Hydrogen in Uranium

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HYDROGEN IN URANIUM

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R. DARRAS and R. CAILLAT

Rapport CEA n° 1239

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DARRAS R .•. CAILLAT R. Report CEA n° 1239 HYDROGEN IN URANIUM Summary: Hydrogen impairs the properties of metals. in particular this can assume conside rable importance with uranium when used as a fuel material. . ~--·· Hydrogen can be associated with uranium in two distinct ways : either dissolved in the metal. or in the form of a hydride. · The solubility of hydrogen in uranium depends on the allotropie form of the metal ; it is in addition greater in molten than in solid uranium. Two types of hydride. both given bythe formula UH3• have been identified. The first. the a-type. is stable at !ow tempera ture. It is generally accompanied by small amounts of the ~-type. into which it is wholly transformed above 14o"C. 1959 9 pages J •,\. Reprinted /rom "Progress in Nuclear Energy, Series V, Vol. 2-Metallurgy and Fuels" PERGAMON PRESS LONDON · NEW YORK · PARIS · LOS ANGELES 1959 1-3 HYDROGEN IN URANIUM

By R. DARRAS and R. CAILLAT Department of Metallurgy and Applied Chemistry, C.E.A., France

HYDROGEN impairs the properties of metals, in particular this can assume considerable importance with uranium when used as a fuel material. Hydrogen can be associated with uranium in two distinct ways: either dissolved in the metal, or in the form of a hydride. The solubility of hydrogen in uranium depends on the allotropie form of the metal; it is in addition greater in molten than in solid uranium. Two types of hydride, both given by the formula UH3, have been identified. The first, the IX-type, is stable at low temperature. It is generally accompanied by small amounts of the //-type, into which it is wholly transformed above 140°C.

1. FORMATION OF URANIUM HYDRIDES (a) IX-Type The IX-hydride is for medon a polished uranium disk which is made the cathode in a solution of perchloric acid or NaOH, the temperature of the bath being always less than 20°C [CAILLAT et al. (1953)]; an increase in bath temperature results in the formation of the /1-hydride. This is to be compared with the appearance of IX and /J-hydrides in the products of corrosion of uranium in an aqueous medium at ambient temperature. (EICHNER et al. unpublished.) The

1X-hydride UH3 also appears in the reaction of pure hydrogen with powdered uranium at very low temperatures, e.g. -40°C [CAILLAT et al. (1953)].

The IX-hydride has a cubic lattice with a parameter a 0 = 4· 153 ± 0·002 KX and contains two atoms of uranium in the unit cell. lts calculated density is equal to 11 · l [MULFORD et al. (1954)]. The IX-hydride is rapidly transformed into the //-type at 140°C. lt was never possible to detect this transformation below ll0°C [CAILLAT et al. (1953)]. (b) //-Type This is the most common form in which the hydride is found. It is formed rapidly at temperatures of the order of 225° -250°C under a hydrogen pressure greater than the hydride disassociation pressure which is a few mm of mercury [SPEDDING et al. (1949a, 1949b); FLOTOW and ABRAHAM (1951)]. The first publications indicated the existence of an incubation period for this reaction. This was due either to impurities in the hydrogen, or to the presence on the surface of the metal of a layer of oxide or nitride [BURKE and SMITH (1947)]; in fact, uranium, carefully cleaned, reacts immediately at the above temperatures with purified hydrogen [CAILLAT and JACQUET (1949)]. The reaction is extremely 19 20 R. DARRAS and R. CAILLAT fast for powdered uranium, obtained, for example, by a previous decomposition of a hydride. The study of this reaction has been described by MALLETT et al. (1955) and more recently by ALBRECHT and MALLETT (1956). Pure ,8-hydride is also formed in an electrolysis similar to that described for the oc-hydride, but with the temperature of the electrolyte about 90°C [CAILLAT et al. (1953)]. Above 100°C, water vapour reacts with uranium to form the ,8-hydride. The reaction between uranium and hydrogen is completely reversible and agreement between different authors on the equilibrium pressures is satisfactory (PERIO to be published). The crystalline structure determined by RUNDLE (1947, 1951) is cubic: a0 = 6·63 KX with 8 atoms of uranium in the unit cell.

2. MICROSCOPIC EXAMINATION OF THE HYDRIDE INCLUSIONS IN URANIUM Uranium hydride has been identified microscopically by various authors in the form of elongated needles [MATTHEWS (1954); MOGARD and CABANE (1954); DICKERSON et al. (1956)]. The hydride inclusions generally appear at grain boundaries and are surrounded by a brown zone [MOGARD and CABANE (1954)]. The size of the inclusions grows as the rate of cooling of the metal decreases [GARDNER and RICHES (1957)]. ROBILLARD et al. (1956), by using a previously recommended method, give details of the thermal treatments which allow the best conditions for the detec tion of the last traces of hydrogen present in the uranium. The specimen is ,8-annealed in a sealed ampoule under vacuum or in argon, and quenched in boiling water; this is followed by an electrolytic etch and controlled oxidation. Very fine inclusions of hydride are then observed surrounded by a brighter ring. [ROBILLARD and CALAIS (1957)]. In uranium, the hydride is present in the ,8-type [MULFORD et al. (1954)].

3. DETERMINATION OF HYDROGEN IN URANIUM Combustion methods have been proposed [BASSETT et al. (1946); GREGG et al. (1949)]. But hydrogen can be extracted easily by heating the metal under reduced pressure and either the volume of collected gas [DARRAS and COBLENCE (1954)], or the increase of pressure in an apparatus of known volume [DAVIS (1956)] measured. Heating generally takes place above 600°C. The extracted gas consists practically of pure hydrogen. To a first approximation the extraction can be considered complete in one hour at 650°C under a vacuum of 10-4 to 5 X 10-5 mm Hg for specimens of 10-20 g [DARRAS and COBLENCE (1954)], although some traces of hydrogen appear to persist after this treatment. The evolved gas can be transferred by a mercury diffusion pump and concentrated by a Toepler pump in a graduated test tube where its volume and pressure are measured. Hydrogen can also be collected during melting under vacuum at 1800°C in a graphite crucible, with or without an iron or platinum bath, as well as nitrogen Hydrogen in Uranium 21 and carbon monoxide resulting from the reduction of uranium oxide [GREGORY et al. (1952); SLOMAN et al. (1952); GREGORY and MAPPER (1953); GRIFFITH et al. (1955); BOOTH et al. (1956); SPEIGHT and GILL (1957)]. This method is, however, slower and less accurate since it requires both considerable blank testing (due to outgassing of the graphite) and an analysis of the collected gaseous mixture. Moreover, some of the hydrogen can be reabsorbed on the metallic deposits formed on the cold parts of the apparatus, following evaporation which cannot be fully avoided under vacuum at this temperature. [DARRAS and COBLENCE unpublished.] As an example, a few measured contents in ordinary specimens are given here: Virgin solid uranium: approx. 2 cm3/100 g Solid uranium remelted under vacuum: less than 0·5 cm3/100 g Virgin powdered uranium: approx. 100 cm3/100 g. The vacuum method of extraction from the solid phase together with micro scopy have been used most in the study ofhydrogen solubility in uranium, parti cularly in relating quantitatively the influence of this gas on the properties of the metal.

4. SOLUBILITY OF HYDROGEN IN URANIUM Because of the formation of hydride, the study of solubility is limited to that region where this compound is unstable, i.e. above 435°C in hydrogen at atmo spheric pressure. The first studies were made at the Battelle Memorial Institute (1943) in the region of 460° -850°C, by the addition of a known quantity of hydrogen to previously outgassed uranium; when equilibrium was reached at the required temperature, the quantity absorbed was measured volumetrically. In these investigations, reported by KATZ and RABINOWITCH (1951) the results were confirmed by heating the hydrogenated metal in a vacuum tight apparatus and measuring the increase in pressure, or by burning the metal in pure oxygen and weighing the water absorbed in a dessicant. Figure 1 shows that the solubility increases sharply at the transformation temperatures oc.-+ fJ (660°C) and fJ-+ y (770°C), as well as at the melting point (1130°C). The solubility is proportional to the square root of the pressure (Fig. 2). DAVIS (1956) who has recently taken up this study again, determines the amount of pure hydrogen absorbed by measuring the variation of pressure in a calibrated burette. The results are essentially similar to the preceding ones, but the straight lines which represent the variation of solubility in oc.-uranium as a fonction of the square root of the pressure do not pass through the origin (Figs. 3 and 4). The author attributes that anomaly to one or several impurities contained in the uranium, which at low pressures, would cause an abnormally high absorption of hydrogen. 22 R. DARRAS and R. CAILLAT

E 24 a. a. . 20 ~ ..ëi 0 ::, 16 0.. C a, 12 Cl 0

-0>, :i:: 8

o.'=:--'-,±--'--=±-cc--1---=±-,---L~1cc----1...... ,±--'-='=-,-1-...,...1,----1__J 450 550 650 750 850 950 1050 1150 1250 Temperature.°C Fig. 1. Solubility of hydrogen in uranium metal in equilibrium with hydrogen at atmospheric pressure.

0-0020 ...--~-~-~-~-~---,--~-~

0·0018

0·0016

00014

j 00012

a; 00010 eCl f 0·0008

0·0006

0·0004 soo•c"ir- 0·0002 C a

0 15 20 ~5 30 35 40 /p(mmHg) Fig, 2. Solubility of hydrogen in uranium metal as a function of hydrogen pressure for 600°, 700°, and 800°C. 1 2·14 p,p.m. p.pm. / 650°C 2·0 / / 1·8 / / I 1·65ppm. / ooo•c / J 1-6 I / v 1-4 J / o,/ l ), ~ /25 J:lp,m. I __/' / 550°c1 1'2 1 / /V V 1·07pp.m. N JIOf-----+--+---+---4+---+------l 1 ,,/ 5~5 •c I 1·0 / -' 1- ::J ro 51---+---+-+---1----Y--.'--+------1 0·6 :::> ...J

0·5~ 5l

0·4 t:,.=685°C atm. X =700°C 2·t------,'-t-,----+-- o =725 °C

1 1 1 1 1 1 Il 1 0 2 6 10 14 18 22 26 0 5 10 15 20 25 30 vP, mm~2 VP, mm1'2

Fig. 3. Solubility of H1 in ex-uranium vs. v'pressure. Fig. 4. Solubility of H 9 in p and y-U as a Weight of U = 201 ·6 g fonction of square root of pressure. Vol. = 10·66 ml. 24 R. DARRAs and R. CAILLAT In fact, these tests were made on uranium wire obtained from ingots of 99·9 % pure uranium, with the following impurities in parts per million:

C 450 Al 20 Fe> 100 Li <0·1 Si 50 Co <5 Be < O·l Ca <10 Ni 25 B 0·5 V < 10 Cu 15 Na< 1 Cr 7 Mg 2 Mn 3

Furthermore, this impurity would be present as a different phase and with a content about only 0·002 %- This· hypothesis is supported by the fact that the oc 650 550 450 400 3·0 ·1 ' " O• - 2·5 \ " : 0 q - 2·0 [\ X " N O•5 :r È - 1·5 ci.. ci.. 3 \ a ~ a -1 ·2 J:"' i 0 •1 i\ ~ 0 1·O 0 •1 \ 0·9 ,1\ - 0·8 -O•3 - 0-7 o THIS INVESTIGATION~ -0·5>- x BMI METHOD 1 0•6 (ABSORPTION) ~~ a B~I MET~OD 2(OUENCH) -0·7 i 1 0·5 1·0 1-1 1-2 1·3 1'4 1·5 1oo_o/r"K Fig. 5. Solubility of hydrogen in œ-uranium vs. reciprocal temperature. absorption is smaller in a specimen of specially purified uranium. It would be interesting to repeat these measurements on uranium purified by zone melting. The same publication gives the solubility as a fonction of temperature; the results seem to be more consistent than those ofprevious works (Fig. 5).

5. EFFECT OF HYDROGEN ON THE MECHANICAL PROPERTIES OF URANIUM In general, hydrogen increases the brittleness ofmetals. For uranium, studies at Los Alamos and the Battelle Memorial Insti~te have shown that hydrogen Hydrogen in Uranium 25 acts unfavourably on tensile strength, hardness and elongation. Details of these results were published by MARSH, et al. (1955). These authors think that (X-uranium gives a semi-brittle-ductile transition in the vicinity ofroom tempera ture, the main effect of the hydrogen content being to affect the reduction in area, i.e. the conditions leading to necking prior to fracture in the tensile test. However, they do not seem to have worked on uranium which was sufficiently free of hydrogen (minimum content 0·3 p.p.m.) for this conclusion to be completely accepted. Furthermore, the observed transition is not specific on passing from the ductile to the brittle region (BERNARD, to be published).

a2 20 ' 0 Ô 16 - 0 ~2 12 '" g -0 - - w 8 - 4 - 0 2 3 4 5 6 7 HYDROGEN CONCENTRATION, p,p.m. Fig. 6. Ductility of Uranium vs. hydrogen concentration. Hydrogen added at 700°C Strain rate = 0·025 in./min. Length of specimen = 1 in. Temperature of Test = 25°C.

The results of a study by DAVIS (1956) of mechanical properties of test pieces rolled in the (X-phase, P-annealed, quenched (leading to a relatively fine grain and no preferred orientation), exposed to hydrogen at 600°C or 700°C, and finally cooled in helium to prevent loss ofhydrogen, are summarized below: 1. Up to a hydrogen content of 0·2 p.p.m., the ductility is little affected; between 0·2 and 0·4 p.p.m., it decreases rapidly; and above 0·4 p.p.m. increased hydrogen content has no further effect on the ductility (Fig. 6). 2. A hydrogen content greater than 0·4 p.p.m. increases the brittle--ductile transition temperature by about 55°C for a-annealed uranium and 30°C for P-annealed uranium. The transition temperature being about -10°C for (X-annealed and about + 15°C for P-annealed hydrogen free uranium, so it becomes about 45°C for both heat treatments of hydrogenated uranium. 3. Uranium annealed under vacuum, in the (X or P-phase has a maximum tensile strength near to 20°C. Hydrogen lowers this characte1istic and brings the maximum to a temperature of approximately 40°C. However, GARDNER and RICHES (1957b), using apurer uranium, (C content: 37 p.p.m.), find that fine or coarse grain boundary uranium hydride precipitates 26 R. DARRAS and R. CAILLAT and hydrogen concentration (from 0· 12 to 3·6 p.p.m.), have a significant effect on the tensile properties of uranium. But, the magnitudes of the changes are small and might not be important from an engineering standpoint. The principal effect of hydride precipitates is an increase in the ultimate strength between 30°C and -20°C; the elongation is decreased and the yield strength increased.

61------+---~...J------+-----+------,

3 '------...... ------1 ------._/

0 100 200 300 400 TEMPERATURE 0 c Fig. 7. Variation of internai friction as a fonction of the temperature for various states of uranium.

BERNARD and BOUDOURESQUES (to be published) (Fig. 7), have determined the variation of internal friction as a fonction of temperature for uranium in various states: as cast under vacuum (curve 1), exposed to dry hydrogen for 48 hr at 450°C (curve 2), and degassed under vacuum for 48 hr after this latter treatment (curve 3). These curves show the considerable influence of hydrogen. Curve 2 with its two sharp peaks suggests two different states of hydrogen in uranium. REFERENCES ALBRECHT W. M. and MALLETT M. W. (1956) J. Electrochem. Soc. 103 (7), 404--409. BASSETT L. G., PFLAUM D. J., RUTMAN R. J., RODDEN C. J. and FURMAN N. H. (1946) A2912, 110. Battelle Memorial Institute; CT 818 1943. BERNARD J., Rev. Métal!. (to be published). BERNARD J. and BoUDOURESQUES B., Rev. Métal/. (to be published). Boorn E., BRYANT F. J. and PARKER A. (1956) AERE C/R 1947. BURKE J. E. and SMITH C. S. (1943) Report LA 37. BURKE J. E. and SMITH C. S. (1947) J. Amer. Chem. Soc. 69 (10), 2500-2. CAILLAT R. and JACQUET P. A. (1949) C.R. Acad. Sei. Paris. 228 (14), 1224-1226. CAILLAT R., CoRiou H. and PERIO P. (1953) C.R. Acad. Sei. Paris. 237, 812. DARRAS R. and COBLENCE G. (1954) Report MCA, 155 (CEA) (unpublished). DAVIS W. D. (1956) KAPL 1548. Hydrogen in Uranium 27

DICKERSON R. F., GERDS A. F. and VAUGHAN D. A. (1956) J. Metals, 8 (4), 456-60. EICHNER C., PERIO P. and CAILLAT R. (unpublished). FLOTOW H. E. and ABRAHAM B. M. (1951) AECD 3074. GARDNER H. R. and RICHES J. W. (1957a)Second Nuclear Engineering and Science Conference, Paper No. 57 /NESC/8. GARDNER H. R. and RICHES J. W. (1957b) HW 43543. GREGG C. C., WARTEL W. S. and KOPELMAN B. (1949) SEP 22. GREGORY J. N., MAPPER D. and WooDWARD J. A. (1952) AERE C/R 1000. GREGORY J. N. and MAPPER D. (1953) AERE C/R 1274. GRIFFITH C.B., ALBRECHT W. M. and MALLETT M. W. (1955) B.M.I. 1033. KATZ J. J. and RABINOWITCH E. (1951) The Chemistry of Uranium, McGraw-Hill, New York, 183. MALLETT M. W., TRZECIAK M. J. and GRIFFITH C.B. (1955) Nuclear Engineering and Science Congress, Cleveland (Ohio) December 1955. MARSH L. L., MUEHLENKAMP G. T. and MANNING G. K. (1955) BMI 980. MATTHEWS C. 0. (1954) TID 5243 pp. 46-58. MOGARD H. and CABANE G. (1954) Rev. Métal!. 9, 617-22. MULFORD R. N. R., ELLINGER F. H. and ZACHARIASEN W. H. (1954) J. Amer. Chem. Soc. 76, (1), 297-8. PERIO P. System U-H-Traité de Chimie Minérale de M. le Pr. Pascal, XV (to be published). RoBILLARD A., DURAND J. and LACOMBE P. (1956) C.R. Acad. Sei., Paris. 242, 508. RoBILLARD A. and CALAIS D. (1957) C.R. Acad. Sei., Paris. 245 (1), 59-62. RUNDLE R. E. (1947) J. Amer. Chem. Soc. 69, 1719. RUNDLE R. E. (1951) J. Amer. Chem. Soc. 73 (9), 4172-4174. SLOMAN H. A., HARVEY C. A. and KUBASCHEWSKI O. (1952) J. Inst. Metals, 80 (7), 391--407. SPEDDJNG F. H., NEWTON A. S., WARF J. c., JOHNSON o., NOTTORF R. W., JOHNS F. B. and DAANE A. H. (1949a) Nucleonics 4 (1), 4-15. SPEDDING F. H. et al. (1949b) Nucleonics 4 (2), 17-25. SPEIGHT K. and GILL G. M. (1957) Metallurgia 329, 155.

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