Western Michigan University ScholarWorks at WMU
Master's Theses Graduate College
12-1997
The Repulping of Wet-Strength Paperboard
Angelo N. Melchiorre
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Recommended Citation Melchiorre, Angelo N., "The Repulping of Wet-Strength Paperboard" (1997). Master's Theses. 4929. https://scholarworks.wmich.edu/masters_theses/4929
This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. THE REPULPING OF WET-STRENGTH PAPERBOARD
by
Angelo N. Melchiorre
A Thesis Submitted to the Faculty of the Graduate College in partial fulfillmentof the requirements forthe Degree of Master of Science Department of Paper and Printing Science and Engineering
Western Michigan University Kalamazoo, Michigan December 1997 Copyright by AngeloN. Melchiorre 1997 ACKNOWLEDGMENTS
I would like to express my sincere thanks to my mother Rosemary, my sister
Doreen, my wifeClaudia and my son Andres' for their emotional and financial support throughout my collegiate career: and to my committee members Professor Dr. Brian
Scheller, Dr. Ellsworth Schriver and Dr. David Peterson for their advice and guidance throughout this project.
Special thanks to Dr. Raja Aravamuthan and Barb Valenski, for their advice, encouragement and support. Lastly, I would like to thank Todd Fytczyk and the pilot plant fortheir assistance.
Angelo N. Melchiorre
11 TIIE REPULPINGOF WET-STRENGTH PAPERBOARD
Angelo N. Melchiorre, M.S.
Western MichiganUniversity, 1997
Beverage carrier paperboard containing the polyamide wet-strength resin is one type of fiber that is presently landfilled. In this study, it was repulped at a 15% consistency and a pH of 10 at 150° F. in a z-bar mixer. Hydrogen peroxide (HP), ammonium perswulfate (AP), sodium persulfate (SP) and dimethyldioxirane (DIYID) were used during repulping. The HP was added at 1.0%, 2.5% and 5.0%, based on
0 .D. weight of the fiber. The remaining chemicals were added at the same oxidation equivalent. During repulping, the pulp was screened using a Britt Jar to determine percent yield over time. Samples were taken every 15 minutes for 2.25 hours. The voltage and amperes were also recorded for each run. The remaining pulp was screened and refined at 0, 15,000, and 18,000 revolutions with a PFI mill. Handsheets were made and tested for tensile and tear. At 2.35% level, the DMD produced the highest percent yield of 92.13%, and the persulfates had a yield of 84.80%. HP provided the smallest yield of 78.63% at a level of 5.0%. At 120-135 minutes using a low level of HP, the chemical made no impact compared to the no chemical runs. The no chemical runs had the highest tensile values, followed by HP, AP, DMD and lastly,
SP. The highest tear values were at 18,000 revolutions forthe low level of AP. TABLE OF CONTENTS
ACKNOWLEDGEMENTS...... 11
LIST OF TABLES...... ············································································ Vil
LIST OF FIGURES...... lX
CHAPTER
I. INTRODUCTION ......
II. ANALYSIS OF LITERATURE ...... 7
Wet-Strength Resins...... 7
Urea- Formaldehyde ...... 7
Melamine-Formaldehyde Resins...... 12
Polyameric Amine/ Amide-Epichlorohydrin...... 16
Glyoxalated Polyacrylamide ...... 20
Mechanism to Impart Wet-Strength ...... 24
Factors AffectingAcid-Curing Wet-Strength Resins...... 28
Factors AffectingAlkaline-Curing Wet-Strength Resins ...... 31
Recovery of Broke...... ,..,.., .,
Wet-Strength Identification...... 34
Factors InfluencingRep ulping...... 36
U-F and M-F Resin Broke Recovery...... 37
PAE Resin Broke Recovery...... 39
lll Table of Contents-Continued
CHAPTER
Non-Chlorine Repulping Aids...... 41
P AMG Resin Broke Recovery...... 43
Chemistry Overview...... 43
Dimethyldioxirane...... 43
Hydrogen Peroxide ...... 44
III. STATEMENTOF THE PROBLEM AND SIGNIFICANCE...... 46
IV. OBJECTIVES OF THE STUDY...... 48
V. EXPERIMENTAL DESIGN...... 49
Overview...... 49
Outline...... 49
VI. EXPERIMENTAL METHODOLOGY...... 51
Preparation of Paperboard and Z-bar Mixer...... 51
Repulping of the Paperboard ...... 5 3
Screening of the Pulp...... 54
Screening, Refiningand Testing of the Pulp...... 54
Statistical Analysis...... 5 5
List ofEquipment...... 55
VII. RESUL TS AND DISCUSSION...... 56
Properties of the Beverage Carrier Paperboard ...... 56
IV Table ofContents-Continued
CHAPTER
Repulping...... 56
Reproducibility of the Process ...... 5 8
Energy Input...... 59
Percent Accepted Material Reliability...... 59
Effect of Hydrogen Peroxide...... 62
Effect of Ammonium Persulfate...... 6 7
Effect of Sodium Persulfate ...... 71
Effectof DMD...... 76
Levels of Charge ...... �...... 80
Effect of Screening on the Pulp...... 85
Effect of Refining on the Pulp...... 85
VIII. CONCLUSI ONS ...... 96
IX. RECOMMENDATIONSFOR FURTHERSTUDY ...... 99
APPENDICES
A. Raw Materials ...... 100
B. Stock Preparation...... l 02
C. Addition ofHydrogen Peroxide...... 104
D. Addition of the Persulfates...... 106
E. Addition ofDimethyldioxirane...... 108
V Table of Contents-Continued
APPENDICES
F. Repulping of the Paperboard ...... 110
G. Screening of the Paperboard...... 113
H. Beverage Carrier Properties, Energy Values and Run Conditions...... 115
I. Tabulated Data forthe Chemicals...... 123
J. CSF, Tensile and Tear Values ...... 134
K. ANOVATables forChemicals ...... 154
LITERATURE CITED...... 159
VI LIST OF TABLES
l. Typical Porperties of Urea-Formaldehyde Wet-Strength Resin...... 8
2. Typical Porperties of Melamine -Formaldehyde Wet-Strength Resin...... 13
3. Typical Properties of PAE Resins...... 18
4. Typical Properties of the PAMG Resin...... 21
5. Run Conditions...... 52
6. Mathematical Values...... 5 8
7. Mean Energy Values...... 60
8. Average Percent Yield for the No Chemical Run...... 61
9. Average Percent Yield forHy drogen Peroxide Runs...... 63
10. Experimental Dunnett Values forH.P...... 64
11. Experimental Newman-Keuls Values forH.P ...... 65
12. Average Percent Yield for Ammonium Persulfate Runs...... 68
13. Experimental Dunnett Values forA.P...... 70
14. Experimental Newman-Keuls Values forA.P...... 70
15. Average Percent Yield forSodium Persulfate Runs...... 72
16. Experimental Dunnett Values forS. P...... 74
17. Experimental Newman-Keuls Values forS. P...... 75
18. Average Percent Yield forDMD Runs...... 76
19. Experimental Dunnett Values forDMD...... 78
Vll List of Tables-Continued
20. Experimental Newman-Keuls Values forDMD ...... 79
21. Percent Yield forAll Chemicals and Concentrations ...... 81
22. Canadian Standard Freeness Values...... 86
23. Tear Values...... 93
Vl LIST OF FIGURES
1. Methylolation...... 9
2. Reaction of Urea With Formaldehyde...... 10
3. Methylene Linkage and Ether Linkage ...... : ...... l 0
4. Condensing Dimethylolurea With Itself...... 10
5. Production of Dimethylene-ether Links...... 11
6. Production of Melamine...... 14
7. Production of Melamine Using Urea ...... 14
8. Reaction of Melamine With Formaldehyde...... 15
9. Melamine-Formaldehyde Acid Colloid ...... 15
10. Structure of PAE...... 19
11. Reactions With Epichlorohydrin...... 19
12. Structure of a Glyoxal-P AM-Derivative...... 21
13. Formation of Hemiacetal Bonds...... 22
14. Reversibility ofPAMG Wet-Strength ...... 23
15. Production ofBisulfiteAdduct ...... 23
16. Production of a Cationic Resin...... 27
17. Acid Hydrolysis of Urea-Formaldehyde Resin ...... 38
18. SimplifiedDioxirane Formation Mechanism ...... 44
19. Concentration of Active Perhydroxy Ions...... 45
IX List of Figures-Continued
20. Flowchart of Experimental Design...... 50
21. Percent Yield forthe No Chemical Run...... 62
22. Effectof Extended Pulping on Yield Using Hydrogen Peroxide...... 63
23. Effect of Extended Pulping on Yield Using Ammonium Persulfate...... 69
24. Effectof Extended Pulping on Yield Using Sodium Persulfate...... 73
25. Effectof Extended Pulping on Yield Using DMD...... 77
26. Effect of Extended Repulping With a Low Chemical Concentration...... 83
27. Effect of Extended Repulping With a Medium Chemical Concentration...... 83
28. Effectof Extended Repulping With a High Chemical Concentration...... 84
29. Tensile Index With No Chemical Addition...... 89
30. Tensile Index Using Hydrogen Peroxide...... 89
31. Tensile Index Using Ammonium Persulfate...... 90
32. Tensile Index Using Sodium Persulfate...... 90
3 3. Tensile Index Using DMD...... 91
X CHAPTER I
INTRODUCTION
The Dictionary of Paper (1) states the definition of wet-strength paper as foUows: "It is a paper which has extraordinary resistance to rupture or disintegration when saturated with water." This property is produced by chemical treatment of the paper or the fibers from which it is made. Wet-strength is to be distinguished from water repellency or the resistance of a paper to wetting when exposed to water. Wet strength is most evident and most significant when it occurs in absorbent papers.
Normally, a paper loses most of its strength when truly wetted with water. A paper which retains more than 15% of its dry strength when completely wetted with water may properly be called a wet-strength paper. Paper can be considered to have wet strength properties if it retains more than 15% of its tensile strength when wet. (2-3).
It is important to note that the wetting agent to be used is distilled water.
Other liquids can be used forimmersion, but the results will vary considerably. T APPI
Test Methods T456 om-87 (4) states: if a liquid other than distilled water is used, report the results as "tensile strength after soaking in . .. (liquid) for ... (time)."
Such results are to be distinguished from "wet-strength" as defined in this method.
As the uses of paper become more diversified, the possibility of the products being exposed to water increases. The following list shows various exposure conditions in which strength in the wet state becomes a useful paper property:
1 2 1. Exposure to weather. Such products are war maps, packing cases, outdoor posters, building paper, and paper bags.
2. Exposure to water of paper products used as drying or wiping media. Such products include paper towels, paper napkins, lens paper, windshield wiping tissue and industrial wiping tissue.
3. Exposure to water of paper used as wrapping for moist materials. Such products include paper bags, and wrappings for meat, vegetables, frozen foods and prepared foods.
4 .. Exposure to water by immersion as part of a processing operation. Such products include photographic paper, blueprint paper, filter paper, saturating paper and tea-bag paper.
As can be seen from the list above, the desirability of the property of wet strength was recognized. Wet-strength resins were mass produced when it was discovered that certain thermosetting synthetic resins gave wet-strength when incorporated in paper m the low-molecular-weight water soluble condition and polymerized in situ. ( 5-6)
A water solution of urea-formaldehyde resin was first introduced as a surface size, followed by heat curing of the resin. in the paper around 193 5. (7) The demand for water resistant packaging and map paper in World War II led to the development of urea-formaldehyde and melamine-formaldehyde resins that could be added directly to the furnish. (7-9) These wet-strength resins could be anchored to the anionic sites on cellulose by an aluminum ion. The anionic· wet-strength resins were replaced by "'.) cationic resms around 1950. The aruoruc sites on the cellulose and fines easily attracted the cationic resin without the bridging that was required with the anionic wet-strength resins. (10) These wet-strength resins have proven to be extremely proficient in imparting wet-strength properties, however, the switch to more alkaline papermaking systems led to the development of new wet - strength resins. The use of formaldehyde could cause some health and safety problems, so there was also a need to go to "safer" wet-strength resins. As formaldehyde standards become more stringent, alternative wet-strength resins must be used. The Longview Fibre Company
(11) conducted extensive research on formaldehydestandards and found that its work areas tested significantly below the 1 ppm limit proposed by OSHA, but still conducted daily monitoring to insure safety.
In 1956, an alkaline curing wet-strength resin was produced by reacting and cross-linking a polyamine with epichlorohydrin. This led to the development of polyamide-polyamino-epichlorohydrin wet- strength resin in 1960. (7) This particular resin has found great success in the paper industry and in still being used extensively today. This is due to the fact that they have a high cationic charge which enables them to be fiber substantive. They also have the ability to cross-link and insoh.ibilize in the absence of acid catalysts. This enables the wet-strength resin to be utilized under neutral pH or acid free papermaking conditions. (12)
Since 1950, all wet-strength resins used commercially as wet-end additives in
North America have four essential properties in common. They are: polymeric, cationic, water-soluble or water-dispersible and network forming (usually 4 thermosetting). The resin must be polymer of substantial molecular weight if it is to be strong enough to protect the fiber-fiber bonds of the paper against swelling and dispersion. The polymeric resin needs to be cationic in order to be adsorbed onto the fiber and fines surface without bridging. For even distribution, the resin needs to be water-soluble. Lastly, all commercial resins are thermo-setting; they form a covalently bonded network by cross-linking themselves and/or cellulose molecules. (10)
The wet-strength resins can be divided into two groups; acid curing and alkaline curing resins. Acid curing wet-strength resins include the following: Urea
Formaldehyde (UF), Melamine-Formaldehyde (MF), Polyacrylamide-glyoxal (PAMG) and Dialdehyde Starch (DAS). The alkaline curing wet-strength resins include the
Polyamide/amine-epichlorohydrin (PAE) resins. The permanence of the wet-strength bond varies according to the material or process used to develop the wet-strength.
This permanence is influenced by a number of factors: (a) The nature of the wet strength agent, (b) pH of sheet during storage, ( c) storage temperature, ( d) relative humidity during storage, (e) degree of cure of the wet-strength agent and (t) the action of micro-organisms. (2) (13)
The strength of paper is determined by the amount of bonding that occurs between the fibers. Refining, through internal and external fibrillation and fiber swelling, will enhance the areas between the fibers in order to increase the strength of the bonds. Paper, depending on the types of fibers used, can have a relatively high dry tensile strength. This strength can be maintained at a final moisture content of approximately 5-7%. As the amount of water in contact with the paper increases, by s humidity or saturation in water, the bonding between the fibers will begin to break apart. The breaking of the bonds between the fibers will significantly decrease the tensile strength of the paper and will ultimately lead to the disintegration of the paper.
The use of wet-strength resins will, to some extent, prevent the total breakdown of the paper. The bonding that takes place when the wet-strength resin is present is dependent on the particular type that is used.
Paperboards containing wet-strength resins have proven to be both difficult, costly and in some instances environmentally unfriendly to recycle. Equipment constraints and modifications, in some instances, make it uneconomical to repulp wet strength paperboard. Chlorine containing compounds, which were first used for repulping wet-strength paperboard, are fast becoming obsolete due to their negative impact on the environment.
Where newsprint and corrugated can be repulped with mechanical action and high temperatures, the recycling and repulping of wet-strength paperboard may require chemical addition, as well as a series of steps utilizing mechanical action. The chemicals that have performed well are either oxidizing or reducing agents. Oxidation involves the loss of electrons and reduction involves the gain of electrons by the chemicals being used. ( 14)
The resins in wet-strength paperboard provide a protective barrier around the fibersthat inhibit the swelling of the fibersduring repulping. Oxidizingagents are used to break through the protective barrier, thus allowing the fiber to swell with water during repulping. This breaks down the wet-strength and allows the paperboard to be 6 repulped.
Important variables that have to be considered when repulping wet-strength paperboard are: temperature, pR consistency at which the repulping takes place and the applied energy. These variables have to be monitored in order to effectively and economically repulp wet-strength paperboard.
An increase in environmental awareness has brought about great changes in the paper industry. Federal mandates, endangered species, the lack of landfill space in some areas of the country and environ-mentalists have put pressure on the paper industry to recycle products that only a few years before would have been regarded as trash. New technology is being developed to handle this source of fibrous material.
Wet-strength paperboard, particularly beverage carriers, is one area of recycling that needs further attention and investigation.
This research focuses on the use of oxidizing agents and their ability to break the wet-strength bonds, as well as on the mechanical energy applied in the process. It is hoped that the knowledge gained from this investigation will lead to a better understanding or improvement in the process necessary to repulp wet-strength paperboard. CHAPTER II
ANALYSIS OF LITERATURE
Wet-Strength Resins
U rea-F ormaldehvde
Urea-formaldehyde (U-F) resins are low in cost, easier for broke recovery and are less susceptible to interference due to dissolved substances in the paper making system than the newer wet strength resins. They contain no organochlorine in the polymer system and will not contribute any adsorbable organic halides (AOX) to the paper making system. The reactive functional groups consist of N-methylol groups,
CH20H groups bound to a hydrogen atom, which, in principle will react with other reactive groups in the resin or with the hydroxyl, carboxyl or aldehyde groups on the fiber. ( 15-16)
Urea-formaldehyde resin can be described as a resin which is a water soluble
U-F condensate containing a cationic modifier in the polymer chain. Currently, nearly all commercial U-F resins are cationic U-F resins. The cationic modifier is usually a polyfunctional amine such as a diethylnetetriamine or triethylenetetramine. (10) (15)
( 17) The use of polyfunctional amines as modifiers not only provides water miscibility at quite high molecular weights, but also provides a cationic charge so that the polymer is directly substantive to the anionic pulp. Urea-formaldehyde wet-strength
7 8 resin is a syrupy liquid (usually colorless to dark amber) that is shipped at 25-40 percent solids in water, with the two most common being 27.5% and 35%. Its viscosity can range from 50-100 centipoise, but at viscositys below l 00 centipoise is usually desired. Storage should be at a near-neutral pH. (8) (10) (15) (17)
Urea-formaldehyde resins do not need pretre�tment in the paper mill. Urea formaldehyde resins are typically added at levels between 1.5-2.5% resin based on pulp solids and can be added, as supplied or diluted, as close to the headbox as possible, but addition is preferably afterthe last stage of refining. (10) (15) The resin must be protected from freezing, as well as stored at temperatures above 32° Celsius.
(17) The cure rate forU-F is slow and the stability is approximately six months. The typical optimum application pH range is 4.0-4.5. (18) See Table l for typical properties of the U-F resin. (17)
Table 1
Typical Properties ofUrea-Formaldehyde Wet-Strength Resin
25% Solids 35% Solids
Percent Solids 25 35
Ionic Character Cationic Cationic
Appearance Amber liquid Amber liquid
Density at 77° F. lbs/gal 9.2 (a) 9.6 (a) 9 Table 1 - Continued
25% Solids 3 5% Solids
Viscosity at 77° F. cps. 15-30 35-60
pH 7.0-7.5 7.0-7.5
Freezing point 29° F. 25° F.
Shelf Life 3 months 3 months
Note: (a) Viscosity increases with age. (b) Resin stratifies and bottom portion will gel ( c) Manufacturer guarantee if stored below 90° F.
The chemistry involved in making a U-F resin consists of two steps. The first stage is methylolation, which involves nucleophilic addition of a nitrogen containing compound onto the carbonyl group formaldehyde to give methylol compound. (15)
See Figure 1.
-NH2 + H2C=O- -NHCH20H
Figure 1. Methylolation (15).
The methylol urea is formed under neutral to slightly alkaline conditions. (19)
In U-F resin, an amide group from the urea is involved in the reaction. Urea and formaldehyde react under neutral to slightly alkaline conditions and high temperatures to form dimethylolurea. (15) (20) See Figure 2 on page 10. High temperatures and 10 low pH, 4-5, promote the second stage of the reaction. This involves condensation polymerization between the methylol compounds to give methylene or ether linkages
HN-cHzOH C-0 + 2HCH0 pH 7-8 I • c�',- NHz HN-CKzOH
Figure 2. Reaction of Urea With Formaldehyde (16) (20). with the elimination of the water molecule in each linkage in the polymerization process. (15) See Figure 3.
-NHCH2OH + HOCH2HN- - -NHCH2NCH2OH- + H2O (i) -NHCH2OH + HOCH2HN- - -NHCH2OCH2NH- + H2O (ii)
Figure 3. Methylene Linkage (i) and Ether Linkage (ii) (15).
The dimethylolurea, will also self-condense under acidic conditions. (16) (22)
See Figure 4.
OH �OH -�-• n C=O' C=O + Ni20 I I HN--·-cH�H HN-af2')H n
Figure 4. Condensing Dimethylolurea With Itself (16). 11 Branching can occur and, under certain conditions, water can be separated (see boxed area) from the methyl groups to give a dimethlylene-ether-bond. Three dimensional networks can also be formed. These molecules have a greater number of functional groups per molecule for reaction with cellulose fibers than dimethylolurea, and this makes them more efficient. (16) (21) See Figure 5.
H-N-CH2+----� OH Hf O-CH2-N-H I I C=O C=O I I H-N-CH2-0H H--0-CHi-N-H
Figure 5. Production ofDimethylene-ether Links (22).
Thus, it is possible to carry out a rapid change from a very soluble, low molecular-weight hydrophilic substance to an extremely insoluble water-resistant material. These are the conditions that favor wet-strength formation: the initial formis able to penetrate and become intimately associated with the fiber surface and upon conversion to the water-insoluble form it becomes a bridge or bond between the fibers which is unaffectedby the presence of water. ( 5)
The U-F resin belongs to the acid curing resins group and chemically, this means that the condensation reaction which results in polymerization of the resin to the water-insoluble stage is initiated by hydrogen ions, which must be supplied by an acidic material. This material can be paper maker's alum or a mineral acid, such as sulfuricacid or hydrochloric acid. The headbox pH of the machine using U-F resin 12 must be below pH 5 and preferablypH 4. 0-4. 5. (5) (16-17)
A typical cationic U-F resin attains about half of its wet-strength property directly on the paper machine, three-quarters during the first few days and the remaining wet-strength property (90-95%) will be achieved after about two weeks of natural aging. (5) ( I 6)
Melamine-Formaldehyde Resins
Further research in the areas of U-F resins led scientists to the discoverv that strong organic bases containing nitrogen, when used as modified, produced water dispersible resins in which the colloidal particles carried a positive charge. This led to the development of melamine-formaldehyde (M-F), which is used to permanent wet strength needed for specialty paper such as currency paper and map paper. (5-6)
Melamine-formaldehyde has many similarities to U-F. Like U-F, M-F is acid curing, contains no organochlorine in the polymer system and will not contribute any adsorbable organic halides (AOX) to the paper making system. It will also react with formaldehyde at slightly alkaline conditions and has a similar chemical nature. (5) (15)
(19)
The M-F resin is available in two forms, a dry powder and a ready to use acid colloid form. The powder is dissolved in dilute acid solution and aged under specific conditions. In the acid colloid form the resin has a strong positive (cationic) charge.
The dry powder form can be shipped in bulk or paper bags, but has to be protected from moisture to avoid caking of the powder. It can be stored for six months and 13 should not be stored at temperatures above 38° Celsius. Freezing is immaterial. (18)
(22)
In the acid colloid form, it should not be stored longer than ten days at 6 percent consistency at temperatures above 28° Celsius. If it is frozen, it can be thawed. but localized temperatures must be avoided. (18) (22) See Table 2 for M-F properties. ( 17)
Table 2
Typical Properties of Melamine-Formaldehyde Wet-Strength Resir
Form Dry Powder Acid Colloid
Concentration 100% 6-12%
Appearance White Tyndal blue
Density 0.4 Approx. l.05
pH NA l.6-2.0
Freezing point jF NA 32° F.
Effect of Freezing None None
Shelf Life Indefinite 1-4 weeks@ 75°F.
Melamine is a trifunctional cyclical amine. It can be produced by two different methods. The first method, which is still considered the most important method commercially, uses Calcium Cyanamid. (23) This was called the "dicy" process. (8) 14 See Figure6 for the production process of melamine.
C-NH, NH -f'N 6 CaCN,- 6NH,CN - 3 mJ-N�NH - 2 H.N� b-NH, ){ Calcium - Cyan.amide- Dicyandiam,ide - Melamine cyan.amide (Dicy)
Figure 6. Production ofMelamine (23 ).
The second method of production involves the use of urea. (23) See Figure 7.
C-NH, 3o-c(NH, ✓'k - I II +3H. "'- H,N-C C-NH1 NH, V Urea - Melamine + Water
Figure 7. Production ofMelamine Using Urea (23).
Melamine reacts with formaldehyde at slightly alkaline conditions (pH 7-8) to form a series of methylol melamjnes. Depending on the number of moles of formaldehyde present, a range of products from monomethylol to hexamethylol melamine can be formed. (15) See Figure 8. The M-F resins are of high molecular weight and are made by condensing polymerization of two or more monomer units with the elimination of water under high temperature and low pH. It is at this low pH 15
Mlamine + x Form-- M.onornethylol Heylol ayd maine or mamin
Figure 8. Reaction of Melamine With Formaldehyde (23).
(about 2) that a number of cations co-react to form a still larger positively charged particle. About 20 of these monomer units will condense to form M-F colloids. (15)
( 19) See Figure 9 on page 16. They will acquire a cationic charge during formation through the association of the amino nitrogen from methylol melamine with hydrochloric acid to give water soluble acid salt.
I l■upto20unb
Figure 9. Melamine-Formaldehyde Acid Colloid (15). 16 In aqueous solution, the acid salt ionizes to give a cationic polymer and negatively charged chloride ion. The condensation reaction, which proceeds rapidly at first, gradually slows down and the system becomes relatively stable with particles of colloidal size, about 100 - 200 A. It has been found that a 3: l molar ratio of formaldehyde to melamine (trimethylol melamine) seems to give the best M-F colloids as wet-strength resin. (5) (15) (17) (24)
Melamine-formaldehyde does differ from U-F in several respects. First, a M-F solution may be prepared in which the resin is substantive to papermaking stock without the aid of alum. The second difference is that the wet-strength which is obtained from the use of M-F resin is more durable than that which is obtained with the U-F resin. It can be said that it is more resistant to hydrolysis then the U-F resin.
This can be attributed to the greater amount of functional groups present in the M-F resin. The M-F resin cures on and offthe machine like the U-F resin. (3) (21) (24)
Polvameric Amine / Amide-Epichlorohvdrin
The acid curing resins, which operated at a pH of about 4.5-5, had senes drawbacks that led to the development of an alkaline cunng wet-strength resm.
Absorbent grades such as toweling and facial tissue are at a handicap at pH 4.5-5 because water absorbency tends to be lower. (9) The polyameric amine/arnide epichlorohydrin (PAE) resins offered high cost-effectiveness as well as improved absorbency in sanitary grades, reduced machine corrosion and compatibility with alkaline sizes. These benefitsled to the immediate acceptance of PAE resin. (25) (26) 17 The PAE resins are cationic water-soluble condensates of an amino-polyamide or a polyamine, and epichlorohydrin. They are used in a manner similar to U-F and M
F resins, except they do not require acidic conditions forfurther polymerization in the paper. The PAE resin may be used at pH 5-9. (27) (28)
The PAE resin can be shipped in bulk by tanker or in 55 gallon drums. It must be protected from freezing in transit and storage. Prolonged exposure to temperatures above 32° Celsius should be avoided and temperatures above 43° Celsius cause quick gelation of the resin and prolonged exposure to these temperatures will cause hydrolysis of the resin and loss in efficiency. (27) The PAE resins are available at solids contents between 12 and 33 percent by weight, and Brookfield viscosities up to about 250 centipoise at 25° Celsius. The PAE is stable for up to three months and is usually added after the last refining stage. (10) The alkaline-curing amine epichlorohydrin resins can be categorized either by the chemistry of their backbone polymers, or by their reactive functionality. These resins are cationic water soluble condensates of an amino-polyamide or a polyamine, and epichlorohydrin. They are used in a manner similar to the U-F and M-F resins, but do not require acidic conditions for further polymerization in the paper. The PAE resin has become the most commercially important thermosetting product for the production of wet strength paper and has the ability to be absorbed by the fiber in the neutral-to-alkaline pH furnishes. (6) (25-27) See Table 3 on page 18 fortypical properties of PAE resins.
(27) The PAE resins are made by reacting polyamine or an amine-containing polymer with an epoxide possessing a second functional group (typically epichlorohydrin) in 18 Table 3
Typical Properties of Polyamide-Epichlorohydrin Polyamine-Epichlorohydrin Wet-strength Resin
25% Solids 35% Solids
Total Solids, wt% 25 35
Ionic Character Cationic Cationic
Appearance Amber liquid Amber liquid
Density at 77° F. lbs/gal 8.9 9.4
Viscosity at 77° F. cps. 120-160 120-180
pH 2.0-4.0 2.0-4.0
Freezing point 27° F. 30° F.
Effect of Freezing Adverse Adverse
water solution. The epichlorohydrin alkylates and crosslinks the polyamine to a
moderate molecular weight. In other words, the epichlorohydrin reacts with the
secondary amine groups and transforms them to tertiary or quartemary groups. Thus, a cationic resin is obtained with reactive groups which promote crosslinking. The crosslinking reaction is then arrested by dilution, and/or by reducing the pH (acidifying the aqueous resin solution) to convert amine groups to their acid salts. (24-25 ) (29)
See Figure IO on page 19 for the structure of PAE. Whether the reaction partner of epichlorohydrin is a polyamide, a polyarnine,or an amine polymer, its amine groups 19 o o ca· o o M I IM H I '" N (CHzrN -J-- --(-C-(C-C-N-(Q-N-(-N-J-(-C-(C-C- -(Clla-t / ' Cl'2 C /Cllt I '� CHON ., I I OH f'2a
Figure 10. Structure of PAE (29). may be primary (1), secondary (2), or tertiary (3). These react with epichlorohydrin by different routes. (25) See Figure 11.
1•: R-NHl + CH,-HCH,Cl -RNH-H,-HCH,Cl '-. / / 0 OH
RNH-CH1-CHCH,Cl + CH,-CHCH,Cl -R-N(CH,-CHC,Cl), I '- / I OH O OH 2•: R,NH + CH,-CHCH,Cl -R,N-CH,-CHCH,Cl \ I I 0 OH
R CH, '+/ ' Cl- R,N-CH,- HCH,Cl - N CH-OH f / '- / OH R CH, +
J•: . R/ + CH1-CHCH,Cl -R/-CH,CH-H, '- / '- / 0 Cl- 0
Figure 11. Reactions With Epichlorohydrin (25).
The most important PAE resins are derived from secondary aminopolyamides, the 3-hydroxyazetidinium ring is likewise their principal reactive functional group and they may be referred to as "azetidinium" resins. (25)
Paper treated with the PAE· resin has a reel wet-strength of 50% and obtains fullwet-strength properties after about 3 weeks. (24) 20 Glyoxalated Polyacrylamide
The glyoxalated polyacrylamide (P AMG) is a water-soluble condensate of moderate molecular weight polyacarylamide and glyoxal containing a cationic modifier in the polymer chain. The cationic group is intro9uced by copolymerization of acrylamide monomer and a basic vinyl monomer. The cationic polyacrylamide is treated in dilute aqueous solution with glyoxal, which adds to the amide group to form reactive functional groups. (10) (30-31)
The P AMG resin is usually sold as dilute aqueous solutions around 6-10 percent solids. They are added at the wet end of the paper machine, at levels between
about 0.25 and 1.0 percent solids based on pulp solids. The resin should be protected
from freezing and heat. It should be stored in the coolest area practical. (10) (31)
It would be more precise to characterize the P AMG resin as an acid curing resin that can tolerate increased pH somewhat better than U-F resins. They are most effective at pH 4.5, but can be used effectively at pH up to around 6, especially in the presence of alum ( l 0) See Table 4 on page 21 for typical properties of the P AMG
resin. (30)
Glyoxalated PAM wet-strength resin is produced by crosslinking a glyoxal
with a low-moderate molecular weight poly-acrylamide (PAM) so that a network
structure with a large number of aldehyde groups is formed. (30-31) See Figure 12 on
page 21. The freealdehyde groups can then react with the freehydroxyl groups of the
cellulose and formhemiacetal bonds. (31) See Figure 13. 21 Table4
Typical Properties of Acrylamide-Glyoxal Wet-Strength Resin
Values
Total Solids, wt% 6.0-10.0
Ionic Character Cationic
Appearance Colorless
Density at 77° F. lbs/gal 8.7
Viscosity at 77° F. cps. 25-60
pH 3.0-3.5
Freezing point 30° F.
Effect of Freezing None
0 PAM SACXIONE 0 0 � II C-CH-HH-C-- 1 I M OH 0 OH 0 IC i II C-NH-CH-CJ-NH-C I OH
Figure 12. Structure of a Glyoxal-P AM-Derivative (25). 22
0 i ?" ,' C - C NH CH CH - 0 C- CNHCHC + HO <
Figure 13. Formation of Hemiacetal Bonds (25).
The hemiacetal formation can take place under neutral conditions, but is an
acid catalyzed reaction. The optimum pH range is 4. 0-7. 5. The P AMG is normally
prepared with a cationic co-monomer of the quartemary ammonium type to provide a
means for self attachment of the finished resin to the fiber. In the case where the
P AMG is anionic, a cationic retention agent is required to attach the finished resin to
the fiber.(10)(30-31)
The major disadvantage to the use of PAMG resin is that the reaction between
it and the cellulose is reversible in the presence of water. The hemiacetal bonds are
susceptible to hydrolysis in water. The hydrolysis is especially quick in the presence of
alkali (caustic and hypochlorite) and/or a high temperature. Upon redrying, however,
the wet strength is regained by the paper, (See Figure 14) but the wet-strength loss
with an alkali is permanent. This is probably due to the destruction of the aldehyde
functionality. This is the reason the resin gives only temporary wet-strength. (10)(30) 23
Sheet Treatment Wet tensile distilled water ib/inch
10 second soak 3.7
4 hour soak 1.9
4 hour soak, press, 3.2
All sheets made with 0.3% glyoxalated PAM.
Figure 14. Reversibility of PAMG Wet-Strength (31).
Glyoxalted PAM can also react with sulfite or the bisulfate ion to form the bisulfate adduct. (31) See Figure 15.
0 0 II I C-HH- I \ OH H 0 OH II I e + C-H-�H-S03 I OH HS03 e
Figure 15. Production ofBisulfite Adduct (31).
The bisulfate ions react quickly with the free aldehyde groups of the wet-strength derivatives. This reaction blocks or inactivates a portion of the reactive aldehyde groups on the resin, and increases storage stability by retarding crosslinking. The final product, due to the inactivated aldehyde groups, will also give rise to negative charges 24 on the wet-strength condensate and thereby reduce the original cationic character of the layer, with a consequent deterioration in the self-retention of the derivative. The reduction of resin cationicity can severely reduce resin retention and performance. (30-
3 1) The gloxalted PAM resin is usually completely cured in the dryer section of the paper machine and post-curing is not necessary. (30)
Mechanism to Impart Wet-Strength
A discussion of the mechanisms of wet-strength resins follows. Each of the three types of resins may follow one or more of the followingpostulates:
1. There is an actual chemical reaction between the wet-strength resin and the cellulose fibers.
2. A crosslinking of the resin with itself, without forming covalent bonds to cellulose or hemicellulose, either: (a) within the hemicellulose (interpenetrating network), or (b) surrounding the area (volume) of fiber-fiber contact, impeding swelling and holding the fibers within hydrogen-bonding distance.
3. The wet-strength not only protects the existing fiber-to-fiber bonds by forming a network over or in the bonding areas, but also forms additional waterproof fiber to resin-to-fiber bonds.
4. Direct covalent linking of cellulose to cellulose, through a resin molecule or network ofresin molecules. (6) (15)
Gruntfest and Young (3 3) have described an experiment which confirmsthe
view that the important effect ofwet-strength resins is due to their influenceon fiber 25 bonding rather than the modification of the fibers themselves. In their laboratory experiments, the low molecular weight resms were shown to be inferior in wet
strength ability.
Most commercial wet-strength agents are synthetic heat-setting resins which
give crosslinked three dimensional networks. This includes U-F, M-F and PAMG.
The U-F and M-F resins are polyfunctional reactive polymers. The reactive functional
groups consist of N-methyl-groups, i.e. CH20H groups bound to a hydrogen atom.
In principle, these groups can react with other reactive groups in the resin or with the
hydroxyl, carboxyl or aldehyde groups on the fiber. (17) In other kinetic studies,
paper treated with U-F and M-F resin was investigated at various temperatures and pH
for the rate of loss of wet strength on soaking in water. From the data collected, the
activation energy of the hydrolysis of the wet-strength was determined to be in
agreement with the activation energy ofhydrolytic cleavage ofthe crosslinked U-F and
M-F resin. (15) (34-35)
Studies by Jurecic, Lindh, Church and Stannett (34) strongly suggest that the
mechanism of cure of the U-F and M-F wet-strengthened paper is the condensation of
the resin itself to a crosslinked water-insoluble polymer. This wet-strength bond itself
probably extends into the fibrils or the fiber walls causing reduced swelling of the
fiber-to-fiber bondsand stronger anchoring ofthe resin fiberbonds.
In other studies by Fineman (36) and Kennedy (37) it was shown that the wet
strength resin network permits water to be imbibed but fixes a limit on the actual ·
volume increase and on the interfiber distance. This overall effect is wet-strength. 26 Studies by Hazard, O'Neil and Stannett further confirmed the results of the previous studies. (38)
The adsorption of wet-strength resin on pulp in a water-pulp-resin system can be postulated to take place in a series of steps. First, the resin in the solution must be transported from the solution to the fiber. A thin fluid film is known to exist at the interface between the fiber and the moving solution. The transport step is assumed to take place across this film. The resin at the fiber surface is still assumed to be in solution. Once the resin is at the surface of the fiber it is free to adsorb on the fiber.
(39)
As far as U-F and M-F resms are concerned, there seems to be enough evidence that the wet-strength is developed by the formation of a restraining (self cross-linked) network of resin around or in the fiber-to-fiber bonding area and thus retarding the loosening of the bonds by water. (6) (10) (40)
The PAE resin is produced when an epichlorohydrin reacts with the secondary amine groups and transforms them to tertiary or quartnary groups. Thus, a cationic resin is obtained with reactive groups which promote crosslinking. (4) See Figure 16.
Pulp fibers and finesin water dispersion have a negative surface charge. This
negative surface charge arises from the formation of an electrical double layer. An initial attraction of the resin to the pulp is primarily electrostatic. The cationic macromolecules are spontaneously adsorbed onto the negatively charged surface of the pulp fibers and fines. The first added resin is completely absorbed. As increasing amounts of resin are added, the wet-strength usually continues to increase but more nH2N-R-N-R-N2 • nH -R -CH 27 TRIAINE OICARBOXLIC ACID (-N-R-N-R-c-R-c), • 2H� POLYAIOE POLYAINE
+ H2�1CH-�- C 0 EPICHLOROHYRIN
H -N-R-N-R-NH,. -c-R-. c- 1 �� �C 0,1 X POLYAIOE AINE RESIN CONDENSATE
Figure 16. Production of a Cationic Resin (32).
slowly, showing diminishing returns. Once it is attached to the pulp, its retention,
before curing, appears to be due to ion exchange with the counter ions of the carboxyl
groups. (10) (26) According to Espy and Rave (40), there is evidence that PAE resins
are predominantly self-crosslinkers rather than cellulose-reactive resins and for them to
impart their wet-strength properties, they must crosslink to a water resistant network
when they dry or age or are cured with heat. (29)
Studies by Bates (41 ), using sucrose or methyl glucoside (4 2) suggested that
the PAE resin does not react with the hydroxyl groups of cellulose, and it imparts its
wet-strength not by new bonding, but by reducing the access of water and its swelling 28 of the pulp, presumably by self-crosslinking. Other studies by Cheradame and Viallet have seen PAE resins as chemically crosslinked fiberbonds. (12) (25)
The P AMG resin is greatly influenced by heat treatment. This leads to a
crosslinking in the paper, hemiacetal and ester bonds being formed between aldehyde,
hydroxyl and carboxyl groupsbetween the cellulose an·d hemicellulose molecules. The
chemical reaction, using polyacrylamide resins, is usually finished in the dryer section
of the paper machine and post-curing is not necessary. (10) (31-32)
Functional wet-strength requires formation of fiber-resin-fiber covalent bonds.
These bonds form where glyoxalated polyacrylamide is adsorbed onto fiber surfaces
within the fiber-to-fiber bonded area, and when paper making and drying conditions
favor the formation of an extensive amount of covalent bonding between resin
networks and each of (at least) two contacting fibers. While the strength of the
covalent fiber-resin-fiber bonds in the wet state appear to provide the majority of the
wet-strength imparted by the resin, other mechanisms may also contribute. These may
include intra-fiber crosslinking, which may reduce the tendency toward fiber swelling
in the wet state, and bond protection by limiting normal hydrogen bond disruption by
water penetration into the bonded area. (3 l)
Factors AffectingAcid-Curing Wet-Strength Resins
The efficiency and effectiveness of the acid-curing wet-strength resins can be
adversely affected by many paper making variables. Such variables include: nature of
the wet-strength resin, pH and temperature at which the paper is made, relative 29 humidity during storage, degree of cure of the wet-strength agent and aruomc contaminants. Before using any wet-strength resins, an overall process examination should be performed on the paper making system in order to determine, if any, the particularwet-strength resin that should be used.
The specific nature of the agent or process has a great deal to do with the permanence of the wet-strength properties imparted. Some materials, such as PAMG, impart only a temporary wet-strength, while others impart a more permanent wet strength. (13) Melamine-formaldehyde has a more durable wet-strength then the U-F resin, which would be more durable then the PAMG resin. (15) (23) (31)
The U-F and M-F, will be examined first. The pH plays an important role in the rate of cure in the case of both these resins. Paper made at a pH of 4. 5 will reach the same ultimate wet-strength as paper made at a pH of 5.5, but this cannot be accomplished within practical time limits. (15) (21) The P AMG resin can be used over a greater range then the U-F and M-F resins. It has a pH range of 4-6, before the wet-strength is drastically affected. (31) ( 43)
A high temperature, over 300° Fahrenheit, will decrease the wet-strength of the U-F and M-F resins dramatically. The rate of cure will increase steadily with higher temperature, until cellulose decomposition occurs. It can then be said that at higher temperatures will speed up the rate of hydrolysis of cellulose, while a lower temperature will retard it. (5) (7) (13) The PAMG resin should have a limited resin stock contact time ( about five minutes) in hot stock systems. (31) 30 A high relative humidity during storage will accelerate the loss of wet strength for U-F, M-F and PAMG resms. This will accelerate the rate of hydrolysis of cellulose. (13) (15) (31)
The last variable that will be discussed is the degree of cure of the wet-strength agent. The dryer section of the paper machine aids i"n the curing of the wet-strength resms. The U-F and M-F resins are thermosetting and when the resin is dried on the hot sheet in the dryer, the condensation reaction continues, forming an insoluble network. (43) The U-F resin will attain about half of its wet-strength property on the papermachine and the remainder after about two weeks of aging. (15) The M-F resin is practically cured as it leaves the paper machine, with the remainder occurring within two weeks. (15) The PAMG resin, The aldehyde groups are believed to react with cellulose hydroxyls, forming hemiacetal bonds. Under machine drying conditions, hemiacetal formation occurs rapidly. The P AMG resin will develop nearly all of their wet-strength on the machine and less on aging or heat curing than the U-F and M-F resins. (43) The curing will occur more rapidly at pH 4-6 then at pH 6-8. (31).
Anionic contaminants can act as "scavengers" for cationic additives such as wet-strength resins by complexing or even precipitating them. The contaminants can render solid furnish components highly anionic, thus favoring adsorption of cationic resin onto the surface of fines with their relatively high surface charge to weight ratios.
Hence, the amount of cationic wet-strength resin adsorbed onto the surface of the fibers is reduced and the efficiency of the resin is lowered. The U-F and M-F resins have strong cationic charges and are not adversely affected by the anionic 31 contaminants. The P AMG resin, which has a relatively low cationic charge, is particularly susceptible to interference from anionic contaminants. The wet-strength efficiency is greatly reduced, as a large portion of the wet-strength resin is consumed in simply rieutralizing the anionic materials. Pre treatment of the system with an inexpensive, highly cationic polymer will helps to remove the anionic contaminants that are present in the papermaking system. (31)
Factors AffectingAlkaline-Curing Wet-Strength Resins
Paper making variables also have an effect on the alkaline-curing wet-strength resms. The PAE resin is affected by the following factors: pH, mineral content
(hardness and salts), temperature (residence time), anionic contaminants, color bodies and chlorine.
The PAE resins and other alkaline-curing wet-strength resins are most often used in a pH range of 6 to 8, but their efficiency is quite adequate in the pH range of 5 to 9. As the pH is lowered to 5 and below, the efficiency of the resin can drop also, for two reasons. First, the self-crosslinking of the resin will be impeded because the free amine groups will be converted to their protonated ( ammonium salt) forms, which will not react readily with azetidinium groups. Second, the anionic carboxylate
(RCOO-) groups on the pulp will be converted to the electrically neutral carboxyl
(RCOOH) groups, reducing the number of anionic sites that retain and react with cationic resin. (25-26) (44) 32 Modest levels of hardness can improve resin performance; up to a calcium hardness level of around 100 ppm. However, high levels of hardness can adversely affect the wet strength response of the resins. The interference is primarily with resin retention; observations of electrophoretic mobility of pulps indicate that calcium complexes with some of the carboxylate groups · that would otherwise attract polyamide resin. (25-26)
At low dosages of PAE resin, high concentrations of sulfate ions can reduce wet-strength response. This may result from shrinking of the hydrodynamic volume of the adsorbed polymer, so that the isolated macromolecules are less able to reach each other to crosslink. At high dosages of PAE resin, high concentrations of sulfate
(several hundreds of ppm) can improve resin performance, probably because shrinkage of hydrodynamic volume is more than compensated by increased resin adsorption.
High concentrations of sulfite ion can start to degrade resin performance, because it can convert some azetidinium rings to nonreactive sulfonatesalts. (25)
Increasing the residence time improves, up to a point, the retention and wet strength response of alkaline-curing resins on pulp. In hot stock with long exposure times, PAE resins tend to lose efficiency. This can be attributed to some of the azetidinium groups may be hydrolyzed and polymer migration away from the surface and into the pores of the fiber. (25)
Anionic contaminants can interfere with the sorption of PAE resins on pulp.
Cationic and anionic polymers can form precipitates or complexes of variable composition, depending on the ratio in the starting mixture. Small amounts of cationic 33 res111, added to a stock containing large amounts of ligninsulfonate, can form a complex with an overall net negative charge, which is of limited attraction to the anionic pulp. The loss of wet-strength efficiency can be considerable. Contaminants can be removed and wet-strength resin performance can improve with thorough pulp washing. (25-26)
Color bodies may be present in some systems as natural components of the water supply or as pulping residuals. The PAE resins can also function as retention aids. Sheet brightness can be affected if the resin retains the color bodies. The resins themselves will not affect the brightness, but can indirectly affect it by retaining the color bodies. (25-26)
The last variable that will be discussed is the presence of chlorine. Positive chlorine or "active chlorine", such as bleach plant residuals, should be avoided. Active chlorine compounds such as hypochlorite are used in broke reworking, to break down the PAE resin network. Bleaching or repulping residuals can break down freshly added wet-strength resin as well. Before adding the resin to such systems, the stock should be treated with an antichlor (reducing agent) such as sodium sulfite. A large excess of antichlor (more than 10-20 ppm in the white water) should be avoided, because sulfitecan attack the functional groups of the PAE resin. (25-26)
Recoveryof Broke
The need to reclaim as much fiberous material from all available sources has introduced new challenges that the paper industry must conquer. The use of wet- 34 strength resins has led to broke recovery problems because the wet-strength resins make recovery of the fibers difficult. The difficulty in repulping wet-strength treated paper is dependent on the particular resin used. An increase in the amount of landfills that are being filled, transportation costs of waste material, new environmental regulations and a move, by society, towards a "greener" earth, have all played a pivotal role in the move to recycle paper and paperboard containing wet-strength resins. However, this has led to a host of new challenges that must be controlled and overcome by the paper industry.
Wet-Strength Identification
To properly treat any paperboard containing wet-strength resins, one must first determine what type of wet-strength resin is present. This can be done in two ways: you may call the manufacturer of the particular product or you may perform certain tests designed for identification. Calling the manufacturer is impractical and highly unlikely, unless one is sure where the produt originated. This leaves the use of qualitative tests, quantitative tests, dye-staining tests and chromatography as the most practical way to determine what type of wet-strength is present. The following tests, which can be found in detail in "The Analysis Of Paper", 2nd, ed. by B.L. Browning
(45), are most effective for the formaldehyde containing resins, (U-F) and (M-F).
An elementary qualitative test for the presence of nitrogen is based on heating a portion of the material with sodium carbonate in a test tube and an evaluation of the evolution of ammonia in the mouth of the test tube. (45) 35 A quantitative determination of nitrogen by the Kjeldahl method, which seems to be the most popular method, may be the most desirable way to test for the presence of wet-strength, since most of the wet-strength resins contain nitrogen. (4 5-4 7) The
Hangar method, is a modification of the Kjeldahl method and is considered simple and more rapid. ( 45)
The use of dye-staining is based upon the retention of acid dyes by substances
such as urea and melamine resins, whereas the dyes are not substantive to cellulose fibers and can be easily washed out. The acid dye Calcocid Alizarin Blue S.A.P.G. has been foundsuitable for this test. ( 45) ( 48)
Lastly, once urea and melamine resms have been subjected to hydrolysis,
separation of the hydrolysis products by paper or thin-layer chromatography will be utilized. ( 45)
According to Browning ( 45) there are no specific tests designed to determine if
the PAE resins are present. Yano, Ohtani, and Tsgue ( 49) have developed a system
whereby the PAE resins can be detected in paper by pyrolysis-gas chromatography
with flame ionization detection. Cyclopentanone derived from the adipic acid moiety
in PAE is used as the key product for determining PAE in paper. This is a relatively
new process which requires special equipment. The use of the PAE resins are
becoming predominant in the industry due to the problems associated with
formaldehyde. Newer methods will be developed as the paper industry researches
cheaper, faster and more environmentally friendly ways to recover paper containing
PAE resins. ( 49) 36 The presence of glyoxal does not represent much of an identification problem, because identification is not really necessary for repulping. Glyoxal gives only temporary wet-strength and this is almost completely lost after the paper is soaked in water for ten minutes, however, in the absent of other aldehydes, glyoxal will give reactions common to most aldehydes. (45)
The four tests previously described usually perform an adequate determination.
However, further tests may be used in determining the presence of urea or melamine.
The following methods may be applied as confirmatory tests for analysis for urea or melamine. The tests for urea include the xanthydrol method, the benzylamine methods and infrared spectrometry. The tests for melamine include the ultraviolet absorbance, hydrolysis to melamine and infrared spectrometry. (45)
Factors Influencing Repulping
It has been shown that the same conditions which enhance polymerization of the resin, can also promote the opposite; hydrolysis. Temperature and pH have to be taken into consideration in order to have the most efficient recovery process.
According to Barthel (50) the use of higher temperatures in the recovery process will increase the rate of breakdown of the resin-fiber bond, which helps to shorten the repulping process and reduce the costs of the entire operation. The pH adjustment is critical for individual wet-strength resins and has to be adjusted to each particular resm. The consistency and refining intensity (mechanical action) must also be examined in order to have as efficient and economical process that is available to 37 recover as much fiber as possible, without actual fiber damage. Wet-strength broke can be defibered entirely by mechanical means, but the power used is enormous and costly, and the fiber that is recovered may be unsatisfactory for reuse, except for filler.
The design of the broke recovery process depends on the following factors: (a) Type and amount of wet-strength resin used, (b) The degree· of wet-strength developed, (c)
The permanence of the wet-strength, (d) The type of fiber in the sheet, (e) The degree of mechanical defiberizing permissible, (f) Repulping equipment available, (g)
Operating costs and (h) Water absorbancy of paper ( 5 l).
U-F and M-F Resin Broke Recoverv
The broke recovery systems of the acid-curing, U-F and M-F, resins will now be discussed. Treatment of these two resins can be easily done if the paper is repulped as soon as it is removed from the paper machine. The wet-strength of the paper is less than one-half of what it would normally be if the paper was left to age. The aging process promotes the crosslinking action of the resins, and the longer the time span between the paper leaving the machine and repulping, the more difficult the repulping and recovery process. (8) (17)
Urea resin treated papers can be easily defibered by cooking at 165° F. and a pH of about 3.0-4.5. (17) (47) (52) However, according to Libby (5), at a pH of 3.5, a temperature of 200° F. and a repulping time of 30 minutes, the wet-strength will be that of untreated paper. The use of mechanical action is chiefly to bring the acid and heat into contact with the paper to be defibered. Chan and Lau (53) have also 38 determined that the crosslinked bonds can be broken through a hydrolysis reaction
• when the medium is adjusted to pH 3.5-4.5. See Figure 17.
I / NH H 1-1_ / CH( 't , CH( CH, Cll, \ I rtH N, /N h � � / CH, '-.... _ - / . C / - CH; N -C , 1H, II ,t H 11 O O H� H l"·" H, NH CH<' CH� tH,. cw, / CH, \ I I I H H /�--H/M - / .C / .CH, -c 1.. I /�-CHI � II I H 11 0 OH 0
Figure 17. Acid Hydrolysis of Urea-Formaldehyde Resin (53).
The low pH conditions induce acid hydrolysis of the amide type groups in
these resins, leading to depolymerization of the resin molecules and fragmentation of
the resin attached to the fibers. The increased temperature promotes the hydrolysis
reaction. These two actions reduce the molecular size of the cured resin sufficiently so
that reswelling and fiber-to-fiberbond destruction can occur. (52) 39 The acids that are generally used for the repulping process contain chlorine.
Sodium hypochlorite, calcium hypochlorite and hypochlorous acid are a few of the more popular ones. Most paper mills want to move away from using chlorine containing compounds because of the environmental problems they cause. Research is being conducted for a non-chlorine repulping aid.
PAE Resin Broke Recovery
The move away from the formaldehyde containing resins has increased the popularity of the PAE resins. The PAE resins are widely accepted for their permanence, efficiency, paper properties, and reduction in machine maintenance. (26)
However, they require a different repulping process than the acid-curing resins.
In the cured polyamide resins, the amide groups in the polymer backbone are not easily hydrolyzed, and the nitrogen-carbon bonds of the crosslinks between chains are not hydrolyzable at all. Therefore, the wet-strength imparted by the polyamide resins is durable, and proper attention to special techniques is required for successful broke reworking. Especially in bleached systems, a combination of chemical treatment and mechanical energy can be highly effective. (10) (26) (51)
Fortunately, the polyamide-type resins undergo alkaline hydrolysis, the rate of hydrolysis is dependent upon the concentration of the base used. Schmalz (54) has shown that sodium hydroxide is successful in repulping the polyarnide-type resin at a pH of about 10. (16) Also, an addition of hypochlorite is an effective repulping agent 40 for this type of broke. This is possibly due to the chlorination of the amide group to forma less stable product. (10) (26) (53) (55)
Espy and Pahl (26) have also used hypochlorous acid or a similar source of positive chlorine for their chemical treatment in repulping cured polyamide-type resins.
They suggest using approximately 0.5 to 2.0% hypochlorite ion (based on pulp) and adjusting the pH of the system to 6.5 to 7. In this pH range, the hypochlorite is present predominantly as hypochlorous acid. At a higher pH, the predominate species is hypochlorite anion which reacts less rapidly; at lower pH, chlorine may be formed and escape unreacted from the system. The temperature should be between 120° and
130° F. (50°-55° C.). (55)
The use of hypochlorite may be effective,but it also has its disadvantages. Its residues also hurt the performance of newly added resin if they are not removed by washing and by using an antichlor (commonly sulfite). Washing, however, may remove too many finesfrom the system. (55)
Recovery cannot be completed without the proper mechanical action. The mechanical equipment should be a high-attrition pulper with a high-speed rotor, working at a high consistency (over 3%). This type of pulper can perform most of the work (at least 75%). To finish the job, a deflaker, which can provide violent action without appreciably affecting :freeness, can despeck undefibered pulp and thus, complete repulping. (25-27)
Hypochlorite, in unbleached systems, may be consumed in side reactions that
bleach the pulp rather than degrade the resin network. Using the mechanical action 41 process for bleached pulp, the pH should be elevated to 11-12, using NaOH and the temperature should be elevated to no higher than 160° F. Higher temperatures can sometimes cause additional resin curing, and thus be counter-productive. (10) (25-27)
Non-Chlorine Repulping Aids
The use of these chlorinated products has caused problems for the paper industry, just as they do in the process to repulp the resins containing fonnaldehyde.
Research has been more successful in the use of non-chlorine repulping aids for the alkaline-curing resins than the acid-curing resins.
Kapadia (56) has developed the use of a peroxide salt, peroxymonosulfate
(PPMS) and determined that they were effective in repulping the alkaline-curing resins. The PPMS was found to be effective under alkaline conditions and higher pH
favors the repulping process. Higher temperature is preferable, however, beyond 150°
F., the effect is not very pronounced. Some difficulty appeared in repulping unbleached kraft. This was due to the presence of more phenolic lignin groups. Also,
the hydrophobic lignin compliments the cross linked resin in providing a barrier against penetration of water during repulping.
Espy and Geist (57-58) have investigated the effects of using persulfates as repulping agents for neutral/alkaline wet-strength resins. The use of persulfate
(S20iJ salts are an effective chlorine-free alternative to hypochlorite (OCl-) and
eliminates the concern about chloroform, tetrachlorodibenzodioxins, and adsorable
organic halides (AO:X). 42 Persulfate repulping favors alkaline conditions and is more rapid at higher temperatures. This pH range is the buffer region for the HOCl:OCl- equilibrium. The decomposition routes and rates of peroxygen compounds, including persulfates, depend in complex fashion on pH, temperature, and trace metals in the system.
During persulfate repulping, the pH decreases to an extent depending on the reagent and the system. In buffered systems, equimolar amounts of different persulfates defibered broke at comparable rates. The relative performance of two salts can vary between pH-buffered and unbuffered systems. A choice among persulfates will depend on convenience and cost-effectiveness under specific conditions. (57-58)
The advantages of using persulfate are listed below: (a) eliminating the unwanted chlorine by-products, (b) persulfates are more effective under moderately alkaline conditions than at neutral pH, ( c) it does not depend on alkaline hydrolysis,
(d) it can be used to repulp polyamide and polyamine wet-strength resins, and (e) if washing is a limitation, persulfates provide less interference than residual hypochlorite.
Some disadvantages include: (a) more expensive than hypochlorite; (b) classified as an oxidizer and thus must be handled with extreme care, including: not storing near heat sources, combustible sources, reducing agents, acids and bases; and ( c) face and eye protection is recommended. Some of the more common persulfates that are used are ammonium, potassium and sodium. These can also be used as indirect additives for foodpackaging. (57-58)
It can be seen that there is still much more research that has to be done in order to find non-chlorine alternatives for repulping neutral/alkaline wet-strength 43 paperboard. Also important in the repulping process is the use of mechanical energy to determine how much is necessary and economical, and how high a consistency can be tolerated in the hydrapulper.
P AMG Resin Broke Recovery
The last wet-strength resin that will be discussed is the P AMG resin. This resin imparts temporary wet-strength properties and the hemjactal bond that is formed is susceptible to hydrolysis in the presence of water. The hydrolysis takes place especially quickly in the presence of alkali and/or high temperature. (6) ( 15)
Chemistry Overview
Dimethyldioxirane
In 1985, dimethyldioxirane (DMD) was isolated as an acetone solution by codistillation at reduced pressure from buffered acetone-caroate mixtures. Thus, a new oxidant was made generally available for preparative purposes that is extremely efficient in its ability to transfer oxygen atoms to a variety of orgaruc substrates, yet selective in its reactivity, and converuently prepared from readily available starting materials. (59-63)
The dioxiranes have some extremely important properties that can be beneficial in the repulping process. They are selective despite their pronounced reactivity, mild towards the oxidized product, perform under strictly neutral conditions and possess 44 catalytic activity. (59) A maJor advantage with DMD is that it is a selective nonchlorine oxidant. (62) This is beneficial for the paper industry as it moves away fromchlorine containing chemicals in its daily operations. See Figure 18.
0 I HSO5- + RJ C=O ------R1-C-R2 + HSO4- / I R2 0
Figure 18. Simplified Dioxirane Formation Mechanism (60).
Hydrogen Peroxide
Hydrogen Peroxide (H2O2) is used for lignin-preserving bleaching, but in recent years its use in the bleaching of chemical pulps has increased considerably. (64)
The use of hydrogen peroxide is strongly affected by pH, which should not exceed
10.5. The concentration of active perhydroxyl ion (-HOO) increases with pH according to the reaction in Figure 19.
H2O2 + OH------Hoo- + H2O
Figure 19. Concentration of Active Perhydroxyl Ions (65). 45 Probably the most important aspect of hydrogen peroxide is its dependence on concentration. The higher the consistency in the pulper for a given amount of hydrogen peroxide, the more effectivethe chemical becomes. CHAPTER III
STATEMENT OF THE PROBLEM AND SIGNIFICANCE
Much of today's paper and paperboard containing wet-strength resins has to be landfilled because the wet-strength resins within the paperboard cannot be broken down. An increase in the trend to recycle, and divert as much material as possible from landfills has led to the need to examine the possibility of reclaiming the fiberous material from paperboard containing wet-strength resins. Reclamation must be done with two considerations: first it must be performed in an environmentally friendly way
and second, the applied energy should be as low as possible for economic reasons.
Beverage carriers are a source of paperboard that contain PAE resins, that for the most part are currently landfiJled. This is due to the difficultyin breaking down the
wet-strength resin network within the paperboard and the high energy cost associated
with the methods being used. As the competition for secondary fiber grows, the paper
industry should look to resources that today have been neglected.
The literature survey has shown how the different wet-strength resins are used
for various applications and how the repulping of each type of resin has to be treated
individually. The popularity of the PAE resins has led to a greater use of this
particular resin. However, the use of this resin has led to difficulties in repulping.
This study wiJI concentrate on studying the effects of chemical charge on
repulping beverage carriers. Three levels of chemical charge will be used; 1%, 2.5%,
46 47 and 5% for hydrogen peroxide, and all other chemicals will be added at the same oxidation equivalent. The consistency, pH, time, temperature and rotor speed will be
held constant throughout the repulping process.
The goal of this project was to determine if a high consistency pulp could be repulped with the help of strong oxidizing chemicals foruse in a recycled board mill. CHAPTER IV
OBJECTIVES OF THE STUDY
The objectives of this experimental study-are: to determine: ( a) the yield
(% accepts) ofrepulping beverage carriers containing PAE wet-strength resins without
using chemicals containing chlorine. The strong oxidizing chemicals that will be used are hydrogen peroxide, sodium persulfate, ammomum persulfate and
dimethyldioxirane, and (b) the quality of the accepted pulp by testing it for tensile and
tear.
48 CHAPTER V
EXPERIMENTAL DESIGN
Overview
The focus of this work was to determine the effect of strong oxidizing chemicals tin varied amounts on the repulping of wet-strength paperboard (beverage carriers). A z-bar mixer was used to repulp the paperboard. During the repulping process, pulp samples were obtained and screened, using a Britt Jar screening device, to determine the percent of accepted material. The amount of accepted material determines the success of the concentration of the chemical used.
Outline
The 18 point paperboard utilized in this study contained the polyamide wet strength resin. It was manufactured by the Mead Corporation. The paperboard was collected by the BFI Corporation and was considered post consumer waste. Tensile tests were performed on the paperboard after soaking in water at a pH of 10 for 30 minutes. It was found that it still retained approximately 26% of its strength.
A z-bar mixer was used to repulp the paperboard and its energy requirements were recorded. Non-chemical runs were performed as the control group. Four chemicals were added at three different concentrations for the treatment groups.
49 50 Samples were taken every fifteen minutes (starting at 30 minutes) for 2.25 hours and screened using a Britt Jar screening apparatus. Material passing through the screen
(accepts) and remaining on the screen (rejects) was collected and weighed. The percent accepts and rejects were recorded for the runs. The percent accepts for the chemical containing runs were compared to the non-chemical runs.
Besides measuring the accepts level, the accepted pulp (pulp remaining in the z-bar mixer after all samples taken) was screened, refined and tested for tensile, wet tensile and tear. The following flowchart shows the experimental design.
BEVERAGE C.-RRIRS PRE-SOAK L ----WATERI ._____ ---J CHEMC.-S !L.M.H Chage, pH ADJLST 1 HEAT Z-BARMIXER l ~...____-STEAM HE.-T SMPLES TAKEN AT SCREE' SA..v!PLES WITH 30. 45, 60. 75. 90. [05. [20. 135 .- BRI JAR .______.MIUTS ~ ----'
06 CuT SCREE: R£"ACING PULP
ACCEPS
PFMi
0, 15,0, 18,0 RV.
NOBL A WOOD HDSHS DRYTSlE WTSiE TG i-----DT Figure 20. Flowchart of Experimental Design. CHAPTERVI
EXPERIMENTAL METHODOLOGY
This study consisted of five components: (I) preparing the paperboard and z bar mixer forrepulping; (2) repulping and collection of the paperboard; (3) screenjng of the pulp samples; (4) screening, refining and testing of the pulp remaining in the mjxer; and (5) statistical analysis.
Preparation of Paperboard and Z-bar Mixer
The beverage carriers were prepared for the experimental runs by cutting into small squares and dispersed in 150° F. water placed in a large beaker. Each run used
200 grams of O.D. pulp. A consistency of 15% was used for repulping. A 5% sodium hydroxjde solution was used to adjust the pH of the system to 10.00. Ethylene diamjne tetraacetate, EDTA, was added to the mjxture at 0.5% based on O.D. fiber.
The mjxture was allowed to stand on a hot plate, in order to allow the paperboard time to soak at 150° F. for80 minutes. Table 5, on page 52, lists the run conditions for the experiment. See Appendix forfurther information.
The hydrogen peroxjde, ammonium persulfate and sodium persulfate were added directly to the paperboard and water mjxture to the appropriate chemjcal loading and then the pH was again adjusted to 10.00. The only difference between the chemjcaJs was that the hydrogen peroxjde was in a liquid form. The DMD had to be
51 52 made in situ, using acetone and oxone. In the case of the hydrogen peroxide, it was extremely important not to exceed a pH of 10. 5, otherwise the peroxide would start to
Table 5
Run Conditions
# of Runs Chemical Concentration
4 None None
3 Hydrogen Peroxide 1%
,., .) Hydrogen Peroxide 2.5%
3 Hydrogen Peroxide 5.0%
3 Ammonium Persulfate 0.47% * ,., .) Ammonium Persulfate 1.18% *
., .) Ammonium Persulfate 2.35% *
3 Sodium Persulfate 0.47% *
3 Sodium Persulfate 1.18% * ,., .) Sodium Persulfate 2.35% *
3 Dimethyldioxirane 0.47% *
3 Dimethyldioxirane 1.18% * ., .) Dimethyldioxirane 2.35% *
* These chemicals were added at the same oxidation equivalent as the hydrogen peroxide. 53 breakdown. Sodium silicate was also added, 5% based on O.D. fiber, to the hydrogen peroxide runs to repress the breakdown of the peroxide ions.
As the paperboard was soaking, the z-bar mixer was prepared for repulping by pre-heating. The repulping compartment was filled with water, the top covered, and the steam line was fitted and turned on. A thermometer was placed in the cover to record the temperature of the water. Once the temperature reached 180-200° F., the steam was turned offand the steam line disconnected. The volt and ampere meter were attached and a no load reading was taken. The z-bar mixer was now ready for repulping.
Repulping of the Paperboard
After80 minutes of soaking the paperboard was ready for repulping. The hot water within the z-bar mixer was removed and the contents of the beaker were added to the z-bar mixer. The steam line was attached to the outside of the mixer for heating purposes. Once again, the cover was placed over the top. The mixture was repulped at a temperature of 150° F. The paperboard was allowed 30 minutes of repulping before the first sample was taken, then samples were taken every 15 minutes for 2.25 hours. The samples were collected from the middle of the z-bar mixer just above the dam with a small wooden spoon. The z-bar was turned off and the sample was removed. After2.25 hours, the entire contents of the z-bar was emptied and the mixer cleaned. 54 Screening of the Pulp
A Britt Jar screening device was used to screen the pulp samples. The agitator
was set to 600 rpm and held constant throughout the screening process. The jar was
filled to approximately 3/4 full and 3.50 wet grams of pulp sample was added. After initial mixing, the outlet was opened to allow for the accepted material to be emptied
into a container. An inlet water supply was turned on to match the outlet water
leaving. The screening process was completed when the outlet water, when viewed in
a graduated cylinder, contained no fibers. The water that was collected was filtered
with a Buchner funnel. The filter pad was then dried and weighed. See Appendix for furtherinformation.
Screening, Refining and Testing of the Pulp
The pulp remaining in the z-bar after 135 minutes was screened using the six
cut Johnson screen. The accepted material was collected with a 200 mesh calendar
screen for testing. An initial freeness test (T 227 om-92) was performed on the pulp.
The accepted pulp was then refined with a PFI mill (T 248 cm-85) at 15,000 and
18,000 revolutions. Handsheets were made with a Noble and Wood handsheet
machine and then conditioned for testing (T 402 om-88). They were then tested for
dry tensile (T 494 om-88), wet tensile (T 456 om-87) and tear (T414 om-88). 55 Statistical Analysis
Statistical analysis of the data was performed using a general linear models
procedure. A repeated measure analysis of variance was also run for this data by the
university computing center. Repeated measures design is used in order to control the
variability between runs, otherwise the variability between runs would become part of
the experimental error, and in some cases, it would significantly inflate the error mean
square, making it more difficult to detect real differences between treatments. In order
to compare the treatments (runs) against one another, the Newman-Keuls test was used. This test analyses all pairwise comparisons using an overall significance level.
To compare the runs that use chemicals against the control runs (no chemical), the
Dunnett test was used. Each test was conducted in the 95% confidence interval.
List of Equipment
Equipment of Western Michigan University used in this experimental work was: (a) Z-bar mixer, (b) Britt-Jar screening device, (c) CorningpH meter, (d) PFI mill, (e) Noble and Wood handsheet maker, (t) Tensile tester, and (g) Tear tester. CHAPTER VIT
RESUL TS AND DISCUSSION
Properties ofthe Beverage Carrier Paperboard
Paperboard containing the polyamide wet-strength resin was obtained from
Browing-Ferris Industries. Twenty-five pounds of paperboard was selected from a one ton bale to be used in the experiment. Initial tests were performed on randomly selected samples to insure the paperboard properties were as consistent as possible. It was determined that the paperboard had a basis weight of 375.85 g/m"2, a caliper of
18 point, a dry tensile value of22.91 N. and a wet tensile of 6.06 N. Raw data can be viewed in Appendix A. The wet-strength was determined after raising the pH of the distilled water used for soaking to 11 and then soaking the strips for 30 minutes. The paperboard retained 26.45% of its original strength. The results confirmed the fact that the paperboard did indeed contain wet-strength.
Repulping
The z-bar rruxer utilizes two agitators, lying in the horizontal plane and separated by a divider, to mix the contents of the container. Once the soak time was completed, the water from the beaker was poured into the z-bar mixer and settled at the bottom of the container, rising no higher than the divider. Small amounts of
56 57 paperboard were added until there were none left. As the paperboard was added, it would mix with the water under the divider and with the other paperboard above the divider. This is unique to the repulping process, because the liquid will remain at the bottom of the container as the paperboard is agitated and the paperboard was not submerged at all time as is the case in normal conventional recycling ( using a hydrapulper). The paperboard was mainly broken down when it passed through the small gap between the agitator and the divider. As the paperboard moved over the top of the divider, it would then mix with the paperboard from the other side. In this initial stage, a watering/dewatering phenomena will occur. As the repulping time progressed, the paperboard was further broken down, thus absorbing the free water until none remained. Once all of the free water was absorbed by the fibers, the remaining repulping action consisted of the pulp from one side of the divider rubbing against the pulp fromthe other side of the divider. This resultant friction from fiber to fiber interaction, caused further breakdown of the bonded fibers. This rubbing action, as indicated by the percent accepts, was effective in liberating the fibers. The fibers become liberated, but not fibrillated or shortened, as is indicated by the high freeness values that are measured at the end of the runs. This, along with the data from the accepted material, indicates that the z-bar mixer was influential in breaking down the paperboard, liberating the fibers and not damaging the pulp in the process. The shearing action of the repulping process is dictated by the consistency of the pulp. At higher consistencies, less water is available forabsorption, thus less water is available to interfere in the fiber to fiber interaction. 58 Reproducibility of the Process
Table 6 lists the standard deviation and coefficient of variation for the average percentage of accepted material for three runs with three samples taken per time
interval. These values were measured during the no chemical run in order to determine how the paperboard would respond to the repulping process. The standard deviation (SD) and the coefficient of variation (CV), which is defined as the standard deviation/mean * I 00, were calculated to determine the variability of the repulping process using the z-bar mixer. These mathematical values were obtained by measuring the average percent of accepted material with a Britt Jar screening device. As the repulping time increased, the standard deviation and the coefficients of variation decreased. This showed that the approximate range of variability of the repulping process was low and the procedure had excellent reproducibility.
Table 6
Mathematical Values
Time Avg. Per. Yield S.D. C.V.
30 58.81 4.73 8.04
60 63.51 2.40 3.78
90 72.28 1.10 1.40 59 Energy Input
The no-load (volts and amps required to run the z-bar mixer with only water)
power was recorded forthe z-bar mixer before the start of each run. The volts and the
amps were then measured and recorded every 15 minutes for the duration of the run.
Table 7 shows the mean volts and standard deviations for the runs. The voltage varied
little throughout the run. In fact, the amps never changed and remained at 5.0. There
was a slight difference in the voltage recorded from day to day, but this depended on
the voltage supply from the source (the university), not the z-bar mixer. This indicates that the z-bar will use the same power for no-load as well as when loaded. The power
required can be eliminated as a variable in the repulping process using the z-bar. Since
the power did not change significantly during the repulping process, the rotor speed
did not change and thus the effect of the mixer on the pulp remained constant for all
the runs.
Percent Accepted Material Reliability
The z-bar mixer was run with no chemical addition in order to determine how
much paperboard would be broken down. This data is then used as a basis for
comparison with other z-bar runs containing chemicals. The hydrogen peroxide was
added at levels of 1.0%, 2.5% and 5.0%. All other chemicals were added at the same
oxidation equivalent. 60 Table 7
Mean Voltage Values
Chemical Charge(%) Volts S.D. Chemical Charge Volts S.D.
No Chemical 199.7 0.2
Amm.Per. 0.47 199.0 0.1 DMD 0.47 198.5 0.0
Amm.Per. 1.18 199.0 0.1 DMD 1.18 198.8 0.0
Amm. Per. 2.35 198.9 0.1 DMD 2.35 199.4 0.0
Sod. Per. 0.47 199.5 0.0 Hyd.Per. 1.0 199.6 0.0
Sod.Per. 1.18 199.2 0.0 Hyd.Per. 2.5 199.7 0.0
Sod. Per. 2.35 198.8 0.0 Hyd. Per. 5.0 199.4 0.0
The same oxidation equivalent was used so that all the chemicals would be applied at the same concentration. This would eliminate the concentration as a variable in the repulping process.
Table 8 shows the average percent yield for the four no chemical runs. Based on the reproducibility of the process, these values are extremely accurate. The standard deviation decreases over time, which indicates that the range of variability was low. The average percent accepts forthe four runs was 74.73%, or almost three quarters of the paperboard was repulped successfully without any chemical addition. shows the percent yield for the four no chemical runs. At 30 minutes the yield was only 53.59°/o. This is rather low, considering that the paperboard had been repulped 61 for 30 minutes. At 75 minutes, it can be seen that the percent yield starts to become extremely close for all the runs. The percent yield started to plateau at 120 minutes.
In other words, the mechanical action of the z-bar mixer needed 120 minutes to repulp the wet-strength paperboard .to its maximum yield. Any further repulping beyond this point would provide minimal amounts of fiber.
A statistical analysis was performed and the chemical containing runs were compared with the no chemical runs. The analysis was started at 75 minutes, because of the large standard deviations for30 to 60 minutes. In this discussion, the Newman
Keuls and the Dunnetts test will be used to determine the significance of the data.
Table 8
Average Percent Yield for the No Chemical Run
Time (min) % Yield S.D.
30 53.59 2.84
45 60.52 2.61
60 63.68 2.31
75 66.71 1.06
90 69.04 0.98
105 72.18 0.96
120 74.21 0.78
135 74.73 0.83 62
Effect of Extended Pulping on Yield No Chemical Addition 80
70
60 g ,,/'.- _:- 50 /,L- - / 9',' / /. , . / 9' ' 0 . !! 4 /,/ ·, . ♦ Yield 1 D Yield 2 • I�-. • 1..:-/ 30 1.r.· • Yield 3 o Yield 4 I,,' ! /2. ---- 20
10
0 0 15 30 45 60 75 90 105 120 135 150 Time (min)
Figure 21. Percent Yield for The No chemical Run. The Yield Number is Equivalent to the Run Number.
Effectof Hydrogen Peroxide
Figure 22 shows the percent yield for the three runs_ Table 9 shows the
percent yield for the hydrogen peroxide runs.- The highest percent accepts for the
chemical charge of 1.0%, 2.5% and 5.0% were 75.47%, 77.78% and 79.35%
respectively. All times were statistically significant, except for 120 and 135 minutes of
the low concentration. Using the Dunnett's test at 120 and 135 minutes, the upper
confidence limit value was smaller than the critical T value. The Newman-Keuls test
showed the difference between the mean values. For the low charge at 120 and 135
minutes, the differencebetween the mean values is extremely small and therefore, not 63 Effect of Extended Pulping on Yield ___ _!Jsing Hydrogen Peroxide 80 70 -.;,.�-- 60 ✓-·- y .. � .-50 /· // "Cl ,,.·, 40 /,/ • ;,," ► 30 (1 (: 20 ♦ No Chem. Yiel O H.P.L 10 • H.P.M. o H.P.H. 0 1 5 60 0 30 45 75 90 105 120 135 150 Time (min)
Figure 22. Effect of Extended Pulping on Yield Using Hydrogen Peroxide.
Table 9
Average Percent Yield for Hydrogen Peroxide
Hydrogen Peroxide 1.0% Hydrogen Peroxide 2.5% Hydrogen Peroxide 5.0%
Time % Yield S.D. Time % Yield S.D. Time % Yield S.D.
30 52.20 2.89 30 52.47 3.61 30 62.34 3.19
45 60.41 2.28 45 60.54 3.09 45 66,09 2.08
60 65.27 1.22 60 68,05 1.94 60 70.47 1.11
75 69.03 1.15 75 71.98 1.17 75 73.42 1. 10
90 73035 0.95 90 73.11 1.18 90 74.90 0.76 64 Table 9 - Continued
Time % Yield S.D. Time % Yield S.D. Time % Yield S.D.
105 74.52 0.78 105 75.81 0.55 105 76.92 0.71
120 74.64 0.70 120 77.21 0.59. 120 78.60 0.71
135 74.67 0.69 135 77.24 0.60 135 78.63 0.72
The time is measured in minutes. statisticallv different. Table 10 lists the statistical values for the Dunnett test. Table 11 lists the statistical values for the Newman-Keuls tests where H, M and L designate a high, medium or low chemical charge and Ct. is the no chemical run. This analysis will test all pairwise comparisons at an overall significancelevel of 0.05.
Table 10
Experimental Dunnett Values for H.P.
Time Chg Dunnetts Test Time Chg Dunnetts Test
75 H 8.7125 120 H 5.6848
L 7.2758 M 4.2948
M 4.3291 L 1.7248
90 H 7.6457 135 H 5.2258
L 6.0990 M 3.8425
M 5.8623 L 1.2725 65 Table 10 - Continued
Time Chg Dunnetts Test Time Chg. Dunnetts Test
105 H 6.2176
M 5.1076
L 3.8209
Critical Value ofDunnett's T= 2.395. Alpha = 0.05.
Table 11
Experimental Newman-Keuls Values for H.P.
Time Chg. New.-Kls. SNK Time Chg. New.-Kls. SNK lYield) group (yield) group
75 H 73.4176 A 120 H 78.6033 A
M 71.9800 A M 77.2133 B
L 69.0333 B L 74.6433 C
Ct. 66.7075 C Ct. 74.2125 C
90 H 74.8967 A 135 H 78.6267 A
L 73.3500 A M 77.2433 B
M 73.1133 A Ct. 74.7300 C
Ct. 69.0425 B L 74.6733 C
105 H 76.9200 A
M 75.8100 A 66
Table 11 - Continued
Time Chg. New.-Kls. SNK Time Chg. New.-Kls. SNK {yield) group (yield) group
L 74.5233 A
Ct. 72.1750 B
Alpha = 0.05. Yields with the same letter { SNK group) are not significantly different.
The Newman-Keuls test shows that starting at the 75 minute time intervaL the
high and medium charge are not significantly different and the low charge and the no
chemical runs are significant. From 90-105 minutes, the high, medium and low concentrations are not significantly different from each other. Beginning at 120 minutes, the high charge is significant from the medium charge, and the low charge and the no chemical runs are not significantly different.
The average percent yield for hydrogen peroxide at 120 and 135 minutes is
74.64% and 74.67%, compared to 74.60% and 74.65% for the no chemical run at the same time. The difference between the means is 0.431 and 0.057, not enough to be statistically significant. However, at all charges, starting at 60 minutes, there was a more rapid increase in the average percent accepts, which is an indication that the chemical is having an effect on the repulping process. The initial attack on the paperboard at the low charge was beneficial in the early repulping time, but was not 67 helpful over the entire repulping process. The low charge started to reach its peak yield at 105 minutes. Using medium and high levels of hydrogen peroxide did help the repulping process considerably.
These levels reached their peak at 120 minutes. The most notable difference, using a high concentration, was in the first 60 minutes of repulping. The initial gains were well above those of the low and medium charge, however, at 135 minutes, the high charge yield was only slightly higher then the medium charge yield. It can be said that the high charge gave the best initial results for the first 60-75 minutes, but overall there was no significant difference between the medium and high charges. For the low charge, it reached its peak earlier because it degraded earlier and mechanical action began to control the process. The other charges may have also degraded over time, but had a significant effect on the board to increase the yield over time, with the help of the mechanical action provided by the z-bar.
Effectof Ammonium Persulfate
Table 12 shows the average percent yield forammonium persulfate. Figure 23 shows the effect of extended repulping on yield using ammonium persulfate.
The highest average yield was 84.80% for the 2.35% level of ammonium persulfate. The Newman-Keuls test shows that starting at the 75 minute time interval, the medium and low charges are not significantly different and the high charge and the no chemical runs are significant. From 90-135 minutes, the high, medium and low charges are significantly differentfrom each other. 68 Table 12
Average Percent Yield for Ammonium Persulfate
Amm. Persulfate1. 0% Amm. Persulfate 2.5% Amm. Persulfate 5.0%
Time % Yield S.D. Time % Yield S.D. Time % Yield S.D.
30 60.24 2.80 30 66.25 3.69 30 70.34 2.30
45 64.17 2.48 45 68.75 2.80 45 74.00 l.96
60 70.76 2.12 60 72.79 1.63 60 77.50 1.84
75 72.96 1.56 75 74.46 1.22 75 80.62 1.14
90 74.58 0.85 90 76.44 1.00 90 82.50 1.13
105 76.36 0.87 105 78.42 0.90 105 84.47 0.96
120 76.41 0.87 120 80.83 0.56 120 84.68 0.77
135 76.44 0.87 135 80.87 0.56 135 84.80 0.69
The time is measured in minutes.
Dunnett's test indicates that the different levels of charge are all significantly different fromthe no chemical run. Each of the runs had a significant increase in yield as compared to the no chemical runs. Even at 102-135 minutes forthe low charge, the values within the 95% confidence interval were still greater than the critical value of
Dunnett's t test. Tables 13 and 14 list the statistical values for the Dunnett and
Newman-Keuls tests. 69 As can be seen by Figure 23, all the repulping times starting at 90 minutes showed significant differences in yield. At these times, the medium yield was only
1.01-1. 06 times that of the low yield. The medium concentration then started to increase more rapidly than the low charge. The low and high charges started to
Effect of Extended Pulping on Yield Using Ammonium Persulfate
90 80 �r--�i@i:.-·�.:.-�_:_---�-�-��-:·.i:�_--,-:� 70 - 60 ... /;- --�� � �-♦-�-�-� •· .... -• . .• .. l5o / .. / .. .· ]► 40 /::··,,.,,_. .. · 30 Jt� ♦ No Chem. Yield □ A.P.L A A.P.M. A.P.H. 20 [. o 10 0 15 0 30 45 60 75 90 105 120 135 150 Time (min)
Figure 23. Effectof Extended Repulping Using Ammonium Persulfate.
plateau at 105 minutes. The medium charge started to plateau at 120 minutes. From
120-135 minutes, the low charge was only 1.02-1.04 times greater than the no
chemical runs. The high charge had high initial gains, starting at 70.34% at 30
minutes. Over the entire repulping process, it had significantly higher yields than the
other charges. 70 Table 13
Experimental Dunnett Values for A.P.
Time Chg. Dunnetts Test Time Chg. Dunnetts Test
75 H 16.1799 120 H 11.8466
M 10.0132 M 7.9966
L 8.5166 L 3.5733
90 H 15.2746 135 H 11.4641
M 9.2179 M 7.5341
L 7.3579 L 3.0141
105 H 13.9934
M 7.9368
L 5.8768
Critical Value ofDunnett's T= 2.395. Alpha = 0.05.
Table 14
Experimental Newman-Keuls Values for AP.
Time Chg. New.-Kls. SNK Time Chg. New.-Kls. SNK (yield) group (yield) group
75 H 80.6233 A 120 H 84.6800 A
M 74.4567 B M 80.8300 B
L 72.9600 B L 76.4067 C 71 Table 14 - Continued
Time Chg. New.-Kls. SNK Time Chg. New.-Kls. SNK (yield) group (yield) group
Ct. 66.7075 C Ct. 74.2125 D
90 H 82.4967 A 135 H 84.8033 A
M 76.4400 B M 80.8733 B
L 74.5800 C L 76.4433 C
Ct. 69.0452 D Ct. 74.7300 D
105 H 84.4733 A
M 78.4167 B
L 76.3567 C
Ct. 72.1750 D
Alpha = 0.05. Yields with the same letter (SNK group) are not significantly different.
Effect of Sodium Persulfate
The third chemical to be discussed is sodium persulfate. Table 15 shows the average percent yield for sodium persulfate. Figure 24 shows the effect of extended repulping on yield using sodium persulfate. The highest yield obtained was 84. 74%
for2.35% level of sodium persulfate.
The Newman-Keuls test shows that starting at the 75 minute time interval, the 72 Table 15
Average Percent Yield for Sodium Persulfate
Sodium Persulfate I . 0% Sodium Persulfate 2.5% Sodium Persulfate5. 0%
Time % Yield S.D. Time % Yield S.D, Time % Yield S.D.
30 62.89 2.64 30 66.44 3.04 30 72.55 2.61
45 68.34 1.78 45 69.88 2.64 45 75.67 1.65
60 72.98 1.28 60 73.90 1.75 60 79.51 1.53
75 74.86 1.10 75 76.68 1.04 75 81.62 1.24
90 75.84 1.13 90 78.75 1.13 90 83.96 0.90
105 77.12 0.84 105 80.24 0.83 105 84.68 0.62
120 77.15 0.84 120 80.28 0.83 120 84.71 0.61
135 77.18 0.84 135 80.32 0.83 135 84.74 0.61
The time is measured in minutes.
medium and low charges are not significantly different and the high charge and the no
chemical runs are significant. From 90-135 minutes, the high, medium and low
charges are significantly different fromeach other.
Dunnett's test indicates that the different levels of charge are all significantly
different fromthe no chemical run. Each of the runs had a significant increase in yield
as compared to the no chemical runs. Even at 102-135 minutes forthe low charge, the Effect of Extended Pulping on Yield 73 Using Sodium Persulfate
90 80 - . --=-� - � ·_·::� --� -��---. ·-1 ·:-�-:- :-C 70 - - .. •· c ---- � -□- -- -. -•- -..� �- •.... - -•-. - · ... 60 / ..... - lso // ,, / . . I . :· j► 40 I I ,' 30 I . 1_- ♦ No Chem. Yield O S.P.L 20 .____[.S.P.M. _ OS.P.H.___J I 10 0 0 1 5 30 45 60 75 90 105 120 135 150 Time (min)
Figure 24. Effect of Extended Repulping Using Sodium Persulfate.
values within the 95% confidence interval were still greater then the critical value of
Dunnett's t test. Tables 16 and 17 list the statistical values for the Dunnett and
Newman-Keuls tests.
As can be seen by Figure 24, all the repulping times showed significant
differences in yield, except from 45-75 minutes. The medium yield then started to
increase more rapidly than the low yield. All the concentrations started to plateau at
105 minutes. From 120-135 minutes, the low charge was 1.03-1.04 times greater than
the no chemical runs. The high charge had high initial gains, starting at 72.55% at 30
minutes. Over the entire repulping process, it had significantly higher yields than the
other charges.
Both persulfates had a similar affect on the repulping process. Statistically, the 74 average percent yields were all within 5% for each level of concentration and within
1% at 120-135 minutes. The high yield of 84.80% at 2.35% for ammonium persulfate was only slightly higher then that of sodium persulfate, which had a value of 84.74%.
However, the sodium persulfate had a higher yield, 72.55%-79.51 % at the 30-60 minute time intervals then the ammonium persulfate, which had values of 70.34%-
77.50% over the same interval. It can be said that there was no real difference, in terms of the repulping, between these two chemicals.
Table 16
Experimental Dunnett Values for S.P.
Time Chg. Dunnetts Test Time Chg. Dunnetts Test
75 H 16.9322 120 H 11.9112
M 11.9955 M 7.4812
L 10.1788 L 4.3445
90 H 16.8067 135 H 11.4498
M 11.5967 M 7.0331
L 8.6900 L 3.8931
105 H 14.0425
M 9.5991
L 6.4825
Critical Value ofDunnett's T= 2.395. Alpha = 0.05. 75 Table 17
Experimental Newman-Keuls Values for S.P.
Time Chg . New.-Kls. SNK Time Chg. New.-Kls. SNK (yield) group (yield) group
75 H 81.6167 A 120 H 84.7133 A
M 76.6800 B M 80.2833 B
75 L 74.8633 B 120 L 77.1467 C
Ct. 66.7075 C Ct. 74.2125 D
90 H 83.9567 A 135 H 84.7400 A
M 78.7467 B M 80.3233 B
L 75.8400 C L 77.1833 C
Ct. 69.0452 D Ct. 74.7300 D
105 H 84.6800 A
M 80.2367 B
L 77.1200 C
Ct. 72.1750 D
Alpha = 0.05. Yields with the same letter (SNK group) are not significantly different, 76 Effectof DMD
The last chemical that was used in the experiment is dimethyldioxirane or
DMD. DMD had to be made in situ. This in itself did not pose a problem, but it did take some extra time to set everything up in order to make the chemical.
Table 18 shows the average percent yield forDMD. Figure 25 shows the
Table 18
Average Percent Yield forDMD Runs
DMD 1.0% DMD 2.5% DMD 5.0%
Time % Yield S.D. Time % Yield S .D. Time % Yield S.D.
30 75.14 2.68 30 74.38 2.35 30 74.81 2.41
45 80.61 2.08 45 78.80 2.28 45 81.13 2.18
60 83.07 1.86 60 88.13 1.85 60 85.07 1.87
75 85.70 0.86 75 88.12 1.07 75 86.99 0.92
90 86.61 0.66 90 89.39 1.05 90 89.65 0.63
105 88.18 0.54 105 89.89 0.69 105 92.03 0.57
120 88.22 0.55 120 90.30 0.68 120 92.09 0.56
135 88.27 0.59 135 89.95 0.68 135 92.13 0.57
The time is measured in minutes. 77 effect of extended repulping on yield using DMD. DMD proved to be extremely capable of repulping the wet-strength paperboard at all charges. The highest yield was
92.13% forthe 2.35% level of charge.
The Newman-Keuls test shows that at the 75 minute time interval, the high, medium and low charges are not significantly different, but all are significantly different than the no chemical runs. At the 90 minute time interval, the high and the medium charges are not significantly different. They are significantly different from the low charge and the no chemical run. Beginning at l 05 minutes, all levels of charge are significantly different.
Dunnett's test indicates that the different levels of charge are all significantly different from the no chemical run. Each of the runs had a significant increase in yield
Effect of Extended Pulping on Yield Using Dimethlydioxirane 100 90 80 ····•·····♦ 70 .... •·•·· 60 / ..... · ·• ····•······ 'i _ · � ... · "i 50 > 40 30 ♦ No Chem. Yel □ D.M.D.L 20 & D.M.D.M. o D.M.D.H. J 10 0 75 0 15 30 45 60 90 105 120 135 150 Tim (min)
Figure 25. Effectof Extended Repulping on Yield Using DMD. 78 compared to the no chemical runs. Even at 102-135 minutes for the low charge, the values within the 95% confidence interval were still greater then the critical value of
Dunnett's t test. Tables 19 and 20 list the statistical values for the Dunnett and
Newman-Keuls tests.
As can be seen by Figure 25, all the repulping times showed significant initial increases in yield over the no chemical runs. It can be seen that the yield for all of the
Table 19
Experimental Dunnett Values for Dl\ID
Time Chg. Dunnetts Test Time Chg. Dunnetts Test
75 H 24.311 120 H 19.0875
M 23.178 M 16.9242
75 L 22.985 120 L 15.2142
90 H 22.1954 135 H 18.6650
M 21.9287 M 16.4884
L 19.1554 L 14.8017
105 H 21.2167
M 19.0767
L 17.3601
Critical Value ofDunnett's T= 2.395. Alpha = 0.05. 79 Table 20
Experimental Newman-Keuls Values for DMD
Time Chg. New.-Kls. SNK Time Chg. New.-Kls. SNK (yields) group (yield) group
75 M 88.123 A 120 H 84.7133 A
H 86.990 A M 80.2833 B
L 86.797 A L· 77. 1467 C
Ct. 66.708 B Ct. 74.2125 D
90 H 89.6533 A 135 H 84.7400 A
M 89.3867 A 135 M 80.3233 B
L 86.6133 B L 77.1833 C
Ct. 69.0452 C Ct. 74.7300 D
105 H 84.6800 A
M 80.2367 B
L 77.1200 C
Ct. 72.1750 D
Alpha = 0.05. Yields with the same letter (SNK group) are not significantlydifferent.charges. runs was within 5% for all the time intervals. DMD had a significant effect on the paperboard during the soaking process. High initial gains, 74.38%-75.14%, were almost greater than the no chemical runs after 2.25 hours of repulping. Since, the 80 DMDhad greatsuccess in the first60-75 minutes of repulping, percent yield increased only slightly until it reached its plateau in 105 minutes for all charges. The medium charge actually had a lower yield than the low charge for the first 45 minutes, but its yield surpassed that of the low charge at 60 minutes and remained higher for the remainder of the run. The high charge, for time 60-75 minutes, had a lower yield than the medium charge. It finally surpassed the medium concentration at 90 minutes. The increase in charges , do however, lead to a higher overall yield. The chemical reaction of DMD lasts approximately 5-10 minutes. A higher concentration had a greater prolonged effect on paperboard. Each increase in charge led to a 2% increase in final yield. Once the cost of the chemical is determined, this 2% gain may not make econorruc sense.
Levels of Charge
Table 21 lists the chemical, charge and percent yield for all the runs. Figure 26 shows the no chemical runs and the low chemical charge forthe fourchemicals. DMD
had a significantly higher yield for all repulping times. At 75 minutes, DMD is 1.30
times greater than the no chemical run, 1.17 times greater than ammonium persulfate,
1.15 times greater than sodium persulfate and 1.24 times greater than the hydrogen
peroxide run. At 105 minutes, DMD is 1.24 times greater than the no chemical run,
1. 15 times greater than the ammonium persulfate, 1. 14 times greater than the sodium
persulfate and 1. 18 times greater than the hydrogen peroxide run. Over the repulping
process, there was little change in the yields compared to DMD. The persulfates had 81 Table21
Percent Yield for All Chemicals and Charge
Time Charge Chemical
N.C. H.P. A.P. S.P. DMD
30 low 53.59 52.20 60.24 62.89 75.14
45 60.52 60.41 64.17 68.34 80.16
60 63.68 65.27 70.76 72.98 83.07
75 66.71 52.20 72.96 74.86 85.70
90 69.92 52.20 74.58 75.84 86.61
105 71.28 52.20 76.36 77.12 88.18
120 74.60 52.20 76.41 77.15 88.22
135 74.65 52.20 76.44 77.18 88.27
30 med 53.59 52.47 66.25 69.92 74.38
45 60.52 60.54 68.75 72.88 78.80
60 63.68 68.05 72.79 75.75 83.13
75 66.71 71.98 74.46 77.61 88.12
90 69.92 73.11 76.44 79.48 89.39
105 71.28 75.81 78.42 80.41 89.89
125 74.60 77.23 80.83 80.45 90.30
135 74.65 77.24 80.87 80.50 89.95
30 high 53.59 62.34 70.34 70.32 74.81 82 Table 21- Continued
Time Charge Chemical
H.P. A.P. S.P. N.C. DMD
45 60.52 66.09 74.00 74.03 81.13
60 63.68 70.47 77.50 78.04 85.07
75 66.71 73.42 80.62 80.59 86.99
90 69.92 74.90 82.50 83.31 89.65
105 71.28 76.92 84.47 84.01 92.03
120 74.60 78.60 84.68 84.05 92.09
135 74.65 78.63 84.80 84.08 92.13
produced the second highest yield, with hydrogen peroxide producing only slightly more than the no chemical run.
Figure 27 shows the no chemical runs and the medium chemical charge for the four chemicals. As compared to the low charge, the medium charge yields start to show a significant increase over the no chemical runs. Once again, DMD produced the highest yield, followed by the persulfates and hydrogen peroxide. At 75 minutes, the DMD is 1.32 times greater then the no chemical run, 1.19 times greater than the ammonium persulfate, 1.08 times greater than the ammonium persulfate and 1. 07 times greater than the hydrogen peroxide run. At 105 minutes, DMDis 1.29 times 83
No Chemical and Low Chemical Addition 100 90 A A . h --A 80 a·---�------:- 70 - ...... � -�...,. -...... �---. ..- � .--:-t -:-:-:-=- ·--=...,._�..::::....,:.-:--.-- --�---:--:-.. l 60 / - "ti /· / _. �� =------=---:-�- :::. ::: . . . -. "i 50 / . •/,,: - -✓· ► / / _,. ,,. / 40 30 20 H.P.L.As.P.L o A.P°i.-A ·i :' ..• ·- N.c.- - • ------o:M~. - o.L·-· 10 0 0 15 30 45 60 75 90 105 120 135 150 Time (min)
Figure 26. Effect of Extended Repulping With a Low Chemical Concentration.
No Chemical and Medium Chemical Addition
100 90 ___ A--_Jl.--�.--zr- 80 "� ·;. - . - j.:::_· .--t-�:_:_=�-:� tf: � -:=:--t 70 ,,:f..•: .. ! : :_-_:_ ---�: �-..� -� -� :__- --• -- l 60 /tf: -----,.------= "ti 50 I/ 1•/_:� ► 40 ._ · 30 , 20 _ · l♦N.C. ■H.P.M. AS.P.M. OA.�M.-�Mn.M:1 10 I/ �/<_,·· 0 0 15 30 45 60 75 90 105 120 135 150 Tim (min)
Figure 27. Effect of Extended Repulping With a Medium Chemical Concentration. 84 greater than the no chemical run, 1.09 times greater than the persulfates, and l.20
times greater than the hydrogen peroxide run. Overall, there was little change in the
yields as compared to DMD.
Figure 28 shows the no chemical runs and the high chemical charge for the
four chemicals. As compared to the low charge, the medium charge yields start to
show a significant increase over the no chemical runs. Once again, DMD produced
the highest yield, followed by the persulfates and hydrogen peroxide. At 75 minutes,
the DMDis 1.30 times greater than the no chemical run, 1.08 times greater than the
No Chemical and High Chemical Addition
100 90 �---1r---A---_�...�- -a- . -- • ��, = ,. 80 __ . .--···-··--- __ . _ _., ___ ..... - . -•· .... ---1·..:._: �, ,...,_,./ 70 / ~.T .. . ·_._ -- -..-- - - ··•...... •...... •--. -. 60 /, ·_ - - - -.- - - - l / / ,· •... ✓- .. ,, 50 1/.· .-·/ ...... I / I '. / , 40 II ,
30 r;f.->.'1
20 ../ [� �-C. ■ H.P.H.• S.P.H. 0 A.P.H. f D.M.D.H. I ·/ - 10 0 0 15 30 45 60 75 90 105 120 135 150 Tim (min)
Figure 28. Effectof Extended Repulping With a High Chemical Concentration.
persulfates and 1.22 times greater than the hydrogen peroxide run. At 105 minutes,
DMDis 1.26 times greater than the no chemical run, 1.09 times greater than the 85 persulfatesand l. 18 times greater than the hydrogen peroxide run. Overall, there was little change in the yieldsas compared to DMD.
Effectof Screening on the Pulp
During the running of the z-bar mixer, all the samples were screened using the
Britt Jar screening device. Upon careful observation, the centrifugal action of the mixer did not allow for the fiber bundles to pass through the holes of the screen. This was important, because the individual fibers were to be the accepted material that was to be measured. However, in order to screen the pulp after the run, a vibrating six-cut screen was used for all 40 pulps. Initial examination of the screened pulp showed that the vibrating action of the screen allowed fiber bundles through. These fiber bundles were still partially contained within the wet-strength network. These fiber bundles proved to be detrimental to the refining process, as well as the strength properties of the handsheets. This will be discussed in the followingsection.
Effect of Refining on the Pulp
A PFI mill was used to refine the pulp because of the small amount of pulp available for refining. Trial pulps were refined and their freeness was measured in order to determine the number of revolutions that were needed to reduce the freeness to 400. Once the number of revolutions was established, handsheets were made after refiningat 0, 15,000 and 18,000 revolutions.
Table 22 shows the Canadian Standard Freeness values for the sample pulps at 86 0, 15,000 and 18,000 revolutions. The lowest freeness values at 15,000 revolutions for DMD, sodium persulfate, ammonium persulfate and hydrogen peroxide were 495,
400, 415 and 518 respectively. The lowest freeness values at 18,000 revolutions for
DMD, sodium persulfate, ammonium persulfate and hydrogen peroxide were 418,
360, 355 and 420 respectively. The high number of revolutions and relatively high freeness values indicate an extremely slow response to the refining process. The fact
Table 22
Average Canadian Standard Freeness Values
Revolutions
Chemical Chg. 0 15,000 18,000
No Chemical 674.75 502.50 435.00
DMD 0.47 663.33 514.67 423.33
DMD 1. 18 672.67 521.67 425.00
DMD 2.35 678.33 520.00 426.67 Sod. Per. 0.47 677.00 483.33 385.00
Sod.Per. 1.18 676.67 461.00 374.67
Sod.Per. 2.35 670.00 410.00 362.33
Amm. Per. 0.47 675.00 476.00 355.00
Amm. Per. 0.47 675.00 476.00 355.00
Amm. Per. 1.18 670.00 465.00 362.33 87 Table 22 - Continued
Revolutions
Chemical Chg. 0 15,000 18,000
Amm.Per. 2.35 676.00 421.67 377.33
Hd. Peroxide 0.47 671.67 521.33 429.00
Hd. Peroxide 1.18 670.67 532.33 422.67
Hd. Peroxide 2.35 678.33 490.00 441.00
that 15,000 revolutions were needed to reduce the freeness significantly proved that there was a barrier to the refining process. This slow reduction in freeness was affected by three factors.
First, the fiber bundles that were allowed to pass through the slotted screen to be used as accepted pulp had a negative affect on refining. Many more revolutions were needed to reduce the freeness values because the fibers were still contained, some partially, within the protective network of the wet-strength resin. This network provided a barrier and thus protected the fibers during the refining process. Secondly, individual fibers that were liberated during repulping, were still coated or partially coated with the wet-strength resin, but not contained within any network. Once again this proved a barrier to the refining process.
Lastly, the oxidizer that was used had a negative effecton the refining process. 88 In any case, the fibers were protected, and this level of protection had to be removed in order to alter the surface of the fibers to promote bonding when making handsheets.
Seven handsheets were made for each pulp at each of the three revolutions. As would be expected, at 0 revolutions where the freeness values were high, the tensile index values were low. The highest tensile index values were recorded for 15,000 revolutions. Refining at 18,000 revolutions reduced the tensile index values to a level lower then 15,000 revolutions.
Figures 29-33, show the average tensile index values graphed over the freeness range. The no chemical runs had the highest average tensile index values for the three refining times (revolutions). At 0 revolutions, its average high of 17.80 Nm/\2/g with a standard deviation of 0.20 is up to 1.66 times greater then the DMD values, up to
2.68 times greater then the sodium persulfate values, up to 1.84 times greater then the ammonium persulfate values and up to 1. 70 times greater then hydrogen peroxide values.
At 15,000 revolutions, its average high of 43.85 Nm/\2/g with a standard deviation of 0.47 is up to 1.50 times greater then the DMD values, up to 1.38 times greater then the sodium persulfate values, up to 1.44 times greater then the ammonium persulfate values and up to 1.23 times greater then hydrogen peroxide values.
At 18,000 revolutions its average high of 37.99 Nm/\2/g with a standard deviation of 0.43 is up to 1.35 times greater then the DMD values, up to 1.40 times greater then the sodium persulfate values, up to 1.29 times greater then the ammonium persulfate values, and up to 1. 10 times greaterthen hydrogen peroxide values. 89 Tensile Index No Che�i_cal Ad�ition 50 �------7
40 rC E Z 30 ,c '0• C : 20 •C 10
0 400 450 500 550 600 650 700 Freness (CSF)
Figure 29. Tensile Index With No Chemical Addition.
Tensile Index Hydrogen Peroxide 50 ..------,
40 •-~=------=---·_:-_·-=- -• -~ ·_:_ :_- :_· _::_ -. -~ -_- - ___._____ ... . - a-: - ---
)( Cl) -0 .E � 20 '- -- "i ' -- C - CD ' ' '- - ¾'' ' 10 I • H.P.L • H.P.M. ..H.P.H. 1 •'
0 400 450 500 550 600 650 700 Freenes (CSF)
Figure 30. Tensile Index Using Hydrogen Peroxide. 90 Tensile Index Ammonium Persulfate 40 �------,
__:_ _ �-�._·.:.· ·__:_ ·--· .. _ _ _ ci30 -----.·-=-...... '- - '-.. � ....._. X --...: . i 20 ....._. .E .....,._ "'- � :--... ·.;; •• (!!. 10 ,--~•~A~_;_.L_-~---~----A._P_.M_._-_~---=~~]
0 350 400 450 500 550 600 650 700 Freeness (CSF)
Figure 31. Tensile Index Using Ammonium Persulfate.
Tensile Index Sodium Persulfate 40 �------'------,
�30 .O ' e � .- X i 20 .E
·.;;.!? i 10 I- ■ S.P.M. I ♦S.P.L 4S.PH I
0 350 400 450 500 550 600 650 700 Freeness (CSF)
Figure 32. Tensile Index Using Sodium Persulfate. 91
Tensile Index CM) 40--r------�
.. ···········•·• ... �30 --- - - :_ ·- < ,._· - -- - E
� 20 .E ..! ·0 C � 10 [♦ D.M.D.L. ■ D.M.D.M. • D.M.D.�
0
400 450 500 550 600 650 700 Freeness (CSF)
Figure 33. Tensile Index Using DMD.
All of the pulps followed the same trend, increasing in strength to 15,000
revolutions and then decreasing from 15,000 to 18,000 revolutions. The tensile index
values show that the no chemical run had the greatest bonding ability of all the pulps.
This is extremely important if strength properties are necessary for the paper and a
lower amount of accepted pulp can be tolerated. Also, this shows the negative effect
of the chemicals on the strength properties of the pulp. The attack on the pulp by the
chemicals helped to break the wet-strength network and liberate the fibers, but left the
fibers vulnerable and weakened before refining. If a lower tensile strength can be
tolerated, then any one of these chemicals can be used. A chemical charge of 5. 0%
(based on A.O.) DMD should be preferred because it has the highest acceptance rate. 92 However, if cost is a major factor, then either of the persulfates would be good chemicals to use. Wet tensile tests were also performed on the handsheets for all the pulps. This was done to explore the possibility of wet-strength remaining in the pulp and still being able to impart wet-strength properties. These values could not be recorded because the strips fell apart before any load could be applied by the tensile tester. Some of the test strips fell apart in the water. This proved the fact that there was no wet-strength actively bonding between the fibers after repulping.
The tear values can be seen in Table 23. The tear index values increased for each of the three refining times for the no chemical runs, as well as for the hydrogen peroxide runs. For sodium and ammonium persulfate, the values increased for the
0.47% run only. The 1.18% and 2.35% runs increased from Oto 15,000 revolutions and then decreased at 18,000 revolutions. The values for DMD increased for the
1.18% run only. The 0.47% and 2.35% run increased from O to 15,000 revolutions and then decreased at 18,000 revolutions. Since the tear values are an indication of the strength of the paper, a lower tear value would be preferred. This would indicate strong bonding. However, weak fibers will also give low tear values regardless of bonding ability.
For all the pulps, the tensile index values decreased from 15,000 to 18,000 - revolutions. In the cases where the tear index values increased for all the refining times, it can be said that maximum bonding was not achieved, but that contradicts the tensile index data. This can be explained by the attack of the chemical on the fiber. At the low concentration, only DMD did not show an increase for the three refining 93 times. The persulfates followed the same trend as each other, and the hydrogen peroxide, which was the weakest of the four chemicals used, followed the same trend as the no chemical runs. Overall, no correlation could be drawn between the tear values.
Table 23
Tear Values
Chemical Chg. Revolutions Average S.D.
No Chemical 0 701.09 25.37
15,000 887.35 9.59
18,000 1051.63 23.54
DMD 0.47 0 569.24 22.05 15,000 1004.54 6.28
18,000 866.42 6.28
1.18 0 537.85 14.50
15,000 895.72 15.80
18,000 945.95 20.18
2.35 0 657.14 15.80
15,000 1136.39 28.77
18,000 983.62 15.80
Sod.Per. 0.47 0 493.90 7.25 94 Table23 - Continued
Chemical Chg. Revolutions Average S.D.
Sod. Per. 0.47 15,000 1029.66 10.87
18,000 1061.05 6.28
1.18 0 523.20 9.59
15,000 832.93 9.59
18,000 828.75 16.61
2.35 0 657.14 18.12
15,000 1136.39 3.62
18,000 983.62 6.28
Am. Per. 0.47 0 717.83 19.18
15,000 1061.05 12.56
18,000 1151.04 22.05
1.18 0 822.47 6.28
15,000 1038.03 19.18
18,000 680.16 9.59
2.35 0 734.57 6.28
15,000 1423.10 32.22
18,000 1023.38 6.28
H.P. 1.0 0 709.46 6.28
15,000 925.02 13.07 95 Table 23 - Continued
Chemical Chg. Revolutions Average S.D.
H.P. 18,000 1086.16 6.28 2.5 0 652.95 6.28 15,000 908.28 13.07 18,000 1086.16 6.28
5.0 0 774.34 20.18 15,000 973.15 6.28 18,000 1027.56 23.77 CHAPTER VIll
CONCLUSIONS
l. Presoaking the paper board before addition to the z-bar mixer was necessary in order for repulping to occur. This pre-wetting led to sufficient fiber swelling which was necessary for repulping. If the paper board was not soaked, then the z-bar mixer would "bind up".
2. The z-bar mixer was extremely successful as a repulping tool. Once the paper board was presoaked the z-bar was able to breakdown the wet-strength paper board to a 74.73% accepts level with no chemical addition at 15% consistency after
135 minutes.
3. Dimethlydioxirane, DMD., had the greatest affect on the final yield. The accepts at a 0.47%, 1.18% and 2.35% concentration were 88.27%, 89.95% and
92.13% respectively or 1.22-1.24 times greater than the no chemical run after 135 minutes.
4. For ammonium persulfate, the accepts at a 0.47%, 1.18% and 2.35% concentration were 76.24%, 80.87% and 84.80% or 1.02-1.14 times greater than the no chemical run after13 5 minutes.
5. For sodium persulfate, the accepts at a 0.47%, 1.18% and 2.35% concentration were 77.18%, 80.32% and 84.74% or 1.03-1.14 times greater than the no chemical run after13 5 minutes.
96 97 6. For hydrogen peroxide, the accepts at a 0.47%, 1.18% and 2.35% concentration 74.67%, 77.24% and 78.63% or approximately 1.05 times greater than the no chemical runs. All run were significantly different from the no chemical runs except the low chemical concentration of hydrogen peroxide. The final yield, 120-13 5 minutes, was not statistically different from that of the no chemical runs.
7. The no chemical runs had the highest tensile index values for all three number of revolutions. For 0, 15,000 and 18,000 revolutions, the tensile index values were 17.80 (N/m"2)/g, 43.85 (N/m"2)/g and 37.99 (N/m"2)/g.
8. The hydrogen peroxide, overall, had the highest tensile index values for any chemical. For 0 ,15,000 and 18,000 revolutions, the tensile index values were 17.80
(N/m"2)/g, 43.85 (N/m"2)/g and 37.99 (N/m"2)/g for the low charge, 10.45
(N/m"2)/g, 38.39 (N/m"2)/g and 34.43 (N/m"2)/g for the medium charge and 15.56
(N/m"2)/g, 40.44 (N/m"2)/g and 36.13 (N/m"2)/g for the high charge.
9. The hydrogen peroxide tensile index values were l 0% higher than those of
DMD and the persulfates.
10. DMD had tensile index values that were either higher than the persulfates, or ranged within 5% of their values.
11. Wet-tensile tests values could not be recorded because the test strips fell apart during testing. This indicates that even if wet strength was present, it is not actively bonding. 98 12. No correlation could be drawn between the tear values. For the no chemical hydrogen peroxide runs, they increased for every refining time. For sodium and ammonium persulfate, they increased for the O. 4 7% charge only. CHAPTER IX
RECOMMENDATIONS FOR FURTHERSTUDY
1. In prepanng the paperboard for this experiment, the board was not presoaked. Studies should be done to investigate the effect of the chemicals on presoaked paperboard.
2. Studies could be done to investigate the effect of the chemicals on the rejected material alone. The rejected material would be collected from a no chemical run and then repulped with chemical addition.
3. The temperature, pH, consistency were held constant throughout this experiment. Studies could be performed where these factors are changed to see their overall affecton the repulping system.
4. This experiment utilized a z-bar mixer to perform the repulping. Due to the nature· of the mixer, the paperboard was subjected to a watering-dewatering phase until it was repulped to the point of absorbing the free water. Studies could be performedto investigate the effectthis has on the paperboard.
5. The use of 18 point paperboard made the soaking process rather long. This experiment could be performed using handsheets (made with wet-strength) in order to investigate how the caliper affects the repulping process and also its effect on the chemical addition.
99 Appendix A
Raw Materials
100 101 The beverage earners were supplied by the BFI Corporation and contain polyamide wet-strength resin. The screens (mesh) needed for the screening process will be supplied by the Ronningen-Petter company. They are 316 stainless steel mesh screens. The screen characteristics are 20 mesh, 890 nominal micron equivalent and
0.035" nominal particle retention. Number four(# 4) Whatman filter papers were used forfiltering the accepted material.
Four chemicals were examined in this study: sodium persulfate, ammonium persulfate, dimethyldioxraine (DMD), and hydrogen peroxide. The sodium persulfate, ammonium persulfate and oxone were supplied by the Aldrich Chemical Company.
The hydrogen peroxide was supplied by the Meijer Company.
The DMD was made in situ from acetone and oxone, where oxone is
2KHSO5·KHSO4·K2SO4_ The sodium persulfate, ammonium persulfate and oxone were in powdered form and the hydrogen peroxide was in liquid form. The hydrogen peroxide was a three percent (3%) solution.
A five percent sodium hydroxide solution was used to adjust the pH. Sodium bicarbonate powder was used in preparing DMD. Ethylene diamine tetraacetate
(EDT A) was used as a chelating agent. These chemicals were supplied by the WMU paper department. Appendix B
Stock Preparation
102 103 The paper board was stored in the testing lab in order to keep the moisture content as high as possible. It has been determined that a higher moisture content aids in the soaking process. The moisture content is taken on a regular basis so as to maintain the proper consistency during repulping. Enough paperboard is cut into small pieces (2" x 2" squares) for the entire experiment. · This is to minimize moisture content fluctuations. Two-hundred grams of paper board, OD., is weighed out before the start of each run.
Two liters of water is heated in a glass beaker with a stir bar, on a hot plate to a temperature of 150° F. The pH is then adjusted to 11 with the 5% sodium hydroxide solution. While the water is being heated, the pieces of paperboard were placed in a large metal beaker. Once the solution is heated, the proper amount of water (needed for a 15% consistency) was weighed and transferred to a metal beaker. When determining the amount of water needed, you must take into account the amount of
5% sodium hydroxide that is needed and add to the water. Appendix C
Addition of Hydrogen Peroxide
104 105 1. Add 200 grams of O.D. paperboard to a beaker.
2. Determine amount of water necessaryfor 15% consistency.
3. Determine amount of hydrogen peroxide necessary for 1%, 2.5%
and 5. 0¾level of concentration.
4. Determine amounts ofEDTA (0.5% based on O.D. weight) and
sodium silicate (0.5% based on O.D. weight).
5. Heat the water to 150° F. using a hot plate and adjust the pH
with 5% sodium hydroxide.
6. Add the EDT A, sodium silicate, water and hydrogen peroxide to
the beaker and mix thoroughly.
7. Readjust the pH if necessary.
8. Let paperboard soak for70-80 minutes on hot plate to maintain
temperature. Appendix D
Addition of the Persulfates
106 107 1. Add 200 gramsofO.D. paperboard to a beaker.
2. Determine amount of water necessary for 15% consistency.
3. Determine amount of persulfate necessary based on the same
oxidation equivalent as hydrogen peroxide.
4. Determine amounts ofEDTA (0.5% based on O.D. weight).
5. Heat the water to 150° F. using a hot plate and adjust the pH
with 50% sodium hydroxide.
6. Add the EDTA, water and persulfate to the beaker and mix
thoroughly.
7. Readjust the pH if necessary.
8. Let paperboard soak for 70-80 minutes on hot plate to maintain
temperature. Appendix E
Addition of Dimethyldioxirane
108 109 1. Add 200 grams of O.D. paperboard to a beaker.
2. Determine amount of water necessary for 15% consistency.
3. Determine amount of oxone necessary based on the same
oxidation equivalent as hydrogen peroxide.
4. Determine amounts ofEDTA (0.5% based on O.D. weight).
5. Heat the water to 150° F. using a hot plate and adjust the pH
with 50% sodium hydroxide.
6. Add approximately 200 ml. of water, EDTA, sodium bicarbonate
and acetone to the beaker and mix thoroughly. The pH will be
adjusted to an initial pH of 7. 0-7. 5 to maximize oxidation yield.
7. Add the oxone to the beaker.
8. After approximately 15 minutes, bring the pH up to 10.0.
9. Readjust the pH if necessary.
10. Let paperboard soak for70-80 minutes on hot plate to maintain
temperature. Appendix F
Repulping of the Paperboard
110 111 The Z-bar mixer was made by the Master Electric Company and is 1112 horse power, 220 volts, 9.6 amps, 1725 rpms and 60 cycles. It is type RA, frame 204RW and style 178340. For this experiment, it has been wrapped on three sides with urethane and also has an adapter for a steam line. An extension cord has been spliced into the power cord in order to record the voltage. A three inch length of insulation was removed to expose the inner wires of the power cord about six inches from the power switch. The white wire was used with the ampere meter.
The Z-bar mixer is a dual agitator apparatus that can operate at high consistencies. Each agitator rotates within its separate chamber and the contents within each chamber will contact each other above the dam separating the chambers.
Once above the darn, the contents will become mixed, thus further helping the repulping process.
Once total saturation of the paper board is achieved, it can be transferred to the
Z-bar mixer. The water was removed and the steam line disconnected from the Z-bar mixer. The pieces of paperboard were added in small quantities as quickly as the z-bar mixer will allow. A metal cover, holding a temperature gauge, was placed over the top of the Z-bar mixer. Then the connector for the steam line will be plugged. The steam line was then positioned on the uncovered (no urethane insulation) side of the
Z-bar and turned on. The steam was monitored in order to maintain the temperature.
An ampere meter was attached to the power supply to record the amps for each run.
A volt meter was attached to the cord that is spliced into the power cord. Readings 112 were recorded forno load and throughout the run. They were then used to determine the energy input.
The contents of the Z-bar mixer were repulped for 2.25 hours and samples were taken every 15 minutes (30 min, 45 min, 60 min, ... ) for pulp evaluation. The first sample was collected at 30 minutes. At selected time intervals, a 15-20 gram pulp sample was collected for evaluation using the Britt Jar screening device. Appendix G
Screening of the Paperboard
113 114 The Britt Jar was used to screen small samples of pulp. It's regular screen was replaced with a 20 mesh screen. A water line is inserted into the container. The container was then filled with water until it was approximately 3/4 full. Three and one-half (3.5) grams of pulp was weighed and diluted in a 200 ml. beaker. The mixer was inserted into the container just above the screen, turned to the torque setting, set to the counter clockwise position and turned on. It is set to 600 rpms. The diluted pulp was then added to the container. Allow to mix for 5 minutes. To drain, position
2000 ml. beaker under drain and open the stopcock. As it is draining, tum on the inlet water. Adjust the inlet water to match the outlet water so that the water level remains fairly constant. Filter the accepts in the Buchner funnel. Drain the outlet water into a graduated cylinder and check forfibers. When no fibers are visible, then the screening can be terminated. Remove the filter paper from the Buchner funnel and replace with a new one. Remove the screen and gaskets from the Britt Jar and place them in a
2000 ml. beaker. Rinse them off with water and drain into Buchner funnel. The accepts and rejects will then be dried in a 105° C. oven over night and weighed.
Percent accepts and rejects can then be calculated. Appendix H
Beverage Carrier Properties, Energy Values and Run Conditions
115 116 Table 1
Beverage Carrier Properies
Test Test
BASIS WEIGH gmA2 Calipr Test Point Test Point 1 373.58 1 18.0 2 373.25 2 17. 7 3 383.13 3 17.7 4 380.82 4 17.7 5 376.44 5 18.0 6 376.54 6 18.0 7 374.13 7 18.0 8 373. 75 8 18.0 9 373.39 9 1 8.0 1 0 373.44 10 17.9 Average 375.85 Average 17.9
Or Tensile Strength (N) Wet Tensile Strengh (N) Test Load Test Load 1 24.68 1 7.023 2 26.28 2 7.898 3 23.96 3 5.890 4 23.53 4 5.407 5 23.23 5 5.922 6 20.90 6 . 5.103 7 22.35 7 6.105 8 21.10 8 5.538 9 22.50 9 5.600 1 0 22.54 10 6.048 1 1 20.76 11 5.345 12 22.78 12 7.380 13 24.76 13 5.741 14 23.10 14 5.621 15 22.50 1 5 6.115 16 24.10 16 5.400 17 22.23 17 6.070 18 23.12 18 5.990 19 22.96 19 7.101 20 20.85 20 5.880 Average 22.91 Average 6.059 Table 2
Energy Values for Iha Experimenlal Runs
No chemical runs #1 run #3
Time (min) Volts Amps Temp (F.) Time (min) Volts Amps Temp (F.)
0 199.6 5.0 150 0 199.6 5.0 150 15 199.6 5.0 150 15 199.9 5.0 152 30 199.6 5.0 150 30 199.9 5.0 152 45 199.6 5.0 152 45 199.9 5.0 152 60 199.6 5.0 150 60 199.9 5.0 150 75 199.6 5.0 150 75 199.6 5.0 152 90 199.6 5.0 152 90 199.6 5.0 150 105 19"9.6 5.0 152 105 199.6 5.0 152 120 199.6 5.0 150 120 199.6 5.0 150 135 199.6 5.0 152 135 199.6 5.0 152 Average 199.6 5.0 151 Average 199. 7 5.0 1 51 S.D. 0.0 0.0 1.03 S.D. 0.2 0.0 1.03
run #2 run #4 Time (min) Volts Amps Temp (F.) Time (min) Valls Amps Temp (F.) 0 199.6 5.0 150 0 199.8 5.0 150 1 5 199.6 5.0 152 15 199.8 5.0 152 30 199.9 5.0 152 30 199.8 5.0 152 45 199.9 5.0 150 45 199.8 5.0 151 60 199.9 5.0 152 60 199.8 5.0 150 75 199.6 5.0 152 75 199.8 5.0 150 90 199.6 5.0 150 90 199.8 5.0 150 105 199.9 5.0 152 105 199.7 5.0 150 120 199.9 5.0 154 120 199.8 5.0 150 135 199.9 5.0 152 135 199.8 5.0 150 Average 199.8 5.0 152 Average 199.8 5.0 151 S.D. 0.2 0.0 1.26 S.D. 0.0 0.0 0.85 Ta 2-
Sodium PeflliNele 0. 47% NII 11 Sodium Peraullal• 0.47%. n,n 12 Sodium P•"""•I• o.◄1% NII n
Time (mini Volll Ampe Temp (f.l Time (mini Volle Amp• hmp(f.l Time (mini Volle Amtl• ,.,.,,.,
0 UICI.I 6.0 160 0 1(1(1.3 5.0 150 0 11111.6 6.0 uo.o II 11111.1 6.0 162 II 11111.3 5.0 150 15 11111.5 5.0 160.0 30 11111.1 6.0 162 30 11111.3 5.0 152 30 11111.5 6.0 uo.o 45 11111.1 5.0 152 45 199.3 5.0 152 45 11111.5 5.0 162.0 60 1118.I 5.0 16: 60 1118.3 5.0 150 60 11111.5 5.0 162.0 76 1118.1 6.0 160 15 11111.3 5.0 150 15 111(1.3 5.0 IU.O 110 1118.8 li.O 160 110 1911.3 5.0 150 110 11111.l 5.0 IU.O 106 11111.I 5.0 162 106 1811.3 5.0 150 105 1811 5 5.0 162.0 120 11111.8 5.0 150 120 1118.3 5.0 150 120 11111.5 5.0 uo.o 136 11111.1 5.0 160 135 199.3 5.0 150 135 11111.5 5 0 uo.o Averege 11111.8 6.0 151 Av•r•g• 1911.3 5.0 150 Average 11111.5 5.0 161 s.o. 0.0 0.0 1.05 so.. 0.0 0.0 0 84 S.O. 0.1 o.o 1.05
Sodlulf Peraullele 1.11% NII II Sodium PerauNala 1.18%. n,n 12 Sodium Peraullele 1.11 % NII 13 Time (mini , . Volle Amp• Temp (F.1 Tim• (mini Volla Ampa l emp Cf I Tlma (mini Volla Ampa hfflll(f.) 0 11111.7 5.0 150 0 198.7 5.0 I 50.0 0 11111.3 5.0 150 II 11111.7 5.0 150 15 1118.7 5 0 150 0 15 11111.l 5.0 150 30 Jllll.7 6.0 !'52 30 1118.7 5.0 150 0 30 11111.3 5.0 160 46 11111.1 5.0 152 45 198.7 5 0 152.0 45 11111.3 5.0 162 10 _11111.7 li.0 162 80 I 118.7 5.0 150 0 60 11111.5 li.0 IU 75 1811.7 6.0 152 n 1118.7 6 0 152 0 H 11111.3 6.0 uo 110 11111.7 6.0 160 110 1118.7 5.0 150.0 110 11111.3 60 160 106 11111.7 5.0 160 105 198.7 5.0 150 0 105 11111.3 5.0 ua 120 11111.7 5.0 152 120 188.7 5.0 150.0 120 11111.3 6.0 IU 135 11111.7 li.O 150 135 188.8 5 0 150.0 135 11111.3 5.0 150 Average 1(111.7 5.0 151 Average 1118.7 5 0 150 AVIIIQI 11111.3 5.0 UI 8.0. 0.0 0.0 1.05 6.0. 0.0 0.0 0.84 so. 0.1 o.o 1.03
Sodium Peraullale 2.35% run. 11 Sodium PerauHaie 2.35% n.n 12 Sodium Per1ulle1a 2.35 11. run 13 Time (min) Volla Ampa ' Te (F.) Time (mini Volle Anip1 hmp (f.l Time (mini Volle Ampa le(f.l 0 1118.1 5.0 150 0 1117. II 5.0 150 0 I Ill.II 5.0 150.0 15 11111.7 5.0 162 ·15 1117.11 5.0 150 I 5 1118.11 5.0 150.0 30 11111.7 5.0 152 30 197.11 5.0 152 30 1111.11 5.0 150.0 46 11111.7 6.0 162 45 197.9 5.0 150 45 1111.11 5 0 150.0 80 11111.7 6.0 162 80 1117.8 5 0 150 tiO 1118.11 5 0 ua o 76 11111.7 5.0 152 75 197.II 5.0 150 75 1118.11 5.0 IU.O 90 11111.7 5.0 160 110 1117.11 5.0 152 110 1118II 5.0 IU.O 106 11111.7 5.0 152 105 197.8 5.0 152 105 1111 II 5 0 150.0 120 11111.7 5.0 150 120 1117.11 5 0 150 120 1118.11 5 0 150 0 135 11111.7 5.0 150 135 197 .II 5.0 150 135 198.11 5 0 150 0 Averege 11111.7 5.0 151 Av11ag• I 117.9 5.0 151 Avau,ge 1118.8 50 151 so. 0.0 0 �7 0.0 0.0 0.117 s.o. 0.0 0.0 1.03 0.0 SD - ,, 00- Table 2-Conllnued
Ammonium Peidal• 0.47% run II Ammonium PerauNale 0.◄7% run 12 Ammonium Pe11.,.a1a 0.41'11. run U
Tim&(mini Voll& Amp& Tamp (F.1 Time (mini Volla Ampa Tamp (f.) Tlma (mini 1/olla Afflfl• Temp (f-l
0 1118.2 1.0 1110.0 0 1118.11 5.0 150.0 0 1111 II 5.0 160 15 lllll.2 6.0 152.0 15 1118.11 5 0 152 .0 15 lll8.II 5.0 uo 30 lllll.2 6.0 154.0 30 1118 II 5.0 152.0 30 1111.ll 5.0 IU ◄5 1118.2 6.0 162.0 45 108.11 5 0 150 0 45 I Ill ll 5.0 162 80 1118.0 6.0 152.0 80 11111.1 5 0 150 0 60 lll8.II 6 0 IU Hi lllll.O 6.0 150.0 H 1110.1 5.0 I 52 0 7 5 1118.ll 5.0 152 80 1811.0 6.0 152.0 110 11111.1 5.0 150.0 110 1118.11 5.0 uo 105 11111.0 !i.O 150.0 105 lllll.l 5.0 I 50 0 105 1118.11 5.0 150 120 lllll.O 5.0 152.0 120 1118.0 5.0 152 0 120 1118 II 5.0 150 135 11111.0 5.0 150.0 135 199.1 5 0 152. 0 135 1118.11 5.0 150 Avatage 11111.1 6.0 161 Avaraga 11111.0 5.0 151 Avor�ge 1118.11 5.0 IU 8.0. 0.1 0.0 1.35 s.o. 0.1 0.0 I 05 S.O. 0.0 0.0 I .Ol
Ammonium Paraullale 1.18% run II Ammonium PerauHala 1.18% ruo 12 Ammonium Peraullala 1.11'11. run U Time (mini Volla Amp• Temp (F.1 Tim• (mini Volla Amps hmp (f I Time (mini \loll, Ampa ltfflll(f .l 0 11111.2 5.0 150 0 108.8 5 0 150 0 11111.3 50 150 15 11111.2 6.0 152 15 198.7 5 0 152 15 11111.3 5.0 150 30 11111.2 6.0 160 30 108.8 5 0 152 30 11111.3 5.0 152 46 11111.0 6.0 160 ◄5 1118. 7 5.0 152 45 11111.3 5.0 IU 80 11111.0 6.0 160 60 1118.7 5 0 150 60 11111.5 5.0 160 76 11111.0 5.0 152 75 1118.7 5 0 152 H 11111.3 5.0 150 110 11111.2 6.0 160 110 198.7 5 0 152 110 11111.3 5.0 IU 106 11111.2 5.0 150 105 108.8 5.0 152 105 11111.3 5.0 150 120 11111.0 6.0 160 120 1118.7 5.0 150 120 11111.3 5.0 160 136 11111.0 6.0 150 135 1118.8 5.0 150 135 11111.3 5.0 150 Average 1118.1 6.0 160 Av.,age 1118.7 5.0 151 Averoga 11111.3 5.0 UI 8.0. 0.1 0.0 0.84 so. 0.1 0.0 I 03 so. 0.1 0.0 0.111
Ammonium Pa,aullala 2.35% run • I Ammonhm ParauHale 2.35 % nin 12 Ammonium Peraulla le 2.35 '11. run U Tlma (mini Volla Ampa hmp(f.l Tlma (mini Volla An1p1 Tamp (f) Tlma (mllll Volla Ampa Tamp (f I 0 11111.3 5.0 uo 0 1118.0 5 0 150 0 11111 3 11.0 uo 15 IIUl.5 6.0 150 15 1118.0 5.0 151 15 11111.3 5.0 150 30 11111.6 6.0 H>2 30 1118.0 5.0 150 30 11111.3 5 0 160 45 11111.6 5.0 150 ◄5 108.0 5 0 150 45 11111.3 5.0 150 10 11111.6 6.0 152 60 108.1 5.0 150 60 11111.5 5.0 162 75 11111.6 6.0 162 75 198.0 5 0 150 H 11111.3 5 0 152 110 11111.5 5·.o I 52 110 108.1 5 0 150 110 11111.3 5 0 152 106 11111.6 5.0 152 105 198.0 5.0 150 105 11111.3 5.0 150 120 11111.6 5.0 152 120 1118.0 5.0 150 120 11111.3 5.0 150 136 11111.5 6.0 150 135 198.0 5.0 150 135 1119 3 50 150 Avarage 11111.5 5.0 151 A11eraoa 108.0 5.0 150 Aveugo 11111.3 50 161 s.o. 0.1 0.0 1.03 S.D. 0.0 0.0 0 J2 so 0.1 0.0 0.117 - •" T� 2-Conllnued
OMO 0.◄7% NII II OMD 0.47% run 12 OMO 0.47% NII U
Time(min) Volta Temp(F.) Time (min) Vona Ampe � hmp (f.) Time (mini Volle Ampa lMlfl Cf .)
0 Ulll.6 6.0 150 0 1117.2 5.0 150 0 1111.11 5.0 uo 16 11111.6 6.0 160 15 1117.2 5 0 150 15 1118.11 5.0 150 30 11111.6 6.0 162 30 1117.2 5.0 152 30 1118.11 5.0 uo ◄6 11111.6 6.0 U2 45 107.2 5.0 152 H, 1111.11 5.0 IU 11111.6 eo 6.0 150 10 1117.2 5.0 152 60 1111.11 5 0 IU 75 11111.6 6.0 150 15 1117.2 5.0 150 75 I Ill.II 5.0 162 110 11111.6 6.0 160 110 I117 .2 5.0 152 (IQ 1118 11 5.0 IU 105 1811.5 5.0 150 105 1117.2 5.0 150 105 1118 II 5.0 uo 120 11111.5 5.0 152 120 1117.2 5 0 150 120 1111.11 5 0 160 136 11111.6 6.0 162 135 1117.2 5.0 152 135 1118.11 5 0 160 Av11ag 111.6 6.0 161 Avera(II 1117.2 5 0 151 Av11•11• 1118 II 5 0 161 s.o. 0.0 0.0 1.03 so. 0.0 0.0 I 05 so. 0.0 0.0 I.Ol
Ot.10 1.18% NII 11 OMO I.18% run 12 OMO 1.18% NII ll Time (mini Voll1 Ampa Temp (F.) Tim• (mini Volle Ampa Temp (f.) Tima (!'!IOI Volla Amp1 hmp(f.) 0 11111.7 6.0 150 0 107.1 5 0 I !)0 0 11111.5 50 160 16 11111.7 6.0 150 15 1117.I 5 0 150 15 11111.5 5.0 IU 30 11111.7 6.0 162 30 107. I 5 0 150 30 11111.5 5.0 IU ◄6 11111.7 6.0 162 45 107. I 5 0 152 45 11111.5 5.0 162 eo 11111.7 6.0 152 60 1117.I 5 0 152 60 11111.5 5.0 150 75 11111.7 5.0 152 7S 1117. I 5 0 152 15 11111.5 5.0 150 80 1811.7 6.0 160 110 I 97. I 5.0 150 110 11111 5 5.0 160 106 1811.7 6.0 150 105 1117. I 5 0 150 105 11111.. 5 5.0 IU 120 1811.7 5.0 160 120 1117. I 5.0 152 120 11111.5 5.0 160 136 188.7 6.0 150 135 1117.1 5.0 150 135 11111.5 5.0 uo Averag 1811.7 5.0 151 Av11age 1117.1 5.0 151 Av11aga 11111.5 5.0 UI 6.0. 0.0 0.0 1.03 so. . 0.0 0.0 I 03 S.0. 0.0 0.0 1.oi
OMO 2.35% NII II OMO 2.35% run 12 OMO 2.35% NII U Tlma(mini Volla Ampa Temp(f.) ,Tim• (min) Volla An1p1 Temp CF I Tlrna Cmlnl Volle Ampa T-,alf ) 0 11111.6 5.0 150 0 1119.8 5 0 150 0 1118.11 5.0 uo 16 1811.6 6.0 150 15 11111.8 5.0 150 1 5 1118.11 5.0 162 30 11111.5 6.0 160 30 11111.8 5.0 152 30 1118.11 5.0 IU ◄6 11111.6 5.0 150 45 11111.8 5.0 152 45 188.1 5.0 160 80 11111.5 6.0 150 60 1911.8 5.0 152 60 1118.11 5.0 uo 75 1118.5 5.0 160 75 1118.8 5.0 152 75 1118.11 5.0 IU 10 111.5 5.0 162 110 11111.8 5.0 150 110 118.8 5.0 IU 105 11111.5 5.0 150 105 lllll.8 5.0 150 105 1118.11 5.0 uo 120 11111.5 5.0 150 120 lllll.8 5.0 150 120 1118.11 5.0 160 135 11111.6 5.0 150 135 1119.8 5.0 150 135 1118.11 5.0 160 Av11aga 11111.5 5.0 150 Av11ag1 11111.8 5 0 15 I Av11a9e 1118.11 5.0 161 s.o. 0.0 0.0 0.63 so. 0.0 0 0 103 so. 0.0 0.0 I.Ol N ,, 0- Table 2-Conllnued
HvdrogenPeroxlde 1. 0%,unll HydrogenPeroxide 1.0% run 12 HydrogenPeroxide 1.0% ,un 13
Tim• (min) Volle Anipe Temp (F.) Tim• (mini Volle Ampe Temp (F.) Time (min) Vona Amp• Temf! (F.)
0 11111.a 1.0 150 0 11111.4 5.0 150 0 11111.7 5.0 150 u 11111.a 6.0 152 15 11111.4 5.0 152 15 11111.7 5.0 IU 30 11111.a 11.0 152 30 1111U 5.0 150 30 11111.7 5.0 152· 46 11111.1 5.0 153 45 1'111.4 5.0 152 45 11111.7 5.0 153 80 11111.a 6.0 152 80 1911.5 5.0 150 80 11111.7 5.0 IU 75 11111.a 6.0 152 75 1911.4 5.0 150 75 11111.7 5.0 150 lilO llilll.l 6.0 150 110 199.4 5.0 152 90 1911.7 5.0 150 106 191i1.I 6.0 150 105 199.4 5.0 152 105 11111.7 5.0 150 120 11i19.8 5.0 150 120 199.4 5.0 152 120 199. 7 5.0 150 135 199.I 5.0 150 135 189.◄ 5.0 150 135 199.7 5.0 150 Averege 199.1 5.0 151 Average 199.4 5.0 151 Average 1119.7 5.0 151 s.o. 0.0 0.0 1.20 S.O. 0.0 0.0 1.05 s.o. 0.0 0.0 1.20
Hydloger\Peroxide 2.5% ,un II Hydrogen Peroxide 2.5% run 12 Hydrog1n Peroxide 2. 5% ,un 13 Time (min) ·vona Ampa Temp (F.) Time (min) Volla Ampa Temp (F.) Tim• (min) Volle Ampa hmp(F.) 0 •199.8 5.0 150 0 199. 8 5 0 150 0 199 7 5.0 150 15 '·199.4 5.0 152 15 199.8 5.0 150 15 199.7 5.0 152 30 IIUl.4 5.0 152 30 190.8 5.0 150 30 11111.7 5.0 152 45 199.4 5.0 152 45 199.8 5.0 152 45 11111.7 5.0 152 80 I 1111.4 5.0 150 80 199.8 5.0 152 60 11111. 7 5.0 152 75 lee.a 5.0 152 75 199.8 5.0 152 75 11111.7 5. 0 150 110 199.8 5.0 150 90 199.8 5.0 150 90 IIIIU 5.0 150 105 11111.a 5.0 152 105 199.8 5.0 150 105 11111.7 5.0 IH 120 11111.a 5.0 152 120 199.8 5.0 150 120 111iu 5.0 150 135 11111.6 5.0 150 135 1119.8 5.0 150 135 1119.7 5.0 150 Average 11111.5 5.0 151 Average 1911.8 5.0 151 Average 11111.7 5.0 151 s.o. 0.1 0.0 1.03 s.o. 0.0 0.0 0.97 s.o. 0.0 0.0 1.05
Hydlogen Peroxide 5.0% ,un 11 HydrogenPeroxide 5.0% run 12 Hydrogen Peroxide 5.0% run n Tim• (min) Volle Amp• Temp (F.) Time (min) Volla Ampa Temp (F.) Time (min) Vona Ampa Temp (F.) 0 11111.7 5.0 150 0 1911.5 5.0 150 0 11111.1 5.0 150 15 11111.7 5.0 150 15 1119.5 5.0 150 15 199.1 5.0 150 30 1911.7 5.0 152 30 199.5 5.0 150 30 11111.1 5.0 150 46 11111.7 5.0 150 45 1119.5 5.0 150 ◄5 199.1 5.0 152 80 1119.li 5.0 150 60 1119.6 5.0 150 60 1911.1 5.0 152 75 11111.5 6.0 150 75 11111.6 5.0 150 75 1119.1 5.0 152 110 11111.7 5.0 152 90 199.5 5.0 152 90 199.1 5.0 150 106 1911.5 5.0 150 105 199.5 5.0 152 105 199.1 5.0 150 120 1119.5 5.0 152 120 199.5 5.0 150 120 199.1 5.0 150 135 199.5 5.0 152 135 199.5 5.0 150 135 199.1 5.0 150 I 5 I Average 1119.6 5.0 151 AeBraoo 199.5 5 .0 150 A._o,age 1911.1 5.0 s.o. 0.1 0.0 1.03 s.o. 0.0 0 0 0.8◄ SO. 0.0 0.0 0.97 - N- i' Table 3 122
Experimental Run Conditions
No Cheicl run 1 run 2 run 3 run 4
consistency (%) 15.3 15. 1 15.0 15.2 pH 10.09 10.27 10.44 10.30
Hydrogen Peroxide 1% run 1 run 2 run 3 consistency (%) 15.2 15.4 15.5 pH 10.17 10.39 10.21 2.5% run 1 run 2 run 3 consistency (%) 15.4 15.1 15.1 pH 10.09 10.32 1 o. 13 501,o run 1 run 2 run 3 consistency (%) 15.1 15.0 15.4 pH 10.11 10.23 10.29
Ammonium Persulfate 0.047% run 1 run 2 run 3 consistency (%) 15.2 15.4 15.4 pH 10.17 10.15 10.24 1.18% run 1 run 2 run 3 consistency (%) 15.3 15.3 15.2 pH 10.21 10.27 10.11 2.35% run 1 run 2 run 3 consistency (%) 15.2 15.4 15. 1 pH 10.07 10.20 10.24
Sodium Persulfate 0.047% run 1 run 2 run 3 consistency (%) 15.4 15.1 15.4 pH 10.21 10.16 10.25 1.18% run 1 run 2 run 3 consistency (%) 15.2 15.2 15.3 pH 10. 11 10.08 10.17 2.35% run 1 run 2 run 3 consistency (%) 15.3 15.1 15.4 pH 10.15 10.29 10.09
OMO 0.047% run 1 run 2 run 3 consistency (%) 15. 1 15.4 15.3 -- pH 10.31 10.16 10.23 1.18% run 1 run 2 run 3 consistency (%) 15.2 15.3 15.3 pH 10.21 10.11 10.17 2.35% run 1 run 2 run 3 consistency (%) 15.1 15.3 15.4 pH 10.35 10.19 10.01 Appendix I
Tabulated Data forthe Chemicals
123 124
Table 4
Accepts and Rejects Weight for Experimental Runs
No Chemical
Accepts Weight (g)
Time Run #1 Run #2 Run #3 Run #4 30 0.2678 0.2991 0.2775 0.2920 45 0.3173 0.3390 0.3053 0.3220 60 0.3272 0.3490 0.3420 0.3322 75 0.3524 0.3522 0.3581 0.3520 90 0.3669 0.3590 0.3665 0.3720 105 0.3867 0.3884 0.3764 0.3792 120 0.4023 0.3887 0.3863 0.3969 135 0.4027 0.3890 0.3962 0.3971
Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #4 30 0.2677 0.2294 0.2475 0.2400 45 0.2182 0.1895 0.2197 0.2100 60 0.2083 0.1795 0.1830 0.1998 75 0.1831 0.1763 0.1669 0.1800 90 0.1686 0.1695 0.1585 0.1600 105 0.1488 0.1401 0.1486 0.1528 120 0.1332 0.1398 0.1387 0.1351 135 0.1328 0.1395 0.1288 0.1349 125
Table 4-Continued
Hydrogen Peroxide 1.0%
Accepts Weight (g) Rejects Weight (g)
Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.2720 0.2990 0.2713 0.2600 0.2400 0.2713 45 0.3107 0.3390 0.3251 0.2213 0.2000 0.2174 60 0.3415 0.3590 0.3526 0.1905 0.1800 0.1899 75 0.3622 0.3790 0.3726 0.1698 0.1600 0.1699 90 0.3920 0.3896 0.4019 0.1400 0.1494 0.1406 105 0.3938 0.4065 0.4021 0.1382 0.1325 0.1404 120 0.3954 0.4067 0.4023 0.1366 0.1323 0.1402 135 0.3955 0.4068 0.4025 0.1365 0.1322 0.1400 Hydrogen Peroxide 2.5% Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.2695 0.2992 0.2685 0.2695 0.2293 0.2600 45 0.3190 0.3387 0.3085 0.2200 0.1898 0.2200 60 0.3690 0.3686 0.3485 0.1700 0.1599 0.1800 75 0.3890 0.3860 0.3738 0.1500 0.1425 0.1547 90 0.3990 0.3886 0.3794 0.1400 0.1399 0.1491 105 0.4114 0.3976 0.4010 0.1276 0.1309 0.1275 120 0.4168 0.4047 0.4109 0.1222 0.1238 0.1176 135 0.4169 0.4048 0.4111 0.1221 0.1237 0.1174 Hydrogen Peroxide 5.0% Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.3487 0.3150 0.3290 0.1798 0.2100 0.2100 45 0.3586 0.3350 0.3590 0.1699 0.1901 0.1800 60 0.3786 0.3645 0.3792 0.1499 0.1605 0.1598 75 0.3939 0.3809 0.3$4. 0.1346 0.1441 0.1446 90 0.3986 0_395·0 0.3990 0.1299 0.1300 0.1400 105 0.4100 0.4049 0.4099 0.1185 0.1201 0.1291 120 0.4192 0.4126 0.4199 0.1093 0.1124 0.1191 135 0.4194 0.4127 0.4200 0.1091 0.1123 0.1190 126
Table 4-Continued
Ammonium Persulfate 0.47% A.O.
Accepts Weight (g) Rejects Weight (g)
Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.3220 0.3390 0.3090 0.2100 0.2000 0.2300 45 0.3420 0.3590 0.3344 0.1900 0.1800 0.2046 60 0.3820 0.3890 0.3706 0.1500 0.1500 0.1684 75 0.3920 0.3990 0.3861 0.1400 0.1400 0.1529 90 0.4020 0.3996 0.4017 0.1300 0.1394 0.1373 105 0.4115 0.4095 0.4109 0.1205 0.1295 0. 1 281 120 0.4118 0.4097 0.4112 0.1202 0.1293 0.1278 135 0.4120 0.4099 0.4114 0.1200 0.1291 0.1276 Ammonium Persulfate 1.18% A.O. Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.3550 0.3349 0.3720 0.1805 0.2006 0.1600 45 0.3674 0.3550 0.3820 0.1681 0.1805 0.1500 60 0.3951 0.3797 0.3920 0.1404 0.1558 0.1400 75 0.4052 0.3921 0.3962 0.1303 0.1434 0.1358 90 0.4152 0.4082 0.4020 0.1203 0.1273 0.1300 105 0.4198 0.4152 0.4220 0.11 57 0.1203 0.1100 120 0.4352 0.4339 0.4267 0.1003 0.1016 0.1053 135 0.4355 0.4341 0.4268 0.1000 0.1014 0.1052 Ammonium Persulfate 2.35% A.O. Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.3620 0.3790 0.3839 0.1700 0.1600 0.1446 45 0.3820 0.4024 0.3993 0.1500 0.1366 0.1292 60 0.4020 0.4190 0.4186 0.1300 0.1200 0.1099 75 0.4220 0.4390 0.4286 0.1100 0.1000 0.0999 90 0.4320 0.4490 0.4386 0.1000 0.0900 0.0899 105 0.4436 0.4590 0.4486 0.0884 0.0800 0.0799 120 0.4459 0.4595 0.4491 0.0861 0.0795 0.0794 135 0.4469 0.4598 0.4498 0.0851 0.0792 0.0787 127
Table 4-Continued
Sodium Persulfate 0.47% A.O.
Accepts Weight (g} Rejects Weight (g}
Tire Run #1 Run #2 Aun #3 Aun #1 Aun #2 Aun #3 30 0.3536 0.3316 0.3251 0.1854 0.1969 0.2139 45 0.3782 0.3607 0.3590 0.1608 0.1678 0.1800 60 0.3990 0.3877 0.3857 0.1400 0.1408 0.1533 75 0.4090 0.3965 0.3972 0.1300 0.1320 0.1418 90 0.4136 0.4028 0.4019 0.1254 0.1257 0.1371 105 0.4178 0.4106 0.4104 0.1212 0.1179 0.1286 120 0.4180 0.4107 0.4106 0.1210 0.1178 0. 1284 135 0.4182 0.41 09 0.4108 0.1208 0.1176 0.1282 Sodium Persulfate 1.18% A.O. Accepts Weight (g} Rejects Weight (g) Time Aun #1 Aun #2 Aun #3 Aun #1 Aun #2 Run #3 30 0.3420 0.3464 0.3744 0.1900 0.1856 0.1611 45 0.3613 0.3662 0.3903 0.1707 0.1658 0.1452 60 0.3845 0.3920 0.4056 0.1475 0.1400 0.1299 75 0.4020 0.4089 0.4156 0.1300 0.1231 0.1199 90 0.4120 0.4220 0.4256 0.1200 0.1100 0.1099 105 0.4220 0.4308 0.4306 0.1100 0.1012 ·0.1049 120 0.4223 0.4310 0.4308 0.1097 0.1010 0.1047 135 0.4225 0.4312 0.4311 0.1095 0.1008 0.1044 Sodium Persulfate 2.35% A.O. Accepts Weight (g} Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Aun #2 Run #3 30 0.3851 0.3986 0.3790 0.1504 0.1299 0.1600 45 0.4052 0.4086 0.3990 0.1303 0.1199 0.1400 60 0.4252 0.4286 0.4206 0.1103 0.0999 0.1184 75 0.4352 0.4386 0.4344 0.1003 0.0899 0.1046 90 0.4551 0.4417 0.4490 0.0804 0.0868 0.0900 105 0.4564 0.4482 0.4528 0.0791 0.0803 0.0862 120 0.4565 0.4484 0.4530 0.0790 0.0801 0.0860 135 0.4567 0.4485 0.4532 0.0788 0.0800 0.0858 128
Table 4-Continued
Dimethyldioxirane 0.47% A.O.
Accepts Weight (g) Rejects Weight (g)
Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.4082 0.3887 0.4074 0.1203 0.1503 0.1281 45 0.4358 0.4223 0.4338 0.0927 0.1167 0.1017 60 0.4487 0.4480 0.4348 0.0798 0.0910 0.1007 75 0.4505 0.4590 0.4642 0.0780 0.0800 0.0713 90 0.4572 0.4636 0.4676 0.0713 0.0754 0.0679 105 0.4661 0.4781 0.4693 0.0624 0.0609 0.0662 120 0.4663 0.4784 0.4694 0.0622 0.0606 0.0661 135 0.4665 0.4790 0.4695 0.0620 0.0600 0.0660 Dimethyldioxirane 1.18% A.O. Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.4074 0.3998 0.3851 0.1246 0.1357 0.1504 45 0.4320 0.4205 0.4105 0.1000 0.1150 0.1250 60 0.4520 0.4453 0.4352 0.0800 0.0902 0.1003 75 0.4 720 0.4753 0.4653 0.0600 0.0602 0.0702 90 0.4820 0.4755 0.4753 0.0500 0.0600 0.0602 105 0.4823 0.4806 0.4781 0.0497 0.0549. 0.0574 120 0.4824 0.4807 0.4785 0.0496 0.0548 0.0570 135 0.4825 0.4808 0.4786 0.0495 0.0547 0.0569 Dimethyldioxirane 2.35% A.O. Accepts Weight (g) Rejects Weight (g) Time Run #1 Run #2 Run #3 Run #1 Run #2 Run #3 30 0.3999 0.4106 0.3886 0.1286 0.1249 0.1504 45 0.4333 0.4431 0.4240 0.0952 0.0924 0.1150 60 0.4505 0.4650 0.4480 0.0780 0.0705 0.0910 75 0.4639 0.4671 0.4634 0.0646 0.0684 0.0756 90 0.4759 0.4818 0.473" 0.0526 0.0537 0.0597 105 0.4879 0.4949 0.4925 0.0406 0.0406 0.0465 120 0.4882 0.4951 0.4929 0.0403 0.0404 0.0461 135 0.4883 0.4954 0.4931 0.0402 0.0401 0.0459 129
Table 5
Percent Acceptsand Rejectsfor Experimental Runs
No Chemical
Accepts %
Time Run #1 Run #2 Run #3 Run #4 Average S.D. C.V.% 30 50.00 56.60 52.85 54.89 53.59 2.84 5.30 45 59.25 64.15 58.15 60.53 60.52 2.61 4.31 60 61. 11 66.04 65.15 62.41 63.68 2.31 3.62 75 65.81 66.64 68.21 66.17 66.71 1.06 1.59 90 68.52 67.92 69.81 69.92 69.04 0.98 1.42 105 72.22 73.50 71. 70 71.28 72.18 0.96 1.33 120 75.12 73.55 73.58 74.60 74.21 0.78 1.05 135 75.20 73.60 75.47 74.65 74.73 0.83 1 .11
Rejects% 30 50.00 43.40 47.15 45.11 46.42 2.84 6.12 45 40.75 35.85 41.85 39.47 39.48 2.61 6.61 60 38.89 33.96 34.85 37.59 36.32 2.31 6.35 75 34.19 33.36 31.79 33.83 33.29 1.06 3.18 90 31.48 32.08 30.19 30.08 30.96 0.98 3.17 105 27.78 26.50 28.30 28.72 27.83 0.96 3.46 120 24.88 26.45 26.42 25.40 25.79 0.78 3.01 135 24.80 26.40 24.53 25.35 25.27 0.83 3.27 130
Hydrogen Peroxide 1.0%
Acxepts "• Rejects%
Time Run ,n Run #2 Run #3 Average 5.0. C.V. % Run #1 Run 112 Run #3 Average 5.0. c.v. % 30 5L12 55.47 50.00 52.20 2.89 5.54 48.88 44.53 50.00 47.80 2.89 6.04 45 58.40 62.89 59.93 60.41 2.28 3.78 41.60 37.11 40.07 39.59 2.28 5.77 60 64.20 66.60 65.00 65.27 1.22 1.87 35.80 33.40 34.99 34.73 1.22 3.52 75 68.09 70.32 68.69 69.03 1. 15 1.67 31.91 29.68 31.31 30.97 1.15 3.73 90 73,68 72.28 74.09 73.35 0.95 1.29 26.32 27 72 25.91 26.65 0.95 3.56 105 74.03 75.42 74.12 74.52 0. 78 1.04 25.97 24.58 25.88 25.48 0. 78 3.05 120 74.33 75.45 74.15 74.64 0.70 0.94 25.67 24.55 25.85 25.36 0.70 2.78 135 74.35 75.H 74.20 74.67 0.69 0.93 25.65 24.53 25.80 25.33 0.69 2.74 Hydrogen Peroxide 2.5% Accepts% Rejects% Time Run #1 Run #2 Run #3 Average 5.0. C.V. % Run #1 Run #2 Run #3 Average S.D. C.V. % 30 50.00 56.62 50.80 52.47 3.61 6.89 50.00 43.38 49.20 47.53 3.61 7.60 45 59.18 64.08 58.37 60.54 3.09 5.10 40.82 35.92 41.63 39.46 3.09 7.83 60 68.46 69.75 65.94 68.05 1.94 2.85 31.54 30.25 34.06 31.95 1.94 6.07 75 72.17 73.04 70. 73 71.98 1.17 1.62 27.83 26.96 29.27 28.02 1. 1 7 4. 16 90 74.03 73.53 71. 78 73.11 1.18 1.62 25.97 26.4 7 28.22 26.89 1.18 4.39 105 76.32 75.23 75.88 75.81 0.55 0. 72 23.68 24.77 24.12 24.19 0.55 2.27 120 77.32 76.58 77.74 77.21 0.59 0.76 22.68 23.42 22.26 22.79 0.59 2.58 135 77.35 76.60 77.78 77.24 0.60 0.77 22.65 23.40 22.22 22. 76 0.60 2.62 Hydrogen Peroxide 5.0% Accepts% Rejects% Time Run #1 Run #2 Run #3 Average S.0. C.V.% Run #1 Run #2 Run #3 Average S.D C.V.% 30 65.97 60.00 61.04 62.34 3.19 5.12 34.03 40.00 38.96 37.66 3.19 8.4 7 45 67.86 63.80 66.60 66.09 2.08 3.14 32.14 36.20 33.40 33.91 2.08 6.13 ,60 71.64 69.43 70.35 70.47 1.11 1.58 28.36 30.57 29.65 29.53 1.11 3.76 75 74.53 72.55 73.17 73.42 1.01 1.38 25.47 27.45 26.83 26.58 1.01 3.81 90 75.43 75.23 74.03 74.90 0.76 1.01 24.57 24.76 25.97 25.10 0.76 3.03 105 77.58 77.13 76.05 76.92 0.79 1.02 22.42 22.87 23.95 23.08 0.79 3.41 120 79.32 78.59 77.90 78.60 0.71 0.90 20.68 21.41 22.10 21.40 0.71 3.32 135 ·79.35 78.61 77.92 78.63 0.72 0.91 20.65 21.39 22.08 21.37 0.72 3.35 131
Tal• 5-ue
Ammonium Persulfate 0.47% A.O.
Accepts o/. Rejects o/.
Time Run 1#1 Run 1#2 Run #3 Average S.D. C.V.% Run 1#1 Run #2 Run #3 Average s.o. c.v. % 30 60.52 62.89 57.32 60.24 2.80 4.64 39.48 37.11 42.68 . 39.76 2.80 7.03 45 64.28 66.60 61.64 64.17 2.48 3.87 35.71 33.-rn 38.36 35.82 2.48 6.93 60 71.80 72.17 68.32 70.76 2.12 3.00 28.20 27.83 31.68 29.24 2.12 7.27 75 73.68 74.03 71.17 72.96 1.56 2.14 26.32 25.97 28.83 27.04 1.56 5.77 90 · 75.56 74.13 74.05 74.58 0.85 1.14 24.-14 25.87 25.95 25.42 0.85 3.34 105 77.35 75.98 75.74 76.36 0.87 1.14 22.oS 24.02 24.26 23.64 0.87 3.67 120 77.40 76.02 75.80 76.41 0.87 1.14 22.60 23.98 24.20 23.59 0.87 3.68 135 77.44 76.05 75.84 76.44 0.87 1. 14 22.56 23.95 24. 16 23.56 0.87 3.o9 Ammonium Persulfate 1.18% A.O. Accepts% Re1ects % Time Run 111 Run #2 Run li3 Average S.D. C.V% Run ill Run �2 Run ;13 Average s.o. C.\J. �� 30 66.29 62.54 69.92 66.25 3.69 5.57 33. 71 37.45 30.08 33. 75 3.69 10.92 45 68.16 66.29 71.80 68. 75 2.80 4.08 31.84 33. 71 28.20 31.25 2.80 8.37 60 73. 78 70.90 73.68 72. 79 1.03 2.25 26.22 29.10 26.32 27.21 1.63 6.01 75 75.66 73.23 74.48 74.46 1.22 1.63 24.34 26.77 25.52 25.54 1 .22 4. 76 90 77.53 76.23 75.56 76.44 1.00 1.31 22.4 7 23.77 24 43 23.56 1.00 4.23 105 78.40 77.53 79.32 78.42 0.90 1. 14 20.60 22.-l7 21.58 21.55 0.94 4.3-l 120 81.27 81.02 80.20 80.83 0.56 0.69 18. 73 18.98 19.80 19.17 0.56 2.92 135 81.33 81.07 80.22 80.87 0.58 0.72 18.67 18.93 19. 78 19.13 0.58 3.04 Ammonium Persulfate 2.35% A.O. Accepts% Rejects% Time Run 1#1 Run 1#2 Run :t3 Average S.D. C.V.% Run #1 Run 112 Run 1#3 Average s.o. c.v. % 30 68.05 70.32 72.64 70.34 2.30 3.26 31.95 29.68 27.36 29.66 2.30 7.74 45 71.80 74.66 75.55 74.00 1.96 2.65 28.20 25.34 24.45 26.00 1.96 7.54 60 75.56 77.74 79.21 77.50 1.84 2.37 24.44 22.26 20.79 22.50 1.84 8.16 75 79.32 81.45 81.10 80.62 1.14 1.42 20.68 18.55 18.90 19.38 1.14 5.89 90 81.20 83.30 82.99 82.50 1. 13 1.37 18.80 16.70 17.01 17.50 1.13 6.48 105 83.38 85.16 84.88 84.47 0.96 1.13 16.62 14.84 15.12 15.53 0.96 6.16 120 83.81 85.25 84.98 84.68 0.77 0.90 16.19 14.75 15.02 15.32 0.7i 5.00 135 84.01 85.30 85.10 84.80 0.69 0.82 15.99 14.70 14.90 15.20 0.69 4.57 132 -
Tabla 5-Contlnuad
Sodium Persulfate 0.47% A.O.
Acepts "• Rejets o
Tme Run #1 Run #2 Run #3 Average s.o. c.v. o Run #1 Run 12 Run #3 Average S.D. C.V. �'o 30 65.60 62.75 60.32 62.89 2.54 4.20 34.40 37.25 39.68 37.11 2.64 7.12 45 70.17 68.25 66.61 68.34 1.78 2.51 29.83 31.75 33.39 31.66 1. 78 5.53 60 74.03 73.36 71.55 72.98 1.28 1. 76 25.97 26.64 28.45 27.02 1.28 4.75 75 75.88 75.02 73.69 74.86 1.1 o 1.47 24.12 24.98 26.31 25.14 1.10 4.39 90 76.74 76.21 74.57 75.84 1.13 1.49 23.26 23. 79 25.43 24. 16 1. 13 4.58 105 77.52 77.69 76.15 77.12 0.84 1.09 22.48 22.31 23.85 22.88 0.84 3.59 120 77.55 77.71 76. 18 77. 15 0.84 1.09 22.45 22.29 23.82 22.85 0.84 3.58 135 77.58 77.75 76.22 77.18 0.84 1.09 22.42 22.25 23. 78 22.82 0.84 3.68 Sodium Persulfate 1.18% A.O. Accepts¾ Re1ec1s % 0 Tme Run #1 Run 1;2 Run 13 Average S.D. C.V.% Run #1 Run #2 Run �3 Average S.D. C.V. � 30 64.29 65.12 69.92 66.44 3.04 4.57 34.88 34.88 30.08 33.28 2.77 8.33 45 67.92 68.84 72.88 69.88 2.64 3.78 31. 16 31. 16 27 12 29.81 2.33 7.82 60 72.28 73.68 75. 75 73.90 1. 75 2.36 27. 72 26.32 24.25 26. 10 1. 75 6.69 75 75.56 76.87 77.61 76.58 1.04 1.35 24.44 23.13 22.39 23.32 1.04 4. 45 90 77.44 79.32 79.48 78.75 1.13 1.44 22.56 20.58 20.52 21.25 1.13 5.34 105 79.33 80.97 80.41 80.24 0.83 1 .04 20.67 19.03 19.59 19.76 0.83 4.22 120 79.38 81.02 80.45 80.28 0.83 1.04 20.62 18.98 19.55 19.72 0.83 4.22 135 79.42 81.05 80.50 80.32 0.83 1.03 20.58 18.95 19.50 19.68 0.83 4.21 Sodium Persulfate 2.35% A.O. Accepts ¾ Re1ects% Tme Run #1 Run #2 Run #3 Average S.D. C.V.% Run 11 Run 12 Run 13 Average S.D. c.v. % 30 71.91 75.42 70.32 72.55 2.51 3.60 28.09 24.58 29.68 27.45 2.51 9.51 45 75.66 77.32 74.03 75.67 1.55 2.17 24.34 22.68 25.97 24.33 1.65 6. 76 60 79.40 81.10 78.04 79.51 1.53 1.93 20.6 18.9 21.96 20.49 1.53 7.48 75 81.27 82.99 80.59 81.62 1.24 1.52 18.73 17.01 19.41 18.38 1.24 6.73 90 84.98 83.58 83.31 83.96 0.90 1.07 15.02 16.42 16.69 16.04 0.90 5.59 105 85.22 84.81 84.01 84.68 0.62 0.73 14.78 15. 79 15.99 15.52 0.65 4.18 120 85.24 84.85 84.05 84.71 0.61 0.72 14.76 15.15 15.95 15.29 0.61 3.97 135 , 85.28 84.86 84.08 84.74 0.61 0.72 14.72 15.14 15.92 15.26 0.61 3.99 133
Tables-continued
Oimethyldioxirane 0.47% A.O.
Accepts"'• Rejects o/.
Time Run #1 Run #2 Run #3 Average S.O. c.v. "· Run 111 Run #2 Run #3 Average S.D. c.v. % 30 77.24 72.12 76.07 75.14 2.68 3.57 22.76 27.88 23.93 24.86 2.68 10.79 45 82.46 78.35 81.01 80.61 2.08 2.59 17.54 21.65 18.99 19.39 2.08 10.75 60 84.90 83.11 81.19 83.07 1.86 2.23 15.10 16.89 18.81 16.93 1.86 10.96 75 85.25 85.16 86.69 85.70 0.86 1.00 14.75 14.84 13.31 14.30 0.86 6.00 90 86.50 86.02 87.32 86.61 0.66 0.76 13.50 13.98 12.68 13.39 0.66 4.91 105 88.20 88.70 87.63 88.18 0.54 0.61 11.80 -11.30 12.37 11.82 0.54 4.53 120 88.24 88.75 87.66 88.22 0.55 0.62 11. 76 11.25 12.34 11.78 0.55 4.63 135 88.26 88.86 87.68 88.27 0.59 0.67 11. 74 11.14 12.32 11.73 0.59 5.03 Dimethyldioxirane 1.18% A.O. Accepts% Rejects% Time Run #1 Run lt2 Run #3 Average s.o. c.v. % Aun /t1 Aun lt2 Aun lt3 Average S.O. C.'J. ,l.� 30 76.58 74.66 71.91 74.38 2.35 3.16 23.42 25.34 28.09 25 62 2.35 9. 16 45 81.20 78.53 76.66 78.80 2.28 2.90 18.80 21.47 23.34 21.20 2.28 10.,5 60 84.96 83.15 81.27 83.13 I. 85 2.22 15.04 16.85 18. 73 16.87 1.85 1 0.94 75 88.72 88.76 86.89 88.12 1.07 1.21 11.28 11.24 13.11 11.88 1.07 8.99 90 90.60 88.80 88.76 89.39 1.05 1. 18 9.40 11.20 11.24 10.61 1.05 9.90 105 90.65 89.74 89.29 89.89 0.69 0.77 9.35 10.26 10.71 10.11 0.69 6.86 120 90.67 89.76 89.35 89.93 0.68 0.75 9.33 10.24 10.65 10.07 0.68 6. i' 1 135 90.70 89.78 89.38 89.95 0.68 0. 75 9.30 10.22 10.62 10.05 0.68 6. 74 Dimethyldioxirane 2.35% A.O. Accepts % Rejects% Time Run #1 Run #2 Run #3 Average S.D. C.V.% Aun 111 Aun #2 Aun #3 Average S.D. c.v. �� 30 75.67 76.68 72.09 74.81 2.41 3.22 24.33 23.32 27.91 25.19 2.41 9.58 45 81.99 82.75 78.66 81.13 2.18 2.68 18.01 17.25 21.34 18.87 2.18 11.53 60 85.25 86.84 83.12 85.07 1.87 2.19 14.75 13.16 16.88 14.93 1.87 12.50 75 87.77 87.23 85.97 86.99 0.92 1.06 12.23 12.77 14.03 13.01 0.92 7.10 90 90.05 89.98 88.93 89.65 0.63 0.70 9.95 10.02 11.07 10.35 0.63 6.06 105 92.31 92.41 91.38 92.03 0.57 0.62 7.69 7.59 8.62 7.97 0.57 7.13 120 92.37 92.45 91.45 92.09 0.56 0.60 7.63 7.55 8.55 7.91 0.56 7.03 135 92.40 92.51 91.48 92.13 0.57 0.61 7.60 7.49 8.52 7.87 0.57 7.19 ' Appendix J
CSF, Tensile and Tear Values
134 13·5
Table 6
Freeness Values for Experim ental Runs
Canandian Standard Freeness Values (CSF)
Chemical Chem. Cone. Revolutions 0 15000 18000
No Chemical Run1 674 500 440 Run 2 680 510 430 Run 3 675 505 425 Run 4 670 495 445 Average 674.75 502.50 435.00
0 15000 18000 Oxone 0.47% Run 1 674 520 430 Run 2 660 514 418 Run 3 656 510 422 Average 663.33 514.67 423.33
0 15000 18000 1.18% Run1 675 525 430 Run2 670 522 425 Run 3 673 518 420 Average 672.67 521.67 425.00
0 15000 18000 2.35% Run1 675 515 430 Run2 680 525 425 Run3 680 520 425 Average 678.33 520.00· 426.67
0 15000 18000 Sodium Persulfate 0.47% Run1 675 485 380 Run2 677 475 385 Run3 679 490 390 Average 677.00 483.33 385.00
0 15000 18000 1.18% Run1 680 460 370 Run2 675 465 374 Run3 675 458 380 Average 676.67 461.00 374.67
0 15000 18000 2.35% Run 1 665 400 360 Run2 670 410 360 Run3 675 420 367 Average 670.00 410.00 362.33 136
Table 6-Continued
Canandian Standard Freeness Values (CSF)
Chemical Chem. Cone. Revolutions 0 15000 18000
Am m onium Persulfate 0.47% Run 1 680 472 355 Run 2 675 476 350 Run3 670 480 360 Average 675 .00 476.00 355.00
0 15000 18000 1.18% Run 1 668 460 360 Run 2 672 465 360 Run 3 670 470 367 Average 670.00 465.00 362.33
0 15000 18000 2.35% Run 1 678 425 375 Run2 680 425 377 Run3 670 415 380 Average 676.00 421.67 377.33
0 15000 18000 Hydrogen Peroxide 0.47% Run 1 675 520 432 Run2 672 526 425 Run3 668 518 430 Average 671 .67 521.33 429.00
0 15000 18000 1.18% Aun 1 675 530 420 Aun2 672 535 425 Aun3 665 532 423 Average 670.67 532.33 422.67
0 15000 18000 2.35% Aun 1 675 530 445 Aun2 682 520 440 � Run3 678 420 438 Average 678.33 490.00 441.00 137
Table 7
Tensile Index for Experimental Runs
Ten sile Index Values (Nm"2)/g
Chemical Chem. Cone. Revolutions Run 1 Run2 Run 3 Average S.D.
No Chemical 0 17.98 17.59 17.84 17.80 0.20 r5ooo 43.43 43.76 44.36 43.85 0.47 18000 37.65 37.84 38.47 37.99 0.43
Oxone 0.47% Run 1 Run 2 Run 3 Average 0 10.86 13.13 12.07 12.02 1.14 15000 30.28 29.78 27.55 29.20 1.45 18000 35.08 33.26 32.85 33. 73 1.19
1.18% Run 1 Run 2 Run3 Average 0 9.90 10.75 11.43 10.69 0.77 15000 31.28 30.01 32.24 31.18 1 .12 18000 30.63 26.60 27.43 28.22 2.13
2.35% Run 1 Run 2 Run3 Average 0 12.05 12.14 11.62 11.94 0.28 15000 38.16 34.37 31.17 34.57 3.50 18000 30.09 29.48 29.94 29.84 0.32
Sodium Persulfate 0.47% Run 1 Run 2 Run 3 Average 0 8.20 10.64 9.27 9.37 1.22 15000 29.48 30.32 30.55 30.12 0.56 18000 37.06 35.28 33.28 35.21 1.89
1.18% Run 1 Run 2 Run 3 Average 0 6.98 6.42 6.49 6.63 0.31 15000 31.49 33.30 30.81 31.87 1.29 18000 27.60 30.46 30.67 29.58 1.72
2.35% Run 1 Run 2 Run 3 Average • 0 6.73 6.89 7.76 7.13 0.55 15000 36.58 34.54 33.69 34.94 1.49 18000 28.11 25.96 27.08 27.05 1.08 138
Table 7- Continued
Tensile Index Values (Nm"2)/g
Chemical Chem. Cone Revolutions Run 1 Run 2 Run 3 Average S.O.
Ammonium Persulfate 0.47% 0 10.03 10.48 8.50 9.67 1.04 15000 32.30 30.67 28.33 30.43 2.00 18000 35.27 33.30 33.70 34.09 1.04
1.18% Run 1 Run 2 Run 3 Average 0 13.82 12.64 13.16 13.21 0.59 15000 32.56 33.85 30.90 32.44 1.48 18000 30.20 30.87 29.58 30.22 0.65
2.35% Run 1 Run 2 Run 3 Average 0 11. 14 11.87 9.45 10.82 1.24 15000 32.04 32.74 33.45 32.74 0.71 18000 29.96 30.13 28.36 29.48 0.!8
Hydrogen Peroxide 0.47% Run 1 Run 2 Run 3 Average 0 15.75 16.06 14.82 15.54 0.65 15000 35.52 35.77 35.75 35.68 0.14 18000 38.25 36.49 38.99 37.91 1.28
1.18% Run 1 Run 2 Run 3 Average 0 10.03 11.26 10.07 10.45 0.70 15000 39.35 37.46 38.36 38.39 0.95 18000 33.60 34.05 35.63 34.43 1.07
2.35% Run 1 Run 2 Run 3 Average 0 16.05 15.04 15.60 15.56 0.51 15000 41.02 38.75 41.55 40.44 1.49 18000 34.37 36.88 37.13 36.13 1.53 -- Table 8
Tensile Index Values 139 Tensile Values Without Chemicats
no chem 1 0 rev no chem 1 15000 rev no chem 1 18000 rev
59.34 1.917 59.58 3.989 59.34 3.259 1.705 3.611 3.463 avg 1.811 avg 3.800 avg 3.361 tensile Index 19.953 tensile Index 41.699 tensile Index 37.031 59.34 1.944 59.34 3.952 59.82 3.605 1.834 3.771 3.454 avg 1.889 avg 3.862 avg 3.530 tensile Index 20.813 tensile Index 42.545 tensile Index 38.576 61.03 1.323 61.03 4.440 61.03 3.640 1.385 4.126 3.662 avg 1.354 avg 4.283 avg 3.651 tensile Index 14.505 tensile Index 45.883 tensile Index 39.112 60.55 1.348 60.55 4.016 60.55 3.205 1.259 3.928 3.060 avg 1.304 avg 3.972 avg 3.133 tensile Index 14.075 tensile Index 42.888 tensile Index 33.824 59.34 1.820 59.34 4.123 59.34 3.666 1.914 3.888 3.545 avg 1.867 avg 4.006 avg 3.606 tensile index 20.570 tensile index 44.132 tensile index 39.725 avg. ten. ind. 17.983 avg. ten. ind. 43.430 avg. ten. ind. 37.654
nc 2 0 rev nc 2 15000 rev nc 2 18000 rev 59.58 1.201 59.58 3.703 59.58 3.109 1.678 3.813 3.520 avg 1.440 avg 3.758 avg 3.315 tensile Index 15.796 tensile Index 41.238 tensile Index 36.372 59.82 2.002 60.06 4.023 59.82 3.611 1.989 3.699 3.512 avg 1.996 avg 3.861 avg 3.562 tensile Index 21.810 tensile Index 42.030 tensile Index 38.925 61.03 1.389 61.03 4.611 60.79 3.666 1.423 4.130 3.787 avg 1.406 avg 4.371 avg 3.727 tensile Index 15.062 tensile Index 46.820 tensile Index 40.079 60.55 1.357 60.55 4.116 60.30 3.195 1.289 4.035 3.101 avg 1.323 avg 4.076 avg 3.148 tensile Index 14.285 tensile Index 44.006 tensile Index 34. 132 59.58 1.923 59.34 4.200 59.82 3.679 1.903 3.916 3.587 avg 1.913 avg 4.058 avg 3.633 tensile Index 20.992 tensile Index 44.710 tensile Index 39.707 avg. ten. Ind. 17.589 avg. ten. ind. 43.761 avg. ten. Ind. 37.843
nc 3 0 rev nc 3 15000 rev nc 3 18000 rev 59.82 1.289 59.82 3.777 59.82 3.098 1.712 3.924 3.631 avg 1.501 avg 3.851 avg 3.365 tensile Index 16.400 tensile Index 42.084 tensile Index 36.77 59.82 2.110 59.82 3.987 59.58 3.676 2.098 3.756 3.543 avg 2.104 avg 3.872 avg 3.610 tensile Index 22.996 tensile Index 42.313 tensile Index 39.61 60.79 1.349 60.79 4.569 60.55 3.723 1 .394 4.218 3.747 avg 1.372 avg 4.394 avg 3.735 tensile Index 14.751 tensile Index 47.252 tensile Index 40.33 60.55 1.345 60.79 4.241 60.55 3.256 1 .278 4.111 3.171 avg 1.323 avg 4.176 avg 3.214 tensile Index 14.285 tensile lndlex 44.913 tensile lndlex 34.70 60.06 1.919 59.82 4.183 60.06 3.767 1.899 4.098 3.751 avg 1.909 avg 4.141 avg 3.759 tensile Index 20.781 t-i1e lndlex 45.253 tensile Index 40.92 avg. ten. Ind. 17.842 avg. ten. Ind. 44.363 avg. ten. ind. 38.47 Table a-Continued
Tensile Values 0.47% 140
oxone 1 0 rev oxone 1 15000 rev oxone 1 18000 rev
61.03 0.867 61.03 2.591 61.76 3.393 0.875 2.387 3.785 avg 0.871 avg 2.489 avg 3.589 tensile Index 9.332 tensile Index 26.66 tensile Index 37.99 61.03 1.450 61.52 3.342 60.30 3.605 1.321 3.203 3.479 avg 1.386 avg 3.273 avg 3.542 tensile Index 14.843 tensile Index 34.78 tensile Index 38.40 60.30 0.964 60.55 2.357 59.82 2.773 0.966 2.389 2.926 avg 0.965 avg 2.373 avg 2.850 tensile Index 10.463 tensile Index 25.62 tensile Index 31.14 60.55 1.114 59.34 3.232 60.55 3.189 1.074 3.007 3.318 avg 1.094 avg 3.120 avg 3.254 tensile Index 11.813 tensile Index 34.37 tensile Index 35.13 59.82 0.827 60.79 2.921 60.55 3.146 0.609 2.647 2.915 avg · 0.718 avg 2.784 avg 3.031 , tensile Index 7.847 tensile Index 29.94 tensile Index 32.72 avg. ten. ind. 10.860 avg. ten. ind. 30.28 avg. ten. ind. 35.08
oxone 2 0 rev oxone 2 15000 rev oxone 2 18000 rev 60.06 1.361 59. .58 3.107 59.82 3.197 1.136 2.997 3.065 avg 1.249 avg 3.052 avg 3.131 tensile Index 13.591 tensile Index 33.
oxone 3 0 rev oxone 3 15000 rev oxone 3 18000 rev 59.82 1.115 60.55 2.185 59.82 2.717 1.058 2.214 2.858 avg 1.087 avg 2.200 avg 2.788 tensile Index 11.87 tensile Index 23.75 tensile Index 30.47 61.03 1.212 59.82 2.654 60.06 2.869 1.258 2.589 2.916 avg 1,235 avg 2.622 avg 2.893 tensile Index 13.23-- • tensile Index 28.65 tensile Index 31.49 60.79 1.098 60.79 2.954 60.79 3.054 1.154 2.963 3.127 avg 1.126 avg 2.959 avg 3.091 tensile Index 12.11 tensile Index 31.82 tensile Index 33.24 60.55 1.11 60.55 2.369 60.55 3.096 1.214 2.387 3.122 avg 1.162 avg 2.378 avg 3.109, tensile Index 12.55 tensile Index 25.68 tensile Index 33.57 60.06 0.989 60.06 2.584 60.06 3.222 0.957 2.536 3.302 avg 0.973 avg 2.560 avg 3.262 tensile Index 10.59 tensile Index 27.87 tensile Index 35.51 avg. ten. ind. 12.07 avg. ten. ind. 27.55 avg. ten. ind. 32.85 Table 8-Continued
Tensile Values 1.18"• 141
oxone 1 0 rev oxone 1 15000 rev oxone 1 18000 rev
61.76 1.039 60.79 2.397 60.79 2.448 0.749 2.537 2.438 avg 0.894 avg 2.467 avg 2.443 tensile Index 9.464 tensile Index 26.53 tensile Index 26.275 61.76 0.738 59.82 3.020 61.52 3.082 0.762 3.025 3.514 avg 0.750 avg 3.023 avg 3.298 tensile Index 7.943 tensile Index 33.03 tensile Index 35.049 60.30 1 .052 59.82 2.856 59.34 2.693 1.267 3.058 2.588 avg 1.160 avg 2.957 avg 2.641 tensile Index 12.572 tensile Index 32.32 tensile Index 29.093 59.58 0.918 60.55 3.170 61.27 3.160 0.926 3.015 3.187 avg 0.922 avg 3.093 avg 3.174 tensile Index 10.118 tensile Index 33.39 tensile Index 33.864 60.55 0.789 60.79 2.929 61.03 2.797 0.950 2.859 2.596 avg 0.870 avg 2.894 avg 2.697 tensile Index 9.390 tensile Index 31.13 tensile Index 28.887 avg. ten. ind. 9.897 avg. ten. ind. 31.28 avg. ten. ind. 30.633
oxone 2 0 rev oxone 2 15000 rev oxone 2 18000 rev 59.34 0.848 60.55 2.722 60.55 2.312 0.873 2.689 2.356 avg 0.860 avg 2.706 avg 2.334- tensile Index 9.478 tensile Index 29.213 tensile Index 25.202 59.34 1.1 01 60.30 3.215 60.79 2.512 1.058 2.958 2.498 avg 1.080 avg 2.969 avg 2.505 tensile Index 11.894 tensile Index 32.191 tensile Index 26.941 59.34 1.004 60.79 2.457 59.58 2.362 1.106 2.443 2.388 avg 1.055 avg 2.450 avg 2.375 tensile Index 11.624 tensile Index 26.350 tensile Index 26.062 60.06 0.577 60.55 2.945 60.79 2.555 0.591 2.938 2.601 avg 0.584 avg 2.942 avg 2.578 tensile Index 6.356 tensile Index 31.761 tensile Index 27.727 61.03 1.391 60.06 2.823 59.82 2.456 1.299 2.791 2.499 avg 1.345 avg 2.807 avg 2.478 tensile Index 14.409 tensile Index 30.556 tensile Index 27.078 avg. ten. ind. 10.752 avg. ten. Ind. 30.014 avg. ten. ind. 26.602
oxone 3 0 rev oxone 3 15000 rev oxone 3 18000 rev 60.55 1.168 60.55 2.898 61.03 2.682 1.145 2.861 2.642 avg 1.157 avg 2.880 avg 2.662 tensile Index 12.488 tensile Index 31.092 tensile Index 28.517 61.03 1.221 59.82 2.786 60.55 2.538 1.134 2.816 2.514 avg 1.178 avg 2.801 avg 2.526 -- tensile Index 12.614 tensile Index 30.613 tensile Index 27.275 60.79 1.115 61.52 3.235 60.79 2.624 1.096 3.311 2.655 avg 1.106 avg 3.273 avg 2.640 tensile Index 11.890 tensile Index 34.784 tensile Index 28.388 60.55 1.165 61.03 3.195 59.58 2.458 1.132 3.185 2.431 avg 1.149 avg 3.190 avg 2.445 tensile Index 12.401 tensile Index 34.174 tensile Index 26.825 60.06 0.698 59.34 2.756 60.55 2.441 0.729 2.783 2.406 avg 0.714 avg 2.770 avg 2.424 tensile Index 7.767 tensile Index 30.514 tensile Index 26.168 avg. ten. ind. 11.432 avg. ten. Ind. 32.235 avg. ten. Ind. 27.435 Table a-Continued
Tensile Values 2.35% 142
oxone 1 0 rev oxone 1 15000 rev oxone 1 18000 rev
60.30 1. 138 60.30 3.683 59.82 2.749 1.144 3.612 2.744 avg 1.141 avg 3.648 avg 2.747 tensile Index 12.371 tensile Index 39.548 tensile Index 30.018 59.82 1.364 61.52 2.958 59.34 2.821 1.082 2.746 2.899 avg 1.223 avg 2.852 avg 2.860 tensile Index 13.367 tensile Index 30.309 tensile Index 31.511 60.55 0.985 61.03 3.726 .61.27 2.317 0.899 3.712 2.311 avg 0.942 avg 3.719 avg 2.314 tensile Index 10.171 tensile Index 39.841 tensile Index 24.692 60.55 0.880 61.27 3.731 59.58 2.961 0.901 3.689 3.093 avg 0.891 avg 3.710 avg 3.027 tensile Index 9.615 tensile Index 39.589 tensile Index 33.217 60.55 1.498 61.52 3.923 60.55 2.829 1.230 3.890 2.918 avg 1.364 avg 3.907 avg 2.874 tensile Index 14.728 tensile Index 41.516 tensile Index 31.027 avg. ten. ind. 12.051 avg. ten. ind. 38.161 avg. ten. ind. 30.093
oxone 2 0 rev oxone 2 15000 rev oxone 2 18000 rev 61.52 1.149 60.06 2.972 59.58 2.666 1.112 2.905 2.685 avg 1.131 avg 2.939 avg 2.676 tensile Index 12.014 tensile Index 31.988 tensile Index 29.360 61.03 1.240 61.76 3.680 59.82 2.706 1.030 3.610 2.771 avg 1.135 avg 3.645 avg 2.969 tensile Index 12.159 tensile Index 38.586 tensile Index 32.450 59.58 1.125 60.55 3.283 61.52 2.513 1.493 3.221 2.496 avg 1.309 avg 3.252 avg 2.505 tensile Index 14.364 tensile Index 35.114 tensile Index 26.616 61.27 1.154 60.79 3.227 60.06 2.679 1.444 3.194 2.685 avg 1.299 avg 3.211 avg 2.682 tensile Index 13.861 tensile Index 34.529 tensile Index 29.1"96 59.58 0.797 61.03 2.993 60.06 2.714 0.717 2.917 2.761 avg 0.757 avg 2.955 avg 2.738 tensile Index 8.307 tensile Index 31.656 tensile Index 29.800 avg. ten. Ind. 12.141 avg. ten. Ind. 34.375 avg. ten. Ind. 29.484
oxone 3 O rev oxone 3 15000 rev oxone 3 18000 rev 59.58 0.777 60.55 2.682 59.82 3.111 0.798 2.699 2.983 avg 0.788 avg 2.691 avg 3.047 tensile Index 8.642 tensile Index 29.051 tensile Index 33.302 60.55 1.266 60.79 3.311 59.58 2.691 1.202 3.295 2.706 avg 1.234 avg 3.303 avg 2.699 -- tensile Index 13.324 tensile Index 35.524 tensile Index 29.612 61.03 1.256 60.79 3.225 61.03 2.289 1 .233 3.282 2.273 avg 1.245 avg 3.254 avg 2.281 tensile Index 13.332 tensile Index 34.992 tensile Index 24.436 60.55 0.996 60.30 2.581 60.55 2.981 1.023 2.553 2.966 avg 1.010 avg 2.567 avg 2.974 tensile Index 10.900 tensile Index 27.833 tensile Index 32.107 60.55 1.111 60.55 2.615 60.06 2.769 1.091 2.656 2.783 avg 1.101 avg 2.636 avg 2.776 tensile Index 11.888 tensile Index 28.457 tensile Index 30.219 avg. ten. ind. 11.617 avg. ten. Ind. 31.171 avg. ten. ind. 29.935 Table a-Continued
Tensile Values 0.47% 143
S.P. 1 0 rev S.P. 1 15000 rev S.P. 1 18000 rev
61.76 0.674 61.27 2.652 61.52 3.444 0.672 2.685 3.412 avg 0.673 avg 2.669 avg 3.428 tensile Index 7.121 tensile Index 28.475 tensile Index 36.431 60.30 0.580 61.52 3.173 60.79 3.318 0.578 3.155 3.291 avg 0.579 avg 3.164 avg 3.305 tensile Index 6.276 tensile Index 33.625 tensile Index 35.540 60.30 0.741 60.55 2.889 . 61.52 3.646 0.742 2.857 3.701 avg 0.742 avg 2.873 avg 3.674 tensile Index 8.041 tensile Index 31.022 tensile Index 39.040 60.55 0.771 59.58 2.368 61.76 3.447 0.774 2.299 3.511 avg 0.773 avg 2.334 avg 3.479 tensile Index 8.342 tensile Index 25.607 tensile Index 36.829 61.27 1.105 59.82 2.634 61.27 3.493 0.995 2.610 3.525 avg 1.050 avg 2.622 avg 3.509 tensile Index 11.204 tensile Index 28.657 tensile Index 37.444 avg. ten. ind. 8.197 avg. ten. ind. 29.477 avg. ten. ind. 37.057
S.P. 2 0 rev S.P. 2 15000 rev S.P. 2 18000 rev 61.76 0.738 60.06 2.778 60.30 3.056 0.736 2.805 3.068 avg 0.737 avg 2.792 avg 3.062 tensile Index 7.801 tensile Index 30.388 tensile Index 33.200 61,76 0.769 60.55 2.991 61.52 3.596 0.762 3.012 3.633 avg 0.765 avg 2.969 avg 3.615 tensile Index 8.103 tensile Index 32.058 tensile Index 38.413 61.27 1.076 61.27 2.695 60.55 3.286 1.123 2.715 3.293 avg 1.100 avg 2.705 avg 3.290 tensile Index 11.733 tensile Index 28.865 tensile Index 35.519 61.27 1.232 59.82 2.771 61.03 3.522 1.258 2.757 3.485 avg 1.245 avg 2.764 avg 3.504 tensile Index 13.285 tensile Index 30.209 tensile Index 37.532 61.52 1.149 60.06 2.769 59.34 2.869 1.160 2.753 2.896 avg 1.155 avg 2.761 avg 2.883 tensile Index 12.269 tensile Index 30.056 tensile Index 31.759 avg. ten. ind. 10.638 avg. ten. Ind. 30.315 avg. ten. Ind. 35.285
S.P. 3 0 rev S.P. 3 15000 rev S.P. 3 18000 rev 60.55 0.878 60.55 2.959 59.58 2.965 0.872 2.981 2.948 avg 0.875 avg 2.970 avg 2.957 tensile Index 9.444 tensile Index 32.069 tensile Index 32.443 60.30 0.775 59.58 2.380 60.55 3.321 0.773 2.350 3.317 = avg 0.774 avg 2.365 avg 3.319 ° tensile Index_ 8'.389 tensile Index 25.952 tensile Index 35.838 60.06 0.762 61.76 3.184 61.52 3.074 0.768 3.205 3.056 avg 0.765 avg 3.195 avg 3.065 tensile Index 8.328 tensile Index 33.817 tensile Index 32.573 60.55 0.881 60.06 2.812 61.27 3.012 0.885 2.844 3.038 avg 0.883 avg 2.828 avg 3.025 tensile Index 9.537 tensile Index 30.785 tensile Index 32.279 61.03 0.986 61.52 2.859 61.76 3.125 0.999 2.814 3.163 avg 0.993 avg 2.837 avg 3.144 tensile Index 10.632 tensile Index 30.145 tensile Index 33.283 avg. ten. ind. 9.266 avg. ten. ind. 30.554 avg. ten. ind. 33.283 Table 8-Continued
Tensile Values 1.18o/o 144
S.P. 1 O rev S.P. 1 15000 rev S.P. 1 18000 rev
61.27 0.684 60.30 2.872 60.30 2.419 0.666 2.813 2.411 avg 0.675 avg 2.843 avg 2.415 tensile Index 7.203 tensile Index 30.820 tensile Index 26. 185 60.79 0.553 61.76 2.678 61.52 3.388 0.525 2.717 3.368 avg 0.539 avg 2.698 avg 3.378 tensile Index 5.797 tensile Index 28.556 tensile Index 35.899 59.82 0.489 59.58 2.835 59.82 2.263 0.506 2.789 2.302 avg 0.498 avg 2.812 avg 2.283 tensile Index 5.437 tensile Index 30.857 tensile Index 24.946 61.27 0.781 60.55 3.460 60.79 2.246 0.736 3.411 2.295 avg 0.759 avg 3.436 avg 2.271 tensile Index 8.094 tensile Index 37 .095 tensile Index 24.419 61.27 0.776 61.52 2.846 60.79 2.459 0.795 2.819 2.481 avg 0.786 avg 2.833 avg 2.470 tensile Index 8.382 tensile Index 30.102 tensile Index 26.565 avg. ten. ind. 6.983 avg. ten. ind. 31.486 avg. ten. ind. 27.603
S.P. 2 0 rev S.P. 2 15000 rev S.P. 2 18000 rev 60.55 0.525 60.55 3.203 60.79 2.776 0.510 3.285 2.770 avg 0.518 avg 3.244 avg 2.773 tensile Index 5.588 tensile Index 35.028 tensile Index 29.824 60.06 0.628 59.58 2.777 60.79 2.829 0.651 2.805 2.855 avg 0.640 avg 2.969 avg 2.842 tensile Index 6.961 tensile Index 32.580 tensile Index 30.566 61.27 0.617 60.55 3.395 60.55 2.797 0.641 3.417 2.814 avg 0.629 avg 3.406 avg 2.806 tensile Index 6.712 tensile Index 36.777 tensile Index 30.293 60.30 0.558 61.27 2.674 61.27 3.267 0.532 2.602 3.227 avg 0.545 avg 2.638 avg 3.247 tensile Index 5.909 tensile Index 28.150 tensile Index 34.648 60.79 0.650 60.55 3.130 80.06 2.494 0.641 3.158 2.458 avg 0.646 avg 3.144 avg 2.476 tensile Index 6.942 tensile Index 33.948 tensile Index 26.953 avg. ten. ind. 6.423 avg. ten. Ind. 33.296 avg. ten. Ind. 30.457
S.P. 3 0 rev S.P. 3 15000 rev S.P. 3 18000 rev 61.27 0.572 59.82 2.919 61.27 2.818 0.596 2.957 2.862 avg 0.584 avg 2.938 avg 2.840 tensile Index 6.232 tensile Index 32.111 tensile Index 30.305 61.03 0.658 61.76 2.677 61.27 3.188 0.625 2.619 3.199 avg 0.642 avg 2.648 avg 3.194 tensile Index 6.872 tensile Index 28.032 tensile Index 34.077 61.27 0.698 61.03 2.615 81.3 2.991 0.727 2.626 2.982 avg 0.713 avg 2.621 avg 2.987 tensile Index 7.603 tensile Index 28.073 tensile Index 31.853 60.79 0.558 60.55 3.225 61.03 2.889 0.528 3.254 2.878 avg 0.543 avg 3.240 avg 2.884 tensile Index 5.840 tensile Index 34.979 tensile Index 30.890 60.30 0.525 60.30 2.870 60.30 2.414 0.561 2.821 2.425 avg 0.543 avg 2.846 avg 2.420 tensile Index 5.887 tensile Index 30.852 tensile Index 26.233 avg. ten. Ind. 6.487 avg. ten. Ind. 30.809 avg. ten. ind. 30.672 Table a-Continued
Tensile Values 2.35o/. 145
S.P. 1 0 rev S.P. 1 15000 rev S.P. 1 18000 rev
60.79 0.650 61.52 3.216 61.03 2.902 0.661 3.266 2.888 avg 0.655 avg 3.241 avg 2.895 tensile Index 7.048 tensile Index 34.444 tensile Index 31.013 60.30 0.591 61.27 3.490 61.76 2.475 0.591 3.405 2.555 avg 0.591 avg 3.448 avg 2.515 tensile Index 6.406 tensile Index 36.788 tensile Index 26.624 60.06 0.599 61.52 3.463 . 61.76 2.612 0.596 3.491 2.578 avg 0.597 avg 3.477 avg 2.595 tensile Index 6.502 tensile Index 36.952 tensile Index 27.471 59.34 0.553 61.76 3.670 61.52 2.626 0.545 3.612 2.585 avg 0.549 avg 3.641 avg 2.606 tensile Index 6.049 tensile Index 38.544 tensile Index 27.690 60.79 0.703 61.76 3.442 61.27 2.620 0.721 3.396 2.583 avg 0.712 avg 3.419 avg 2.602 tensile Index 7.658 tensile Index 36.194 tensile Index 27.760 avg. ten. ind. 6.733 avg. ten. ind. 36.584 avg. ten. ind. 28.112
S.P. 2 0 rev S.P. 2 15000 rev S.P. 2 18000 rev 61.52 0.642 61.76 3.31 61.03 2.554 0.646 3.35 2.502 avg 0.644 avg 3.33 avg 2.528 tensile Index 6.840 tensile Index 35.28 tensile Index 27.082 61.27 0.713 60.55 3.03 60.06 2.369 0.702 3.06 2.324 avg 0.708 avg 2.97 avg 2.347 tensile Index 7.550 tensile Index 32.06 tensile Index 25.543 60.55 0.591 60.79 3.09 59.82 2.302 0.580 3.08 2.285 avg 0.586 avg 3.08 avg 2.294 tensile Index 6.322 tensile Index 33.15 tensile Index 25.067 59.58 0.564 61.27 3.39 59.82 2.366 0.561 3.37 2.319 avg 0.563 avg 3.38 avg 2.343 tensile Index 6.173 tensile Index 36.04 tensile Index 25.602 61.52 0.714 61.52 3.40 60.79 2.474 0.710 3.42 2.459 avg 0.712 avg 3.41 avg 2.467 tensile Index 7.568 tensile Index 36.19 tensile Index 26.527 avg. ten. Ind. 6.891 avg. ten. Ind. 34.54 avg. ten. Ind. 25.964
S.P. 3 0 rev S.P. 3 15000 rev S.P. 3 18000 rev 60.06 0.649 59.82 2.997 61.76 2.615 0.633 2.915 2.586 avg 0.641 avg 2.956 avg 2.601 tensile Index 6.978 tensile Index 32.307 tensile Index 27.529 60.55 0.675 81.03 3.256 60.55 2.455 0.684 3.208 2.426 avg 0.680 avg 3.232 avg 2.441 tensile Index 7.337 tensile Index 34.624 tensile Index 26.352 61.03 0.707 61.52 3.285 61.27 2.618 0.698 3.276 2.598 avg 0.703 avg 3.281 avg 2.608 tensile Index 7.526 tensile Index 34.863 tensile Index 27.829 60.79 0.701 61.27 3.221 61.76 2.652 0.691 3.205 2.607 avg 0.696 avg 3.213 avg 2.630 tensile Index 7.486 tensile Index 34.285 tensile Index 27.836 61.76 0.901 60.55 3.005 60.79 2.389 0.887 2.991 2.415 avg 0.894 avg 2.998 avg 2.402 tensile Index 9.464 tensile Index 32.371 tensile Index 25.834 avg. ten. ind. 7.758 avg. ten. ind. 33.690 avg. ten. Ind. 27.076 Tale a-ontinued
Tensile Values 0.47"/o 146
A.P. 1 0 rev A.P. 1 15000 rev A.P. 1 18000 rev
60.55 0.991 61. 76 3.245 61.52 3.383 1.150 3.212 3.351 avg 1.071 avg 3.229 avg 3.367 tensile Index 11.559 tensile Index 34.177 tensile Index 35. 783 61.52 1.187 59.58 2.590 61.76 3.415 1.105 2.614 3.453 avg 1.146 avg 2.602 avg 3.434 tensile Index 12.179 tensile Index 28.553 tensile Index 36.353 60.55 0.950 61.27 3.164 . 61.27 3.146 0.935 3.132 3.181 avg 0.943 avg 3.148 avg 3.164 tensile Index 10.177 tensile Index 33.592 tensile Index 33.757 59.34 0.749 60.79 3.033 61.76 3".380 0.711 3.047 3.314 avg 0.730 avg 3.040 avg 3.347 tensile Index 8.043 tensile Index 32.695 tensile Index 35.432 59.58 0.709 60.55 2.999 60.55 3.221 0.785 3.016 3.264 avg 0.747 avg 3.008 avg 3.243 tensile Index 8.197 tensile Index 32.474 tensile Index 35.012 avg. ten. ind. 10.031 avg. ten. ind. 32.298 avg. ten. ind. 35.267
A.P. 2 0 rev A.P. 2 15000 rev A.P. 2 18000 rev 59.82 0.687 60.79 3.044 60.30 2.969 0.713 3.067 2.918 avg 0.700 avg 3.056 avg 2.944 tensile Index 7.651 tensile Index 32.862 tensile Index 31.915 61.76 1.388 60.79 3.019 61.52 3.173 1.301 3.037 3.159 avg 1.345 avg 3.028 avg 2.969 tensile Index 14.233 tensile Index 32.566 tensile Index 31.553 61.03 0.814 59.34 2.417 60.30 3.047 0.809 2.442 3.058 avg 0.812 avg 2.430 avg 3.053 tensile Index 8.696 tensile Index 26.768 tensile Index 33.097 61.76 1.262 60.30 2.863 60.55 3.219 1.224 2.805 3.233 avg 1.243 avg 2.834 avg 3.226 tensile Index 13.159 tensile Index 30.728 tensile Index 34.833 60.79 0.803 60.79 2.823 60.55 3.248 0.810 2.839 3.256 avg 0.806 avg 2.831 avg 3.252 tensile Index 8.671 tensile Index 30.448 tensile Index 35.114 avg. ten. Ind. 10.482 avg. ten. ind. 30.674 avg. ten. Ind. 33.302
A.P. 3 0 rev A.P. 3 15000 rev A.P. 3 18000 rev 59.34 0.744 60.06 2.859 61.27 3.305 0.715 2.819 3.289 avg 0.730 avg 2.839 avg 3.297 tensile Index 8.038 tensile Index 30.905 tensile Index 35.182 61.03 0.829 59.58 2.395 61.03 3.294 0.819 2.412 3.278 avg 0.824 avg 2.404 avg 3.286 tensile ·Index 8.827 tensile Index 26.375 tensile Index 35.202 59.82 0.717 60.30 2.749 61.27 3.248 0.698 2.761 3.261 avg 0.708 avg 2.755 avg 3.255 tensile Index 7.733 tensile Index 29.871 tensile Index 34.728 61.27 0.862 59.34 2.150 61.27 3.371 0.867 2.159 3.314 avg 0.865 avg 2.155 avg 3.343 tensile Index 9.225 tensile Index 23.738 tensile Index 35.667 60.79 0.804 60.55 2.842 59.34 2.505 0.807 2.858 2.527 avg 0.805 avg 2.850 avg 2.516 tensile Index 8.659 tensile Index 30.773 tensile Index 27.721 avg. ten. ind. 8.496 avg. ten. ind. 28.332 avg. ten. ind. 33.700 Table 8-Continued
Tensile Values 1.18% 147
A.P. 1 0 rev A.P. 1 15000 rev A.P. 1 18000 rev
60.30 1.458 60.55 3.119 59.82 2.607 1.412 3.131 2.589 avg 1.435 avg 3.125 avg 2.598 tensile Index 15.559 tensile Index 33.743 tensile Index 28.395 59.58 1. 1 so 60.06 2.832 61.03 3.224 1.123 2.801 3.201 avg 1.137 avg 2.817 avg 3.213 tensile Index 12.471 tensile Index 30.660 tensile Index 34.415 59.82 1.213 60.30 2.856 59.34 2.309 1 .189 2.816 2.288 avg 1.201 avg 2.836 avg 2.299 tensile Index 13.126 tensile Index 30.749 tensile Index 25.325 59.34 1.286 60.55 3.012 60.55 3.082 1.257 3.029 3.014 avg 1.272 avg 3.021 avg 3.048 tensile Index 14.009 tensile Index 32.614 tensile Index 32.911 61.03 1 .307 60.79 3.262 59.82 2.770 1.291 3.251 2.716 avg 1.299 avg 3.257 avg 2.743 tensile Index 13.916 tensile Index 35.024 tensile Index 29.979 avg. ten. ind. 13.816 avg. ten. ind. 32.558 avg. ten. ind. 30.205
A.P. 2 0 rev A.P. 2 15000 rev A.P. 2 18000 rev 60.79 1 .281 60.06 2.605 59.58 2.191 1.251 2.621 2.124 avg 1.266 avg 2.613 avg 2.158 tensile Index 13.616 tensile Index 28.445 tensile Index 23.675 59.34 0.991 60.79 3.091 60.55 3.138 0.994 3.055 3.112 avg 0.992 avg 3.073 avg 2.969 tensile Index 10.935 tensile Index 33.050 tensile Index 32.058 60.30 1.195 61.76 3.412 60.06 2.808 1.171 3.440 2.791 avg 1.183 avg 3.426 avg 2.800 tensile Index 12.827 tensile Index 36.268 tensile Index 30.475 60.06 1.133 61.27 3.294 60.06 3.017 1.148 3.271 2.993 avg 1.141 avg 3.283 avg 3.005 tensile Index 12.415 tensile Index 35.027 tensile Index 32.712 60.55 1.227 61.52 3.443 61.76 3.377 1.258 3.422 3.314 avg 1.243 avg 3.433 avg 3.346 tensile Index 13.416 tensile Index 36.479 tensile Index 35.416 avg. ten. ind. 12.642 avg. ten. Ind. 33.854 avg. ten. Ind. 30.867
A.P. 3 0 rev A.P. 3 15000 rev A.P. 3 18000 rev 60.55 1.232 60.06 2.827 61.27 3.377 1.262 2.114 3.315 avg 1.247 avg 2.471 avg 3.346 tensile Index 13.465 tensile Index 26.893 tensile Index 35.705 60.79 1.248 60.30 2.935 60.79 3.205 1.126 2.911 3.221 -_ avg 1.187 avg 2.923 avg 3.213 tensile Index 12.767 tensile Index 31.692 tensile Index 34.556 61.52 1.278 60.79 3.195 59.34 2.153 1.294 3.151 2.144 avg 1.286 avg 3.173 avg 2.149 tensile Index 13.667 tensile Index 34.126 tensile Index 23.672 61.76 1.407 60.55 3.127 60.30 2.843 1.426 3.104 2.831 avg 1.417 avg 3.116 avg 2.837 tensile Index 14.995 tensile Index 33.640 tensile Index 30.760 59.34 0.988 59.34 2.569 59.34 2.099 0.987 2.542 2.111 avg 0.987 avg 2.556 avg 2.105 tensile Index 10.880 tensile Index 28.156 tensile Index 23.193 avg. ten. ind. 13.155 avg. ten. Ind. 30.902 avg. ten. ind. 29.577 Table a-Continued
Tensile Values 2.35% 148
A.P. 1 0 rev A.P. 1 15000 rev A.P. 1 18000 rev
60.79 1.068 60.06 2.655 60.06 2.655 1.021 2.676 2.676 avg 1.045 avg 2.666 avg 2.666 tensile Index 11.234 tensile Index 29.016 tensile Index 29.016 60.06 0.819 61.27 3.393 60.55 2.838 0.811 3.377 2.852 avg 0.815 avg 3.385 avg 2.845 tensile Index 8.872 tensile Index 36.121 tensile Index 30.719 59.82 0.797 59.34 2.370 ·60.55 2.840 0.781 2.352 2.855 avg 0.789 avg 2.361 avg 2.848 tensile Index 8.623 tensile Index 26.013 tensile Index 30.746 61.76 1.417 61.27 3.343 59.82 2:652 1.433 3.323 2.664 avg 1.425 avg 3.333 avg 2.658 tensile Index 15.085 tensile Index 35.566 tensile Index 29.050 60.79 1.095 60.79 3.103 60.06 2.772 1.111 3.123 2.788 avg 1.103 avg 3.113 avg 2.780 tensile Index 11.863 tensile Index 33.480 tensile Index 30.262 avg. ten. ind. 11.135 avg. ten. ind. 32.039 avg. ten. ind. 29.959
A.P. 2 0 rev A.P. 2 15000 rev A.P. 2 18000 rev 61.03 1.205 60.55 2.953 60.30 2.840 1.195 2.966 2.855 avg 1.200 avg 2.960 avg 2.848 tensile Index 12.855 tensile Index 31.956 tensile Index 30.874 61.52 1.136 59.82 2.609 61.76 3.060 1.111 2.619 3.091 avg 1.124 avg 2.969 avg 3.076 tensile Index 11.940 tensile Index 32.450 tensile Index 32.558 60.55 0.996 60.79 3.176 60.30 2.864 1.110 3.155 2.839 avg 1.053 avg 3.166 avg 2.852 tensile Index 11.370 tensile Index 34.045 tensile Index 30.917 60.55 0.978 59.82 2.628 60.06 2.718 0.989 2.641 2.727 avg 0.984 avg 2.635 avg 2.723 tensile Index 10.620 tensile Index 28.794 tensile Index 29.637 59.34 1.131 61.76 3.465 59.34 2.410 1.151 3.423 2.434 avg 1.141 avg 3.444 avg 2.422 tensile Index 12.571 tensile Index 36.459 tensile Index 26.685 avg. ten. Ind. 11.871 avg. ten. Ind. 32.741 avg. ten. Ind. 30.134
A.P. 3 0 rev A.P. 3 15000 rev A.P. 3 18000 rev 60.79 1.074 61.27 3.393 59.34 2.511 1.026 3.376 2.502 avg 1.050 avg 3.385 avg 2.507 tensile Index 11.293 tensile Index 36.115 tensile Index 27.616 60.30 0.846 61.03 3.246 59.34 2.399 0.866 3.212 2.411 avg 0.856 avg 3.229 avg 2.405 tensile Index 9.281 tensile Index 34.592 tensile Index 26.498 59.34 0.649 61.76 3.498 61.27 2.918 0.667 3.472 2.904 avg 0.658 avg 3.485 avg 2.911 tensile Index 7.250 tensile Index 36.893 tensile Index 31.063 61.27 1.117 81.27 3.082 59.82 2.693 1.136 3.065 2.681 avg 1.127 avg 3.074 avg 2.687 tensile Index 12.021 tensile Index 32.797 tensile Index 29.367 59.34 0.668 59.58 2.439 59.34 2.481 0.677 2.451 2.469 avg 0.673 avg 2.445 avg 2.475 tensile Index 7.410 tensile Index 26.830 tensile Index 27.269 avg. ten. Ind. 9.451 avg. ten. Ind. 33.445 avg. ten. ind. 28.363 Table 8-Continued
Tensile Values 0.47o/o 149
H.P. 1 0 rev H.P. 1 15000 rev H.P. 1 18000 rev
61.27 1.232 61.03 3.478 59.34 3.075 1.230 3.461 3.063 avg 1.231 avg 3.470 avg 3.069 tensile Index 13.136 tensile Index 37.168 tensile Index 33.814 61.52 1.399 60.79 3.272 60.55 3.681 1.381 3.262 3.656 avg 1.390 avg 3.267 avg 3.669 tensile Index 14.772 tensile Index 35.137 tensile Index 39.611 61.76 1.944 60.06 3.245 "61.76 3.858 1.995 3.227 3.871 avg 1.970 avg 3.236 avg 3.865 tensile Index 20.849 tensile Index 35.226 tensile Index 40_.910 60.30 1.146 60.55 3.293 61.03 3.452 1.168 3.277 3.469 avg 1.157 avg 3.285 avg 3.461 tensile Index 12.545 tensile Index 35.470 tensile Index 37.072 60.79 1.632 61.76 3.278 61.27 3.722 1.614 3.258 3.744 avg 1.623 avg 3.268 avg 3.733 tensile Index 17.455 tensile Index 34.596 tensile Index 39.834 avg. ten. ind. 15.751 avg. ten. ind. 35.519 avg. ten. ind. 38.248
H.P. 2 0 rev H.P. 2 15000 rev H.P. 2 18000 rev 61.76 1.997 60.06 3.315 59.58 3.014 2.009 3.289 3.011 avg 2.003 avg 3.302 avg 3.013 tensile Index 21.204 tensile Index 35.945 tensile Index 33.058 60.55 1.455 60.55 3.376 61.03 3.291 1.436 3.407 3.316 avg 1.446 avg 3.392 avg 2.969 tensile Index 15.608 tensile Index 36.620 tensile Index 31.806 60.79 1.117 61.52 3.417 61.52 3.655 1.131 3.468 3.688 avg 1.124 avg 3.443 avg 3.672 tensile Index 12.089 tensile Index 36.585 tensile Index 39.019 61.76 1.514 59.82 3.177 61.76 3.858 1.529 3.112 3.891 avg 1.522 avg 3.145 avg 3.8-z5 tensile Index 16.107 tensile Index 34.368 tensile Index 41.016 60.55 1.404 60.55 3.286 61.03 3.510 1.424 3.255 3.498 avg 1.414 avg 3.271 avg 3.504 tensile Index 15.268 tensile Index 35.314 tensile Index 37.538 avg. ten. Ind. 16.055 avg. ten. Ind. 35.766 avg. ten. ind. 36.487
H.P. 3 0 rev H.P. 3 15000 rev H.P. 3 18000 rev 61.27 1.230 61.03 3.478 61.52 4.233 1.242 3.401 4.213 avg 1.236 avg 3.440 avg 4.223 tensile Index 13.189 tensile Index 36.847 tensile Index 44.880 60.79 1.569 61.27 3.489 60.55 3.560 1.582 3.468 3.511 avg 1.576 avg 3.479 avg 3.536 tensile Index 16.945 tensile Index 37.118 tensile Index 38.175 60.55 1.406 60.55 3.355 60.79 3.581 1.421 3.369 3.570 avg 1.414 avg 3.362 avg 3.576 tensile Index 15.263 tensile Index 36.302 tensile Index 38.455 60.79 1.148 59.34 3.089 59.82 3.417 1.161 3.111 3. 427 avg 1.155 avg 3.100 avg 3.422 tensile Index 12.417 tensile Index 34.155 tensile Index 37.401 61.76 1.555 59.82 3.127 60.30 3.316 1.523 3.155 3.332 avg 1.539 avg 3.141 avg 3.324 tensile Index 16.292 tensile Index 34.329 tensile Index 36.040 avg. ten. ind. 14.821 avg. ten. ind. 35.750 avg. ten. ind. 38.990 Table 8-Cont,nued
Tensile Values 1.18o/o 150
H.P. 1 0 rev H.P. 1 15000 rev H.P. 1 18000 rev
61. 76 0.964 61.76 3.778 60.55 3.172 1.001 3.768 3.165 avg 0.983 avg 3.773 avg 3.169 tensile Index 10.401 tensile Index 39.942 tensile Index 34.212 61.03 0.993 60.06 3.608 61.76 3.493 0.998 3.615 3.482 avg 0.995 avg 3.612 avg 3.488 tensile Index 10.664 tensile Index 39.314 tensile Index 36.919 59.82 0.840 61.27 3.635 60.30 3.015 0.842 3.648 3.029 avg 0.841 avg 3.642 avg 3.022 tensile Index 9.191 tensile Index 38.858 tensile Index 32.766 60.30 0.905 61.52 3.772 59.82 2.917 0.906 3.761 2.934 avg 0.905 avg 3.767 avg 2.926 tensile Index 9.817 tensile Index 40.028 tensile Index 31.974 60.79 0.937 60.55 3.563 59.82 2.945 0.935 3.589 2.931 avg 0.936 avg 3.576 avg 2.938 tensile Index 10.067 tensile Index 38.613 tensile Index 32.111 avg. ten. ind. 10.028 avg. ten. ind. 39.351 avg. ten. ind. 33.596
H.P. 2 0 rev H.P. 2 15000 rev H.P. 2 18000 rev 61. 76 1.110 61.76 3.997 60.79 3.181 1.115 3.981 3.189 avg 1.113 avg 3.989 avg 3.185 tensile Index 11.777 tensile Index 42.228 tensile Index 34.255 61.52 0.997 60.79 3.686 61.76 3.459 0.998 3.674 3.474 avg 0.998 avg 3.680 avg 2.969 tensile Index 10.601 tensile Index 39.579 tensile Index 31.430 61.76 1.248 59.34 3.197 61.52 3.403 1.224 3.185 3.411 avg 1.236 avg 3.191 avg 3.407 tensile Index 13.084 tensile Index 35.158 tensile Index 36.208 60.79 1.190 59.34 3.156 60.55 3.152 1.145 3.176 3.142 avg 1.168 avg 3.166 avg 3.147 tensile Index 12.557 tensile Index 34.883 tensile Index 33.980 60.55 0.765 59.34 3.224 61.27 3.215 0.767 3.216 3.229 avg 0.766 avg 3.220 avg 3.222 tensile Index 8.269 tensile Index 35.478 tensile Index 34.381 avg. ten. ind. 11.258 avg. ten. Ind. 37.465 avg. ten. Ind. 34.051
H.P. 3 0 rev H.P. 3 15000 rev H.P. 3 18000 rev 60.79 1.120 61.76 3.951 61.52 3.451 1.136 3.962 3.441 avg 1.128 avg 3.957 avg 3.446 tensile Index 12.132 tensile Index 41.884 tensile Index 36.622 61.27 1.063 61.52 3.764 61.76 3.512 1.039 3.758 3.526 avg 1.051 avg 3.761 avg 3.519 tensile Index 11.215 tensile Index 39.970 tensile Index 37.253 60.55 0.771 59.82 3.616 61.76 3.525 0.774 3.624 3.533 avg 0.773 avg 3.620 avg 3.529 tensile Index 8.341 tensile Index 39.565 tensile Index 37.358 59.82 0.852 59.58 3.178 60.55 3.174 0.854 3.192 3.161 avg 0.853 avg 3.185 avg 3.168 tensile Index 9.327 tensile Index 34.951 tensile Index 34.202 59.58 0.851 59.34 3.211 59.82 2.987 0.852 3.223 3.002 avg 0.852 avg 3.217 avg 2.995 tensile Index 9.345 tensile Index 35.444 tensile Index 32.728 avg. ten. ind. 10.072 avg. ten. ind. 38.363" avg. ten. Ind. 35.633 Table a-Continued
Tensile Val.-s 2.35% 151
H.P. 1 0 rev H.P. 1 15000 rev H.P. 1 18000 rev
61.76 1 .656 61.27 3.785 60.06 3.171 1 .642 3.777 3.162 avg 1 .649 avg 3.781 avg 3.167 tensile Index 17.457 tensile Index 40.346 tensile Index 34.470 61.03 1.519 61.76 4.099 59.34 3.136 1.502 4.082 3.121 avg 1.511 avg 4.091 avg 3.129 tensile Index 16.182 tensile Index 43.303 tensile Index 34.469 60.79 1.447 61.03 3.838 60.79 3.252 1.441 3.845 3.259 avg 1.444 avg 3.842 avg 3.256 tensile Index 15.530 tensile Index 41.153 tensile Index 35.013 58.82 1.374 60.79 3.784 60.30 3.103 1.382 3.792 3.111 avg 1 .378 avg 3.788 avg 3.107 tensile Index 15.317 tensile Index 40.740 tensile Index 33.688 58.82 1 .431 60.79 3.707 60.30 3.160 1.410 3.651 3.150 avg 1.421 avg 3.679 avg 3.155 tensile Index 15.789 tensile Index 39.568 tensile Index 34.208 avg. ten. ind. 16.055 avg. ten. ind. 41.022 avg. ten. ind. 34.370
H.P. 2 0 rev H.P. 2 15000 rev H.P. 2 18000 rev 60.55 1.372 61.52 3.919 61.76 3.984 1.361 3.907 3.976 avg· 1 .367 avg 3.913 avg 3.980 tensile Index 14.755 tensile Index 41.585 tensile Index 42.133 59.34 1.256 60.79 3.778 59.34 3.235 1.244 3.771 3.244 avg 1.250 avg 2.969 avg 3.240 tensile Index 13.772 tensile Index 31.932 tensile Index 35.692 59.34 1.322 59.82 3.394 60.30 3.279 1.310 3.369 3.261 avg 1.316 avg 3.382 avg 3.270 tensile Index 14.500 tensile Index 36.958 tensile Index 35.455 60.55 1.409 61.76 4.094 59.58 3.277 1.415 4.012 3.263 avg 1.412 avg 4.053 avg 3.270 tensile Index 15.246 tensile Index 42.906 tensile Index 35.8�3 61.03 1 .589 61.03 3.776 60.30 3.258 1.572 3.764 3.244 avg 1 .581 avg 3.770 avg 3.251 tensile Index 16.932 tensile Index 40.387 tensile Index 35.249 avg. ten. Ind. 15.041 avg. ten. Ind. 38.754 avg. ten. Ind. 36.882
H.P. 3 0 rev H.P. 3 15000 rev H.P. 3 18000 rev 59.58 1.254 61.76 4.066 59.82 3.305 1.226 4.033 3.312 avg 1.240 avg 4.050 avg 3.309 tensile Index 13.607 tensile Index 42.869 tensile Index 36.160 61.52 1.492 61.52 3.987 60.55 3.319 1.482 3.995 3.328 avg 1 .487 avg 3.991 avg 3.324 tensile Index 15.803 tensile Index 42.414 tensile Index 35.886 60.55 1 .405 59.34 3.313 81.52 3.890 1.412 3.326 3.875 avg 1.409 avg 3.320 avg 3.883 tensile Index 15.209 tensile Index 36.574 tensile Index 41.261 61.76 1.612 61.76 4.105 60.55 3.326 1.622 4.096 3.333 avg 1.617 avg 4.101 avg 3.330 tensile Index 17.118 tensile Index 43.408 t-ile Index 35.951 60.79 1.514 61.27 3.977 60.79 3.388 1.506 3.981 3.378 avg 1.510 avg 3.979 avg 3.383 tensile Index 16.240 tensile Index 42.459 tensile Index 36.384 avg. ten. ind. 15.595 avg. ten. ind. 41.545 avg. ten. ind. 37.129 152
Table 9
Experimental Tear Values
Tear Values (mN)
Chemical Chem. Cone. Revolutions Run Number
No Chemical Run 1 Run 2 Run 3 Average S.D. 0 696.90 678.07 728.29 701.09 25.37 15000 885.25 878.98 897.81 887.35 9.59 18000 1028.09 1051.63 1075.18 1051.63 23.54
DMD 0.47% Run 1 Run 2 Run 3 Average 0 571.33 546.22 590.17 569.24 22.05 15000 1010.82 998.27 1004.54 1004.54 6.28 18000 860.14 866.42 872. 70 866.42 6.28
1.18% Run 1 Run 2 Run 3 Average 0 483.44 508.55 621.56 537.85 73.58 15000 878.98 897.81 910.37 895.72 15.80 18000 916.65 948.04 973.15 945.95 28.31
2.35% Run 1 Run 2 Run 3 Average 0 671. 79 659.23 640.40 657.14 15.80 15000 1111.28 1130.11 1167.78 1136.39 28.77 18000 966.87 985.71 998.27 983.62 15.80
Sodium Persulfate 0.47% Run 1 Run2 Run 3 Average 0 489. 72 502.27 489.72 493.90 7.25 15000 1042.21 1023.38 1023.38 1029.66 10.87 18000 1067.33 1061.05 1054.77 1061.05 6.28
1.18% Run 1 Run 2 Run3 Average 0 521.11 533.66 514.83 523.20 9.59 15000 841.31 822.47 835.03 832.93 9.59 18000 809.91 835.03 841.31 828. 75 16.61
2.35% Run 1 Run2 Run3 Average 0 408.10 439.49 439.49 429.02 18.12 15000 747.13 747.13 753.41 749.22 3.62 18000 722.02 709.46 715.74 715.74 6.28 153
Table 9-Continued
Tear Values (mN)
Chemical Chem. Cone. Revolutions Run Number
Ammonium Persulfate 0.47% Run 1 Run 2 Run 3 Average s.o. 0 734.57 696.90 722.02 717.83 19.18 15000 1048.49 1073.61 1061.05 1061.05 12.56 18000 1148.95 1130.11 1174.06 1151.04 22.05
1.18% Run 1 Run 2 Run 3 Average 0 816.19 828. 75 822.47 822.47 6.28 1 5000 1017.10 1042.21 1 054. 77 1038.03 19.18 18000 678.07 690.62 671.79 680.16 9.59
2.35% Run 1 Run 2 Run 3 Average 0 728.29 740.85 734.57 734.57 6.28 15000 1387.53 1450.31 1431.48 1423.10 32.22 18000 1017.10 1029.66 1023.38 1023.38 6.28
Hydrogen Peroxide 1.00% Run 1 Run 2 Run 3 Average 0 709.46 715. 74 703.18 709.46 6.28 15000 935.48 929.20 910.37 925.02 13.07 18000 1092.44 1086.16 1079.88 1086.16 6.28
2.50% Run 1 Run 2 Run 3 Average 0 652.95 646.68 659.23 652.95 6.28 15000 922.92 904.09 897.81 908.28 13.07 18000 929.20 935.48 941.76 935.48 6.28
5.00% Run 1 Run 2 Run 3 Average 0 765.96 759.69 797.36 774.34 20.18 15000 966.87 979.43 973.15 973.15 6.28 18000 1017.10 1010.82 1054. 77 1027.56 23.77 Appendix K
ANOV A Tables forChemicals
154 155 Tests of Hypotheses forBetween Subjects Effectsfor Hydrogen Peroxide.
Source DF Type ill SS Mean Square F Value Pr > F
Cone 3 255.30573679 85.10191226 78.05 0.0001
Error 9 9.81356167 l.09039574
Univariate Tests of Hypotheses for Within Subjects Effectsfor Hydrogen Peroxide.
Adjusted Pr > F
Source DF Type ill S S Mean Square F Value Pr > F G-G H-F
Time 4 340.01536733 85.00384183 123.90 0.0001 0.0001 0.0001
Ti*Conc. 12 29.25680487 2.43806707 3.55 0.0016 0.0066 0.0016
Error 36 24.69849667 0.68606935
(Time)
Greenhouse-Geiser Epsilon = 0.6916
Huynh-Feldt Epsilon = 1.3621 156 Tests of Hypotheses forBetween Subjects Effects for Ammonium Persulfate.
Source OF Type III SS Mean Square F Value Pr> F
Cone 3 1304.94270500 434.98090167 186.01 0.0001
Error 9 21.04589500 2.33843278
Univariate Tests of Hypotheses for Within Subjects Effects for Ammonium Persulfate.
Adjusted Pr> F
Source OF Type III SS Mean Square F Value Pr> F G-G H-F
Time 4 288.60957267 72.15239317 131.86 0.0001 0.0001 0.0001
Ti*Conc. 12 37.69270333 3.14105861 5.74 0.0001 0.0007 0.0001
Error 36 19.69829667 0.54717491
(Time)
Greenhouse-Geiser Epsilon = 0.6006
Huynh-Feldt Epsilon = 1.1078 157 Tests of Hypotheses forBetween Subjects Effects forSodium Persulfate.
Source DF Type illSS Mean Square F Value Pr>F
Cone 3 1432.57829372 477.52609791 195.07 0.0001
Error 9 22.03124167 2.44791574
Univariate Tests of Hypotheses for Within Subjects Effects forSodium Persulfate.
Adjusted Pr >F
Source DF Type ill SS Mean Square F Value Pr>F G-G H-F
Time 4 168.24750956 42.06187739 95.29 0.0001 0.0001 0.0001
Ti*Conc. 12 59.13973000 4.92831083 11.16 0.0001 0.0001 0.0001
Error 36 15.89095000 0.44141528
(Time)
Greenhouse-Geiser Epsilon = 0.6555
Huynh-Feldt Epsilon = 1.2576 158 Tests ofHypotheses for Between Subjects Effectsfor DMD.
Source OF Type ill SS Mean Square F Value Pr> F
Cone 3 4475.56404449 1491.85468150 1042.82 0.0001
Error 9 12.87532167 l.43059130·
Univariate Tests of Hypotheses for Within Subjects Effects for DMD.
Adjusted Pr > F
Source DF Type III SS Mean Square F Value Pr> F G-G H-F
Time 4 162.95229267 40.73807317 49.49 0.0001 0.0001 0.0001
Ti*Conc. 12 76.56493821 6.380411 52 7.75 0.0001 0.0005 0.0001
Error 36 29.63220333 0.82311676
(Time)
Greenhouse-Geiser Epsilon = 0.4553
Huynh-Feldt Epsilon = 0. 7548 LITERATURE CITED
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