesh Pd foil Annealed 600°C 0.1 M UOH 0.1-1.0 A 1oopm 4x1 5mm

3 34 PtMesh Pd foll Wd rolled 0.1 M UOD 0.1-1.0 A lawn 4x1 5mm

35 Pt Mesh Pd foil Cold Rolled 0.1 M UOH 0.1-1.0 A lmm 4x1 5mm

5 36 PtMesh Pd foil Annealed 600°C 0.1 M UOD 0.1 -1.O A 1oopm Pd deposit 4xl5rnm

6 37 PtMesh Pd foil Annealed 600°C 0.1 M UOH 0.1 -1 .o A 1OOpm Pd deposit 4x1 5mm

7 38 pt Mesh Pd foil Cold rolled; 0.1 M UOD 0.1 -1.O A 100pm Pd deposit 4x1 5mm

8 39 Pt Mesh Pd foil Cold rolled 0.1 M UOH 0.1-1.0 A . 100pm Pd deposit 4x1 5rnm Operation of Cell 17 (October 25, 1989)

0 ~lllrrrlllllrrrrrl~I,rrrrlllll,lrlrllrl,111111 I 111111111~111111111rrrrr~ 11 0 100 200 300 400 500 600 700 800 Time (min)

Figure All.1 Temperature excursion seen in cell 17 , 0 Excess Heat Estimation With The Kalman Filter

Raj K. Rajamani

Florent Bourgeois

1-263 Table of Contents

Page

1. Introduction 1-265

2. Mathematical Model 1-266

3. Kalman Filter Algorithm 1-269

4. Experimental Analyses 1-270

4.1 Algorithm verification 1-270

4.2 Estimation of radiation coefficient 1-270

4.3 Excess heat estimation in D20 cell 1-271

5. Conclusions 1-271

6. References 1-271

1-264 1. Introduction

The cold-fusion electrolytic cell experiments present a classic parameter estimation problem: a varying potential is imposed on the cell to maintain constant current through the cell; the cell dissipates the electrical energy input as products of decomposition and heat loss to the surrounding bath, while some heat is produced in the cell due to the alleged nuclear process. Current understanding of the electrochemical phenomena coupled with heat-transfer theory permits accurate calculation of the heat dissipated; however, the heat generated within the cell must be inferred from a balance of the electrical energy input to the cell with the heat dissipated by the cell to the surrounding. This heat-balance problem is a dynamic heat-balance problem, since the temperature of the cell varies with time. Furthermore, the problem can be classified as on-line, since one intends to calculate heat produced within the cell at every instant.

There are a few methods of doing the dynamic heat balance. However, each method assumes that a mathematical model of the cell, in this case a differential equation with time as the independent variable, is available. This model should incorporate a term for variation of cell temperature with time in addition to the usual terms for heat input and heat output. What is of interest is the term that stands for the heat generated within the cell. This first method uses the classical optimization approach. The model is solved with appropriate initial experimental conditions, and the unknown heat generation value is determined by forcing the model results to match the experimental data. The matching is usually done with any number of optimization methods which seek to minimize the sum of squares of the deviation between model prediction and experimental data. With such an approach, the heat production calculations would have to be done after the experiment is completed and not during the experiment. An alternative is the Kalman filter approach, which enables either on-line calculations or off-line calculations.

The Kalman filter has undergone extensive study since the publication of the classic papers by Kalman (1960) and Kalman and Bucy (1961). Voluminous literature is found in the aerospace industry for control and guidance problems. Numerous applications of the Kalman filter are also found in chemical and metallurgical processing problems. The Kalman filter deserves special attention in the

1-265 electrochemical cell problem, because of its ability to estimate parameters in the presence of measurement noise, input noise, and unmeasured process disturbances. A detailed exposition of the filter theory is found in the text authored by Maybeck (1979). Suffice it to say that the Kalman filter equations specify an optimal estimate of the state of a linear, time-varying, dynamic system observed sequentially in the presence of additive white Gaussian noise. The estimate obtained at each time is the maximum likelihood estimate, conditioned on all observations, up to that time. This is equivalent to the least square estimate of the state, since the disturbance noises are Gaussian.

2. Mathematical Model

The electrolytic cell model adopted here is the one due to Pons and Fleischmann. This model, shown in Table 1, is a dynamic heat-balance model, which accounts for the following subprocesses:

Input: 1) Joule heating due to electrical energy input, and 2) any excess heat generated within the cell. output: 1) Electrolytic decomposition of D20, 2) evaporation of D20, 3) radiation heat loss, and 4) convection heat loss.

The model shown in Table 1 would be termed a lumped parameter model, since there is no dependence of temperature with respect to spatial directions. This is a key assumption in the model, since it implies that a uniformity in temperature exists everywhere in the cell and is established very quickly under any transient heat effects. The model becomes very useful for the analysis of heat generation, since most of the parameters, such as specific heat of D20 liquid, latent heat of vaporization of D20, vapor pressure of D20 etc., are readily available in the Handbook of Chemistry. Only the parameter kr, the radiation heat-transfer coefficient, must be evaluated carefully by means of other experiments.

1-266 Table 1. Model for the Electrolytic Cell

Two assumptions: output 1. Negligible temperature gradient within the cell.

2. Heat loss due to radiation.

Input

energy used to heat up the D,O Energy input + 2

"+(T,4 heat necessary to vaporize (dM,,,) moles of D,O

Qf + 0.0 Excess enthalpy generated cP,D,O.v [ T] Ae W.pOr.tion heat necessary to warm up the vapor formed

heat loss by radiation Finally, Q or the heat produced within the cell is the parameter being estimated with the Kalman filter. Upon substituting the thermodynamic values, the resulting model equations are:

75.089 M(t) -de, = - 1.54)l + 75.089 dt .w

r 1

Equation (2) expresses the fact that D20 is being continually depleted both by electrolysis and by the saturated vapor being carried off by the products of electrolysis. Equation (3)gives the rate of D20 carried off by products of electrolysis. The vapor pressure P of D20 liquid can be found in thermodynamic tables or can be computed with the help of the Classius-Clapeyron equation. Finally, Eq. (4) gives the mole-rate of evolution of electrolytic products assuming 100% Faradaic efficiency.

The radiation term dominates all other dissipation terms in determining the Qf value. Radiation, as expressed in Eq. (l),implies that it accounts for both convective losses and radiative losses to the cell surroundings. Further, it is assumed in this analysis that Kr can be determined accurately in another experiment and that the kr value does not change with variations in cell temperature.

1-268 Finally, the model does not have a term for recombination of the gases within the cell, since recombination is a remote possibility in these cells.

3. Kalman Filter Algorithm

As mentioned earlier, a detailed explanation of the filter may be found elsewhere. Only the pertinent algorithmic calculations are given here. In the estimation problem, the primary state variables are cell temperature and the heat generation term (Qf) denoted by the 2 x 1 state vector X(t). It is natural, then, to append the equation

--dQf - w(t) dt

which implie that a ero m an white Gaussian nois drives the unknown Qf ralue.

The calculations are done in two steps; first, the optimal state estimate is predicted, and then a set of corrector equations correct the state estimates and the error variance covariance matrix P(t). In the following, the superscript n-n indicates prediction, and "+" indicates correction. @is the linearized matrix cell model Eqs. (1) and (2),K is the Kalman-gain matrix, H is the matrix that converts observation values into state variable values, and Z is the vector of observations. Matrices Q and R represent zero mean, white Gaussian noise of the process and observation, respectively.

Prediction:

X(tl-1 = @(tptj-l) X(t,t1)

n(r;) = W,J~-JE(~,:~)@T(tp~,-J + Q

Correction:

~(tj)= ~(tj-1_ti '(ti) W(tJ Ed '('3 + B(tjI1-l

X(tj+) = X(tj-> + E(qz - liUJ X(t;)l

E(ti+)= E(tj-1 - JS(qli(qn(tj-)

1-269 The Kalman filter computer program takes as input the mass of D20 liquid initially in the cell, the thermodynamic parameters, and the radiation constant. Then it reads cell temperature, bath temperature, cell current, and cell voltage at every sampling instant from a file or directly from the experimental set-up if it is run on-line. At every sampling instant it gives the estimate of heat generated in the cell.

4. Experimental Analysis

4.1 Algorithm verification

A computer program incorporating the Kalman filter algorithm outlined above was written. To verify this code, a cell simulation code using the model equations shown in Table 1 was also written. A number of excess heat pulses in the range 0.1 to 1 watt were simulated and the results were used to verify Kalman filter code. In all cases the filter algorithm identified the excess heat pulse correctly. Due to the on-line nature of the algorithm the computed pulse lagged the simulated pulse by at least one sampling interval. In fact the filter correctly identified a real heat pulse introduced into some of the experimental cells in our group.

4.2 Estimation of radiation coefficient

The filter algorithm may be used to determine the radiation coefficient kr also. However, to do this the cell operation must not have produced any heat at all. In such a case, the algorithm can be executed with different values of radiation coefficient until the excess heat value over the entire time period is nearly zero. In other works, for a particular value of kr, the algorithm should estimate a value for excess heat of around zero for the entire item. The cell operation not producing any excess heat at all is the operation of a cell with H20 as electrolyte.

Figure 1 shows the temperature history of an H20 cell in the first five days of a ten-day operation. This is the Pons-and-Fleischmann-type cell, with a vacuum jacket partially silvered from the top to the midsection. Usual operating procedures were followed: initially the cell was filled with 60 cc of LiOH, cell current was maintained at 0.4 amps, bath temperature maintained at 3OoC, and the cell topped with 3 cc of LiOH every 24 hours. The small dips in the temperature profile appearing every 24 hours is due to topping the cell with fresh electrolyte. Figure 2 shows the excess heat estimated for the data shown in Figure 1. Radiation coefficient values in the range 5.6

1-270 x 10-10 to 5.9 x 10-lo were input to the filter algorithm, and the best value giving rise to zero excess heat is 5.80 x 10-'0. It is then concluded that the best value characterizing the heat loss from the Pons-and-Fleischmann-type cells operated under conditions mentioned earlier is 5.8 x 10-10 WK-4. It should be noted that the radiation coefficient is assumed not to vary with temperature of the cell.

4.3 Excess heat estimation in D20 cell

Indeed the primary use of the Kalman filter algorithm is for the estimation of excess heat in D20 cells. Figure 3 shows the temperature history of a D20 cell during the first five days of a ten-day operation. In fact this cell was operated in series with the D20 cell mentioned earlier. Therefore, the cell conditions are: current 0.4 amps, electrolyte volume 60 cc of LiOD initially with 3 cc addition every 24 hours and 30°C bath temperature. Note that this cell operates at 2°C higher than the H20 cell, and it draws slightly higher voltage for the current to be maintained at 0.4 amperes. Figure 4 shows the Kalman filter analysis of the data shown in Figure 3. For a radiation coefficient value of 5.8 x 10-10, the excess heat is slightly negative in the range -0.05 to -0.07 watts. The negative values are attributed to a slight difference in the radiation coefficient due to the presence of D20 in the cell instead of H20. However, for a value of 6.05 x 10-10, the excess heat is positive. The fact that the excess heat values are extremely dependent on the values of radiation coefficient has been known, and Kalman filter analysis too points to that.

5. Conclusions

The Kalman filter algorithm was very suitable for the analysis of excess heat in electrolytic cells. Due to the very nature of the algorithm it can be used on-line and all the more off-line. Either it can be used to evaluate the radiation coefficient in H20 cells or excess heat in D20 cells. The filter was used in the analysis of a number of cell data provided by other researchers of the National Cold Fusion Institute. The excess heat values were in agreement with values determined by optimization programs.

6. References

1. Kalman, R. E., "A New Approach to Linear Filtering and Prediction Problem," Trans. ASME, J. Basic Eng., 82, 35 (1960).

1-271 2. Kalman, R. E. and R. S. Bucy, "A New Approach to Linear Filtering and Prediction Problems," Trans. ASME, J. Basic Eng., 83, 95 (1961).

3. Maybeck, P. S., Stochastic Models, Estimation and Control, Academic Press, 1979, p. 207

1-272 Tempera tu re ...-..-..-..- Voltage

60 8

6 30 t

Time (sec) Figure 1. Temperature and voltage recorded during 1- to 10-day period for the H,O cell. [Cell current 0.4 A, bath temp. 30OC.l m N 7 0 7 01 0 0 0 0 0 0 I I I I

0 0 0 0 0 d- -w CJ rQ) cn cn 0 Q) 0 0 0 X 0 0 W M

0 0 0 0 0 N

0 L -+3 W 0 I 0 Q) 0 Q 0 0 E c 0 I- I-

0 O 0 (D hl

1-274 Temperature ... - .. - .. - .. - Voltage

0 100000 200000 300000 400000 Time (sec)

Figure 3. Temperature and voltage recorded during 1- to 10-day period for the D,O cell. [Cell current 0.4 A, bath temp. 30OC.l rc) hl T 0 7 64 0 0 0 0 0 0 I I

0 0 0 0 0 N

0 0 0 0 0 7

0 O 0 0 0 0 W In Tt m N

1-276 Explosive Compaction of Electrode Materials

and Metal Deuterides

Sivaraman G u ruswamy

Michael K. McCarter

Milton E. Wadsworth

1-277 Table of Contents

Page

Abstract 1-279

1. Introduction 1-279 2. Experimental Work 1-279 2.1 Experimental Facility 1-279 2.2 Experimental Arrangement 1-279 2.3 Materials Investigated 1-281

2.4 Preparation of the Deuterides 1-282

3. Results and Discussion 1-282 3.1 Consolidation of Palladium and Other Alloys 1-282

3.2 Consolidated of Deuterides of Ti and Pd 1-282

4. Conclusions 1-284

5. Acknowledgements 1-284

6. References 1-284

1-278 Abstract

The objective of this investigation was to produce electrode materials, with unique composition/microstructures for cold fusion experiments, by explosive compaction. Compaction of metal powders, deuteride powders and metal matrix composites to cylindrical rod by contact explosive charge was studied. Materials compacted included Pd, Pd-Ti, PdDx, Au-Pd-Pt and NiTi, metal matrix composite materials such as TiAI-Sic. Compaction of the powders, packed in a copper tube positioned centrally in a shaped vessel assembly containing perchlorate-aluminum- based liquid explosive, was performed inside a large explosive chamber in the IRECO explosives laboratory at the University of Utah. Limited microstructural characterization was performed using optical and scanning electron microscopy. Attempts to look for possible nuclear products due to piezonuclear fusion during explosive compaction of deuterides of Pd and Ti is described. However, no clear evidence of nuclear reactions was observed in the limited experiments performed. Additional experiments using larger explosives charges and improved experimental arrangement in increasing the efficient absorption of neutrons, if any, in activation foil detectors are required.

1. Introduction

Explosive compaction of powders to an integral solid form is attractive in the fabrication of alloys with unique microstructure and metal matrix composites [l-41.The feasibility of approaching theoretical densities without the destruction of microstructure inherent to initial starting material makes this process very attractive in the consolidation of rapidly solidified amorphous and microcrystalline alloys [l]. Amorphous and microcrystalline Pd alloys are of interest to cold fusion research. Amorphous alloy offers a wide range of Pd nearest neighbor configurations while the microcrystalline alloys have a very high grain boundary region. Nonequilibrium metastable microstructures such as Pd/Zr or Pd/Ti composite electrodes consisting of individual Pd and Ti grains in the microstructure can be fabricated by this technique.

The main goal of the experiments was to consolidate rapidly solidified Pd based alloys and fabricate the composite electrodes as described above for "solid-state fusion" experiments. The initial consolidation studies were performed using copper powder. Once a satisfactory solid Cu product was obtained from Cu powder, Pd, NiTi,

1-279 deuterides of Pd and Ti and hydrides of Pd and Ti, based on the suggestions that piezonuclear fusion of D-D atoms is possible, activation foils were used to monitor if any nuclear reactions occurred. The consolidated products were monitored for gamma ray, X-ray emissions, and delayed neutron emissions. The report describes the compaction process and microstructural characterization of the products obtained using optical and scanning electron microscopy, X-ray diffraction, and hardness measurements.

2. Experimental Work

2.1 Experimental Facility

The experiments were carried out in the IRECO Explosives Laboratory at the University of Utah. This facility is involved in the study of fracture behavior of rocks and other materials for applications in mining engineering. The facility has several gas guns, explosive chambers, ultrahigh-speed photography cameras for recording blasts at rates up to of about 2 million frames per second, instrumentation to measure shock wave velocities, and support of explosives experts. The facility is also being increasingly utilized for the studies involving novel material synthesis and compaction studies.

2.2 Experimental Arrangement

The powders were packed in small increments into a copper tube closed at one end with a tight-fitting steel rod and compressed using a Carver press at a compaction pressure of 5-10 tsi using a tool steel mandrel. Except for deuterides/hydrides of Pd compacted under D2 or H2 overpressure, other powders were compacted in a tool steekopper tube assembly as shown in Figure la. The open end of copper tubing was then sealed with a rubber or steel cap. In the case of deuteridedhydrides of Pd compacted under gas overpressure, the arrangement shown in Figure 1b was used.

The copper tube assembly containing compressed powder was placed centrally in a charge container as shown in Figure 2. The detonator was placed in the bottom of the PVC container and bondedkealed with glue. The size of the container and hence the amount of explosive charge was varied during our experimentation. The liquid- slurry explosive IRECO 207X was prepared by mixing the two components, perchlorate-base liquid component A and aluminum-based component B, just prior to carrying out the compaction, poured into the container, which was closed with the cap

1-280 assembly containing the compacted copper tube. The weight of the explosive charge was between 60 to 100 grams.

The compaction was carried out in an inner steel vessel 18 inches in diameter and 5 feet high, inside of an outer large explosive chamber 2 meters in diameter and 3 meters high, made of Kevlar-based composite structure. The PVC container cavity is conically shaped at the bottom, as shown in the figure, to help develop a planar shock wave front. The shock wave velocity was measured in several explosive compaction experiments using two triggers placed at different locations of the container (Figure 3). Typical shock wave velocities achieved in these experiments was about 15,000 feet per second. The detonation velocity is related to the compaction pressure by the following relation [9],

D.P = 2.325 x 10-7 p (VOD)2

and the estimated compaction pressures is about 7 GPa.

2.3 Materials Investigated

Different materials compacted by this explosive technique include copper, Pd + Ag powder mix, Pd + Ti powder mix, NiTi alloy powder, deuterides of Pd and Ti, and hydrides of Pd and Ti. Results of Table I lists the cold fusion research related materials consolidated by explosive compaction technique and the characteristics of different starting materials used are presented in Table II.

In the case of deuterated Pd and Ti powder implosion, the possibility of Iow- level nuclear activity due to piezonuclear fusion was investigated. Pd and Ti hydride compaction were experiments used as controls. Paraffin wax was used as a moderator and gold indium activation foils were used as passive detectors. Experimental arrangement is shown in Figure 4. BF3 and GM counters were placed around the explosion chamber but were not found to be useful. Typical shock wave front velocity was around 15,000 feet/sec. The compacted deuterides and the hydrides (control specimens) were removed quickly and sent for monitoring any delayed neutron emission, Pdfli Kct X-rays and to monitor the activity of Au and In foils. Ti deuteride specimens were sectioned using a low-speed lsomet saw, and the cut samples were sent for bulk tritium analysis using a technique that traps all of the tritium in liquid form suitable for tritium counting.

1-281 2.4 Preparation of the Deuterides

Deuterides were prepared by gas-phase loading using D2 gas. Ti deuterides were prepared in a Lindberg tube furnace using alumina tube with McDanel Universal end seals. The furnace was evacuated and backfilled with UHP argon and reevacuated before introduction of D2 gas. The system was purged before all the valves were closed. The gas pressure was about 20 psi gauge. In the case of Ti gas, adsorption occurred rapidly at around 450°C, and the amount of gas absorbed was sensed by drop in system pressure. Titanium powder used was minus 100-mesh powder from Aldrich and had been kept under argon cover. The oxide film on Ti powder was anticipated to slow the kinetics of D/H absorption, but no problems were experienced. In the case of Pd, deuteration was done at room temperature at a pressure of 600 psi, just prior to detonation, and the pressure was maintained during detonation in some of the experiments. High-purity Pd powder (99.995+) specially prepared and donated by Metallor, USA, was used in this experiment. Formation of deuterides was checked by X-ray diffraction and Ti deuteride was found to be stoichiometric.

3. Results and Discussion

3.1 Consolidation of Palladium and Other Alloys

The compaction results obtained in the case of Cu, Pd, Pd-Au-Pt, Pd-Ti powder mix were very similar. Good compaction was achieved in the outer regions but the pores in the central region were not completely eliminated. Use of larger charge and control of the shape of the shock wave front may eliminate the central porosity completely. Radial cracks were observed mostly in the central region in many specimens and these may be attributed to tensile stresses from reflected waves and control of shock wave front shape can eliminate this problem. The shock pressures in these experiments were in the range of several GPa which is one of two orders of magnitude greater than the static yield stress levels for different metals.

3.2 Consolidation of Deuterides of Ti and Pd

The Figures 5 and 6 show SEM micrographs of explosively compacted PdD and TiD2. While good compaction was observed in all cases, microcracks were observed along some particle boundaries. Excellent bonding at the Au/Cu and

1-282 Au/deuteride interfaces was obtained as can be seen from Figures 5 and 6. Hardness values of the compacted PdDx was 105 VHN, a value comparable to the hardness of deuterated solid palladium indicating that the consolidation obtained by explosive technique was good.

In PdDx, Pd atoms are arranged in face centered positions and D atoms occupy octahedral positions in an ordered manner. It was suggested by Pons and Fleischmann [6] that electrochemically induced loading of Pd under high electrochemically induced D2 pressures may induce nuclear reactions. Subsequent to their announcement, low-level neutron emissions have been reported in gas phase loaded PdDx and TiDx [7-91 under non steady state conditions. In the experiments performed here, the possibility of inducing nuclear reactions in solid D loaded Pd at room temperature by shock compression (piezonuclear fusion) was explored. Localized temperatures in the regions of particle contact can increase to levels several times the melting point of metals during a short time interval though the bulk of the material essentially remains near room temperature. If nuclear reactions did occur, the high-energy particles that may be released during such a reaction may result in Pd or Ti Ka emission and the compacted deuterides were monitored for Pd and Ti X-ray emission using Si-Li detector. If neutron emission was involved, activation of Au and In foil was possible and hence the In foils and the compacted tube containing Au were monitored using Ge detector at energies of 41 1.794 kev for Au(n,y) and 1293.49 kev for In (n,y). The x-ray films however, did not show any indication of nuclear radiation at high levels. No increase in activity of Au and In was observed except in one explosive compaction experiment involving TiD2 where small increase in activity of Au and In was observed. Second set of experiments with deuterides were unsuccessful in reproducing the observed enhancement in Au and In activity. Changes in moderator type and arrangement so to increase the neutron absorption by the activation foils has been suggested and need to be incorporated in future experiments. Analysis of deuterides for tritium showed no significant increase in tritium levels. The electrodes were dissolved in hot HCI in a closed system, which was subsequently neutralized, and the solution was distilled to obtain a clear liquid suitable for tritium counting. Enhancements observed were typically from a background of 29 + 1 to counts as high as 35 + 1 DPM/ml of the distilled liquid. While the enhancements are statistically significant, the absolute magnitude of enhancement is still too small to be conclusive. No clear evidence of X-rays from Pd or Ti, or delayed neutron emissions in the 48 hour time period over which the monitoring was done.

1-283 4. Conclusions

Satisfactory compaction of several metals and metal deuterides, of interest to cold fusion research, was obtained. Some porosity remained in the central region of the compact. Increase of compaction pressure and control of shock wave front profile can eliminate this problem. Titanium and palladium deuterides did not show any clear evidence of piezonuclear fusion effects. However, more experiments using large explosive charges and improved nuclear detection capabilities, are required before any definitive statement can be made. Satisfactory crack free densification of deuterides was achieved.

5. Acknowledgements

Authors are grateful to the support of this work by the State of Utah and the National Cold Fusion Institute. Support of the experimental facility by IRECO explosives company is gratefully acknowledged. Enthusiastic help of Geoffrey Bedell, Rob Byrnes, Dal Sun Kim during explosion experiments and Myong R. Kim in the microscopic studies are gratefully acknowledged. Authors like to thank Mr. Shu-Xing Wang, Physics Group, for his timely and valuable help in nuclear measurements on compacted deuterides, and Dr. Krystyna Cedzynska for help with tritium analysis.

6. References

1. G. E. Korth, J. E. Flinn and R. C. Green, "Metallurgical Applications of Shock Wave and High Strain Rate Phenomena," edited by L. E. Murr, Karl P. Staudhammer and Marc A. Meyers, Marcel Dekker, Inc., New York, pp. 129- 148, (1986).

2. M. S. Vassiliou, C. G. Rjodes and M. R. Mitchell, Advanced Materials and Processes, (2), pp. 70-71, (1990).

3. L. E. Murr, "Metallurgical Applications of Shock Wave and High Strain Rate Phenomena," L. E. Murr, Karl P. Staudhammer and Marc A. Meyers, Eds., Marcel Dekker, Inc., New York, pp. 329-341, (1 986).

4. Metals Handbook, Vol. 7, 10th Edition, American Society for Metals, p. 305, 692, (1 984).

1-284 5. Explosives and Rock Blasting, Atlas Powder Company, Dallas, Texas, 1987, p. 18.

6. M. Fleischmann, S. Pons, and M. Hawkins, J. Electrochem., 261 (1989) 301.

7. H. 0. Menlove, N. M. Fowler, E. Garcia, M. C. Miller, M. A. Paciotti, R. R. Ryan, and S. E. Jones, Los Alamos National Lab. preprints, LA-UR89-1974 and LA- UR89-3633.

8. Govt. of India, AEC Report:BARC-l500, P. K. lyengar and M. Srinivasan, Eds., 1989.

9. J. T. Dickinson, L. C. Jensen, S. C. Langford, R. R. Ryan, and E. C. Garcia, J. Mat. Res. 5,pp. 109-122 (1990).

1-285 Table 1. List of material systems explosively compacted.

Copper Palladium Tiiani um

PdAg alloy powder NIT alloy powder

40Au20Pd40Pt alloy powder + Ti powder mix

NiT-O.05pm AI,O, powder

TiD, TiH,

PdD, PdH,

Table 11. Characteristics of materials used.

' MATERIALS. INITIAL POWDER CHARACTERISTICS

Tiianium Powder Aldrich Chemical Co., 99.9+% Purii, -100 Mesh

IPalladium Powder I Johnson Mathey, Palladium black, 99.9 + % Purity Palladium II Metalor USA, Precipitated from solution, 99.995 + % I Purtty, MicroTrac Mean Particle Size 129 pm Microtrac Mean Particcle Size 34 pm 1 Nilipowder Alfa, Johnson & Mathey, -325 mesh, 99.9+%

1-286 COPPER CAP

POWDER

GOLD SLEEV COPPER SLEEVE

STEEL MANDREL

COPPER SHELL /

/ METAL POWDER GOLD SHE

STEEL TUB1

Figure 1. (a) Powder tube assembly for explosive compaction of metal and composite powders and (b) used in the explosive compaction of PdD, under 600 psi D, pressure.

1-287 DETONATOR, 17

PARAFFIN ,

VELOClTY PROBE

PVC

Figure 2. Explosive container assembly

1-288 Tube #3, PdDx-Press., D=l.25", 2"-Target Space, 207X (90.02 g.) I 1 I 8 I I 1 8 1 +-- +-- ; ...... t...... 7 +; ...... - 6

...... "- 5

v) 3 4 0> 3

...... I

...... I 1 I I ( 1 I 1 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 MILLISECONDS

Figure a. Voltage versus time profiles for two sensors placed at known distances along the shock wave propagaton direction.

1-289 PARAFFIhl

X-RAY F TARGET

Figure+ Experimental arrangement during the implosion of deuterides

1-290 133x

Figure 5. Micrograph of a cross section of explosivety compacted TI deuteride specimens.

133x ~ ~- ~~ ~ ~~- - ~~

Figure 6. Micrograph of a cross section of explosively compacted PdD,.

1-291 Measurement Of D/Pd Ratio Using Dilatometry And Factors Influencing The Deuterium Loading Level

Sivaraman Guruswamy Jun Li Narendran Karattup

1-292 Table of Contents

Page

Abstract 1-294

1. Introduction 1-294

2. Microstructural Changes In Palladium After Deuterium Loading 1-295

2.1 Mechanical Integrity 1-295

2.2 Microstructure 1-296

2.3 Surface Chemical Analysis 1-297

3. Determination of D/Pd Ratio: Dilatometry 1-297

4. Conclusions 1-299

5. Acknowledgements 1-300

References 1-300

1-293 Abstract

Metallurgical changes that occur in palladium electrodes after short and long term loading with deuterium are summarized. Changes in microstructure, hardness, surface condition and mechanical integrity are described. Factors that limit D loading of Pd above a critical D/Pd ratio at which all octahedral positions in Pd are occupied by D atoms are discussed as this may be a precondition to achieve nuclear fusion in solid state. In-situ measurements of D/Pd ratio using dilatometry technique under different conditions of electrolyte, current density, cathodic overvoltage and electrode composition are presented. Results indicate achieving D/Pd > 1 is difficult and D/Pd ratios measured lie between 0.7 to 0.97.

1. Introduction

Hydrogen and its isotopes exhibit unusually high solubility in palladium and the solubility depends on the hydrogen pressure in equilibrium with the metal and the temperature [l-31. Pons and Fleischmann suggested that high surface pressures/ fugacities obtained during electrochemical loading may result in completely filling of all octahedral interstitial sites and compressing the D loaded palladium lattice may result in nuclear reactions involving D atoms [4]. The electrode microstructure, chemical composition and the defect structure, defect density and defect distribution in the electrode can influence the extent of loading and therefore the possibility of nuclear reactions in solid state as proposed by Pons and Fleischmann .

While deuterium atoms can exhibit ionic, covalent or metallic character in the compounds or alloys it forms, in transition metals like Pd, it forms a metallic bond. It donates its electron to the conduction band and it remains as a proton [5]. At concentrations of less than 2%, the a- phase, an interstitial solid solution of D in Pd metal, is formed. At concentrations in excess of above about 2%, an intermetallic alloy phase (P-phase) of PdD, is formed in which H or D atoms have an ordered arrangement in interstitial sites of the Pd lattice. The stoichiometry of the P-phase depends on the hydrogen partial pressure. The two phases that form in the Pd-D system are both metallic and are relatively soft. In both a and P phases, Pd atoms occupy the face centered cubic lattice. Of the octahedral and tetrahedral sites, octahedral sites are energetically more favorable for occupation by D atoms [3]. However energetics for the occupation of either site at high concentrations of D have

1-294 not been investigated. Lattice parameter and hence the dimensions of the electrode changes with D content. In the D/Pd ratio range of 0-1.0, the variation is linear with concentration [6]. Growth stresses arising from the large change in dimensions during the formation of the P-phase, lead to plastic deformation of the lattice and therefore the dilation is observed to be different along different axes of the electrode [7].Both the diffusion co-efficients and total hydrogen content are influenced by dislocation density.

The effects of hydrogen or deuterium loading at high current densities and extended periods of time on the physical behavior of Pd and other metals have not been reported in detail in the literature. In this investigated a large number of electrochemical loading experiments, dealing with calorimetry and nuclear products monitoring, were carried out and the details of these experiments are summarized in another report. Metallurgical analyses were performed on some of the electrodes from those experiments that (i) showed temperature excursions (ii) were subjected to long term loading; and (iii) were operated at high current densities. Critical current densities and overvoltages at which high loading can be achieved were determined by in-situ dilatometric measurements. Measurements of cathode dilation in-situ as a function of current density, electrolyte composition, pH and poison addition at constant current were made. Measurements of dilation, anodic overvoltage, cathodic overvoltage, total cell voltage and current maintaining cathodic potential constant were carried out to determine the lowest overvoltage at which loading can be done slowly enough to minimize plastic deformationldamage of the cathode due to loading. AC impedance measurements of the cathode/electrolyte interface in the electrochemical cells using Pd, Pd alloy or intermetallic alloy cathodes in LiOD and Li2S04 electrolytes were also performed. This report discusses the measurement of D loading using dilatometry and the factors that influence loading.

2. Microstructural Changes In Palladium After Deuterium Loading

The electrodes that have been in use for periods ranging from few days to 11 months were examined using the scanning electron microscope, optical microscope, transmission electron microscope and electron microprobe.

2.1 Mechanical Integrity

Many of the electrodes exhibited severe cracking after electrochemical loading, in particular after long term loading and when loaded at high current densities. The

1-295 nature and extent of cracking and the time after which they appear varied widely, from fine surface and subsurface cracks to large macro-cracks. A 99.995 purity Pd rod from Metalor, USA, deuterated for nearly 11 months showed extensive visual damage as shown in Figure 1. The surface contains a high density of fine cracks and microcracking is observed in the interior region around large cracks. Hardness measurements on the cross section show wide variations from 110 VHN to 180 VHN due to extensive microcracking in the sample. The optical microscopy image of the cross section shows extensive cracking and surface relief associated with subsurface cracks. Extensive cracking was also observed in a 0.5 mm wire electrode subjected to current densities from 1000 - 3000 mA/cm* over a period of about 3 months. The results show that independent of the source of electrode and dimension of the electrode, extensive internal micro-cracking of the electrodes occurred. Variations in hardness by many experimenters can be attributed to these surface and subsurface cracks. These surface and internal cracks will not allow high loading of Pd. This suggests the need for loading and unloading of D so as to have minimal differential stress across the specimen.

2.2 Microstructure

Transmission electron microscopy examination of the electrodes subjected to short term loading, of about a week, under controlled cathodic potentials, showed that extensive plastic deformation of the electrode occurred at all cathodic overvoltages used, from -1.6 and -3.2 V with respect to Pt reference probe. Current densities varied from a few FA to in excess of 600 mA/cm2. The X-ray diffraction pattern confirmed the presence of p hydride phase which is a metastable phase. The large dislocation density compared to the annealed starting material was observed in all of these electrodes suggesting that, at almost all practical current densities, plastic deformation of the electrodes will occur (Figures 2 and 3). The damage observed is due to the large strain associated with p hydride phase formation and/or the deformation resulting from high pressure hydrogen bubbles. In electrodes subjected to long term loading between 3 to 11 months, there was also similar extensive damage. Figure 4 shows a TEM micrograph of electrode after about 11 months of electrolysis. Specimen preparation of this sample was particularly difficult and the image is less clear due to extensive strain, high dislocation density and micro-cracks. An X-ray diffraction pattern showed that the major phase was p hydride. Only minor amounts of a phase were observed. The D/Pd ratio in the sample was estimated to be around 0.7. The polished

1-296 sections of the annealed palladium and electrodes loaded under different cathodic overvoltages are shown in Figures 5 and 6. Micrographs show extensive surface relief typical of that seen in shear transformations, in all the deuterated palladium specimens loaded at different cathodic overvoltages.

2.3 Surface Chemical Analysis

Limited surface chemical analysis was performed on different electrodes that either showed a temperature excursion or were subjected to large current density charging, using CAMECA 50 SX electron microprobe, XPS, Auger electron spectroscopy and SlMS analysis. Surfaces were covered with elements such as Al27, Na23, Li7, Ca40, Fe56, Lis, C12, Pd106, Cdll3, Pt, Rh, Co, Si, 0 and C. Except for Cd and Co, other elements are expected to be transferred from the electrolyte, anode, quartz glass vessel or from handling. High surface enrichment of Li and only a small amount of Pd was observed by SlMS analysis. These observations in this and other investigations suggest that control of impurities from the electrolyte phase and the cell components is very important. Use of electrolytically prepurified D20 and extreme care in handling of cell components during assembly and during operation are needed. In electrodes that have been run at high current densities exceeding 1000 mA/cm2 in LiOD electrolyte, extensive Pt transfer to the Pd cathode (30-40% Pt on the surface) was observed. SlMS analysis of the palladium cathode JM2 and a reference pure palladium sample were analyzed using a primary beam of 10.5 keV 02+and positive spectrometry. Small deviations of isotopic abundance compared to pure Pd reference was noted but not considered significant. Room temperature mass spectrometry of gases evolved from electrode JM2 showed H, H2, HD and D2 but no evidence of He4.

3. Determination Of D/Pd Ratio: Dilatometry

Monitoring of the dilation of the Pd cathode gives an indication of Pd loading. Different techniques that are employed to monitor the D/Pd ratio are the resistivity measurement, dilation measurements, measurement of shift in rest potential and gravimetry. All methods have certain limitations, making estimation of the D/Pd ratio difficult. Most of these measurements tend to overestimate the measured D/Pd ratio when there is cracking or deformation and any data presented must be used with caution. While gravimetry is direct, in-situ measurement is difficult due to bubble evolution, and density change due to internal cracks. Defects such as dislocations,

1-297 point defects and microcracks introduced during charging influence resistivity values. Cracks or fissures and plastic deformation can influence dimensional changes and hence D/Pd estimation by dilatometry. In-situ dilatometry was adopted in this work for the D/Pd ratio estimation because of the relative ease of the technique. Use of intermittent diameter measurements and gravimetry to correlate dilation to D/Pd ratio allows reasonable prediction of D/Pd ratios. Errors due to internal and external cracks and bending of the rods can introduce errors. However, this technique allows one to evaluate effects of different variables such as poisons, current density, surface treatments and microstructure on the D uptake of the electrode with relative ease. Figure 7 shows the length change as a function of charging time of a 99.995 Pd cathode with no surface treatment at a current density of 100 mA/cm2 in a 0.1 molar LiOD. In about 4-5 days, a plateau in the loading versus time curve was reached. Weight and diametral measurements of the electrode were done immediately after the electrolysis was stopped and were used in conjunction with the axial dilation value to determine the D/Pd loading. Loading beyond a D/Pd ratio of 0.93 has been observed using 100 mA/cm2 current density in LiOD. Addition of the poison had little effect. Turning the power off resulted in a rapid length change in the first two hours. In another experiment, even after several weeks, no change in length was observed until anodic discharge is done, indicating the metastable nature of the deuteride.

In the first set of experiments, the same 10 cm Pd cathode was used to study the influence of current density, addition of poisons and addition of D2S04 to adjust the pH to around 2.0. Therefore, the history of the specimens in each of those tests were different. In the next series of experiments, a number of 1 cm electrodes from the same original batch were used to test the effect of current density, annealing temperature and poisons in the electrolyte on the initial rate of uptake and maximum uptake of deuterium. Increases in current density or addition of thiourea at the 50 mMolar level did not result in any significant increase in dilation in this experiment, although the D/Pd ratio obtained was lower. Increasing the current density from 100 to 200 mA/cm* did not seem to increase the extent of loading. The initial loading rates were also similar.

It was then decided to fix the overvoltage at a constant value and follow the kinetics of loading. The objective was to determine the overvoltage level at which D loading can be done at a very slow rate so that any deformation/damage to the electrode due to differential stresses can be eliminated. In these experiments, the

1-298 voltage between the cathode and a platinum reference probe placed adjacent to the cathode was controlled at fixed values. In the initial experiment, the cathodic overvoltage was stepped up in increments to determine the current values and maximum extent of loading achieved at each level (Figures 8-10). The effect of the addition of thiourea on these measurements are shown in Figures 9 and 10. Next experiments were performed at cathodic potentials of -1.0, -1.4, -1.6, -2.4 and -3.2 V with respect to the platinum probe. At cathodic potentials below about -1.2 V with respect to Pt reference probe, no loading was observed. It was observed that at cathodic potentials below the -2.4 V level, there is a significant effect of overvoltage on the initial loading rate (Figures 11 and 12). The final loading levels seem to be influenced by the change in overvoltage but the extent of increase was small as the potential of the cathode with reference to platinum reference probe was increased from -2.4 to -3.2. Hardness variation of samples as a function of loading is shown in Figure 13. For cathodic current densities from less than one mA to as high as 600 mA/cm2, no significant difference in hardness was observed. Diametral strains were larger compared to axial strain. The ratio of diametral elongation to axial elongation seemed to increase with current density in many experiments but no specific correlation could be found.

Dilation measurements were performed for a number of alloys including high purity Pd annealed at 600°C and 125OoC, Pd-25Ag, Pd-lOCu, Pd-5Li and Pd-lOCe alloys at overvoltages of -1.6 and -2.4 V relative to Pt reference probe. In none of the alloys and current densities used did the D/Pd ratio exceed 1.0. In pure Pd annealed at 1250°C, at -3.2 V cathodic potential, the D/Pd ratio achieved was 0.95. Specimens annealed at 600°C showed a marginally higher D/Pd ratio. In most of the alloys the D/Pd ratio achieved was less than 0.8 except in the case of Pd-Li where a value of 0.96 was measured at a cathodic potential of -2.4 V.

4. Conclusions

Dilatometry measurements indicate that achieving loading levels of D/Pd ratio greater than 1.0, suggested as a precondition for nuclear reactions, is difficult to achieve. In all the experiments carried out under a variety of different conditions, maximum loading achieved was about 0.93 in pure palladium at a cathodic potential of -3.2 relative to Pt reference probe. Loading level varied with cathodic overpotential at overvoltages between -1.6 to -3.2. Plastic deformation resulting from D loading causes non-uniform dimensional changes. Diametral changes are larger than axial

1-299 changes. Simultaneous measurement of axial and diametral expansion is required to accurately predict the D/Pd ratio. Addition of alloying elements in general reduced the maximum D/Pd ratio achieved and in all cases the D/Pd ratio obtained was less than 0.8. Microstructural studies indicate that at almost all practical current densities employed by different investigators, from few hundred pA/cm* to 600 mA/cm*, plastic deformation of palladium electrode occurs. The resulting dislocation density is likely to result in an overestimation of D/Pd ratio. Extensive micro and macrocracking observed in palladium at high current densities or extended charging times lowers the maximum loading that can be achieved.

5. Acknowledgements

The investigators are grateful to Professor M. E. Wadsworth and Professor J. G. Byrne for their invaluable discussions and participation. The investigators are thankful to Myong R. Kim and H. Hwang for their assistance in microscopy work. Dr. D. P. Agarwal, of Leach and Garner Co., and Dr. Ravi Nadkarni, Metalor, USA for providing generously the palladium rods whenever needed. Help of Dr. John Morrey of Battelle Northwest Laboratories, with surface analytical work, is gratefully acknowledged.

References

1. F. A. Lewis, in "The Palladium Hydrogen System", Academic Press, New York (1 967) 7.

2. Handbook of Precious Metals, Ed. E. M. Savitskii, Hemisphere Publishing Corporation, New York (1989) 167.

3. R. Lasser, in Tritium and Helium-3 in Metals, (1990) pp 48-61.

4. M. Fleischmann, S. Pons, and M. Hawkins, J. Electroanal. Chem., 261 (1989) 301.

5. H. J. Goldschmidt, Interstitial Alloys, Plenum Press, New York, 1967.

6. J. E. Schirber and B. Morosin, Phys. Rev. 12 (1975) 117.

7. F. M. Mazzolai, P. G. Bordoni, and F. A. Lewis, J. Less Common Met., 74 (1980) 137.

1-300 b

Figure 1. Scanning electron micrographs showing extensive cracking in palladium cathode after 11 months of D charging. (a) Surface region and (b) interior region. c -#

Figure 2. Transmission electron microscope image of annealed palladium showing low dislocation density. Specimen was annealed at 1250°C 3 hours.

Figure 3. Transmission electron microscope image of annealed palladium after loading at a cathodic potential of -2.4 V relative to platinum reference electrode. Specimen was initially annealed at 1250°C for 3 hours.

1-302 Figure 4. Transmission electron microscope image of initially annealed Palladium after loading at current densities varying from 60 mA/cm2 to 600 mA/cm2 over a period of 11 months.

Figure 5. Optical micrograph of palladium electrode annealed at 1250°C for 3 hours.

1-303

- __I.Ix_1-111 CY

Figure 6. SEM micrograph of palladium electrode initially annealed at 1250°C for 3 hours and deuterated in 0.1 M LiOD at a cathodic potential with respect to

pt reference probe of (a)-1.6 V and (b) -2.4 V.

1-304 1600.00

n 1200.00 2 .-0 E v 800.00 C .-0 + 0 0 400.00 -0 w

0.00 I~~~,,,r,~,,,,,,,,,,,,l,,,l,~,, 0.00 2000.00 4000.00 6000.00 Time (rnin)

Figure 7. Dilation of the cathode as a function of D charging time during charging of the 1 cm Palladium cathode in 0.3 M Li,SO, (D,O)electrolyte.

Figure 8. Variation of current and anodic potential as the cathodic potential was increased from -2.0 to -1.4 V.

1-305 -250.00 > 1 LL- Dilatation W iLlo.00 1 v, > W - 0 '3 i50.00 1 C Q) 4-l a0 .-0 190.00 7 D 0 C Q 4 n 4 E W 0.00 4,I I I 8183 1 18 1, 8 11 1, I,' 8 8 8 11 7 1 I 1'1 1 "" I " 1 "I' ' I I ' "I' " " I " 1 " " " I """"' 1' 3 """I -5.50 -5.00 -4.50 -4.00 -3.50 -3.00 -2.50 -2.00 -1.50 -1.00 Cathodic Potential (vs REF, V)

Figure 9. Variation of current and anodic potential as the cathodic potential was decreased from -1.2 to -5.0 V after thiourea addition to the cell.

-:o.oo -

,m.oo

4 0.00 IIrI I~~n,~~~~~~~~~I~,,~,,~,,l~,,,,,,,,l,,,,,,,,,l,,~~,,,,,,,~,,,~,,~l,,,,,,,,,, -5j.50 -5.00 -4.50 -4.00 -3.50 -3.00 -2.50 -2.00 -1.50 Cathodic Potential (vs REF, V)

Figure 10. Variation of current and anodic potential as the cathodic potential was increased from -5.0 to -1.2 V after thiourea addition to the cell.

1-306 D-Cell 5

400 1

Total Voltage (V) .L C :200: 3 0 Anodic Potential (V)

Cathoaic Po:ential (V)

-2 00 --- 00 50000 35000 Time (hoJr)

Figure 11. (a) Dilation of 1 cm Pd cathode annealed at 1250" C as a function of charging time at a cathodic potential of -1.6 V with respect to reference platinum probe and (b) Variation of anodic potential, total cell voltage and cell current as a function of charging time.

1-307 400.00 3

Dilatation (p)

I I rni-rq~,~wnl,I,, 5.00 10.00 15.00 2'020, , , , , , , I , , , , , I , , , , ,, , , 45.001 45.00 - Time (hour)

15.00

44 c 10.00 E) 0.1 '(mA) L 3 0 +j 5.00 - - Q) CT 0 -& >0 0.00 Anodic Potential (V)

Figure 12. (a) Dilation of 1 crn Pd cathode annealed at 1250" C as a function of charging time at a cathodic potential of -2.4 V with respect to reference platinum probe and (b) Variation of anodic potential, total cell voltage and cell current as a function of charging time.

1-308 Cathode Potential vs Hardness

200 - I I I I nz - > 175 - fi s W - % 150 - c, - ' 125 Before electrolysis 5 - & 100 - 4 E 75 - s -

4 I I 1 1

Figure 13. Hardness of palladium electrode as a function of cathodic potential with respect to Pt reference probe.

1-309 Ultrasonic Energy Effects on Palladium Electrodes in Cold Fusion Cells

Larry L. Anderson

Wisanu Tuntawaroon

Department of Fuels Engineering University of Utah April 1991 Copyright 0 1991 National Cold Fusion Institute University of Utah

1-310 Table of Contents

Page

1. Overall Summary 1-312

2. Introduction 1-312

3. Experimental Set-Up and Procedures 1-312

4. Detailed Experimental Results 1-313

5. Discussion 1-315

6. Conclusions 1-316

References 1-317

1-311 1. Overall Summary

The objective of this project was to determine if ultrasonic treatment of palladium electrodes could enhance their ability to take deuterium into their lattice where nuclear reactions could take place. A secondary objective was to determine if compositional changes actually took place in the electrodes and if so what the changes were. These objectives were not achieved although it was determined that ultrasound did influence the cell temperature and power level.

2. Introduction

When a liquid-solid interface is subjected to high intensity ultrasound, acoustic cavitation occurs near the solid surface and asymmetric bubble collapse takes place which generates a high speed jet of liquid which impinges on the solid surface (1). This impingement and related shock waves can produce highly reactive surfaces. In the case of some catalytic materials, activity changes as a result of ultrasonic treatment, can be dramatic' [nickel catalyst activity was increased by a factor of 105with ultrasonic treatment of one hour] (2). Such changes can be the result of cavitation changing the surface composition. Since the surface of palladium can become contaminated by several different substances during electrolysis its reactivity and susceptibility to hydrogen (or deuterium) can be affected. At least three methods were initially conceived as possible ways to treat the electrodes which would be used in the experiments. Because the surfaces of electrodes were easily contaminated by the many reactive materials present in the electrolytic cells only one method was used: electrolytic cells were fitted with ultrasonic cell disrupter (titanium) horns.

3. Experimental set-up and procedures

Cells were constructed with facility to include a sonicator ultrasonic processor with a 1/2 inch tapped horn which could transfer sonic energy to the cell. Cells were scheduled to be run in pairs with one being operated with ultrasound and the other operated without ultrasonic energy input. A standard cell similar to those used by others at the NCFl (B type) was used. Figure 1 shows such a cell without a tapped horn to introduce ultrasonic energy into the cell. To install an ultrasonic horn into the cell an additional 5 mm hole was drilled in the teflon cap.

1-312 Palladium electrodes were cylindrical in shape and had dimensions of 6.7mm diameter and 10.5mm length. Anodes were made of platinum with a diameter of 0.3mm and length of 10.5mm. The anodes were constructed into a net with anodekathode surface area ratio being at least 3.0. Cell number 1 was operated for 24 days, all with ultrasonic energy supplied. Figure 2 shows the temperature and power input for cell number 1 for the time it was in operation.

After it was determined that the location of the ultrasonic horn and cathode were not ideal for the generation of cavitation bubbles on the cathode surface cells 2, 3, 4, and 5 were constructed so that maximum impingement onto the cathode surface was assured. These cells were then run in pairs with one of the pair being subjected to ultrasound and the other operated without ultrasound.

4. Detailed Experimental Results

Cells 2 and 3 : These two cells were operated simultaneously with attempts made to operate the cells under identical conditions.

The starting conditions for cell number 2 (operated with ultrasound) was:

Cell current = 49 mA (constant)

Cell voltage = 6.1 4 volts

Bath temperature = 24.31 "C

History and operation

days of operation = 22

days with ultrasound treatment = 22

Cell temperature (average) = 26.43 "C

Power input = 300.86 mW

Ultrasonic treatment: 1 hour each day

From Figure 3 we can see that the temperature and power were mostly high for the first few days and then after about ten days the power dropped off dramatically and

1-313 did not return to the initial conditions.

The starting conditions for cell number 3 (operated without ultrasound) was:

Cell current = 49 mA (constant)

Cell voltage = 7.24 volts

Bath temperature = 24.26 "C

History and operation:

days of operation = 22

Cell temperature (average) = 25.93 "C

Power input = 354.76 mW

Although this cell operated at a lower temperature (by 0.5 "C) than cell number 2, the temperature history was very similar to number 2, i.e. after about ten days the temperature dropped dramatically and did not return to the initial value (Figure 4).

Cells 4 and 5: These cells were operated as a pair with number 4 receiving ultrasonic treatment and number 5 operated without ultrasound.

The starting conditions for cell number 4 (operated with ultrasonic treatment) was:

Cell current = 48 mA ( constant)

Cell voltage = 6.23 volts

Bath temperature = 24.03 "C

History and operation:

days of operation = 22

Cell temperature (average) = 26.33 "C

Power input = 299.04 mW

1-314 Ultrasonic treatment- 1 hour each day

From Figure 5 we see that the average temperature is 2.3 OC higher than the bath temperature and that the power of this cell is maintained at an high level during the whole period of operation.

The starting conditions for cell number 5 (operated without ultrasonic energy) was:

Cell current = 52 mA (constant)

Cell voltage = 6.8 volts

Bath temperature = 24.12 "C

History and operation:

days of operation = 22 days

Cell temperature (average) = 25.98 "C

Power input = 353.36 mW

From Figure 6 it is seen that while the temperature level for Cell number 5 had some variations, the power of the cell was constant and showed no unusual behavior.

5. Discussion

The duration of the project herein described was short and limited in scope. The limitation of funds and manpower reduced the possibility of complete measurements and monitoring of the properties of the electrodes and the processes occurring in the cells. Therefore, the results obtained must be considered as only preliminary. There were no measurements of tritium or neutron release and the electrode surface compositions were not looked at in detail. The cell pairs operated to give an indication of the possible influence of ultrasound on the initiation or maintenance of energy- producing reactions showed that the cells which had ultrasonic energy added during their operation were more active than those without such input. That is the only conclusion that can be made about the experiments conducted. The technical literature is also not particularly helpful in this problem. While there has been

1-315 extensive examination and research on the physical effects of cavitation on extended metal surfaces, the emphasis has not been primarily concerned with the chemical effects of ultrasound (3).

Further work will need to be done to see if the differences in activity of the cells can be utilized to enhance or initiate energy-producing reactions. Such would necessarily include monitoring of the surface composition of the electrodes, especially of oxide or other inhibiting layers which could impede such reactions as those between deuterium-palladium. Work would also have to be done to determine the optimum placement of the ultrasonic processor horn relative to the electrode surface.

6. Conclusions

The operation of electrolytic cells assisted by ultrasonic energy input shows some possibility of enhancement to energy-producing reactions. No experiments were conducted which resulted in high energy (thermal) "spikes". Cells which were activated by the input of ultrasonic energy were always more active, i.e. had higher temperatures and cell power, than comparable cells operated at the same initial conditions.

1-316 References

1. K. S. Suslick and S. J. Doktycz, "Effects of Ultrasound on Surfaces and Solids", Advances in Sonochemistry, Vol. 1, (1990), Ed. by T. J. Mason, 197-202.

2. K. S. Suslick and D. J. Casadonte, "Heterogeneous Sonocatalysis with Nickel Powder", J. Am. Chem. SOC.,Vol. 109, (1987), 3459.

3. K. S. Suslick and S. J. Doktycz, "Effects of Ultrasound on Surfaces and Solids", Advances in Sonochemistrv, Vol.l, (1990), Ed. by T. J. Mason, 207.

1-317 I ‘.e/Teflon Cop

Eloctrolyto Too Lovol

Ouortr Coll Tub.

Acrrlic Jockot

In PT Anodo Cog. Support Rod8

Pd Cathod,

PT Anodo Wlro Cog. k tollo on Bottom Support

Figure 1. Schematic of typical cell used for the experiments wherein ultrasound effects on electrolytic and accompanying reactions was studied.

1-318 2 -3 rn E 10- Q)

3 rn Q)

@ 8- n - d Temperature oll

4- s0 e

8 2 1 I 8 I 0 10 20 30 Days

Figure 2. Data obtained for Cell number 1, treated with ultrasound for 24 days.

1-319 1.2

I Y Power Input I 1.o - d Temperature I - I 0.8 I I

I 0.6 I I

r 0.4 I I

I 0.2 - I

0.0 w i m I W 10 20 30 0 Days

Figure 3. Data obtained for Cell number 2 operated for 22 days with ultrasound treatment for one hour each day. The ultrasonic energy input was 475 watts from a 1/2 inch tapped horn.

1-320 2l

I Y Power Input Id Temperature

0 8 1 I 8 0 10 20 30 Days

Figure 4. Data obtained from Cell number 3 operated for 22 days without ultrasonic energy input. Cell number 3 was operated in parallel with Cell number 2.

1-321 II Y Power Input + d Temperature

0 10 20 Days 30

Figure 5. Data obtained from Cell number 4 operated for 22 days with ultrasound treatment for one hour each day at 475 watts from a 1/2 inch tapped horn.

1-322 4

I Y Power Input 2 I 3 CI d Temperature E! - EQ) 3- 8 . t) 2- ol) c. 3n I .-t L. 1-

Figure 6. Data from Cell number 5 operated for 22 days without ultrasonic energy input. Cell number 5 was operated in parallel with Cell number 4.

1-323 Nuclear Measurements on

Deuterium-Loaded Palladium and Titanium

Haven E. Bergeson

Steven C. Barrowes

Kevan C. Crawford

Xuan-Ming Du

Lori Knight

Yong-Qing Li

Fariborz Lotfi

Gary M. Sandquist

Shu-Xing Wang

Joseph West

1-324 Table of Contents

Page

Abstract 1-326

Introduction 1-326

Detectio n Capabi Ii t ies 1-327 Gamma Rays 1-327 X-rays 1-329 Tritium Detection 1-333 Neutron Counting Systems 1-337 Monte Carlo Simulation 1-340 Ne ut ron Energy Specto meter 1-341 Charged Particle Detection 1-343

Experimental Results 1-347 Gamma Rays 1-347 X-Rays 1-348 Tritium Detection 1-350 Neutron Counting Results 1-351 Gas Discharge Ex pe ri me nts 1-364 Gas Loading Experiments 1-373 High-Loading Electrochemical Experiments 1-376 Fuel-Cell Type Experiments 1-379 Monte Carlo Neutron Simulation 1-381

Conclusions 1-384

Acknowledge me nt s 1-385

Ref e re nces 1-387

1-325 Abstract

Nuclear detection capabilities have been built up and many cells observed for nuclear radiations or byproducts. The most firm positive result has been significant tritium production in at least five different types of experiments. Significant neutron bursts have also been found in three types of experiments. No significant excesses of gamma rays or x-rays have been found. Significant progress was also made toward setting up a charged-particle experiment and establishing an underground laboratory, where higher quality measurements would be possible.

Introduction

When a new field of nuclear science is opened up, as with the claims of nuclear fusion occurring at room temperature in deuterated palladium, there are not many guidelines on what to expect. Accordingly all types of nuclear radiations should be checked for, and if possible several should be measured in the same experiment, to establish correlations.

The first nuclear by-product measurable at NCFl was tritium in the form of electrolyte or recombined D20. This was done with a commercially available Beckman LS 5000 TD, which works by liquid scintillation counting and has given re Iiable resu Its.

An immediate possibility when nuclear reactions are occurring is gamma rays. Their detection would constitute a nuclear signature. A good gamma ray spectrometer was thus purchased and employed in the search for both gammas and neutrons.

If nuclear reactions occurred without giving any gamma rays, then one would expect either energetic charged particles or energetic neutrons. One would not expect all the energy to go directly to the lattice in the form of heat, although that has been suggested by a theorist from Italy [l] and others [2].

If energetic charged particles occur, then they should produce some x-rays, especially in the low energy range of palladium L x-rays. Accordingly a good x-ray spectrometer was purchased and used.

Neutrons were reported by a number of groups. From our earliest set-up, using the gamma ray detector, to our latest set-up with four helium-3 counters monitored by

1-326 an event logger, the efficiency improved by over a factor of 200. With the latter set-up we have detected neutron bursts from gas loaded cells and from electrolytic cells in a water bath.

Many of these measurements are made difficult in a surface laboratory due to the cosmic ray background of X-rays, gamma rays and neutrons, which fluctuates with air pressure and with solar flare activity. A site for an underground laboratory was searched for and located, but plans could not be implemented because funds were held up for use by lawyers for patent protection.

Direct measurement of energetic charged particles has been reported by several groups. A vacuum chamber for such an experiment was designed, built and tested. It would be a collaborative effort with BYU, if time and funding permitted, and would simultaneously measure charged particles, x-rays and neutrons. The times of these emissions would be recorded within a few microseconds, allowing detailed reconstruction and understanding of many of the events.

This final report gives details on the development of these various detectors of nuclear radiations and by-products, and summarizes results found to date. Other groups will report some of these results as they apply to their experiments.

There are enough positive findings to entirely rule out a strictly chemical explanation, but not enough to detail the kind of nuclear process that is occurring. This young field is quite complex, and final conclusions regarding its potential will not be possible for some time to come.

Detection Capabilities

Gamma Rays

In conventional nuclear reactions, gamma rays are often produced. In addition, among processes occurring naturally in or around the earth, nuclear reactions are the only source of gamma rays. Thus, any significant excess of gamma rays above the cosmic-ray background level would be proof of a nuclear process at work.

In December, 1989, a high quality gamma ray detector was purchased from EG&G Ortec, along with the necessary high-voltage power supply, spectroscopy amplifier and multi-channel analyzer (MCA). The detector employs a high purity

1-327 germanium (HPGe) crystal with an efficiency of 55% relative to a standard sodium iodide crystal. Of course, the energy resolution for HPGe (1 keV at 122 keV, 2.1 keV at 1.33 meV) is far superior to that of sodium iodide.

The HPGe detector crystal and preamplifier are both run at liquid nitrogen temperature to reduce noise. The detector is equipped with a dewar for liquid nitrogen with a 48-hour holding time.

No improvements were made on the detector itself, but a troublesome noise pickup problem demanded considerable attention.

It was found that a large number of counts occurred in the lower channels at certain times. This was of potential interest because the energy associated with those channels was approximately 21 keV, the energy of K-alpha x-rays from palladium.

It was then found that if large signal pulses were fed into the amplifier, pulses large enough to saturate the MCA occurred. These large pulses also caused spurious counts in the low channels. The noise in the lower channels was code named "big stuff", since it could be simulated by large, saturating pulses.

The big stuff pulses were noticed to come within an hour or two of 11 AM on alternate days, and could be picked up even in remote parts of the building. It lasted only for a minute or two each time, making it very difficult to observe directly or to determine its exact nature.

Without knowing the exact nature of the pickup, it was not possible to pinpoint the source or devise an effective shielding strategy. We could, however, be wary of its existence so as not to be fooled by it. If we had seen real gamma ray signals, one would expect them to show a line spectrum or other spectrum different from that of big stuff.

On the other hand, cold fusion reactions are known to occur in spurts or bursts. There have been many reports of bursts: heat bursts, neutron bursts, tritium bursts and small pockets of tritium, and even helium-4 in electrodes after an experiment.

If a nuclear reaction were taking place, in a burst mode, there could be simultaneous gamma rays in the HPGe detector. Simultaneous gammas would be interpreted as a single large gamma ray by the detector, exactly like a "big stuff" signal.

1-328 Hence it was necessary to show that the big stuff pickup occurred in all parts of the building rather than just in the vicinity of active cells.

If additional time were available for research, it would be desirable to track down the source of the big stuff interference and somehow eliminate it. Only then would the HPGe detector be sensitive to simultaneous gammas from active cells.

if the big stuff pickup could not be eliminated, an additional HPGe detector could be purchased and operated a few meters away from the active cell. Any pickup on the remote detector would indicate that the noise signals were present and must be subtracted out.

No positive gamma ray results were obtained in any of the cells monitored.

X-rays

X-ray detection seemed a very likely possibility since any energetic charged particles produced by a fusion reaction would likely produce some x-rays.

Si(Li) Detect0 r

In ordinary circumstances the best x-ray detector would be a lithium-drifted silicon (Si(Li)) detector. A high quality Si(Li) detector was obtained from EG&G Ortec in June, 1989. The silicon crystal operates at liquid nitrogen temperature, to reduce noise, and is surrounded by vacuum behind a thin (25 micron) window of beryllium.

The data from the Si(Li) detector was taken with high quality electronics tailored to the need. The preamplifier was built into the nose of the detector to reduce noise in three ways:

(1 ) Operation at liquid nitrogen temperature along with the detector crystal;

(2) Very short connector leads to reduce electromagnetic pickup; and

(3) Enclosure in an aluminum shield.

Shielded coaxial cables were used, along with a high quality spectroscopy amplifier and multichannel analyzer (MCA) board in the computer.

1-329 For low energy x-rays, the thinness of the beryllium window is very important, since it is the only absorber between the sample and the detector crystal that cannot be removed by designing a thinner cell. Beryllium is the least absorbing metal available in nature, as it has the smallest atomic number of any room-temperature metal.

X-rays hitting the silicon crystal convert their energy by causing energetic electrons, which leave ionization along their paths. This causes a well-defined electrical pulse in proportion to the energy of the original x-ray. Because of the good energy resolution, Si(Li) detectors are the best available for identifying the x-rays characteristic of the various elements.

The main improvement made on the Si(Li) detector was to add some foam insulation to its dewar portion. This extended its liquid nitrogen holding time from 24 hours to 36 hours (a good convenience) and reduced its sensitivity to mechanical vibrations which otherwise cause spurious signals.

An additional improvement was a grounded, lead-shielded cap with a protective screen window in front. The lead shielding reduces the cosmic ray and environmental x-ray background by 12% at 1.5-2.0 keV, by 43% at 2.3-3.8 keV, and by 68% at 21 keV.

Thin-Walled Ce lls

The Si(Li) was used to monitor a number of cells with various wall thicknesses. It was soon realized that low energy x-rays would be the most likely due to more possible production modes and that cell wall thickness would be crucial due to the very rapid attenuation of low energy x-rays.

A group of cells was specially constructed from a polyethylene tube with a window cut out and replaced by very thin polyethylene (HandiWrap), 13 micrometers thick. A set of eight such cells were constructed, four with light water and four with heavy water.

The primary difficulty with such measurements is the rapid attenuation of low energy x-rays. For example at 3 keV, the average energy of palladium L x-rays, the attenuation length in water is 0.05mm, while at 21 keV the attenuation length is about

1-330 1.4cm. Attenuations in polyethylene are only slightly less.

To have a chance to see 3 keV x-rays, these thin-walled cells were run outside the water bath with just air cooling, and with the palladium cathode almost touching the thin polyethelene window.

As these cells were run, the palladium tended to bend and twist, causing most to eventually break holes in the thin polyethylene, shortening the runs. The results from these runs are presented in Section Ill of this report.

Baseline Shiftina Problem

One difficulty needs mention which was discovered while these runs were being taken. On a number of occasions, there were no counts in the lowest 15-20 channels for the first two to five minutes of a run, after which these channels accumulated counts in the normal manner. This phenomenon was not noticed except at the beginning of a run.

In trying to simulate the effect to better understand it, it was found that if the amplifier was bombarded with a high rate of signal pulses the amplifier baseline would shift up or down, giving too many or too few counts in low-energy channels for up to several minutes.

One way this might have happened would be in response to a large number of real x-ray pulses which might occur at the beginning of a run. Another possibility would be a large number of noise pulses picked up at the beginning of a run. A third possibility might be a large number of radio frequency electromagnetic pulses produced when the hydrogen loading exceeded 0.65 in various crystal domains. At such times microcracking occurs, with accompanying radio frequency noise. Such noise, if strong enough, could pass through the thin beryllium window.

To eliminate pickup of radio frequency noise emitted either by the sample or by electronic modules or power supplies, a lead-shielded cap was added, electrically grounded. The problem was apparently solved by the shielded, grounded cap, since it did not recur afterwards.

The problem remains somewhat puzzling, however, because it seemed to occur only during D20 runs and only at the start of those runs. Efforts to duplicate the effect

1-331 have not been entirely satisfactory, leaving unresolved questions and preventing any clear-cut conclusions concerning the x-ray observations on thin-walled cells.

The main difficulty with using the Si(Li) detector was the amount of absorber material between the cathode (source of the presumed x-rays) and the detector crystal. This absorber usually included several mm of water (H20 or D20), a vessel wall made of thin polyethylene or teflon or glass, at least lcm of air, and the 25 microns of the beryllium window.

If x-ray film were placed in a water-tight, light-tight envelope (of black polyethylene) and attached very near the cathode inside the cell, it would have less absorber and be able to detect lower energy x-rays.

It was reported by S. Szpak [3] of Naval Ocean Systems Center in San Diego that he had obtained film darkening in several D20 cells (but no H20 cells). One picture he showed contained a clear image of his cathode, which was a mesh of nickel wire, with co-deposited palladium and deuterium. Although the film had apparently moved during the experiment, giving a triple image, the prospects for this technique seemed very promising.

In the same experiments with the darkened x-ray films, an elevated tritium content was found in each case. Since these tritium analyses were done at NCFI, we verified that correct procedures were used, giving the x-ray results good credibility.

It was necessary to first find out which type of x-ray film was most sensitive and what thickness of black polyethylene or other material would be best for the film packets.

Many x-ray films are optimized for medical or dental purposes where the x-rays used are above 20 keV. For such uses a phosphor screen is often added behind the film to absorb more x-rays and return a green or blue glow, further exposing the film. Because of this, most x-ray technical people did not know what film would be most sensitive to low energy x-rays. Accordingly, we tested several films ourselves by exposing them to x-rays from an iron-55 x-ray source.

The best films for our purpose were Kodak Ektaspeed and XAR. Ektaspeed is a

1-332 commonly used dental x-ray film, about twice as sensitive as Ultraspeed, the other commonly used dental film. About equally sensitive was Kodak XAR film for autoradiography. Inferior results were obtained with TMAX-3200, the fastest black and white optical film available.

Although the Ektaspeed film was preferred for its small size, the film packet had more absorbing material than desirable. It had a white polyethylene outer envelope with black inner surface. Inside that was a piece of stiff black paper and a lead foil backing. Experiments showed that stiff black paper was very non-uniform owing to its fiber construction, creating effectual light leaks. Since black polyethylene was more uniform, a thinner absorber layer could still be light tight. The envelopes were thus made of black polyethylene, about O.lmm (4 mils) thick and heat-sealed to make the film packets.

If successful x-ray results were obtained, it was planned to use some optically flat glass cell vessels with powdered glass scintillator in suspension. A high quality time-exposure photograph would then show a blue glow in regions with many x-rays; the profile of this glowing scintillation light could then be studied to reveal the approximate energy spectrum of the x-rays.

Tritium Detection

Liauid Sc intillation Cou ntinq

The primary method of tritium detection is by liquid scintillation counting (LSC) done with a commercial instrument, a Beckman LS 5000 TD.

The Beckman uses two photomultiplier tubes, shielded by about two inches of lead from cosmic-ray gammas and x-rays. The two tubes work in coincidence to reduce the effects of electronic noise.

The sample (usually 1 ml of water or heavy water) is added to 10 ml of liquid scintillation cocktail and shaken vigorously. If a tritium atom in the sample decays, the decay electron produces a flash of light as it moves through the scintillator, causing both photomultiplier tubes to simultaneously register a pulse.

If both tubes do not record pulses simultaneously, no tritium count is recorded. In this way most noise events can be eliminated, since they originate in one tube or the

1-333 other, but not both. (They originate as a single photon or a single electron).

The main sources of single-tube noise are photolumenescence, chemilumenescence, and thermionic electrons within a phototube. Photolumenescence can be eliminated by storing the sample in the dark for several hours prior to testing, and transferring the sample to the machine under darkroom light. This same dark storage also reduces chemilumenescence by allowing the chemical reactions time to die down before a count is taken.

Thermionic electron emission from the photocathode or dynode surfaces is very temperature dependent, and can thus be reduced by keeping the tritium laboratory relatively cool.

The circuitry included within the Beckman monitors the single-tube noise events and calculates how many random coincidence events will occur during a sample counting. This is printed out with each sample result as the random coincidence monitor (RCM) percentage. Experience supports the manufacturer's claim that readings are reliable if and only if RCM is below 5%. As RCM exceeds 5%, the readings become progressively higher in a non-linear fashion, making it important to disregard such data.

When samples are clear and colorless the RCM percentage is usually below 2%. On the other hand, when samples are colored or contain chemical impurities of various types, high RCM values may occur and be difficult to eliminate without distilling the sample.

Cosmic rays contribute some counts in both tubes simultaneously, as when a muon or electron has enough energy to penetrate the lead shield and the sample itself. One must therefore run background samples.

The accuracy of an individual reading depends upon the total number of tritium decays counted. Since the standard deviation for N total counts is the square root of N, one chooses an accuracy level, such as 5%, and the machine stops the sample run when there are enough counts to give that accuracy.

The Beckman automatically does a calibration on each sample, since counting efficiency depends strongly on the amount of chemical quenching (reduced scintillation efficiency due to chemical quenching in the samples) and color quenching

1-334 (absorption of light by colors in the sample). A radioactive source (Cs-137) is placed near a sample, and light pulses due to Compton-scattered electrons, are recorded. The efficiency is computed by comparing the measured energy of the Compton edge from irradiating the sample to the Compton edge from irradiating a standard, stored in memory. The measured counts per minute (CPM) for the sample are then divided by this efficiency to calculate the actual decays per minute (DPM).

A feature called automatic quench compensation (AQC) adjusts the window of pulse heights accepted as counts. This reduces background by rejecting counts too large to have come from tritium decay with a given amount of quenching. If the AQC feature is not used, these large counts are included as legitimate counts. In darkly colored samples, the artificially large counts result in very exaggerated DPM values, due to the division by very low efficiency values. One must therefore use the AQC feature for consistent results.

Cosmic rays sometimes cause unusually high readings. When standard precautions are observed, reliable tritium counts are obtained, and tritium readings over 3 DPM above background are meaningful. Background is usually 27 DPM for light water and about 35 DPM for heavy water, although some heavy water supplies have considerably higher backgrounds. Because of possible cosmic ray interference, we always count a sample at least three times to be certain that results are consistent and that no unusual readings are used.

The reliability of these tritium counts has been established by adding small, known amounts of tritiated water to test samples. When the samples were clear and thus high-efficiency (35-60%), accurate results were obtained. When the samples were colored (color quenched), the AQC feature still gave reasonable but slightly distorted results. Fortunately, most samples were clear and no corrective factor was needed.

The results of tritium counting are mentioned in the presentations by the various experimental groups. They are given for samples of the electrolyte or for samples of hydrogen (or deuterium) gas recombined with oxygen to make water again.

Gas-p hase Tritium Detection

Because of the bursty nature of cold fusion reactions, it was considered desirable to have up-to-the-minute information on tritium production. Any tritium

1-335 production bursts could then be correlated with heat bursts, neutron bursts, etc.

The LSC method accumulates tritium production over periods of hours to days, depending on sampling schedule, and thus is not sensitive to shorter tritium bursts.

The basic idea of an on-line tritium detector would be to direct the evolved hydrogen or deuterium gas over some plastic scintillators, which would be viewed simultaneously by two photomultiplier tubes.

Any tritium decays would send the decay electron at 0-18.6 keV into the scintillator. The scintillation light would be picked up simultaneously by the two photomultiplier tubes, satisfying the requirements of a coincidence circuit and recording the pulse.

Two design criteria must be optimized in a working instrument: low enough noise counts and high enough signal counts. A figure of merit would then be proportional to the signal counts from a given sample divided by the square root of the noise counts.

Noise reduction is accomplished by : (1) starting with photomultiplier tubes designed for single-photon counting, (2) use of a quiet preamplifier designed for low- noise applications of photomultiplier tubes, and (3) use of a fast coincidence circuit with a narrow coincidence window.

Enhancement of signal can be accomplished by increasing the surface area of scintillators, by using a large number of very thin pieces of scintillator. The scintillators chosen were 0.35 mm x 4 cm x 30 cm, with about 1.6 mm spacing between layers and 35 layers. This design put 0.5 liter of evolved D2 gas in close contact with the sci nti llato r.

The range of 3-18 keV decay electrons in hydrogen or deuterium gas would be 1.5-34mm, allowing almost all of the electrons over 3 keV to reach the scintillator.

With LSC, one can reliably detect an increase of 5 DPM per ml with about 30 minutes of counting time. The number of tritium atoms present in the 1 ml sample would be 4.6 x 107, compared with 6.7 x 1022 hydrogen or deuterium atoms, or one in 1.44x 1015.

The on-line or gas-phase tritium detector would contain 0.5 liter or 0.044 mol of

1-336 hydrogen atoms compared with 0.1 1 mol in 1 ml of water. This is 0.4 times as much, which would mean the sample would need 2.5 times as much tritium concentration for reliable detection in the same time, assuming each system counts essentially all of the tritium decays and has similar noise rates.

If tritium were being produced at concentrations 16 times the background rate for LSC, it would be detectable in five minutes with the gas-phase detector, other factors being equal. At lower concentrations, the counting would take longer and the gas-phase detector would lose its "on-line" advantage over LSC.

The gas-phase tritium detector was turned over to a graduate student as an MS instrumentation project, and a number of difficulties have prevented successful operation of the detector to date. To assure success would probably require more expensive photomultiplier tubes and preamplifiers to reduce noise, and more careful handling of the thin scintillators to prevent cracking and crazing.

The need for the on-line tritium detector has not been as great as anticipated since tritium production has not reached the high levels where up-to-the-minute information would be possible. If the need arises and funding becomes available, the experience gained on this project will expedite the construction of a workable on-line tritium detector.

Neutron Counting Systems

The first neutron counting system used at NCFl (other than the BF3 counters used for neutron safety monitoring) was a high purity germanium detector to observe the gamma rays given off when neutrons are captured by protons (hydrogen nuclei).

After several improvements in that system, some helium-3 gas proportional counters were set up. Each helium-3 tube has an efficiency 30 times that of the proton capture system.

A new electronics system would be needed to handle the inputs from many helium-3 tubes at once and also to record the time of each neutron within a few microseconds. With such timing information, neutron bursts can be identified. A burst of neutrons, produced instantaneously within a detector, is spread out in time by making many elastic collisions with hydrogen atoms in the moderator (water or paraffin wax). This reduces the neutrons to thermal energies and on the average takes about

1-337 125 microseconds.

An "event logger" circuit was developed, which records neutron times with f 4 microseconds on four separate channels and transfers these to computer memory within 50 microseconds.

With these advances, our neutron detection capability is beginning to become competitive with leaders in the field. What is still needed is several times as many helium-3 counters, a faster event logger circuit, and an underground laboratory to shield out cosmic-ray neutrons from our experiments. These advances would be feasible if research funding continued another six months, putting our neutron capabilities at the forefront of the field.

The advances made thus far are listed in Table 1. Each entry lists the efficiency, background counting rates from cosmic-ray gammas and neutrons, and the resulting detection limit (number of source neutrons per hour showing three standard deviations above the background).

Setups 1-4 used the high purity germanium (HPGe) gamma ray detector to detect the 2.225 MeV gamma rays from capture of a thermal neutron by a proton (hydrogen nucleus) in water. Setup 1 had no shielding; setup 2 added a 5 cm shell of lead bricks; setup 3 replaced the previous rectangular water container with a Marinelli beaker; setup 4 added an inner 10 cm shell of borated parafin wax bricks, to reduce cosmic ray neutrons.

Setups 5-7 use helium-3 gas proportional counters for neutron detection. No lead shielding is needed, since these counters are not sensitive to gamma rays. Wax shielding is used where possible, since it stops low energy neutrons before they reach the detectors. Setup 5 has two helium-3 tubes in a water bath; setup 6 has two helium-3 tubes in a parafin wax moderator; setup 7 has four helium-3 tubes in a wax moderator ring.

Setup 8 is a future arrangement which would use 12 helium-3 tubes in a wax moderator ring, and would use the great shielding potential of the underground laboratory, which was fully designed but was stopped at the funding level.

Detection limits for single-neutron events were set at three standard deviations above background rates. For bursts, three neutrons detected within 51 2 microseconds

1-338 TABLE 1

NEUTRON DETECTION IMPROVEMENTS

DET LIMIT 9PPROXIMATE PERCENT EFFECTIVE BACKGROUND DET LIMIT SOURCE-N START DATE SETUP EFFICIENCY GAMMNh NEUTROWh SOU RC E-N/h PER BURST ~ ~~

02 15 90 1 0.024 104 36 209,000

03 14 90 2 0.024 25 47 150,000

04 21 90 3 0.05 25 59 78,000

05 17 90 4 0.05 16 20 51,000

07 27 90 5 1.2 0 1225 12,600

08 28 90 6 2.8 0 760 4,200

01 17 91 7 4.5 0 1040 3,000

Future a 13.5 0 18 130 is statistically significant at the 5% level, as having a correlated origin, yielding the burst limits quoted. The burst capability did not exist until the event logger circuitry came on line beginning about January 17, 1991.

The event logger circuitry tags each neutron with its detection time within an 8- microsecond window. With four input channels, four neutrons can thus be well timed. The information must then be read into memory, which takes about 50 microseconds, before other neutrons can again be detected.

Since a burst of neutrons, produced instantaneously, is spread over a few hundred microseconds by the slow-down or moderation process, one event logger could detect, at most, about 20-30 neutrons in a burst. In practice, bursts of over 10 have only incomplete information. This effectively limits our burst sizes to 220 source neutrons with setups 5-7. If more neutrons are emitted, we can only say there were 220 or more.

The next improvement would be the fast event logger, using a faster microchip. It should record neutron pulses as close as 0.1 microseconds apart on each of 32 inputs, up to a total of about 2,000 detected neutrons in the burst. This would infer several times as many source neutrons, an order of magnitude more than have been detected by anyone thus far. The time needed to develop the fast logger is estimated to be approximately 1-2 months.

With the underground laboratory for shielding and the fast logger for detection of larger neutron bursts, we could study burst sizes from 5 to 5,000 source neutrons. This capability should be very useful in studying the nuclear mechanism responsible for these bursts.

Monte Carlo Simulation

One other item of progress in neutron detection is a better theoretical understanding of the neutron bursts as they affect the detectors. This was accomplished by a computer program which simulates the various random scatterings and eventual capture of each neutron. Called a Monte Carlo program because of the random or chance element in each neutron's behavior (or any subatomic particle's behavior), this program simulates a burst of source neutrons at a given energy to see if such a burst accounts for the type of events seen.

1-340 After detecting a 9-neutron burst in one event logger, it was apparent that we needed a better understanding of the theoretical response of our detector to a burst of ne ut rons.

The best method available for this would be a Monte Carlo program, in which hypothetical neutrons are started at the center of the detector, given random directions and started on their hypothetical journey. Using the correct cross section for each neutron at its current energy, they are allowed to interact as real neutrons would, taking a random walk from one elastic collision to another, always with a small chance for capture on a proton or detection if any helium-3 tubes are encountered, until they are either detected, captured or escape altogether.

By tallying the results from a large number of such random neutrons, one can predict the efficiency and times of detection for a burst of neutrons at any particular en ergy .

The experimental efficiency of the detector can only be calibrated using the Americium-beryllium neutron source. Using the Monte Carlo program we can understand the efficiency as a function of energy and predict the die-away time for bursts as a function of the number of helium-3 tubes in use.

The efficiency as a function of energy will be shown in the results section, as calculated by the Monte Carlo program. A decline in efficiency with growing energy is expected, due to the reduced elastic scattering cross section at high energies. This allows many of the high energy neutrons to escape from the detector without hitting any protons or after hitting just one or two. Lower energy neutrons are less likely to do this.

Neutron Energy Spectometer

While helium-3 counters are the best way to count thermalized neutrons, they provide no information on the energy spectrum of the neutrons produced.

The most common method of measuring a neutron's energy is to let the neutron collide with a proton or hydrogen nucleus and then detect the recoil energy of the proton. Another method is to let the neutron make two such collisions and measure the time of flight between the collisions. Both methods have been successfully used

1-341 on cold fusion experiments, but the time-of-flight method is far more involved and expensive.

Our proton-recoil detector uses a liquid scintillator made by Bicron, equivalent to NE213. This scintillator gives a different time response to scintillations made by electrons and protons. While the electrons (which come from gamma rays) give a fast response, the recoil protons give a slower response. Accordingly, pulse-shape discrimination provides the key to separate neutron induced signals from gamma induced signals.

The pulse-shape discrimination is accomplished by means of gating circuits. When a signal is detected a gate is already open for the prompt signal. After 125 nanoseconds, this gate is closed and a second gate is opened for the slow signal. The ratio of these two signals gives a fairly clean distinction between neutrons and gammas, while the magnitude of the slow signal is proportional to the proton recoil energy .

The proton recoils with any energy between 0% and 100% of the neutron's energy. Thus one cannot simply use the recoil energy as the neutron energy. If a beam of mono-energetic neutrons hit the detector, the recoil energies should resemble a step function, i.e. with a consistent number of particles per MeV until the maximum energy, then zero particles at higher energies. Thus the inferred neutron spectrum is the negative derivative of the recoil spectrum.

This project has been an MS instrumental project of Yong-Qing Li. Many difficulties were overcome and the apparatus is in working order to be used on an experiment, but no experiments on live cells have been done with it yet.

The efficiency for neutrons which hit the working volume (2.0 liter) is about 3.9%, as measured with an Americium-beryllium neutron source.

Like any other neutron detector, it would benefit from being operated in an underground laboratory away from the background of cosmic-ray neutrons and gammas.

If any cell becomes a good producer of neutrons, we would want to expose that cell to the neutron energy spectrometer to determine the energy spectrum produced.

1-342 Charged Particle Detection

Bursts of charged particles have been reported by about five different experiments, including those of Ed Cecil [4] of the Colorado School of Mines, using silicon surface barrier detectors and Xing-Zhong Li [5] of Beijing, China, who uses plastic track detectors.

In the experiment of Ed Cecil, the sample was a thin foil of titanium alloys loaded with deuterium at 700°C. The sample was then cooled and placed in a vacuum chamber facing the silicon surface barrier detector.

Bursts of charged particles hitting the detector were partially identified by covering half of the detector with a thin AI absorber. This split the energy peak, tentatively identifying the particles as tritons, 3He, or possibly alpha particles.

In order to duplicate and possibly confirm the charged particle measurements, a vacuum chamber was designed, built, and vacuum tested. As shown in Figure 1, the design includes two silicon particle detectors: one 10 microns thick (B) and the second 300 microns thick (A). in the thin detector, the particle's energy loss rate is measured and in the thick detector the total energy is measured. By comparing these two quantities with known behavior, we should obtain the identity and energy of each particle.

This would be a significant improvement by itself. In addition, the other side of the sample would be visible to the Si(Li) detector, to measure the energy spectrum of x-rays produced. Since this would be a vacuum environment, the only absorber would be the thin beryllium window on the Si(Li) detector, allowing x-rays above 1.0 keV to be detected.

This experiment was planned to be run in collaboration with BYU, using their neutron detector. The vacuum chamber with the particle detectors and the Si(Li) detector would fit into the chamber of their neutron detector.

The circuitry would be called the "pulse height logger", similar to the event logger now used for neutron counting, but with the added capability of recording the pulse heights from at least three of the four detectors. The events would then be reconstructed by software, providing for the first time some detailed correlations

1-343 Si(Li)

X-Ray

Detector

Figure I. Vacuum Chamber for Charged Particle Detection between the particles observed within each event.

This joint experiment could be run in a surface laboratory, but it would be a great advantage if it were run in an underground laboratory, as indicated in Figure 2. The underground laboratory (at site A) would reduce the neutron background by at least a factor of 200, and cause a similar reduction in the x-ray background.

Not only would the cosmic-ray background in a surface laboratory fill up our data storage with useless events, it would cloud the interpretation of the meaningful events, at least in the minds of many scientists. Because the pulse height logger would record the event times within a few microseconds, it would be possible with extra effort to extract many meaningful events from the background, but there would probably be categories of events which could not be meaningfully extracted.

This joint experiment has great potential for clarifying exactly what reactions are occurring. Such detailed understanding will ultimately be necessary before full advantage can be taken of any economic potential of cold fusion. Without this understanding, the processes involved may remain a mystery and efforts to utilize them may continue to resemble the black arts, with spurts of unrepeatable success and many rules of thumb but no reliable formulas.

While it may be supposed that the fusion processes can be made useful and reliable by an empirical, technological approach, this is not very likely. In past centuries the art of violin making was developed in this way, but the violin makers could hear, touch and feel the objects of their labor. Even with those advantages, it took the particular genius of Antonio Stradivari to discover a category of superior instruments. Modern engineers have since discovered the resonances he employed, allowing violas, cellos and bass viols to be built with similar excellence. In fusion experiments, we are blind and deaf without scientific research of an intense, multidisciplinary kind.

This charged particle experiment is of a comprehensive kind, simultaneously detecting many different nuclear products in a time-correlated way. This kind of comprehensive experiment probably holds the greatest promise for advancing our understanding of cold fusion.

1-345 Overburden Profile for Mutual Tunnel 1600-

1400

1200. Mountain Profile 1000...... *.-..* .-.I-- --- c, ,p-- a, a, -Y- 800. m .-0 E 600

400

200 Site B 1.5% slope n 0

-200 I I I 1 I I I I 1 1 I I 1 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 21 10 Horizontal feet Figure 2. Experimental Results

Gamma Rays

No positive results with gamma rays have been achieved thus far. Results using the gamma ray detector to detect neutrons captured by protons in water will be discussed under neutrons.

The gamma detector was employed for neutron detection until July, 1990, then it monitored for gamma rays from cells in the laboratory of Pons and Fleischmann.

There seemed to be some low energy gammas near 21 keV from one of the cells (21 keV is the energy one would most expect from excited palladium atoms). This was near the low end of the sensitivity and required some checking before it could be considered valid. Upon checking, these signals turned out to be spurious, but not entirely uninteresting.

It was found that when oversized signals were input to the MCA, it produced counts only in these lower channels around 21 keV. Thus the spurious counts might be due to saturating pulses from the detector.

Saturating pulses from the detector might be caused by a burst of simultaneous gammas contributing to a single pulse. If such gammas were within a few microseconds they would register as a single large pulse.

If gamma bursts were the cause, how could they be separated and identified? One method would be to back the detector away until single gammas would be recorded. But this would make the signal harder to find amid the still-strong background. An improvement on that would be to have a nearby and a remote gamma detector, with a pulse height event logger which would identify pulses received simultaneously. The nearby detector could be operated at low gain such that oversize pulses might be accurately recorded. Both detectors should be shielded by at least 10 cm of lead to reduce the cosmic ray background, or preferably operated in an underground labo rat0ry .

During the checkout of these saturating pulses, code named "big stuff," it was found that they occurred in large quantity for a minute or two on alternate days at about 11 :00 AM, plus or minus two hours. The times did not correspond to any known

1-347 changes to the cells, or to anything else. It was then determined that these pulses were probably not from the cells, since they could be picked up as well with the detector in remote parts of the building.

Whether any saturating pulses were actually produced by working cells could not be determined, due to the possibility that the noise pulses might be produced at various times in small quantities. Thus until the source of the noise pulses is identified and shielded out, our measurements cannot tell with certainty whether gamma bursts are occurring.

X-Rays

We have no clear-cut positive x-ray findings.

None of the x-ray films were darkened significantly, either by signals or by the effects of hydrogen gas which sometimes diffused into the black polyethelene packets.

The observations made with the Si(Li) detector were subject to the base-line shifting problem discussed earlier, and also to the big stuff problem discussed under gamma ray detection.

In runs where the baseline shifting problem was not present, there were some hints of x-ray findings as shown in Table 2a and Table 2b.

Three regions of interest were selected along with two other regions for comparisons. The regions of interest were: (1) near 21.124 keV, the energy region containing the K-alpha x-rays of palladium -- these would be the most prominent x- rays from a palladium sample bombarded with energetic charged particles; (2) from 2.3 to 3.8 keV, the energy range of palladium L x-rays -- these would be expected along with K-alpha x-rays; (3) 1.5 to 2.0 keV, a low-energy range which could be populated by hereto unknown processes or by noise pickup. The control regions for comparison were around 5 keV and around 10 keV.

There are a number of values more than three standard deviations from the background, but they have problems. For example, compared to background, cell 32 has significant deficiency in the first two energy ranges. Since a cell cannot reasonably produce less x-rays than the background cells (H20 based), this must be interpreted as resulting from noise pickup during the background runs. Thus, although

1-348 TABLE 2a

X-Ray Results from Thin-walled Cells, in Counts/24h

Time Enerav Ranae or Center Value (keV1 _o 15-2,o 33-3.8 a l-QQ 21,134

Backgruu nd Lead Cap 60.4 621 995 151 114 62

Cell 32 4.4 363 665 165 121 72

Cell 34 46.3 671 1145 165 03 67

Cell 36 5.7 2004 2763 407 85 46

Cell 38 60.7 732 1115 173 01 68

Background Plastic Cap 20.0 767 1730 359 284 196

Cell 38 18.0 708 1636 378 291 192

Cell 38 20.0 856 2042 397 313 206

TABLE 2b

Number of Standard Deviations from Background 1 1.5-2.0 2.3-3.8 5_0 10.0 21.124

Cell 32 -5.4 -5.2 0.5 0.3 0.4

Cell 34 2.1 4.8 1.2 -1.1 0.6

Cell 36 14.9 16.2 6.1 2.5 -1.1

Cell 38 4.8 4.2 2.0 -1.3 0.7

Cell 38 -1.4 -1.4 0.6 0.3 -0.1

Cell 38 2.0 4.6 1.3 1.1 0.5

1-349 cell 34 seems equivalent to background except in the L x-ray region, no strong claims can be made.

Cell 36 shows large excesses in the first three energies, probably indicating high noise pickup during this run. Cell 38 also shows noise pickup, though not as much.

A better case can be made for the last two runs on cell 38. During the first run, results were quite similar to the plastic-cap background. During the second run there seems to be an excess in the L x-ray region.

Although this result is positive, it is clouded by the unresolved noise problems in the other runs. The indication is that another series of similar runs should be made, with several improvements to reduce noise and increase running times. Without additional runs, no firm conclusions can be reached.

Observation of L x-rays is difficult because of the massive attenuation in as little as 1 mm of H20 or polyethelene. An ideal experiment in which to continue these observations would be the charged-particle measurement, with attached Si(Li) detector and a surrounding neutron detector. The neutron detector would enhance the shielding, and the only absorber would be 25 microns of beryllium.

Tritium Detection

These results are mentioned in more detail by the groups initiating the experiments. Each cycle was set for enough counts to give a 5% standard deviation, and each sample was counted at least three cycles. Cycles with high RCM percentages were rejected, as were cycles with unusually high readings which might be caused by interference from cosmic rays.

Because correct standard precautions were followed, all of the readings quoted in this report by groups at NCFl are believed to be reliable and correct.

For example, an electrode from gas discharge experiment GPL21 had six samples cut out and analyzed for tritium in the metal lattice. Three samples were near the background level of 27.1 * 1.1 DPM /ml, while the other three were at 40.1, 80.5 and 97.5 DPM/ml. Each of the latter three were significantly above the background, although they were located at various places along the rod.

1-350 In an electrolytic cell where high loading ratios are now being consistently achieved, high tritium levels are also being consistently achieved. A number of samples exceed 450 DPM/ml, well over 10 times the background counting rate of 38 DPM/ml for the D20 used in the electrolyte. When it is considered that each measurement cycle obtains a 5% standard deviation, this ratio departs from unity by well over 200 standard deviations. A parallel experiment, using the same materials but without the high loading technique, obtained only the background level of tritium. Samples taken during the process of the high loading experiments showed growing tritium levels, as one might expect if the effect is genuine.

Many experiments have been run in which tritium levels were not above background, underscoring the consistency and accuracy of this technique and the reliability of the above counts.

In every run a background sample is always included (a 1 ml sample of deionized water in 10 ml of scintillation cocktail) to show that the machine gives correct readings where no added tritium is present. In the above runs with high tritium counts, the background sample count was always normal, about 27 DPM/ml.

We therefore have great confidence that the tritium counts are reliable as quoted by the various NCFl groups.

Neutron Counting Results

Pons/Fleischmann Cells

The first run began 7/27/90 and continued until the cell went dry, shutting off the current on 7/30/90. The raw data points are displayed in Figure 3. All five of these runs were done with two helium-3 counters and considerable wax shielding around the water bath.

It is apparent that something was affecting the neutron rate, but we know that two corrections must first be applied before any conclusions can be drawn.

The first is for barometric pressure. Measured values for this correction coefficient at six neutron monitors worldwide [6] range from -0.94% per mm of mercury to -0.99%. The latter value, for the Thule, Greenland, monitor was assumed.

1-351 Neutron Measurement, Pons’ Cell 221 Begin 27 July 1990 1400.

1350

2 1300. r ti Q 1250. +v) t 0 1200

1150.

1100. I I I I I I I I 10 20 30 40 50 60 70 € 0 Elapsed Hours

Figure 3.

1-352 The second correction is for rate changes in cosmic ray neutrons due to such things as solar flares and Forbush decreases. Neutron monitors at Thule, Greenland, Deep River in Ontario, Canada, and Climax, Colorado, track each other rather well, [7] as shown in Figure 4. None would be exact for Utah, so corrections were made according to Thule, Greenland, rates.

To make the corrections, the barometric and neutron data were fitted with a series of line segments and compared to an average when no cell was in place. The corrected rates are shown by the line added to the data in Figure 3.

The second run also scanned cell 221, starting 8/2/90. The corrected background rate is added, as before, in Figure 5. The obvious step-function increase lasting from 8/6/90 to 8/13/90 corresponds to the placing of the gamma detector near this cell, along with its large (almost 200 kg) lead shield. This was not a good idea, for although the lead does indeed shield the gamma ray background, it also acts as a known source for spallation neutrons.

Spallation neutrons can be produced in any high-atomic-number material by collisions of cosmic ray neutrons (or gammas) with the heavy nucleus. If the energy is sufficient, the nucleus is then shattered, spraying neutrons and protons in all directions. The presence of the lead apparently increased the count rate by about 120 neutrons per hour. When the predicted background is raised by this amount, the fit is seen to be reasonable.

The third run was done on cell 223, starting on 8/17/90, as shown in Figure 6. An attempt was made to impose a square wave on the efficiency by moving the two helium-3 detectors back and forth between a near position and a far position , 2.5" and 5" from the cell.

If background rates were the same at the two locations, then the efficiency would be 1.18% for 16 hours, then 0.47% for 8 hours, allowing any steady neutron production from the cell to show up as a square wave.

As it turned out, neutron detection was higher at the remote location. The reason was probably the absence of a pyrex glass cell near the remote location, since pyrex is borosilicate glass, and boron has a high cross section for absorbing thermal neutrons. After an empty pyrex cell was installed near the remote location (at about 80 hours) the differences between the count rates became only 3 to 4% instead of 7%.

1-353 COSMIC RAY INDICES (Neutron Monitor) Bertels Rotation 2128 (May 1989) 16 19 20 21 22 23 24 26 26 27

1061:

100%

9 6%

1061:

100%

951:

106%

100%

9 5%

4 6 6 7 8 9 10 11 12 13 14 15 18 17 18 19 20 21 22 23 24 25 26 27 28 29 30 MAY

Figure 4.

1-354 Neutron Measurement, Pons' Cell 221 Begin 02 Aug 1990 900

800-...... +...... i...... 4 ......

L ......

550 ...... +......

500 I I I I IIIIIIIII 111I I 111 I IIIII 1 E j 144 0 24 48 72 120 168 192 216 240 264 288 312 336 360 3 ' Elapsed Hours

Figure 5.

1-355 Neutron Measurement, Pons' Cell 223 Begin 17 Aug 1990 - "Square Wave" 700

......

...... i...... __.. ~.,...... ,-.---*.---.--. ,.,-*---,-.----.-. . ,...... ,. .::: L ...... : ,..-...: : > ...... : ,_.__.

450 I I I I I I I 0 24 48 72 9 120 144 168 1 12 Elapsed Hours

Figure 6.

1-356 The remaining differences could be due to non-identical shielding at the two locations. Because the shielding could not be made identical, due to the presence of a supporting pillar near the tank, this approach was discontinued.

The fourth run, with cell 221, is shown in Figures 7 a-c. The two helium-3 counters in the water bath gave a combined count rate of about 520 per hour. At the same time, a newly installed background counter in a separate room gave about 340 per hour.

During a time when there was no cell in the bath, the ratio between these two rates was accurately measured. That standard ratio is used to infer the relative ratio for each hour, which is the heavy line in the figure. (The relative ratio is live counts divided by background counts divided by the standard ratio.)

It can be seen that this relative ratio is consistent with 1.0 f 0.07 for this entire run, showing no excesses in the rate of single neutrons detected.

No event logger was available at the time of this run or the following one, so nothing can be said about whether neutron bursts were present or not.

The fifth run, using cell 221, started on 9/26/90 and is similar initially (see Figures 8 a-c). Equipment problems prevented a background measurement on day 271. After that time, the relative ratio centers a few percent higher than 1.0, while the background counting rate seems to have dropped about 3% on the average. This could be caused by a tighter arrangement of the wax moderator after it was worked on. Indeed the relative ratio averaged above 1.O for most of the a day after the cell was off.

On day 279 there was an apparent spike on the live count rate at about 10 AM. That is the hour in which the cell was turned off. Whether this spike was due to mechanical vibrations or moving of the cables on the helium-3 counters, or was a neutron excess caused by the sudden change in current, is difficult to assess. It is believed to be noise, however, since work was done on the cell at the time.

Before a firm claim of neutrons could be made, the experiment should be repeated, taking advantage of event logger circuitry and being careful to log the time of any mechanical vibrations or disturbances of the cables. The event logger can distinguish some types of noise events by the time relationships and distribution of neutrons between the various tubes.

1-357 NEUTRON DATA IN PONS’LAB (8/31/I 990 1O:OO AM-9/5/1990 12100AM) 700 2.2

600 2

n I 500 1.8 I W -0 400 1.6 ,. :. ....:. : ’...... ;-.. II:!z ...; .... .$, ,,,A: ; ...... a, *: : : a. .::I: / :: ..: ..I...... , * . . W 300 ’:...... *;.g...... :,-+...... u 1.4 > 4 200 1.2 W U

1 I! ?,..; ?,..; ...... c. 100 I .. ’ 1 .I. I 1. . :y 0 0.8 2 2 242.5 243 243.5 244 244.5 245 245.5 246 24 i.5 2 7 DAYS

Figure 7a.

1-358 NEUTRON DATA IN PONS’LAB (9/5/1990 1100 AM-9/10/1990 1200 AM) 700.

600

500

400

300

200

100

0 2 DAYS

Figure 7b.

1-359 NEUTRON DATA IN PONS’LAB (9/10/1990 1100 AM-9/13/1990 8100 AM) 700 2.2

600 ..: ...... -...... 2

n I 500 1.8 I W 0 400 ..;...... 4...... ---b...... z 300 1.4 -9

200 1.2 4w a 100 1

0 I I I I I I I I I .0.8 252 252.5 253 253.5 254 254.5 255 255.5 256 256.5 257

Figure 7c.

1-360 NEUTRON DATA IN PONS’LAB (9/26/1990 11 :OOAM-1 0/1/1990 12:OO AM) 700 2.2

.. 2

n I ...... ^ ...... 1.8 I W -0 400 ...... i- ...... i...... i ...... ;...... 1.6 U2 .I .4 >W

...... ?i .I .2 W U -1

:. - I I .0.8 268 268.5 269 269.5 270 270.5 271 271.5 272 272.5 2 3 DAYS

Figure 8a.

1-361 NEUTRON DATA IN PONS'LAB (1 0/1/1990 1:OO AM4 0/6/1990 12100 AM) 700 -72.2 600 ...... - ....

n ...... 1.8 ! 500 v 0 400 ...... 3 ...... <...... 1.6 i hj'... 5. :..,*..;;. 4...... :..; : ... ::, .. ;. .. ; ; ; ...!...... i ...: !ii I.,.; . ...: :; *?:.,* *: '*'' W ..... 2...... 6 ...... 300 .$..... I; ...... i -1'.4>

200 1.2 W5 U 100 1

0 I I I I 1 I I I 10.8 2 3 273.5 274 274.5 275 275.5 276 27 3.5 277 277.5 278 DAYS

Figure 8b.

1-362 NEUTRON DATA IN PONS’LAB (1 0/6/1990 1 :OOAM-1 0/8/1990 8:OO AM) 700-

600-

n I 500- I v 0 400. i= 4 U W 300 >

200 4W a 100

Figure 8c.

1-363 In these five runs, no apparent evidence for neutron production was found. From the counting rates one can calculate the standard deviation on the relative ratio each hour to be 7.0%. The data fall above 1:21 (three sigma) only once in run four, about what one could expect (0.4 times). Thus for any one-hour period in run four, the excess neutrons did not exceed 21% of background, or 109 neutrons per hour, or 9.250 source neutrons in one hour.

In run five the ratio exceeds 1.21 once in the first seven days, then does so several times, the average ratio seeming to have permanently shifted upward, possibly due to a change in the background detector, as mentioned earlier. Thus the limits set for run four are probably applicable to run five also. The highest reading other than the noise spike was a ratio of 1.27. Even if there was no shift in the average ratio, to find such a reading once in about 550 hours has a 6% probability. Thus no positive changes in neutron rates beyond the stated limit were observed.

No information on neutron bursts is available, since the event logger circuit was not available at that time.

Gas Discharge Experiments

The apparatus consisted of a glass vacuum chamber with two electrodes (either palladium or titanium), which had been cleaned by a high voltage discharge and loaded with deuterium.

The vessel was then placed in the wax ring moderator detector for neutron counting for several days (See Figure 9).

The earliest runs used the gamma-ray spectrometer to detect 2.224 MeV gamma rays when a thermalized neutron was captured by a proton. The efficiency is listed on the first line of Table 1. As runs progressed, the efficiency was improved, as shown in the table.

The method of data collection involved a large number of computer disks, reading out the entire gamma ray spectrum each hour or oftener. To locate runs of interest, an overall significance was assigned by comparing the overall rates with an uncorrected background average, as shown in Table 3.

For runs which showed an overall excess, detailed plots were made, to see if

1-364 Table 3

Before Final Activation After Final Activation ~ Davs Neutro ns/24 h Backa rou nd Davs Neut rons/24h packa ro u nd GPL13 0.96 1129 168 1.17 1115 1168 2.89 1087 1168

GPL14 1.57 1236 168 5.00 1209 1168 GPL17 5.63 1161 168 0.19 1168 1168 1.88 1180 1168

GPL18 1.75 1189 1168 5.1 0 1175 1168 5.90 1180 1168

GPL19 1.04 1174 1168 1.87 1173 1168 9.82 1156 1168

GPL20 0.83 1171 1168 5.09 1163 1168 GPL21 1.18 6946 6438 5.72 7039 6725

GPL23 1.21 7082 661 0 4.68 6805 6343

GPL28 2.28 5980 661 0 3.68 6240 7241 GPL31 0.88 6262 6266 2.26 7043 6993

1-365 A

0 0 A B A 0 0

Figure 9. Ring of Neutron Counters in Wax Moderator and Shield

1-366 any production spikes were apparent, and the expected background was corrected for the effects of pressure and neutron monitor changes.

Two of these early runs (GPL10 and GPL12) showed an overall significance of 4.7 and 7.2 standard deviations, after corrections in the expected background (see Figures 10 and 11). These runs showed neutron excesses of 50% and 64% over background. The heavy horizontal line is the average corrected background, with lines one standard deviation above and below.

There are two reasons to doubt that these were neutrons produced in the gas- loaded cell. The first is the difficulty of reproducing such neutron excesses in the next 19 experiments, even with increasing sensitivity. The second is an unlikely but possible way to explain these results as an artifact.

Efficiency calibrations have been done with an Americium-beryllium source, which produces neutrons of energy up to 10 MeV, averaging 4-5 MeV. The best container for such a source is made of thick paraffin with boric acid powder mixed in. Such a container was furnished by our nuclear engineering collaborators along with the source, for safety.

Although it was our policy to have this source in a remote part of the building during neutron runs, strict notes were not kept at the time. Since we believed the container to be an effective shield of the neutrons from the source, it is possible that a run or two could have been done with this source in its container but temporarily stored in room 26 next to the neutron energy spectrometer.

It was later measured that the container shielded out only a third of the neutrons from the source, leaving the other two thirds for detection by any nearby detectors. (The usual remote location would effectively remove over 95% of those remaining.) During these two runs, the source in its container could easily have been close enough to the counting experiment to account for the excess, if it was left in room 26 by mistake. Only time and additional experiments can resolve this question.

We now turn to runs made after the event logger was included in the setup, introducing burst sensitivity for the first time, with four helium-3 tubes in a wax ring moderator. The results for the whole days of these runs are listed in Tables 4 a-c.

Looking first at the background average, at the bottom of Table 4c, and

1-367 NEUTRON MEASUREMENT RUN GPL10 - 3/28/1990 90 85 - ...... i ...... i...... j ......

...... i...... ;...... 6...-.----...... --.--.-......

...... ,I......

HOURS

Figure IO.

1-368 NEUTRON MEASUREMENT RUN GPLl2 - 4/23/1990

0 2 4 6 8 10 12 14 16 18 1 3 HOURS

Figure 11.

1-369 comparing this with the averages for runs after activation (Table 4a) and after D2 gas loading but before activation (Table 4b), there is no overall enhancement in the rate of two-neutron bursts.

Looking at individual runs for two-neutron bursts, the most significant would seem to be the last two background runs but neither exceeds the average by three standard deviations.

Any extra doubles should be roughly proportional to the rate of single neutrons, since these are the main cause of spallations in the various nuclei. After it is ascertained what the coefficient is, the rates of doubles might be corrected for this effect. The same spallations would affect the background rate of triples, etc.

Looking at triples, none of the runs are significantly above the background.

Table 4a

Neutron Bursts After Discharge Activation

Run Bursts per 24 Hours with N Neutrons -Start Davs -2 i! -4 -5 Laraer GPL34 2 123 2.5 0.5 0.0 0 112219 1

GPL35 4.60 96 1.3 0.2 0.2 0 211 I91

GPL36 5 107 1.4 0 0.2 0

GPL37 5 119 1.8 0 0 0 212519 1

GPL39 4 108 3.0 0 0 0 311 9/91

GPL4O 3 105 1 .o 0 0 0 312519 1

GPL41 5 100 2.8 0 0 0 313019 1

GPL43 4 105 1.8 0 0 0 51319 1

TOTAL 32.60 107 1.9 0.1 0.1 0

1-370 Table 4b Neutron Bursts Before Discharge Activation

Run Bursts De r 24 Hours with N Neutrons Start Davs -2 s -4 5 Laraer GPL34 2 107 2.5 0 0 0 112219 1

GPL35 3 94 2.7 0 0 0 211 /9 1

Total 5 99 2.6 0 0 0

Table 4c

Neutron Bursts with no Cell (Background)

Bursts Der 24 Hours with N Neutrons m Davs 23 -4 5Laraer 1/19/91 2.97 107 3.7 00 0

112819 1 1.87 101 0 00 0

212019 1 4 103 2.0 00 0

31419 1 1 115 2.0 00 0

3/15/9 1 2 140 0 00 0

411 819 1 1 146 4.0 00 0

Total 12.84 114 1.9 00 0

1-371 Table 5

Neutron Bursts After Discharge, with 8 Tubes

Run Bursts Der 24 Hours with N Neutrons aa!l Davs 2 3 -4 5 Ja~a GPL38 5.94 447 16.8 1.2 0.5 0.2 3/7/9 1

Background 0.85 487 16.5 2.4 0 0 31619 1

Backg rou nd 2.06 486 20.9 1.5 0 0 311 3/9 1

Background Total 2.91 487 19.6 1.7 0 0

Looking at the bursts of four or five is a more difficult question, since none were seen in the background. An argument is needed to predict the number expected. If all of the doubles and triples are the result of spallations of the heaviest nearby nuclei, then the ratio of triples to doubles should be equal to the probability, given a double, of detecting one more neutron. In the background runs, this probability is thus 1.7%. The same probability should apply if one has a triple and asks the chances for adding another neutron, so long as the shattered nucleus has plenty of neutrons left. Thus the ratio of higher multiples should be multiplied by a number less than or equal to 1.7 YO for each increase in multiplicity.

By this argument, based on 3,480 doubles in 32.6 days, one should expect to have 59 triples, 1.O quadruple, and 0.017 bursts of five, etc. The Poisson probability of having two or more quadruples is then 27%, but the probability of two or more quintuples is 1.4 X10-4.

The policy during background runs was to have an empty pyrex vessel in the detector both as a source of spallations and as an absorber of thermal neutrons. We should also have included a small amount of palladium to equal the electrode masses, though it seems unlikely that such a small quantity could significantly affect the

1-372 outcome.

Therefore neutron bursts are apparently being seen which would be very unlikely from the cosmic ray background. Additional runs are needed, of course, both with deuterium and with hydrogen (or with no loading at all).

One run was also done with eight helium-3 tubes instead of four. It is summarized in Table 5. (These tubes were subsequently used in other experiments.)

One sees that the rate of doubles is multiplied by almost four, as one would expect for almost twice the efficiency. The rate of triples is likewise about eight times higher, etc. This also means one can predict the number of any multiplicity as 2 x 1.71% times the previous multiplicity. The result, starting with doubles, is 487, 16.7, 0.57, 0.019, 0.0007, which describes the background rather well.

The live data is also described not too badly: 447, 15.3, 0.52, 0.018, 0.0006. The possible exception is at the high multiplicities. The Poisson probability for the three quintuples is 1.8 X 10-4, and for the single event with eight neutrons is 4.2 x 10-6.

This run emphasizes the value of more counters, to give higher efficiency, and also the need for more runs, especially if those runs could be done in an underground laboratory with very low background.

A strange aspect of the eight-neutron burst must be mentioned. All four channels of the event logger registered a neutron in the first 0-8 microsecond bin. In fact three of these were less than 1 microsecond from each other.

This apparent flash of very prompt neutrons could be caused in three ways: (1) if there were many high energy neutrons, perhaps 20-50 MeV; (2) if there were no neutrons at all, but a flash of gamma rays, adding up to simulate neutrons; (3) if there were neither of the above, but a pulse of electromagnetic radiation given off by microcracking associated with the later neutrons.

Gas Loading Experiments

A series of recent experiments was done with titanium powder loaded with deuterium under the heating influence of a tube furnace, and with cooling cycles down to liquid nitrogen temperature (-196°C).

1-373 These were done with four helium-3 tubes in the wax ring moderator, and thus relate to the background rates shown in Table 4c.

As can be seen in Table 6, the rate of doubles averages above the rate for background runs, but not significantly.

Triples average slightly above the expected number, but not significantly. Nor is the one quadruple significant by itself.

Run JMl had 20 triples when 9.7 were expected according to background, with a Poisson probability of 2.6 x 10-3.

The most significant event was a burst of nine neutrons in run JM1. Considering the total number of doubles in these runs and the ratio 0.0171 from each higher multiple, one would expect 9xlO-lO bursts of nine. This burst was much like the burst of 8 in the gas discharge experiment, starting with four neutrons in the first time bin (0-8 microseconds). Whether this "flash" is caused by high energy neutrons, by gammas, or by electromagnetic waves from microcracking, it still must be associated with the five neutrons which followed.

A five neutron event by itself would have only a 1% probability during the combined runs. Events where four tubes are triggered simultaneously, followed by no thermalized neutrons, are usually considered noise of unspecified origin. Such "noise" events happen less than twice per month, so the odds of such an event occurring by chance within 100 microseconds of the only burst of five would be less than 1.7 x 10-12 This burst occurred at 2:44 a.m., when the building was totally vacant and quiet.

If the measured efficiency of 5% is used, one infers that this burst began as approximately 180 neutrons from the source event, or as 100 source neutrons plus whatever was responsible for the "flash".

Having argued that the "flash" was somehow associated with the real events of this large burst (and the previous burst of eight), one might ask whether such flashes have been seen with smaller bursts. The answer is positive. There was also a flash plus two neutrons on 3/3/91 during a data run and a flash plus one neutron on 2/16/91 during a data run. (By chance these were all during non-working hours.)

1-374 No flash-plus-neutron events were seen in background runs. All four events were many hours into a run. The probability of a rare noise event (or a flash) being accompanied by a neutron within 51 2 microseconds is 1.5 x 10-4. Thus, whenever there is at least one neutron associated with the flash, the event is probably real.

One might look for flashes where only three helium-3 tubes counted simultaneously, to see if they had accompanying neutrons. From January 19 through June 11, during non-working hours, there was only one such 3-flash, and it had no accompanying neutron. During working hours there were only two 3-flashes, again without neutrons (thus believed to be noise).

This suggests that whatever causes the flashes is usually more than large enough to fire four tubes, so that 3-tube flashes are rare. More study will be needed to understand the nature of these events.

Table 6 Neutron Bursts From Gas Loaded Experiments

Run Bursts Der 24 Hours with N Neutrons rn Davs 2 3 -4 5 Laraer JM1 5 117 4.0 0 0 0 4/5/9 1

JM2 4 132 2.5 0 0 0.25 411 1/91

JM3 6.22 112 2.4 0 0 0 412519 1

JM4 3 113 1.7 0 0 0 51919 1

JM5 3 102 2.7 0 0 0 511 619 1

JM6 1.54 121 1.3 0.6 0 0 512719 1

JM7 0.97 144 3.1 0 0 0 5/29/9 1

Total 23.73 117 2.7 0.04 0 0.04

1-375 High-Loadi ng Electrochemical Experiments

A series of electrochemical experiments was run, in which high deuterium loading and high tritium production was achieved. The neutron detection setup consisted of two helium-3 tubes in the water bath as shown in Figure 12, and two identical helium-3 tubes in a separate water bath, where the hydrogen control cell was run.

The neutron counting results are listed in Table 7.

Ta ble7 Neutron Bursts in High Loading Cells

D20, Bursts Der 24 h H20. Bursts De r 24h m Davs 2 3 -4 More 2 3 -4 More 31 1419 1 4 88 1.8 0 0 50 0.3 0 0

312 619 1 8 79 1.6 0.3 0.1 45 0.5 0 0

41519 1 6 60 0.5 0 0 31 0.5 0 0

41 1219 1 9 58 1.1 0.1 0 36 0.3 0 0

412219 1 2 77 0.5 0 0 36 0.5 0 0

412519 1 11 61 1.2 0 0 32 0.5 0 0

51719 1 6 62 1.7 0.2 0 34 0.5 0 0

Subtotal 46 67 1.2 0.1 0 37 0.4 0 0

511 419 1 3 44 0 0 0 39 0.3 0 0

No Cells 312019 1 4 86 0 0.3 0 48 0 0 0

One notices in the subtotal of the first seven runs that the number of doubles and triples are consistently higher in the D20 runs than the H20 runs. But the

1-376 A C 0 0 0

Figure 12. Arrangement of Neutron Counters in Water Bath Moderators significance of this is countered by the fact that this is also true of the run with no cells on 3/20/91. This must indicate that something else besides the D20 cell is producing many of the doubles here.

A possible source was indeed located and removed prior to the 5/14/91 run. There was a lead brick hidden behind the D20 water bath, used as a weight to stabilize a ring stand. When cosmic rays hit heavy nuclei, the nucleus can be shattered with an attendant spray of neutrons. These spallation neutrons occur as a burst and may be detected as doubles, triples, or higher multiplicities. There was also a lead brick behind the H20 bath, but farther behind. Thus fewer neutron bursts would be detectable from it.

The only run done after removal of the lead bricks was the 5/14/91 run, which showed reduced numbers consistent with equal rates in the two tanks. In addition, the run on 3/20/91 had more doubles in the D20 tank, with no cells present.

One must assume that the nearby lead brick which raised the doubles also raised the triples, etc. To find out approximately how much, a calibration run has been made with 12 lead bricks near each tank. Since each spallation event involves only one lead nucleus, the rate of such events will simply be proportional to the number of lead bricks (assuming the geometry is roughly identical).

The production of doubles by the average lead brick (half were behind the tank, half in front) was 9.7 +_ 0.5, not enough to explain the doubles excess with no cells (3/20/91) or the reduction by 23 when the bricks were removed (5/14/91 run). This suggests that each lead brick in the stack was less effective than a single lead brick, perhaps due to some shielding of the neutrons produced. From the average lead brick there were 0.40 triples and 0.04 quadruples per day.

Of the five quadruples, all occurred in the D20 tank except one, which had three neutrons in the D20 tank and one in the H20 tank. The expected number of these, based on the lead-brick background run, would be 1.9, not quite a significant difference.

The event of greatest interest is the large multiplicity burst during the 3/26/91 run, on 3/29/91 at 12:24 pm. This burst had 7 neutrons in the D20 tank plus 3 in the H20 tank plus five others without complete information, for a total of 15 neutrons observed.

1-378 This event resembled the two large bursts mentioned earlier, in having a large number (7) during the first 24 microseconds. Assuming this event to be genuine, the three neutrons in the H20 tank probably had over 5 MeV initially, to penetrate about 15 cm of water, then 10 cm of borated wax, then another 10-20 cm of water to reach the detectors. Neutrons with less than 5 MeV would have little chance to survive this journey. Yet, by their time correlation, these three were definitely part of the same burst event.

Was this really an event with 15 neutrons detected? If we assume so, and consider the efficiency of about 1.2%, it would imply approximately 1,250 source neutrons. The existence of the two large bursts mentioned previously support this interpretation.

On the other hand, these counters had been found a few days earlier to be vulnerable to noise pickup when the cooling pump was switched on or off. The pickup was through electrical contact between the helium-3 tubes and the water in the tank. The temporary solution was a verbal caution and a small sign reminding laboratory personnel not to switch this pump during runs. The better solution came a few days later with the installation of a heavy ground for the tanks and insulating sleeves for the counters. Even though it seems quite unlikely that this switch was thrown (there being no need, and all having been cautioned), it is possible that it was thrown by mistake. If that were so, the event could have been an artifact. During the diagnostics of this problem three days earlier, with dozens of switch throws one could generate a few artificial candidate events, though none very similar. Further, there are no other events on the 28th or 29th that resemble the switching events, so deliberate multiple switching is ruled out. Thus the explanation as an artifact of switching seems quite remote, though not entirely impossible.

The best conclusion would come by finding more such events, with the improvements in place which rule out any interpretation as an artifact. We would be fortunate if this could be done in the short time remaining.

Fuel-Cell Type Experiments

A series of experiments were done with a fuel-cell type experiment, with the cell inside a stainless steel pressure vessel in a water bath. Two helium-3 neutron counters were in the water bath, monitored by an event logger.

1-379 This environment was troublesome for the neutron counters. The tank had a self-contained cooler, causing mechanical vibrations and an environment of warm air near the electronics. Both of these were found to cause noise counts and on some days the noise counts entirely prevented data collection.

The experiments were successful in producing some tritium and some heat excursions (reported in another section), and the runs with useable neutron burst data are shown in Table 8. The background should be comparable to that in Table 7, including the presence of a lead brick near this tank on these runs.

The background rate for doubles is less than during live runs, suggesting neutron production. But it is more than during H20 runs on Table 7, suggesting extra nuclear spallations due to the greater amount of heavy materials in the self-contained temperature regulation equipment. Because of past difficulties with helium-3 counters during these experiments, no conclusions about neutron production are justified.

The rate of triples does not exceed the background rate.

Table 8 Neutron Bursts from Fuel Cell Type Experiment

Bursts Der 24 Hours with N Neutrons -Start Davs -2 -3 -4 -More

411 719 1 4 67 0 0 0

412319 1 4 81 1.5 0.25 0

51219 1 4 67 1.5 0.25 0

511 0191 11 66 1.1 0 0

512319 1 4 105 1.0 0.25 0

Total 27 74 1.0 0.1 0

Background

611 419 1 3 58 1.0 0 0

1-380 The three quadruples are not quite significant, since by the argument used before, we would expect 0.6 quadruples based on the numbers of doubles and triples in the background.

Thus no significant neutron bursts were seen in these experiments.

This should not cast doubt on the tritium results for two reasons: (1) tritium and neutrons are produced by different possible reactions, and (2) the physical dimensions of this cell are very small, reducing the likely number of neutrons produced. For this reason a better detector might be required, along with the low background of an underground laboratory.

Monte Carlo Neutron Simulation

The Monte Carlo program was set up for our wax ring detector and run for at least 5000 source neutrons at each of the energies plotted in Figure 13. The figure shows the calculated detection efficiency versus energy, labeled MC/4, which drops from 11-4% at 0.5 MeV to 0.24% at 50 MeV.

The efficiency of 5%, measured with an Americium-beryllium source calibrated against a Californium-252 source borrowed from BYU, fits well with this efficiency curve for an average energy of 4-5 MeV. The efficiency of the wax ring detector with 8 tubes was also calculated, indicated by MC/8.

Another result checked with this program was the die-away time for neutrons in this detector, shown in Figure 14. For live runs with 4 helium-3 tubes this modulation time was approximately 140 microseconds, and with 8 tubes about 110 microseconds.

Menlove's detector with 51 helium-3 tubes and an efficiency of 44% is reported to have a die-away time of less than 43 microseconds. The difference is understandable, because the more helium-3 tubes present, the greater chance of a neutron being captured by helium-3 before it has time enough to be captured by a proton.

The height of the curves in Figure 14 are irrelevant, being determined just by the amount of data. The slope reveals the die-away time.

1-381 Monte Carlo Efficiency Calculations Wax Ring, 4 or 8 Helium-3 Tubes

...... _I... ;MI ....._ . . /!q i ...... _...... i...... L,.i...... : : !...... h ...... 8 ...... I. > ...... _...... 0 MC/4... z 1 ... W \ - ...... -0 ...... LL ...... LL ... W ...... 3 ...... _,.__..__,....I.. 5 ...... I...... 3 00.1 - ---iii -1.o 3.0 L ENERGY (MeV)

Figure 13.

1-382 Wax Ring Detector 1000

......

-.I. 1 ''-- ', ...... -- t Live/4 ...... LA...... ,?,, ...... i...... :::,-...... -.\ -.\ x,' '\I : ...... x. *.* . t: '*e .....,,, I, ...... l.iA ...... -...... <.... > - ...... 2..... r ...... +..M 8:::::::::::...... f...... *...... - ...... +;,...... ,...... - ...... - *. - ...... A..&...... >".L...... :.:- ...... - ...... i...:w:: ..... :5...... -...... 1...... -*.,-- , .- ...-..-. -I-- ..I-. I - ...... __..- --.I MC/4 -*=..:, -.* 'L 1 1 1 I I I Detection Time in Microseconds

Figure 14.

1-383 When checked for the four-tube detector, the calculated die-away time was approximately 105 microseconds as shown. For the eight-tube configuration the calculated die-away time was down to about 100 microsecnods, in approximate agreement with our live run with eight tubes.

Conclusions

Looking for the nuclear products of an unknown nuclear reaction has involved many possibilities. Looking for all of them is necessary but very time consuming. This was compounded by the low levels of nuclear particles encountered, by the problems of cosmic ray background particles, and by the unpredictable nature of the experiments.

One could not predict which experiments would be successful and which would not. In addition, for the successful experiments, one could not predict the time- behavior. In particular, most nuclear instruments are designed to measure on particleat a time; these instruments become saturated and ineffective if the particles come in a burst lasting a few microseconds or less.

One exception is tritium measurements, since only the integrated production is measured. Our tritium measurements have been carefully calibrated and carefully done. Positive and significant tritium production has been measured in at least five different types of experiments. These amounts are solid evidence that some type of nuclear reaction has occurred.

Neutron production has been more difficult to measure. Although two early gas- discharge experiments showed an excess, some doubt exists due to the failure to repeat this and the possibility that the calibration source, in its shielded container and in the next room, could have caused those excesses.

Since Neutron bursts of over 100 detected neutrons have been reported by several authors, we built up a system capable of measuring these bursts, and made burst runs on four different types of experiments.

Because the wax moderator spreads the burst out over hundreds of microseconds, existing helium-3 neutron counters can be used successfully without becoming saturated.

1-384 Small but significant numbers of neutron bursts have been found in gas discharge experiments, in gas loading experiments, and in high-loading electrochemical cell experiments. More runs should be done, with a higher efficiency detector (more helium-3 tubes) and a lower cosmic ray background (underground laboratory). Nevertheless, our present results support others' findings of low levels of neutron bursts.

No solid findings of gamma rays or x-rays can be reported. If either of these is produced in bursts shorter than a few microseconds, the instruments would not give sensible results. This possibility has not been fully explored.

The charged particle experiment has not been run yet, and may not be run until other funding can be found. It is almost ready, but writing of this report was a first priority.

The underground laboratory is still in the form of plans made, in abundant detail. If other funding becomes available it could be moved forward with good speed and allow its great advantages in a search for low levels of nuclear particles from unknown processes.

Considerable progress has been made and some good milestones have been achieved, in building the capabilities necessary for fully exploring the nuclear phenomenon at hand. In addition, definite nuclear byproducts have been found in both tritium and neutron bursts.

In spite of this progress, the task is certainly incomplete. Additional time would be required to finish the programs we have begun, and years of research effort by many groups will probably be required before a good answer can be given to what now is the main question: Granted that low levels of nuclear reactions do occur, will this study ever lead to an economically viable source of commercial energy, which can fulfil the dreams of its proponents and supporters?

Acknowledgements

Since the Physics Group has monitored for nuclear radiation products cells almost exclusively built by other groups, it is indebted to essentially all other workers at the National Cold Fusion Institute. Specifically, we acknowledge the efforts of the

1-385 following in providing cells for monitoring:

1. The Chemistry Group headed by Drs. Pons and Fleischmann; despite a grueling schedule, Joey Pons, Marvin Hawkins, and others allowed us to monitor the cells having the greatest interest worldwide to those following cold fusion studies;

2. The Engineering Group, especially Dr. Andy Riley and John Cook who pioneered a number of useful approaches to cold fusion study, some of which were especially valuable for nuclear radiation studies;

3. The Metallurgy Group headed by Milton Wadsworth who gave the most consistent encouragement to our work; Siva Guruswamy directed the building and operation of a large number of cells with thin walls to reduce absorption of X-rays in addition to cells more peculiarly adapted to metallurgical interests; he also worked with innovative shocked alloys; John Peterson worked with gas-loaded palladium which provided the first clear neutron bursts;

4. The Surface Chemistry Group headed by Fritz Will and including Krystyna Cedzynska, and Ming-Chang Yang; this group has developed controlled loading techniques resulting in tritium loading techniques resulting in tritium production;

5. James Mclntyre has refined gas-loading techniques which have given evidence of neutron bursts.

The Physics group is also indebted to the State of Utah for support, to the State Energy Advisory Council for continued interest and encouragement, to James Brophy and Hugo Rossi for getting us involved in the first place, and once again, to Fritz Will for bringing integrity and a truly scientific approach to these difficult matters. Finally, one of us (HEB) wishes to thank the colleagues in his academic department who respected his freedom to work in an area with which they were extremely uncomfortable.

1-386 References

1. G. Preparata, "Theoretical Ideas on Cold Fusion" (preprint).

2. S.R. Chubb and T. A. Chubb, "Lattice Induced Nuclear Chemistry" presented at Anamalous Nuclear Effects in Deuterium /Solid Systems, at BYU, 22-24 October 1990.

P.L. Hagelstein, "Coherent Fusion Reaction Mechanisms", presented at Anomalous Nuclear Effects in Deuterium/Solid Systems, at BYU, 22-24 October 1990.

3. S. Szpak, et al. "On the Behavior of Palladium deposited in the Presence of Evolving Deuterium" (preprint).

4. F. E. Cecil, H. Liu, D. Beddingfield, and C.S. Galovich, "Observation of Charged Particle Bursts from Deuterium Loaded Thin Titanium Foils" (preprint).

5. X. Li, S. Dong, K. Wang, Y. Feng, L. Chang, C. Luo, R. Hu, P. Zhou, D. Mo, C. Song, Y. Chen, M. Yao, C. Ren, and Q. Chen, "The Precursor of 'Cold Fusion' Phenomenon in Deuterium/Solid System," presented at Anomalous Nuclear Effects in Deuterium/Solid Systems, at BYU, 22-24 October, 1990.

6. Solar-Geoohvs ical DUI 515 Supp, July 1987, p. 30

7. Solar-GeoD. hvsical Dm,549, pp. 148-149.

1-387 Table of Contents, Volume II Engineering

Table of Contents 2-iii

Board of Trustees' Preface 2-iv

1. Flow Calorimetry and Related Experiments 2- 1 A. M. Riley, R. M. Winter, J. D. Seader and D. W. Pershing

2. Seebeck Calorimetry 2-85 A. M. Riley, J. Cook, R. M. Winter, J. D. Seader and D. W. Pershing

3. Measurement of Absorption of Deuterium in Palladium During 2-1 23 Electrolysis of Heavy Water A. M. Riley, J. D. Seader, D. W. Pershing, D.C. Linton and S. Shimizu

4. Heat Conduction Calorimeters for Electrolysis of Heavy Water 2-194 at Low Power Input A. M. Riley, J. D. Seader, D. W. Pershing and J. Cook

5. Development Of An Improved Heat-Flow Calorimeter 2-226 A. M. Riley, J. D. Seader, D. W. Pershing and J. Cook

6. Determination of Critical Cold Fusion Parameters by Measuring 2-241 Excess Triti u m From Small-Cell Electrolysis Experiments A. M. Riley, J. D. Seader, D. W. Pershing, T. Williams and D.C. Linton

7. Search for Neutron Emission from Deuterated Palladium at 2-248 Low Temperatures A. M. Riley, J. D. Seader and D. W. Pershing

8. High Pressure Liquid Cell Development 2-253 B. F. Boehm, M. Case, T. Chen, X. Li and B. Lloyd

Tables of Contents, Volumes I and Ill 2-279

Table of Contents, Volume 111 Collaborative and The0 retical Studies

Table of Contents 3-iii

Board of Trustees' Preface 3-iv

1-388 1. Temperature Dependence and Reproducibility of Cell 3- 1 Constants in FP Type Calorimetric Cells C. Walling and M. Hawkins

2. Diatomic Hydrogen in a Potential Well 3-14 K. J. Bunch and R. W. Grow

3. Enhancement of Cold Fusion Reaction Rates 3-37 G. M. Sandquist and V. C. Rogers

4. Low Temperature Nuclear Reactions by Deuterons in Metals 3-47 G. M. Sandquist and V. C. Rogers

5. Isotopic Hydrogen Fusion in Metals 3-66 V. C. Rogers and G. M. Sandquist

6. Evaluation And Verification Of Cold Fusion 3-84 G. M. Sandquist and V. C. Rogers

7. Deuterium Concentration and Cold Fusion Rate Distributions in 3-103 Palladium V. C. Rogers, G. M. Sandquist and K. K. Nielson

8. Limits on the Emission of Neutrons, Gammas, Electrons and 3-1 12 Protons from Pons/Fleischmann Electrolytic Cells M. H. Salamon, M. E. Wrenn, H. E. Bergerson, K. C. Crawford, W. H. Delaney, C. L. Henderson, Y. Q. Li, J. A. Rusho, G. M. Sandquist and S. M. Seltzer

9. Self-consistent Field Potential-Energy Surfaces of the DD Pair 3-127 in the Presence of Small Palladium Clusters

10. Fusion Rate Calculations for Hydrogen Isotopes from 300°K to 1 MeV 3-165 J. Nichols, M. Gutowski and J. Simons

11. A New Look at Solid State Fractures, Particle Emission, and 3-197 "Co Id" Nuclear Fusi0 n G. Preparata

12. Theories of "Cold" Nuclear Fusion: A Review 3-205 G. Preparata

Tables of Contents, Volumes I and II 3-237

1-389 REPORT OF LEGAL COUNSEL

Gregory P. Williams Van Cott, Bagley, Cornwall & McCarthy

July 1, 1991

We have been requested to provide a brief summary of the legal work performed with respect to cold fusion matters for inclusion in the Final Report of the National Cold Fusion Institute (the "NCFI" ) to the Fusion/Energy Advisory Council.

1. Leaal ReDresentation. Attorney Peter Dehlinger of Palo Alto, California, was retained by the University of Utah (the University" ) to prepare the initial patent applications relating to cold fusion. Following the filing of these applications, the first public announcements concerning the Pons-Fleischmann discoveries were made, and thereafter the Utah legislature appropriated funds for cold fusion, including an appropriation of $500,000 to the Utah Attorney General for related legal work. The Attorney General retained the Salt Lake City firm of Giauque, Williams, Wilcox & Bendinger (now known as Giauque, Crockett & Bendinger) to represent the University with respect to cold fusion matters. The firm of Arnold, White & Durkee of Houston, Texas, was retained to serve as primary patent counsel. The Salt Lake City firm of Van Cott, Bagley, Cornwall & McCarthy has also served as counsel to the University since April 15, 1990.

The NCFI was formed as a Utah non-profit corporation affiliated with the University in August 1989 to be the focus of cold fusion work. All of the legal firms named above have served as counsel to the NCFI, as well as the University. These firms have represented the University and the NCFI only with respect to specific and discrete projects as requested.

The initial appropriation for legal work has been exhausted and additional funds were designated to cover the anticipated legal work of the University and the NCFI for the balance of 1991.

2. Patent Matters. To date, nine patent applications have been filed with the United States Patent and Trademark Office on behalf of scientists affiliated with the University and/or the NCFI, and these applications have been assigned to the NCFI. Patent counsel have filed several amendments to the applications as well as a considerable amount of additional information in support

1-390 of the applications. Certain of the applications have been filed in foreign countries. All of the applications, foreign and domestic, are pending. Generally speaking, the patent offices have been challenging the applications based primarily on the fact that most of the reported cold fusion experiments world-wide have proved negative. Patent counsel have been responding to the patent offices but their ability to respond may be diminished if cold fusion research directed at the production of a demonstration device does not continue. Moreover, the patent process could be jeopardized if funding is not available to continue processing the appl i cations . Patent counsel are now investigating additional discoveries and it is possible that one or two new patent applications will be filed in the United States within the next several weeks.

There is no way of knowing what patent applications have been filed relating to cold fusion by parties not affiliated with the University or the NCFI. However, it is known that there are many such applications.

3. CorDorate and Contract Matters. The NCFI was formed as a Utah non-profit corporation affiliated with the University. Legal counsel have provided services related to the formation of the corporation, its qualification as a non-profit corporation under the Internal Revenue Code, and various other corporate matters. Portions of this work are on-going. In addition, counsel has provided services from time to time relating to possible structures for seeking and accommodating outside funding and for eventually licensing cold fusion technology.

A contract between Drs. Pons and Fleischmann and the University relating to cold fusion inventions has been concluded, and there have been many additional matters involving Drs. Pons and Fleischmann and their counsel. Some of these matters, such as those involving the prosecution of the pending patent applications are on-going. There have been many other contract matters covering a wide range of subjects.

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