49
mrniui mm M|W*»»W«*M""«**« OW-TEMPERATÜRE TRACT10M RUBBER SOLE COMPOIIO FOR QMS COMBAT FOOTWEAR by D D C SEP18B67 Vincen» S. Javisr —,
mrniui mm
M|W*»»W«*M""«**«
OW-TEMPERATÜRE TRACT10M RUBBER SOLE
COMPOIIO FOR QMS COMBAT FOOTWEAR
by
D D C
SEP18B67
Vincen» S. Javisr
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DIS1HRIBUTIOK OF SEIS DOCUMENT IB ÜKU|MKif,
lb a finding« in thi* regere are not -$» fee construed AS «a , official Department of the A*i»y position itnlaa* *o de*ig»*ted by other Authorized docwaent*.
Citation of trade aaaes in this report dee.«,, met constitute an official indorsement or approval of Cite uac #£ »och Tit«»». ' :
Sea troy this report when no longer needed. Do not xeturxt it to the originator.
Distribution of this document is unlimited
AD
TECHNICAL RBPORJ
67-72-CM
LOW-TEMPERATURE TRACTION RUBBER SOLE COMPOUND FOR DMS COMBAT FOOTWEAR
by
Vincent S. Javier Rubber, Plastics and Leather Engineering Branch
Project reference: ICO24401A329 Series: C&OM-34
March 1967
Clothing and Organic Materials Division U. S. ARMY NATICK LABORATORIES Natick, Massachusetts 01760
FOREWORD
There is a need for a new rubber sole and heel compound for the Army combat footwear readily produced by application of the direct molded sole process. Although the presently °->pted standard sole compound has been exhibiting satisfactory wear properties and durability, it does not provide the combat boot with adequate traction at low temperature and on snow and ice. This deficiency of the present outsole compound was confirmed by the U. S. Army troops who conducted an actual wear test in Alaska on the newly adopted combat boots.
It was for this reason that this laboratory initiated a rubber compounding development program aimed at obtaining a soling material which would provide both adequate traction on snow and ice and satis- factory wear serviceability.
This report discusses the development and evaluation of the new rubber compound designed solely for the Army combat boot with the direct molded sole construction.
S. J. KENNEDY Director Clothing and Organic Materials Division
APPROVED:
DALE H. SIBLING, Ph.D. Scientific Director
W. M. MANTZ Brigadier General, USA Commanding
iii
CONTENTS
SfiS*
List c£ Tables v
Abstract vi
I. Introduction 1
II. Development of Folyblend Buna N Rubber Compound for Direct Molded Sole Footwear 2
III. Development Compounding of Styrene-Butadiene for 3 DMS Footwear
IV. Experimental and Test Procedures 5
V. Results and Discussion 6
VI. Conclusions 6
VII. Recommendation 7
VIII. Acknowledgments 7
IX. References 7
Appendix A: Compounding Materials: Trade Names, Identification and Supplier 34
Appendix B: Material Suppliers: Names and Addresses 39
iv
I
f
LIST OF TABLES
Page Exploratory Compounding
I. Natural Rubber-Containing Compounds 6
II. Styrene-Butadiene-Containing Compounds 9
III. Chlorosulfonated Polyethylene-Containing Compounds 12
IV. Polychloropreuc-oontaining Compounds 14
V. Polyblend-Containing Compounds 19
Development Compounding
VI. Development of Polychloroprene-Containing Compounds - Compounding Recipes and Test Results 23
VII. Development Compounding of Polyblend-Containing Rubber ■• Compounding Recipes and Test Results 24
VIII. Development Compounding of Styrene-Butadiene-Containing Rubber/EPDM Rubber in SBR Compounds 25
IX. Development Compounding of Styrene-Butadiene-Containing Rubber - Effect of ZnO Loading in SBR 1502 26
X. Development Compounding cf Styrene-Butadiene-Containing Rubber - Compounding Recipes and Properties 27
XI. Comparison of Formulation of Standard and Styrene- Butadiene Rubber, DMS Soling Compound 28
XII. Comparison of Physical Properties of Rubber Soling Compound SBR-29b and Standard DMS 29
XIII. Vulcanizing Cement for the Standard DMS Compound 30
XIV. Vulcanizing Cement for Styrene-Butadiene Rubber Sole Compound 31
XV. Wellco Ro-Search Modified SBR Formulations - Soling and Cement Compound 32
XVI. Test Data - Wellco Ro-Search Fabricated DMS Boots using SBR Compound 33
ABSTRACT
A new direct molded sole rubber compound designed primarily to give better traction at low temperature, and on snow and ice, than the present standard vinyl-modified Buna N rubber compound, has been successfully developed by utilizing Styrene-Butadiene rubber (SBR), type 1502.
The vulcanizates of this new compound exhibited good physical properties which are comparable with the physical properties exhibited by the present standard sole compound. In addition, this new compound also displayed excellent ozone resistance and good low-temperature behavior - a property which makes this compound more suitable for wear on snow and ice.
Furthermore, the test results on the finished boot samples showed that the new SBR compound has satisfied not only the curing conditions imposed by the CHMA and Wellco process but also the physical requirements, except for solvent resistance, which are specified in Military Specifica- tion, MIL-B-43154, for the standard direct molded sole (DMS) combat boot.
vi
IMPROVED LOW-TEMPERATURE TRACTION RUBBER SOLING FOR DMS FOOTWEAR
I. Introduction
One of the many items developed by the U.S. Army Natick Laboratories under the Army Research and Development program is the Army combat boot with the direct molded sole construction. The development of this item was accomplished by utilizing the technique brought about by the CEMA process^. This technique fabricates shoes by molding and bonding in one operation the sole and heel to the bottom part of the leather shoe upper. The new technique, therefore, has eliminated stitching, nailing, and cementing, which were the conventional operations used in attaching rubber soles and heels to the boot uppers. Another good feature of this process is an improvement in the end product; that is, the rubber bond is not only made more waterproof than the conventional construction, but contributes to much longer shoe life.
In contributing to the successful development of the direct molded sole combat footwear, the Rubber Technology Group of the Clothing and Organic Materials Division undertook intensive compounding development of rubber stocks that could perform satisfactorily under the curing conditions and problems imposed by the CEMA Vulcanizing Process.
The process of vulcanizing the sole and heel directly to the shoe upper consists of inserting a lightweight aluminum metal last into the shoe upper to provide some degree of rigidity. The lasted shoe upper, firmly held in locked position, is then placed over the sole mold.
The mold consists of three parts, a bottom plate and two side plates. The two side plates are cut to the proper contour and size to form the edges of the sole. Before placing the lasted upper over the sole mold, a weighed amount of unvulcanized rubber sole and heel is placed on the bottom plate and the curing cycle is started automatically. The side plates move in against the lower edge of the shoe to form a tight seal and then the bottom plate moves upward, forcing the uncured compound against the shoe upper bottom and out into the mold.
The force for closing the side and bottom plates is provided by hydraulic pressure acting on the pistons attached to the plates. The heat for vulcanization of the sole and heel compound is supplied by electric heaters inside the bottom and side plates of the mold.
At the end of the curing cycle, the pressure is released and the side molds open to the full extent of their travel. The sole mold is withdrawn and the shoe is left free on the last away from the source of heat. The final step is removal of the metal last from the finished shoe.
Basically, this technique of vulcanizing the sole and heel to the leather upper has presented problems in the formulation of a satisfactory sole and heel rubber compound. One of the problems is the low molding pressure. The side mold pressure must be kept low to prevent cutting and other damages to the leather of the shoe by the side plates. The pressure on the bottom plates should also be low tc prevent the compound from flowing through the seal formed by the side plates and the shoe. Thus, the CEMA process maintains operating pressure much lower than the opera- clng pressure used by the conventional rubber vulcanizing process.
One other problem to consider with this process is the low heat input for vulcanization. Since the leather from which the shoe is made is not resistant to high temperature, the side plates' temperature must be kept as low as practicable to prevent deterioration of the leather during vulcanization. Furthermore, the major heat for vulcanization is applied only to the bottom plates of the sole mold and to a small area of the side mold. And since there is no direct heat contact between the bottom plates and the surface upon which the sole is molded, the problem of obtaining a satisfactory cure which would give the molded-on-sole satisfactory wear and adhesion properties at the interface of the rubber and the leather becomes even more difficult.
The short vulcanization cycles pose another problem. Normally, the direct molded sole process is designed to produce one pair for each cycle. This, again, is in contrast to the conventional procedure of using multicavity molds and multi-platens process. Thus, for efficiency and economy, the curing cycle must be as short as possible to enable a maximum hourly output of finished shoes per vulcanizer.
To perform satisfactorily under the set of curing restrictions cited above, the compound should be fast curing and should have an excellent flow under low pressure. For example, a representative compound might be satisfactory with respect to the rate of cure but not acceptable for adequate mold flow. On the other hand, the mold flow might be satis- factory but the cure rate might be too slow and the compound would not be acceptable.
II. Development of Polyblend Buna N Rubber Compound for Direct Molded Sole Footwear
The development of a polyblend rubber compound started when this new type of elastomeric compound was first introduced commercially. Since this was a new product, this laboratory undertook evaluation studies of it for military applications. It r^as found that the vulcanizates of this new material exhibited amazingly good physical properties, including excellent gasoline and ozone resistance. At that time, gasoline resist- ant soling for combat footwear was being considered, and, for this reason, the program of developing this new polyblend nitrile rubber for direct
molded sole combat footwear was initiated. A series of compounding formulations were tried and, finally, under the joint effort cf Naugatuck Chemical Division of U.S. Rubber Company and this laboratory, a sole and heel formulation which performed satisfactorily under both the curing and molding conditions of CEKA process was obtained.
Using this formulation, Endlcott Johnson Corporation, under contract, fabricated the first samples of direct molded sole combat footwear which were then subjected to actual wear test by Army troops. Wear test results, however, indicated failure of the boots to maintain satisfactory wear life. Sole and heel separations from the shoe upper, due to weak bond, were found to be the most consistent failures. This type of failure was quickly over- come by developing an improved vulcanizing rubber cement for use with this compound for direct molded sole process. This improved cement has now given the Army direct molded sole footwear excellent wear durability. The rubber compounding recipe is given in Table XI and test results are shown in Table XII.
III. Development Compounding of Styrene-Butadiene for BMS Foctwear
The reported unsatisfactory traction performance on snow and ice^) of the direct molded sole combat leather boot with the standard vinyl- modified Buna N rubber compound created the need for a new rubber soling material which would give improved traction qualities at low temperature and on snow and ice.
An attempt, therefore, was made by this laboratory to develop a soling compound which would provide combat footwear with adequate traction, particularly on snow and ice. Development effort was directed toward obtaining softer compounds which will remain flexible and soft in tempera- tures as low as 0°F, thus allowing greater retention of traction character- istics by the outsole at lower temperatures^).
Exploratory compounding was then undertaken, and a series of formu- lations utilizing most of the available general purpose rubbers, such as (Natural, Polychloroprene, Chlorosulfonated Polyethylene, Styrene-Butadiene, and even blends of cis-Polybutadiene with vinyl-modifled Buna N and with other rubbers, were explored. The compounding recipes and properties of these compounds are given in Tables I to V.
Compounds which displayed desirable properties were carefully noted. Among those compounds worth investigating was the Polychloroprene- containing compound. Two candidate compounds were evaluated and DMS combat footwear samples, using compound 63-C-45, were fabricated by this labora- tory and were actually wear tested^) by some Army troops at Fort Lee, Virginia,proving ground. Tal?le VI gives the recipes used in development compounding and the properties of the compounds. Difficulties in mass producing this compound led to continued development for a new compound.
The polyblend-containing compounds, likewir displayed excellent abrasion resistance and these compounds also wert worth investigating because blending cis-Polybutadiene with vinyl-modified Buna N, which is the rubber used in obtaining the present DMS compound, gave significant improvement to abrasion characteristics. The recipes used in compound- ing and the properties obtained are given in Table VII.
Although the Polychloroprene and polyblend-containing compound exhibited desirable properties, neither one of these compound«« was con- sidered to satisfy the Army's need for a new DMS rubber compound with improved traction on snow and lie. The personnel responsible for under- taking this project believed that a cheaper and a better quality sole compound could be obtained with Styrene-Butadiene-containing compound. The good low-temperature behavior, easy processing characteristics and cheaper cost of the Styrene-Butadiene rubber are the chief reasons for selecting Styrene-Butadiene-containing compound for the development of the needed sole and heel material.
Three phases of compounding development work were, therefore, performed on the SBR-containing rubber. The first was to obtain an ozone-resistant compound. SBR is known to be susceptible to ozone attack, but its compatibility to blend with Ethylene-Propylene Diene rubber (1PDM)(6) made it possible to obtain an SBR compound with excel- lent ozone resistance. Table VIII gives the recipes used in compounding and the test results obtained.
The next phase was compounding for abrasion resistance. SBR com- pound reinforced with hydrated silica does not usually display high abrasion performance. However, good physical property, including abrasion resistance, could be obtained with SBR 1502, reinforced with HiSil 233, by the omission of zinc oxide(5) in the compound. Normally, zinc oxide is needed in conventional rubber compounding as an activator and stabilizer. Table IX gives the effect of varying the zinc oxide loading in the compound and the recipes used.
Lastly, the compounding development included obtaining a stock which would perform satisfactorily under the Military Specification requirement for sole and heel compound and under the curing and molding conditions of th. CEMA vulcanizing process. The Mooney viscometer was then employed to measure the cure rate and flow characteristics of the candidate compounds. The recipes used in compounding and the properties obtained are shown in Table X. The best overall properties are exhibited by compound SBR-29b and, therefore, represented the new rubber sole com- pound for the DMS combat footwear. The new compound, whose formulation is given in Table XI, was evaluated against the present OMS compound, and Table XII gives the comparative properties of the two compounds.
IV. Experimental and Test Procedures
All rubber compounding and vulcanization were done in this Laboratory with the conventional standard laboratory rubber-processing equipment.
In addition to the nrepared and molded-slab samples for evaluation, samples of combat boots were also fabricated, utilizing the CEMA equipment available in tbese Laboratories, to determine the molding and curing characteristics of the compound when processed by the SMS technique.
The vulcanizing rubber cement used in molding the rubber sole and heel directly to the leather upper was also prepared according to the recipes listed in Table XIII, Vulcanising Cement for Vinyl-Modified Buna N Standard Compound and Table XIV, Vulcanizing Cement for SBR Compound.
The new SBR compound was further evaluated in production quantities by Wellco Ro-Search, Inc. One hundred pairs of DMS boots were made by this Company for evaluation. Wellco Ro-Search production personnel, however, believed that the new soling compound needed modification to suit their processing and molding equipment. A slight modification of the compound was made, and, using this modified formula, the one hundred pairs of combat boots were fabricated. The modified formulation for both rubber and cement compound is given in Table XV.
I Laboratory tests were also performed on the Wellco Ro-Search fabri- cated boots and the results are tabulated in Table XVI. The boots are presently under wear test.
1
The following test methods were used in the evaluation of these properties:
Property Tested Fed. Test Method, Std 601
Tensile strength 4111 Ultimate elongation 4121 Stress Ä 300X elongation 4131 Hardness 3021 Abrasion 14111 Volume swell 6211 Cure characteristics ASTM Designation D16+6 Cutgrowth ASTM Designation D1052 Ozone resistance Test was run according to
Par. 4.4.5, Test for Ozone Resistance, of MIL-B-43154
Bond strength Test was run according to Par. 4.4.6 of MIL-B-43154
Bond strength by dead weight application was run in accordance with Par. 4.4.6 of KLL-B-43154 except that a 20-pound dead weight was used for separation instead of the machine method of ASTM 0-413.
V. Results and Piscussion
It was shown in Table VI, Development of Polychloroprene-Containing Compounds, that Neoprene WRT can be compounded to give a good quality non- mark sole and heel compound.
Likewise, test results obtained with Folvblend-containing compounds listed in Table VII showed significant improvement in abrasion resistance of vinyl-modified Buna N when blended with cis-Polybutadiene-type rubber in varying amounts.
With the development compounding of Styrene-Butadiene-containing compounds, it was shown by test results in Table VIII that SBR 1502 can be definitely protected from ozone attack by blending it with Royalene X-400, an oil-extended Bthylene-Propylene Diene rubber, plus addition of antiozonant in normal amount. Likewise, the test results obtained with compounds listed in Table IX, Effect of ZnO Leading in SBR 1502, have shown that the most desirable properties of SBR 1302, reinforced with HiSil 233, can be obtained by omitting zinc oxide, which is normally needed in conventional rubber compounding.
Finally, the new compound SBR-29b, listed in Table XI, was evaluated against the present standard DMS compound. The test results, as shown in Table XII, showed the experimental compound to have properties, excepting gasoline resistance, comparable with the properties of the standard sole compound. This would indicate that satisfactory wear performance can be expected of this newly developed compound. The hard- ness property at 0°F, on the other hand, indicated that the SBR compound displayed less tendency to harden than the vinyl-modified Buna N compound. Again, this would demonstrate that the new SBR soling compound can be expected to provide better traction at low temperature and on snow and ice.
In addition, the test data obtained with the Wellco Ro-Search modi- fied SBR compound (listed in Table XV with test results on both the molded slab samples and finished boots shown in Table XVI) also compared favorably with the test data obtained with the original experimental compound SBR-29b, Furthermore, the test data also showed that the new compound can be satisfactorily produced by the direct molded sole technique.
VI. Conclusions
a. A high quality non-mark soling compound with very desirable
'
physical properties, excellent ozone resistance and good low temperature serviceability for direct molded sole combat footwear can be obtained with Styrene-Butadiene rubber type 1502.
b. A soling material with an unusually high abrasion characteristic and with good gasoline resistance can be obtained by blending is-Poly- butat'iene rubber with vinyl-modified Buna N.
VII. Recommendation
It is recommended that the new SBR base rubber compound be adopted for use in the Army Boot, Combat, Man's, Leather, Black, Direct Molded Sole, Mildew Resis"ant.
VIII.Acknowledgments
The author wishes to express his appreciation for the advice offered him by Mr. C. B. Griffis, for the assistance of Mr. Leonard Lulkc. with the milling, mixing, and curing operations and Mr. Charles Shurtleff with the physical testing, and Mr. D. S. Swain and Mr. L. H. l'Hollie-; for assistance in obtaining production quantities of boots.
IX. References
1. Rubber World, 1959, December, p. 376-382.
2. U.S. Army Test and Evaluation Command, U.S. Army Infantry Board, Fort Benning, Georgia^Project No. 8-4-6001-01, Final Report of Check Test of Boot, Combat, Leather, Direct Molded Sole, August 1965.
3. Elastomer Branch Report No. 41, "Investigation of Factors Affecting the Frictional Characteristics of Rubber Soling Material," by Angus Wilson, U.S. Army Natick Laboratories Natick, Mass, September 1961.
n
4. U.S. Army Quartermaster Research and Engineering Field Evalu- ation Agency, Fort Lee, Virginia, Final Letter Report, Engineering Design Test of Boots, Combat, Leather, DMS Con- ventional vs. Special Soling, TECOM 8-3-6000-02K, 26 May 19f.4.
5. Pittsburgh Plate Glass Company, Pittsburgh, Pa., Technical Service Bulletin, "HiSil in SBR Compounds," 6 October 1964.
6. Clothing and Organic Materials Division Technical Report No, 7, "Silica-Reinforced Ethylene-Propylena Diene Rubbers," by Peter Dunn and Vincent S. Javier, U.S. Army Natick Laboratories, Natick, Mass, August 1965.
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22
TABLE VI. DEVELOPMENT OF POLYCHLOROPRENE-CONTAIKIHG COMPOUNDS (Recipes and Test Results)
Ingredients*
Neoprene WRT XLC Magnesia ZnO Neozone A Flexzone 3C HiSil 233 SRF Black Stearic acid Light process oil Diethylthiourea Methyl tuads DOTG Sulfur
a. Compounding Recipe
63-C-19 63-C-45 (Parts by weight)
100 100 1 1 5 5 1 I 2 2
45 45 5 5
0.5 15 15 1.5 1.75 0.5 0.5 0.5 0.5 1 1
b. Test Recults at 12 min cure time/307°F
y
Physical properties
Hardness, Shore A Original After 1 hr 9 0°F After 70 hr 9 212°F
Abrasion Index Original After 70 hr 9 212°F
Outgrowth, Z, after 50,000 flexes Original After 70 hr 9 212°F
Properties of specimens taken from soles of Direct Molded Boots:
Hardness, Shore A Aged 70 hr 9 212°F
Outgrowth, X, after 50,000 flexes After 70 hr 9 212°F
Abrasion Index Original Aged 70 hr 9 212°F
Bond strength, lb.
66 6o 76 77 75 79
85 76 93 82
50 50 300 300
65 75
200
79 83 190
* See Appendix A for identification of materials listed by trade name.
23
TABLE VII. DEVELOPMENT COMPOUNDING OF POLYBLEND-CONTAINING RUBBER (Recipes and Test Results)
a. Ingredients*
Paracril Ozo Budene 501 Turgum S Octamine UOP 88 NALCO L-1718 HIS11 233 Phil Black 0 ZnO Stearic acid Sunproof Jr. Captax Altax DOTG Methazate Sulfur, spider Metalyn 100
b. Test Physical Properties Hardness, Shore A Original After 70 hr 0 212°F
Hardness, Shore A After 1 hr 0 0°F
Abrasion Index Original After 70 hr 8 212°F
Cutgrowth after 50,000 flexes, After 70 hr 9 212°F
Volume Swell in Ref Fuel B, of ASTM, 70/30 Isooctane/Toluene After 46 hr, %
Properties of Specimens taken from
Standard 63- 63- 63- 63- Compound NV-37 NV-38 NV-39 NV-39(x)
Compounding Recipes
100 80 95 90 90 20 5 10 10
3 3 3 3 3 1 1 1 1 1
1 1 1 1
45 45 45 45 45 3 3 3 3 3 3 3 3 3 3 1.5 1.5 1.5 1.5 1.5 1 1 1 1 1.5 1.5 1 1 1 0.5 0.5 1 1 1 0.5 0.5 0.25 0.25 0.25 0.5 0.5 0.25 0.25 0.25 0.5 1.5 1.5 1.5 1.5 1.5
20 20 20 20 20
Results at 10 min cure time/310°F
68 65 65 65 66 78 76 75 76 77
100 96 100 98 98
101 182 122 166 140 118 180 131 168 147
18
275
49 29
120
35
soles of Direct Molded Boots Hardness, Shore A Unaged 66 Aged 70 hr & 212°F 77
Abrasion Index Unaged 97 Aged 70 hr @ 212°F 107
Cutgrowth after 50,000 flexes, % Aged 70 hr 0 212°F 0
36
65 75
121 141
* See Appendix A for identification of materials listed by trade name.
24
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TABUS IX
DEVELOPMENT COMPOUNDING OF STYRENE-BUTADIENE-CONTAINING RUBBER - EFFECT OF ZnO LOADING IN S3R 1502
(Recipes and Test Results)
Ingredients* 65-
SBR-0 65-
SBR-3 65-
SBR-5 65-
SBR-1-
a. Recipes
SBR 1502 Royalene X-400 ZnO Stearic acid Agerite resin I UOP 88 HiSil 233 Phil Black 0 Al tax DOTG Tetrone A Sulfur
90 20
1 3
45 3 1.5 0.75 0.5 3
90 20 3
1 3
45 3 1.5 0.75 0.5 3
90 20 5
1 3
45 3 1.5 0.75 0.5 3
90 20 1 1 1 3
45 3 1.5 0.75 0.5 3
b. Test results at 15 min cure time/310°F
Tensile strength, psi Ultimate elongation, X Stress 9 3007.
2400 1250 590 300 750 1200
1400 2350 320 610 1200 650
Hardness, Shore A Original 67 70 71 68
Outgrowth after 50,000 flexes, 7. Aged 70 hr @ 212°F 600 900 900 400
Abrasion Index Original 145 83 79 137
* See Appendix A for identification of materials listed by trade name,
26
TT-lST — J - . ■' '
TABLE X. DEVELOEMENT COMPOUNDING OF STYRBNE-BUTADIBNE-COWAINING RUBBER
Ingredients* SBR-29 SBR-29b SBR-76 SBR-78 SBR-93 SBR-110
a. Compounding Recipes
SBR 1502 90 90 90 90 90 90 Royalene X-400 20 20 20 20 20 20 HiSil 233 50 50 50 50 50 50 KPC Black 3 3 3 3 3 3 Carbowax 4000 1.75 Stearic acid 1 1 1 1 I 1 ZnO 1 2 Sundex 53 10 10 12 10 Cumar MH-1 10 UOP 88 2 1.0 1.5 1.5 1.0 1 Flexzone 3C 2 1.5 1.5 1.5 1.5 1.5 TP-110 5 5 Agerite resin D 1 1 I 1 1 1 Captax 1.5 1.5 1.5 1.5 Altax 1.5 1.5 DOTG 0.5 0.5 0.8 0.8 0.5 0.75 Tetrone A 0.8 Thionex 0.25 Methazate 0.5 1.0 0.8 1 1.0 Sulfur 2.0 2.5 2.5 2.5 2.5 2.0 Reogen
b. Properties at indicated (cure time, min/temp,°F)
(12/307) (10/307) (12/310) ( 12/310K10/310) (10/310) Hardness, Shore A Original 57 63 60 60 61 61 After 2 hr & 0°F 70 12 73 71 73 72 After 70 hr @ 212°F 67 72 70 70 70 68
Abrasion Index Original 34 99 107 102 69 118 After 70 hr 9 212°F 140 141 121 87 119
Outgrowth after 50,000 flexes, % After 70 hr 0 212°F 150 150 4 200 250 200
Mooney Score?, Large Rotor, & 300°F Kin. viscosity 78 84 74 76 74 a)
Scorch time, T5, Min. 5.0 3.8 5.1 5.6 2.5 <0 JO 4-> a)
Cure time, T35, Min. 6.2 5.3 7.5 6.0 3.0 • -<
Ozone Cracking Test © «1 0 >
50 ♦ 10 pphm 9 100°F 5E 4
No sign of crack after 7 days 7 days 7 days 7 days 7 days
* See Appendix A for identification of materials listed by trade name.
2,7
TABLE XI
COMPARISON OF FORMULATION OF STANDARD AND SBR, DMS SOLING COMPOUND
Ingredients* Std. DMS (Parts by
SBR-?9b weight)
Polyblend (Psracril Ozo) 100 Styrene-Butadienc rubber 1502 90 Royalene X-400, KPDM 20 Turgura S 3 Octamine 1 Agerite resin D 1 Flexzone 3C 1.5 ÜOP 88 1.0 HiSil 233 45 50 EPC Black 3 3 ZnO 3 Stearic acid 1.5 1 Metalyn 100 20 Sundex 53 10 Sunproof Jr. 1 Captax 1.5 1.5 Altax 0.5 DOTG 0.5 0.5 Methazate c: 1.0 Sulfur, spider 1.5 2.5 Press cure, Time, Min/Temp,°F 10/310 10/307
* See Appendix A for identification of materials listed by trade name.
28
TABLE XII. COMPARISON OF PHYSICAL PROPERTIES OF RUBBER SOLING COMPOUND SBR-29b AND STANDARD DMS
Samples and Footwear
Std. DMS SBR-29b
a. Properties Tested on Press Cure Samples
Tensile strength, psi » 1800 1850 Ultimate elongation, X 680 700
I Stress Q 300X elongation, psi 800 480 Hardness, Shore A Unaged 70 65 Aged 70 hr Q 212°F 80 74 After 1 hr 6 0°F 100 74
Abrasion Index Unaged 102 99
f Aged 70 hr « 212°F 124 141 Vol. Swell after 46 hrs in ASTM Ref. Fuel B at room temperature Percent change 18 200
Ozone Cracking Test in Ozone Chamber at 50 + 10 pphra, ozone
j After 7 days S 100°F No sign of crack No sign of crack Mooney Viscosity - Large Rotor @ 300°F
| Minimum viscosity Scorch time, Min, T5 Cure time, Min, T35
Measured Specific Gravity Cutgrowth, %, after 50,000 flexes Aged 70 hr 0 212°F 0 150
b. Properties Tested on Finished Footwear
Bond strength, lb Rubber outsole to leather 225 155
Rubber soling Hardness, Shore A Unaged 70 63 Aged 70 hr @ 212°F 80 72
Abrasion Index Unaged 99 93 Aged 70 hr 8 212°F 110 131
Cutgrowth, %, after 50,000 flexes Aged 70 hr 0 2.2°F 25 55
Ozone Cracking Test in Ozone Chamber w/50 ♦ 10 pphm ozone 7 days 0 100°F No sign of crack No sign of crack
29
6 84 3.0 3.8 3.8 5.3 1.23 1.12
TABLE XIII
VULCANIZING CEMENT FOR THE STANDARD DMS COMPOUND
Masterbatch
Ingredients
Faracril CLT Octamine ZnO Phil Black 0 Stearic acid Cumar P25 Durez 12687
Total
Parts by "Weight
100 1.5
10 40 1
15 40
207.5
Part A Part R
Masterbatch Captax Methazate DOTG Spider sulfur
207.5 5 1 1
207.5
5.0 Total 214.5 212.5
MEK 645 639
Immediately before use, parts A and B are equally mixed. (See Appendix A)
30
TABLE XIV
VULCANIZING CEMENT FOR SBR RUBBER SOLE COMPOUND
Masterbatch
Ingredients
S3R 1502 Agerite Resin D EPC Black ZnO Stearic acid
Total
Parts by Weight
IOC 1
45 5 1.5
152.5
Masterbatch Sulfur Captax Methazate
Total
Part A
152.5 6
158.5
Part B
152.5
3 2
157.5
31
TABUS XV
WELLCO RO-SEARCH MODIFIED SBR FORMULATIONS
Soling and Cement Compound
a. Soling Compound b. Vulcanizing Cement
Ingredients* Parts by "Wt.
Neoprene AC 100 MgO 4 ZnO 5 HiSil 233 25 Agerlte stallte 2 Durez 12687 40
Add to solvent A-l Thiocarbanilide 4
Solvent: 2.25 parts toluene 2.25 parts MEK 1.00 part neoprene 620
* See Appendix A for identification of materials listed by trade name.
Ingredients* Parts by Wt.
SBR 1502 84 Royalene X-400.EPDM 20 fcnO 2 HiSil 210 50 Philliprene 1603 9 Agerite resin D 1 Stearic acid 1 Flexzone 3C 1.5 OOP 88 1.5 Sundex 790 7 Captax 0.82 Methazate 0.25 Carbowax 4000 1.75 Sulfur, spider 2.0
32
TABLE XVI
TEST DATA - WELLCO RO-SEARCH FABRICATED DMS BOOTS USING SBR COMPOUND
Properties Tested
Hardness, Shore A Original After 1 hr & 0°F After 70 hr 9 212°F
Abrasion Index Original Aged 70 hr <? 212°F
Cutgrowth, X, after 50,000 flexes Aged 70 hr @ 212°F
Ozone resistance d 50 + 10 pphm ozone and 0 100°F After 7 days exposure
Original, stress-strain Tensile strength, psi Ultimate elongation, % Stress @ 300% elongation, psi
Bond s ;rengch, lb Original After 7 days <? 158°F
Bond strength, dead weight application of 20 pounds After 4 hr @ room temperature
After 4 hr @ 158°F
Molded Slabs Samples from Finished Boots
63 73 70
63
71
92 93
88 89
100
No crack No crack
NA 2400 840 300
NA 170 NA 140
NA
NA
No appreciable separation
No appreciable separation
33
APPENDIX A
COMPOUNDING MATERIALS
Trade Name, Identification and Supplier (Code)*
Materials (Trade Name)
Agerite Powder
Agerite Resin D
Akroflex C
Al tax
Amax #1
Aminox
Budene 501
Butyl eight
Butyl oleate
Butyl stearate
Carbon black, Types
ETC
MPC
Phil Black 0
SRF
Captax
Carbowax 4000
Identification
Phenyl-B-Napthylamine
Polymerized trimethyl dehydro- quinoline
35Z N N'Diphenyl-P-phenylendlamine
Benzothiazyl disulfide
N-oxydiethylane-benzothiazole- 2-sulfenaraide
Reaction product of diphenylamine and actone
Cispolybutadiene type rubber
Activated dithiocarbamate
Easy processing channel
Medium processing channel
High abrasive furnace
Serai-reinforcing furnace
2-Mercaptobenzothiazole
Polyethylene glycol
Supplier*
18
18
4
4
18
10
19
18
20
20
•2,7
2,7
12
2,7
18
21
* See Appendix B for name of supplier
34
Materials (Trade Name)
Chemivic 100
Circosol 551
Circosol 591
Cumar MH-1
Cumar P25
DBP
DIDA
Diethylene glycol
Diethylthiourea
D10A
DOA
DOS
DOTG
DPG
Durez 12687
Dutrex 20
Eastozone 33
Flexol TOF
Flexzone 3C
APPENDIX A (Cont'd)
COMPOUNDING MATERIALS
Identification
Butadiene-Aerylonitrile/ Polyvinylchloride blend
Naphthenic type oil
Naphthanic type oil
Coumarene-idene resin medium grade
Para coumarene-indene resin
Dibutyl phthalate
Di-isodecyl adipate
Di-isoctyl aoipate
Di-atyl adiphate
D±-otyl sebacate
Di-orthotolylguanidine
Di-phenylguanidine
Phenolic resin
Aromatic Hydrocarbon oil, (no longer supplied)
N,N'-bis(l,4 dimethylphenyl-p- phenyl tried iamine
Tri (2-ethylhexyl) phosphate
N-i sopropy1-N'-pheny1-p- phenylenediamine
Supplier
19
15
15
11,1
1
8,22
8
20
4
8
21
21
4
8
23
22
21
10
35
Materials (Trade Name)
Flexzone 6-H
HiSil 233
Hycar 1072
Hypalon 40
Light process oil
Litharge
XLC magnesia
Metalyn 100
Methazate
Methyl tuads
Mistron vapor
NA-22
NA-33
NALCO L-1718
NBC
Neoprene W
Neoprene WRT
Neozone A
Neozone D
Octamine
APPENDIX A (Cont'd)
COMPOUNDING MATERIALS
Identification
N-phenyl-N'-cyclohexyl-p-phenylene diamine
Hydrated silica
Carboxylic acid terpolymer
Chlurosulfonated polyethylene
Naphthenic oil (light colored)
Lead oxide
Extra light magnesium oxide
Methylated tall oil ester
Zinc dimethyl dithiocarbamate
Tetramethylthiuram disulfide
Magnesium silicate
2-Mercapt iomidazo1ine
Modified mercaptiomidazoline (no longer supplied)
Folyalkanalpolyamine
Nickel butyl carbamate
Polychloroprene
Polychloroprene
N-phenyl-alpha-napthylamine
N-phenyI-beta-napthylamine
A reaction product of diphenylamine & diisobutylene
Supplier
10
13
5
4
25
24
25
6
10
4
14
4
9
4
4
4
4
4
10
36
APPENDIX A (Cont'd)
COMPOUNDING MATERIALS
Materials (Trade Name) Identification Supplier
Paracril CLT Butadiene-acrylonitrile copolymer 10
Paracril Ozo Nitrile-polyvinylchloride resin blend
10
Paragon clay Hydrated aluminum silicate 7
PER 200 Pen tacrythri ta1 6
Permalux Di-ortha-tolylguanidine, salt 4
Philliprene 1603
Red iron oxide
Reogen
Royalene X-400
Santocure
SBR, type
1500
1502
1504
1023
1778
1712c
Stearic acid
Sulfur
of dicatechol borale
Styrene-butadiene rubber, master- batched with carbon black
Mixture of an oil soluble sulfonic acid w/high molecular weight
Ethylene-propylene diene-oil extended rubber
N-cyclohexyl-2-benzothiazole sulfenamide
Styrene-butadiene copolymer
12
28
18
10
10,12,29
10,12,29
10,12,29
10,12,29
19
19
20
18
37
Materials (Trade Name)
Sundex S3
Sundex 790
Sunolite wax
Sunproof Jr.
TCP
Tetrone A
Thermoflex A
Thionex
Thiuram M
Triethanolamlne
TP-90-B, plasticizer
TP-110, plasticizer
Turgum S
Unads
Ü0P 88
UOP 688
Wingstay 100
ZnO
APPENDIX A (Cont'd)
COMPOUNDING MATERIALS
Identification
Aromatic type oil
Aromatic type oil
Selected blend of waxy hydrocarbons
Mixture of selected waxes
Tricresylpho3phate
Dipentamethylene thiuram tetrasulfide
p-p dimethoxydiphenylamine and 25X diphenyl-p-phenylene diamine
Tetramethylthiuram monosulfide
Tetramethylthiuram disulfide
A high molecular weight polyether
Polyether plasticizer
Terpene resin acid blend
Tetramethylthiuram monosulfide
N.N'-bisd-raethyl heptyl)-p- phenylene diamine
Unsymetrically substituted phenylene diamine
Mixture of diaryl-p-phenylene diamine
Zinc oxide
Supplier
15
15
26
10
8,13
4
4
4
20
16
16
7
18
17
17
19
20,27
38
APPENDIX B
MATERIAL SUPPLIERS
Number
1. Allied Chemical Corporation, Philadelphia, Pennsylvania
2. Cabot Corporation, Boston, Mass.
3. Diamond Alkali Company, Cleveland, Ohio
4. E. I. duPont deNemours and Company, Inc., Wilmington, Delaware
5. B. F. Goodrich Chemical Company, Cleveland, Ohio
6. Hercules Powder Company, Wilmington, Delaware
7. J. M. Huber Corporation, New York, N. Y.
8. Monsanto Chemical Company, Akron, Ohio
9. Nalco Chemical Company, Chicago, Illinois
10. Naugatuck Chemical Company, Naugatuck, Connecticut
11. Neville Chemical Company, Pittsburgh, Pennsylvania
12. Phillips Petroleum Co., Rubber Chemicals Div., Akron, Ohio
13. Pittsburgh Plate Glass Company, Pittsburgh, Pennsylvania
14. Sierra Talc and Clay Company, So. Pasadena, California
15. Sun Oil Company, Philadelphia, Pennsylvania
16. Thiokol Chemical Corporation, Trenton, New Jersey m
17. Universal Oil Products, Des Piaines, Illinois
18. R, T. Vanderbilt Company, Inc., New York, N. Y.
19. Goodyear Chemicals, Akron, Ohio
20. The C. P. Hall Company, Akron, Ohio
21. Union Carbide Corporation, New York, N. Y.
22. Eastman Chemical Products, Kingsport, Tennessee
39
APPENDIX B (Cont'd)
MATERIAL SUPPLIERS
Number
23. Hooker Chemical Corp., Durez Plastics Div., Niagara Falls, N.Y.
24. National Lead Company, New York, N. Y.
25. Marine Magnesium Products Div., Merch Co. Inc., Rahway, N. J.
26. Witco Chemical Company, Inc., New York, N. Y.
27. St. Joseph Lead Company, New York, N. Y.
28. Eaton Chemical & Dye Stuff Company, Detroit, Michigan
29. Goodrich Gulf Chemicals, Cleveland, Ohio
40
Unclassified Security Clasjlficaüon
DOCUMENT CONTROL DATA • R&D (Security claaalfleallan e/ Uli: boa> <rf aa*«i»el and Indixint jmwijWjW guaj aa anfaiW »hit Of art mil npon I* clttttlttd)
I. ORIGINATING ACTIVITY fCorpor.1. «-(hod
U. S. Army Natick Laboratories Natick Massachusetts QlZfiQ
1*. BIPORT ittuniTY C LAMIPICATION
Unclassified 2* tnour
1 REPORT TITLE
LOW-TEMPERATURE TRACTION RUBBER SOLE COMPOUND FOR CMS COMBAT FOOTWEAR
4. DESCRIPTIVE NOTE* (Typ» el raaert ana* Inefcialva data«;
Evaluation Report |. AUTHORW (Lm»t nan*. Ilrmt nmrn». Initial)
Javier, Vincent S.
« REPORT DATE
March 1967 7«. TOTAL O. OP PA«II
40 la. CONTRACT OR OR ANT NO.
t, PROJCCTNO. 1CO24401A329
IRf«>
67-72-CM,
• a. 9TMBM. REPORT HO(S) (Any o«Mr niaaaara «at nmy 6» aaai^iaa1
C&OM-34 10. AVAILASILITV/LIMITATION NOTICE*
Distribution of this document is unlimited. Release to CFSTI Is 'Authorized.
II. SUPPLEMENTARY NOTES 12. SPONSORINO MILITARY ACTIVITY
U. S. Army Natick Laboratories Natick Massachusetts 01760
It. ABSTRACT
A new direct molded sole rubber compound designed primarily to give better traction at low temperature, and on snow and ice, than the present standard vinyl-modified Buna N rubber compound, has been successfully developed by utilizing Styrene-Butadiene rubber (SBR), type 1502.
The vulcanizeces of this new compound exhibited good physical properties which are comparable with the physical properties exhibited by the present standard sole compound. In addition, this new compound also displayed excellent ozone resistance and good low-temperature behavior - a property which makes this compound more suitable for wear on snow and ice.
Furthermore, the test results on the finished boot samples showed that the new SBR compound has satisfied not only the curing conditions imposed by the CEMA and Wellco process but also the physical requirements, except for solvent resistance, which are specified in Military Specification, MIL-B-43154, for the standard direct molded sole (DMS) combat boot.
DD FORM I JAN (4 1473 Unclassified
Secu.ity Classification
Unclassified Security Classification
KEY WORDS LINK B LINK C
Development SPR Rubbers Rubber Synthetic rubber Vulcanizates Low-temperature Direct-molded sole (DMS) Combat footwear Testing Evaluation Physical properties Traction Wear resistance Military requirements
8 8,9 9 9 9 0 4 4
9 9 8 8 9 9 9 4
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Unclassified SecurityCIa Sim cation
