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W1 :al Report 53-12o I SHELL `A DEVELD - / cowpAr:/ '' . TECHNICAL Elevated FILES lemperature Resistant Modified Epoxide Resin Adhesives for Metalls for United States Air Force Materials Laboratory i Wright Air Development Center Wright-Patterson Air Force Base, Ohio Contract No. AF 33(616)- 334 7 Task No. 73401 Final Report December I, 1955 - November 30. 1956 Except for use by or on behalf of the United States Government, rn accordance with contractual arrange ments, all rights with respect to this report, in cluding, without limitation, technical information, data, drawings, and specifications contained herein, are reserved by Shell Development Company. SHELL DEVELOPMENT COMPANY EMERYVILLE, CALIFORNIA WADC TECHNICAL REPORT 53-126 Part 4 ELEVATED TEMPERATURE RESISTANT MODIFIED EPOXIDE RESIN ADHESIVES FOR METALS Marguerite Naps Shell Development Company November, 1956 WRIGHT AIR DEVELOPMENT CENTER ABS-043713 NOTICES When Government drawings, specifications, or other data are usei for any purpose other than in connection with a definitely related Governnent procurement operation, the United States Government thereby incurs no respon sibility nor any obligation whatsoever; and the fact that the Government may have formulated, furnished, or in any way supplied the said drawings, speci fications, or other data, is not to be regarded by implication or otherwise as in any manner licensing the holder or any other person or corporation, or conveying any rights or permission to manufacture, use, or sell any patented invention that may in any way be related thereto. The information furnished herewith is made available for study Upon the understanding that the Government's proprietary interests in and relating thereto shall not be impaired. It is desired that the Judge Advocate (WCJj Wright Air Development Center, Wright-Patterson Air Force Base, Ohio, be promptly notified of any apparent conflict between the Government's proprij etary interests and those of others. This document may not be reproduced or published in any form in whole or in part without prior approval of the government. Since this is a progress report the information herein is tentative and subject to changes 9 corrections, and modifications. ' TECHNICAL REPORT 53-126 4 ELEVATED TEMPERATURE RESISTANT MODIFIED EPOXIDE RESIN ADHESIVES FOR METALS Marguerite Naps Shell Development Company November, 1956 Materials Laboratory Contract No. AF 33(6l6)-3347 Project No. (7340) Wright Air Development Center Air Research and Development Command United States Air Force Wright-Patterson Air Force Base, Ohio ABS-0437171 FOREWORD This report was prepared by Shell Development Company under USA? Contract No. AF 33(616)-3347. This contract was initiated under Project No. 7340, "Rubber, Plastics, and Composite Materials", Task No. 13401, "Structural Adhesives". The work was administered under the direction of the Materials Laboratory, Directorate of Research, Wright Air Development Center, with Mr. T. Martin acting as project engineer. This report covers work conducted from December 1, 1955 through November 30, 1956. WADC TR 53-126 Pt 4 AiBS-04371 $ TABLE OF CONTENTS Introduction ............................................................................................ Adhesives Based on Experimental Resin X-131 With No Modifying Resins .................................................................................... Adhesives Based on Experimental Resin X-131 With EPON 1009 and EPON 834 ................................................................................................... Adhesives Based on Experimental Resin X-131 and Vinyl Resins . Adhesives Based on 80/20/20 X-131/EP0N 1009/Formvar 15/95 E . Adhesives Based on New Experimental Resins ................................... Procedures for Metal Treatment and Adhesive Bond Preparation . Page 1 1 4 7 13 19 22 WADC TR 53-126 Pt 4 iv ABS-04372Q LIST OF TABLES Table No. 1 Effect of Test Temperature on the Shear Strength of X-131/Dicyandiamide Bonds to Type 301 Steel ....................... gage 41 2 Effect of Exposure Time at 500F on the Shear Strength of X-13l/Dicyandiamide Bonds to Type 301 Steel ....................... 42 3 Effect of Postcuring on the Shear Strength of X-131/ Dicyandiamide Bonds to Type 301 Steel ................................... 43 4 Effect of Drying Time at 200F of X-13l/Dicyandiamide Tapes an the Shear Strength of Bonds to Type 301 Steel . 44 5 Effect of Dicyandiamide Concentration on the Shear Strength of X-131 Bonds to Type 301 Steel .............................................. ^5 6 Effect of Aluminum Filler Concentration on the Shear Strength of X-13l/Dicyandiamide Bonds to Type 301 Steel . . . 46 7 Effect of Copper 8-Quinolinolate on the Shear Strength of X-13l/Dicyandiamide Bonds to Type 301 Steel ....................... . . 47 8 Shear Strength of Bonds to Type 301 Steel From X-131 Adhesives With 4-6 PHR Curing Agent E.................................. . . 48 9 Shear Strength of Bonds to Type 301 Steel From X-131 Adhesives with 13 PHR Curing Agent E ....................... 49 10 Shear Strength of Bonds to Type 301 Steel From X-131 Adhesives Cured with Benzimidazolyl Guanidine . . . 50 11 Shear Strength of X-13l/Diaminodiphenylsulfone Bonds to Type 301 Steel .............................................................. 51 12 Shear Strength of Bonds to Type 301 Steel From X-131 Adhesives Cured With 4,4',4''-Triaminotriphenylmethane . . . . 52 13 Effect of X-131/EP0N 1009 Resin Ratio on the Shear Strength of Bonds to Type 301 Steel Cured With Dicyandiamide ............... 53 14 Effect of X-131/EP0N 1009 Resin Ratio on the Shear Strength of Bonds to Type 301 Steel Cured With Diaminodiphenylsulfone..................................................................... 54 15 Effect of Drying Time at 200eF of X-131/EP0N 1009/ Dicyandiamide Tapes on the Shear Strength of Bonds to Type 301 Steel ................................................................................. 55 WADC TR 53-126 Pt 4 v ABS-0 3721 LIST OF TABLES (CONTD) Table No. Page 16 Shear Strength of Bonds to Type 301 Steel From X-131/ EPON 834 Hot Melt Adhesives Cured With Diaminodiphenylsulfone ...................................................... 56 17 Effect of Formvar 15/95 E Concentration on the Shear Strength of X-13l/Dicyandiamide Bonds to Type 301 Steel ............... . . 57 18 Effect of X-13l/Formvar 15/95 E Resin Ratio on the Shear Strength of Bonds to Type 301 Steel Cured With Diaminodiphenylsulfone......................................................... . . . 58 19 Effect of BF3-400 on the Shear Strength of Bonds to Type 301 Steel Fran 100/20 X-13l/Formvar 15/95 E Adhesives Cured With Diaminodiphenylsulfone ......................................................... 59 20 Comparison of the Shear Strength of Bonds to Type 301 Steel From 100/20 X-13l/Formvar 15/95 E Adhesives With Asbestos and Aluminum Fillers............................... ... .......................... ...... 60 21 Effect of Bisphenol-A on the Shear Strength of 100/20 X-13l/Formvar 15/95 E Bonds to Type 301 Steel . . . 61 22 Shear Strength of Bonds to Type 301 Steel From 100/20 X-13l/Formvar 15/95 E Adhesives Cured With Melamine 62 23 Shear Strength of Bonds to Type 301 Steel From X-131 Adhesives Cured With Curing Agent BF3-400 ....................... 24 Shear Strength of Bonds to Type 301 Steel From 100/20 X-13l/Formvar 15/95 E Adhesives Cured With Acid-Type Curing Agents ............................................................................. 63 64 25 Shear Strength of 100/20 X-13l/Formvar 15/95 E Bonds to Type 301 Steel (Formulation No. 1219) ............................... 65 26 Effect of 500F Exposure on the Shear Strength of 100/20 X-13l/Formvar 15/95 E Bonds to Type 301 Steel (Formulation No. 1219) ............................................................. 66 27 Effect of Postcure on the Shear Strength of 100/20 X-13l/Formvar 15/95 E Bonds to Type 301 Steel (Formulation No. 1219) .............................................................. 6l 28 Bend Strength of X-131 Adhesive Bonds to Type 301 Steel WADC TR 53-126 Pt 4 vi LIST OF TABLES (CONTD) Table No. ?age 29 Comparison of the Shear Strength of Type 301 Steel Adhesive Specimens Cut With a Do-All Band Saw and a Mill Saw............... 69 50 Shear Strength of Bonds to Type 301 Steel From X-131/ Gelva C-3-V-30 Adhesives Cured With Diaminodlphenyl- " 70 31 Shear Strength of Bonds to Type 301 Steel From X-131/ Gelva C-3-V-30 Adhesives Cured With Diaminodiphenylsulfone and Benzyldimethylamine Promoter ... ....................... 71 32 Shear Strength of Bonds to Type 301 Steel From X-131/ Gelva C-3-V-30 Adhesives Cured With Dicyandiamide ................... 72 33 Summary of the Shear Strength of Bonds to Type 301 Steel From Formulation No. 1236, Batches 1 Through 13 ....................... 73 34 Summary of the Shear Strength of Bonds to Type 301 Steel From Formulation No. 1236, Batches 14 Through 27 ...... 74 35 Summary of the 600F Shear Strength of Bonds to Types 301 and 17-7 PH Steel and to Titanium From X-131 Resin Adhesives ................... ......................................................................... 75 36 Effect of Elevated Temperature Aging on the Shear Strength of Formulation No. 1236 Bonds to Type 301 Steel ....................... 76 I 37 Long Time Load Strength at 500F of X-131 Adhesive Bonds to Type 301 Steel ................................................................................ 77 38 Properties of Experimental Resin X-131 ...................................... 78 39 Comparison of the Shear Strength of Bonds to Type 301 Steel From Formulation No. 1236 Prepared With Various X-131 Resin Lots ........................................................................................ 79 40 Effect of Postcure on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to Type 301 Steel (Formulation No. 1236) ................................................................. 80 41 Effect of Metal Surface Treatment on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar I5/95 E Bonds to Type 301 Steel ......................................................................... 81 WADC TR 53-126 Pt 4 vii LIST OF TABLES (CONTD) Table No. k2 Shear Strength of Bonds to Type 301 steel From an 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesive Tape With Stainless Steel Carrier ............................................................. Page 32 ^5 Effect of Salt Spray Exposure on the Shear Strength of Bonds to Type 501 Steel From Formulation No. 1236 . . . . , 83 44 Comparison of the Shear Strength of Bonds to Type 301 Steel From Formulation No. 1256 Adhesive Tapes Prepared With Methylal and Acetone ..................................................................... 84 45 Effect of Method of Bond Preparation on the Shear Strength of Formulation No. 1236 Bonds to Type 301 Steel ................... 85 46 Effect of X-131 Resinous Primers on the Shear Strength of Formulation No. 1236 Bonds to Type 301 Steel ....................... 86 47 Room Temperature Storage Stability of X-131 Supported Adhesive Tapes With Diaminodiphenylsulfone ............... 48 Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesive Bonds to Type 17-7 PH Steel (Formulation No. 1236) ............................................................. 87 88 49 Shear Strength of Bonds to Titanium (C-110 M Alloy) From 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesive (Formulation No. 1236) ............................................................. 89 50 Effect of Diaminodiphenylsulfone Concentration on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to Type 301 Steel ............................................................................. 90 51 Effect of Aluminum Filler and Diaminodiphenylsulfone Concentrations on the Shear Strength of X-13l/Formvar 15/95 E Bonds to Type 301 Steel................................................................. ... 91 52 Effect of Bisphenol-A on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to Type 301 Steel ... 92 53 Shear Strength of Bonds to Type 301 Steel From 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesives Cured With Dicyandiamide Dispersed in the Resin Solution ............... 54 Shear Strength of Bonds to Type 301 Steel From 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesives Cured With Melamine .................................................................................... 93 94 WADC TR 53-126 Pt 4 viii ABS-0 4372 T.TST OF TABLES (CONTD) Page Identification and Properties of Experimental Modified X-131 Resin........................................................................................... Shear Strength of Bonds to Type 301 Steel From Experimental Modified X-131 Resin Cured With Dicyandiamide........................... 95 96 Shear Strength of Bonds to Type 301 Steel From Experimental Modified X-131 Resin Cured With Diaminodiphenylsulfone . . . 97 Shear Strength of Bonds to Type 301 Steel From Experimental Resin X-141 Cured With Diaminodipbenylsulfone ....................... . 98 Shear Strength of Bonds to Type 301 Steel From Experimental Resins LR2047-76 and LR2047-83 Cured With Diaminodiphenylsulfone ..................................................................... 99 Shear Strength of Bonds to Type 301 Steel From Experimental Resin LR2047-98 Cured With Di aminodiphenylsulfone................ 100 Shear Strength of Bonds to Type 301 Steel From Experimental Resin LR2047-126 Cured With Diaminodipbenylsulfone .... 101 Summary of the 600F Shear Strength of Bonds to Type 301 Steel From New Experimental Resins ................................... 102 Shear Strength of Bonds to Type 301 Steel Fran Resins Cured With Combinations of Pyromellitic Dianhydride and Maleic Anhydride ............................................................................................ 103 Shear Strength of Bonds to Aluminum From Resins Cured With Combinations of Pyromellitic Dianhydride and Maleic Anhydride ................................................................................ 104 Shear Strength of Experimental Resin X-801-3 Adhesive Bonds to Type 301 Steel Cured With Diaminodipbenylsulfone . . 105 Shear Strength of X-131/X-401-3 Adhesive Bonds to Type 301 Steel .................................................................................... 106 Shear Strength of Bonds to Type 301 Steel From X-131/X-701 Adhesives Cured With Dicyandiamide .............................................. 107 68 Shear Strength of Bonds to Type 301 Steel From Blends of X-131 Resin and Experimental Resin LR2047-199 ................ 108 ^ WADC TR 53-126 Pt 4 ix LIST OF TABLES (CONTD) Table No 69 Comparison of the Shear Strength of X-131 Adhesive Bonds to Clad Aluminum Alloy and Type 301 Steel........................... 70 Identity and Source of Materials Evaluated in High Temperature Adhesive Formulations ............................... 109 110 WADC TR 53-126 Pt 4 4BS-Q4372 LIST OF ILLUSTRATIONS Figure No. 1 Effect of Test Temperature on the Shear Strength of X-151 Adhesive Bonds to 501 Steel .................................................. 2 Effect of Exposure at 500F on the 500F Shear Strength of X-15l/Dicyandiamide Bonds to 301 Steel ................................... 3 Effect of Exposure at 500F on the 500F Shear Strength of Bonds to 301 Steel From X-131 Adhesives Cured With Dicyandiamide and Diaminodiphenylsulfone.................................. 4 Effect of X-131/EP0N 1009 Ratio on the Shear Strength of Bonds to 301 Steel Cured With Dicyandiamide and Diaminodiphenylsulfone ..................................................................... 5 Effect of Formvar 15/95 E Concentration on the Shear Strength of X-13l/Dicyandiamide Bonds to 301 Steel ................................... 6 Effect of Formvar 15/95 E Concentration on the Shear Strength of X-131/Diaminodiphenylsulfone Bonds to 301 Steel ............... 7 Effect of Exposure at 500F on the 500#F Shear Strength of 100/20 X-131/Formvar 15/95 E Bonds to 301 Steel ....................... 8 Effect of Postcuring at 400#F on the Bend Strength of X-13l/Formvar 15/95 E Adhesive Bonds to 301 Steel ................... 9 Effect of Aging at 500F on the 500*F Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to 301 Steel . 10 Effect of Aging at 500F on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Adhesive Bonds to 301 Steel . 11 Effect of Aging at 600F on the 600F Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to 301 Steel . 12 Comparison of the Shear Strength of Bonds to 301 Steel From Formulation No. 1236 Prepared With Various Lots of X-131 Resin (No Postcure) ............................................................................ 13 Comparison of the Shear Strength of Bonds to 301 Steel From Formulation No. 1236 Prepared With Various Lots of X-131 Resin (Postcured 2 to 4 hr at 400F) .......................................... 9 3[3 34 38 20 23 24 25 26 27 WADC TR 53-126 Pt 4 xi LIST OF ILLUSTRATIONS (CONTD) Figure No. Rage 14 Effect of Aging at 500F on the 500F Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to 301 Steel With Various Surface Treatments .......................................................... 30 15 Effect of Aging at 500F on the 500F Shear Strength of Bonds From Formulation No. 1236 to Type 17-7 PH Steel ............... 32 16 Effect of the Concentration of Diaminodiphenylsulfone on the Shear Strength of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E Bonds to 301 Steel............................................................................ 3^ WADC TR 53-126 Pt 4 xii HIGH TEMPERATURE METAL TO METAL ADHESIVES Introduction This report summarizes the preparation and evaluation of heat resistant adhesives based on Experimental Resin X-131 and other experimental! resins. The principal task of this project was the development of a resinous adhesive which is useful for bonding corrosion resistant metals for service at 500F Elevated temperature adhesives based on Experimental Resin X-131 (previously designated EPON X-15100) were investigated briefly under Contract AF 33(616)-2430 and described in WADC Technical Report 53-126, Part 3 (September, 1955). The adhesives showed premising performance at temperatures up to 500F for bonding stainless steel. Further development work was undertaken under the current WADC Contract AF 33(616)-3347. The studies were directed primarily to techniques for improving the adhesion to metal surfaces, the extensibility and toughness of the resin, the thermal stability on long time aging, and the reproducibility of adhesive performance. Exploratory investigations were also made of the utility of five new solid experimental resins and five new liquid experimental resins for the formulation of heat resistant adhesives for stainless steel. These resins are characterized, in general, by greater functionality compared with that of X-131 and commercial EPON resins. Adhesives Based on Experimental Resin X-131 With No Modifying Resins Picyandiamide Cure Experimental Resin X-131 cured with dicyandiamide and containing aluminum dust filler appeared to be the most promising heat resistant adhesive developed under Contract AF 33(616)-2430 [see WADC Technical Report 53-126, Part 3 (September, 1955)]. The adhesive was vised in the form of a supported tape with glass fabric 112-Volan A as the carrier. An acetone solution of X-131 resin {60$ solids) was blended with the curing agent dissolved in boiling solvent at a 1/2/3 weight ratio of dicyandiamide/water/acetone. The homogeneous solution was then stirred *ith finely divided aluminum dust (MD105). After concentration to about 85^ solids by stirring and mild heating, the solvent dispersion was applied to the glass fabric with simple doctor knives. The impregnated fabric v;us dried for 15 minutes at 200F to remove solvents. Manuscript released by author April, 1957 for publication as a WADC Technical Report. WADC TR 53-126 Pt 4 1 ABS-04 B729 Maximum adhesive bond strength and heat resistance occurred wita a loading of 100 phra) aluminum dust filler and 6 phr dicyandiamide (Formulation No. 1145). The adhesive ves quite brittle, however, and the reproducibility of bond performance was poor. Adhesive shear strength for bonds to stainless steel was about 2000 psi at room temperature, 750 to 1000 psi at 500F, and 600 psi after 200 hours at 500F. The test results for fourteen batches of supported adhesive tape (previous and current work) follow: '* Surface Treatmentd) Tensile Shear Strength,a) psi at 77F at 500F at 500F After 200 hr at 500rF Range Avg Range Avg Range Avg Method Ab) 1605-2205 2010 420-1050 745 330-1035 590 Method Bc) 1650-2595 2195 710-1460 1080 300-905 620 a) Bonds to type 301 steel cured one-half hour at 330F. b) Used for 12 batches of adhesive tape in 14 tests. c) Used for 6 batches of adhesive tape in 7 tests. d) Refer to the section on metal treatment for a description of the methods used. The effect of test temperature on the shear strength of X-131/ dicyandiamide bonds to half-hard type 301 steel is shown in Figure 1 and Table 1. Illustrative data follow: Test Temperature Tensile Shear Strength, psi -70 F 77F 500F 600 F 2525 2200 420 60 . Deterioration in adhesive strength upon aging at 500F was quite rapid. Loss in bond strength occurred on relatively short exposure periods of 3 to 48 hours. After longer periods of 168 to 224 hours, the adhesive strength-increased to values about 70$ f the original strength at 5008F. The effect of exposure time at 500F upon the shear strength of bonds from Formulation No. 1145 is shown graphically in Figure 2. The exDerimental data are summarized in Table 2. Typical data follow: a) In conformance with the practice used in all previous reports on heat resistant adhesive formulations, the abbreviation "phr" is used to designate the concentration of all types of ingredients as parts by weight per hundred parts of total polvenoxide resin. --------- ' WADC TR 53-126 Pt 4 2 AflS-04373Q WADC TR 53-126 Part 4 3500 isd 'mSuaj^s 3 snsuaj, A$S-0 4373 -70 0 100 ................... ............................... ......... 200 300 T est Tem perature, F 400 t 500 ............................. ...... F ig u re 1. E F F E C T O F T E S T T E M P E R A T U R E O N T H E S H E A R S T R E N G T H O F X -131 A D H E S IV E BONDS TO 301 S T E E L 600 1400 WADC TR 53-126 Part 4 O o CsJ O 00 NoO o 0u31 o o = <\J ^ o o o in o o rt 0) (U h 00 s aox W o vO T03) cd ~co cd o `^V4 \D w T3> 5| fe 3 S po o 4- P rO --i i jcCd X 4') oc oo OJ .*- (-1 3 X;)u ---** 'mtf o 2: oTf rNJ co 3 o 6fx o Ife A0S-O43732 Exposure T-fm* at 500F, hr Tensile Shear Strength, psi 0 790 8 350 48 260 168 370 200 525 Further development work and formulation studies of the X-151/ dicyandiamide/aluminum dust adhesive were undertaken with the hope of! improving 1) initial shear strength values at room temperature and 5O0F, 2) heat resistance to aging at 500F, and 3) reproducibility of bond performance. No significant improvement in shear strength or reproduci bility was observed in the following experiments: 1. Postcuring X-13l/dicyandiamide adhesive bonds for one to three hours at 400F improved adhesive shear strength slightly at room temperature, 500F and at 500F after 200 hours' aging at 500F (Table 3). 2. Postcuring X-13l/dicyandiamide adhesive bonds for one to three hours at 500F reduced adhesive shear strength at the three test conditions (Table 3). 3. Increasing the drying period of the supported adhesive tape from 15 minutes to two hours at 200F increased the initial strength at room temperature slightly and the 500F strength about 30#. Bond strength after 200 hours' exposure at 500F was not altered appreciably, however (Table 4). 4. No significant change in adhesive shear strength was observei as the dicyandiamide concentration was increased from 6 to 14 phr (Table 5) 5. No significant change in adhesive shear strength was observed as the aluminum dust filler loading was increased from 75 to 200 phr with 6 phr dicyandiamide as the curing agent (Table 6). 6. Copper 8-quinolinolate (0.5 to 2.0 phr) had no apparent I effect on the shear strength or on the heat resistance of X-13l/dicyandiamide adhesives (Table 7). Evaluation of Various Curing Agents Four new compounds, benzimidazolyl guanidine, 2,6-diaminopyridin^ (Curing Agent E), 4,4',4"-triaminotriphenylmethane and mixed isomers df diaminodiphenylsulfone, were evaluated as curing agents for X-131 adhesiven in comparison with the performance of dicyandiamide. All of these confounds are more soluble than dicyandiamide and can be handled more readily in acetone solutions of X-131 resin. The shelf life of the adhesive solution^ and tapes with each of these compounds except diaminodiphenylsulfone was very limited, however. The adhesive bonds and shear strength test results WADC TR 53-126 Pt 4 5 for 100/100 X-13l/aluminum dust tapes are summarized in Tables 8 and 9 (Curing Agent E), Table 10 (benzimidazolyl guanidine), Table 11 (diamino diphenylsulfone) and Table 12 (4,4s4"-triaminotriphenylmethane). Mediocre bond strength was obtained with all of the curing agents except diaminodiphenylsulfone. This compound was slightly superior to dicyandiamide in the development of strength at 500F and markedly superior in strength retention on 500F exposure. Figure 3 shows the effect of aging at 500F on the 500F shear strength of X-131 bonds cured with dicyandiamide and diaminodiphenylsulfone. Illustrative test data are giv^ below for X-131 adhesive bonds cured one-half hour at 310 to 330F with the new curing agents. Curing Agent, phr Tensile Shear Strength, pisi at 77#F at 500F at 500F Afftler| 200 hr at 500 6e 13E 10 benzimidazolyl guanidine 20 " " 23.5 4,4',4"-triaminotriphenylmethane 30 diaminodiphenylsulfone 6 dicyandiamide 1875 1665 1175 1425 Q65 2300 2100 1200 425 530 110 525 1090 85O 1000 285 595 415 375 885 600 Adhesives Based on Experimental Resin X-131 With EPON 1009 and EPON 834 X-131/EP0N 1009 Adhesive Tapes EPON 1009 (molecular weight 4000) was used in combination with Experimental Resin X-131 with the hope of reducing the brittleness of X--13$adhesives. Supported adhesive tapes with glass fabric 112-Volan A were prepared with 90/10, 80/20 and 70/30 X-131/EP0N 1009 resin ratios as follows: 1. Prepare a solution of X-131 in acetone (60% solids). 2. Dissolve the curing agent, dicyandiamide or diaminodiphenyl sulfone, in the resin solution to form a homogeneous blend. a) Dicyandiamide must be added in boiling solvent at a 1/2/3 dicyandiamide/water/acetone weight ratio to achieve compatability. b) Diaminodiphenylsulfone dissolves in the X-131 resin solution. Heating must be avoided to prevent premature reaction. VADC TR 53-126 Pt 4 6 ABg-04B734 Isd `itoOOS JB mSuaa^s -Baqs ausuax WADC TR 53-126 Part 4 7 O as H O 2 w OS H co OS < w K co eOO in W X E-* w1 2 O fci J fe0c O CPO ro co soO o in H < W OS D c<1 4 i>d S5 w X a. -* a o 2 03 a u a. o c> ^ 9 JXdS1 ac> o CO OCu X w < Q 0u3) Q 2 2 Ui c u cHo w fcl om fe w o E-1 C/3 CO <L3WU, Q 2 O X H [ii A^S-< 14373 4 ~ 3. Add EPON 1009 solution (50$ solids in acetone or methyl ethyl ketone). i 4. Disperse finely divided aluminum dust (MD105) in the resin curing agent solution. 5. Concentrate the solvent dispersion to about 80$ solids by stirring at room temperature. - 6. Apply the concentrated adhesive dispersion to glass fabric, 112-Volan A. 1 7. Dry the impregnated fabric about one hour at room temperatur^ and 15 minutes at 200F. Thickness of tape is 12-14 mil. The effect of X-131/EP0N 1009 resin ratio, in the range of 100/0 to 70/30, on the shear strength of adhesive bonds to type 301 steel is give|n in Table 13 for dicyandiamide cures and in Table 14 for diaminodiphenyi- sulfone cures. These data are also plotted in Figure 4. The limited test data, though somewhat erratic, indicated the following for adhesives cured with dicyandiamide or diaminodiphenylsulfone: : 1. The brittleness of the X-131/EP0N 1009 adhesives decreased with increasing EPON 1009 content. This behavior was reflected in the increased (20 to 30$) room temperature shear strength. 2. The shear strength at 500F was reduced 20 to 30$ by the replacement of 10 to 30 per cent of the X-131 resin with EPON 1009. 3. There was no appreciable difference in the thermal stability of adhesives with 100/0, 90/10, 80/20 and 70/30 X-131/EP0N 1009 resin ratio^ (as judged by the 500F shear strength data for specimens aged 200 hours at 500#F). I Typical test results for bonds to full hard type 301 steel cured with 6 phr dicyandiamide at contact pressure for one-half hour at 330#F follow: 5 X-131/EP0N 1009, by wt 100/0 90/10 80/20 70/30 Tensile Shear Strength, psi at 77F at 500F at 500"F After 200 hr at 500CF ! 1930 770 680 | 2225 755 635 ; 2205 585 1235 2335 655 780 2800 WADC TR 53-126 Part 4 ca = ffi A^S-04373 r Illustrative data follow for bonds to half-hard type 301 steel cured at 100 psi with 30 to 21.5 phr diaminodiphenylsulfone for one-half hour at 240F plus one-half hour at 350F and postcured for two hours at 300F. X-131/EP0N 1009. by wt Tensile Shear Strength, psi at 77#F at 500F at 500F After 200 hr at 500F 100/0 90/10 80/20 70/30 2255 2315 2255 2640 1075 750 775 785 780 900 700 885 The effect of the drying time at 200F applied to X-131/EP0N 1C09/ dicyandiamide adhesive tapes on adhesive bond performance was also studied briefly (see Table 15). The initial strength at room temperature increafed 2% (to 2700 psi) and the 500F shear strength increased 8o (to 102$ psi) as the drying period was increased from 15 minutes to 120 minutes at 200* F. Shear strength at 500#F for bonds aged 200 hours at 500F decreased ; (to 415 psi) progressively as the drying time at 200F was increased. Hot Melt Blends of X-131 and EPON 834 EPON 834, a viscous liquid epoxide resin, was used in combinati on with Experimental Resin X-131 (softening point 170F) to improve the flow and wettability of the solid resin. Hot melt adhesives were prepared wi rX-I31/EPON 834 resin ratios of 50/50, 60/40 and 70/30. Diaminodiphenylsvilfone at a concentration of one amine hydrogen atom per epoxide group was the curing agent. The reinforcing filler, aluminum dust, was used at a Xoadi):|ng of 100 parts by weight per hundred parts of total resin. Bonds to type 301 steel were assembled with glass cloth reinforcement and cured for one-haijf hour at 240F plus one-half hour at 330F at 100 psi. The test results are given in Table 16. The X-131/EP0N 834 adhesives were characterized by brittleness and mediocre heat resistance. The data follow: X-131/EP0N 834. by wt Tensile Shear Strength, psi at 77F at 500F at 500F After 200 hr at 500#F 50/50 60/40 70/30 100/0 1560 1945 3215 2815 375 375 no U40 550 525 445 830 TR 53-126 Pt 4 10 Adhesives Based on Experimental Resin X-131 and Vinyl Resina Experimental Resin X-131 was modified with high molecular weight vinyl resins of high softening point with the hope of increasing the extensibility of the adhesive bonds. The resins included 1) Formvar 15/95 polyvinyl formal, and 2) Gelva C-3-V-30, carboxylic-modified polyvinyl acetate. X-13l/Formvar 15/95 E Adhesive Tapes Formvar 15/95 E (softening point 387#F) was dissolved in tetrahydrofuran and combined with acetone solutions of X-131 resin. Supported adhesive tapes with good bond performance were prepared with glass fabric (112-Volan A) as the carrier in the following manner: 1. Prepare a solution of X-131 resin in acetone (60$ solids). 2. Dissolve the curing agent in the X-131 resin solution to form a homogeneous blend. a) Dicyandiamide must be added in boiling solvent at a 1/2/3 dicyandiamide/water/acetone weight ratio. b) Diaminodiphenylsulfone and acid-type curing agents evaluated in this work dissolve directly in the resin solutions at room temperature. Heating should be avoided to preclude premature cure. 3. Add Formvar 15/95 E solution (10$ solids in tetrahydrofuran). 4. Disperse the filler (aluminum dust or asbestos fibers) in the resin-curing agent solution. 5. Concentrate the adhesive dispersion to a solids content of 58-60$ by stirring at room temperature. 6. Apply the concentrated solvent dispersion of the adhesive to glass fabric (112-Volan A). 7- Dry the impregnated fabric about one hour at room temperature and 15 minutes at 200F. Thickness of tape, 12-14 mils. Formvar 15/95 E Concentration The effect of the concentration of Formvar 15/95 E on the performance of X-131 adhesives was investigated with two curing agents, 1) dicyandiamide and 2) diaminodiphenylsulfone. X-131 adhesive tapes were prepared with 10, 15, 20, and 30 phr Formvar 15/95 E, 100 phr aluminum dust filler and 4 phr dicyandiamide. The addition of 10 phr Formvar 15/95 E improved the toughness and adhesive strength at room temperature with little WADC TR 53-126 Pt 4 11 ABS-04 3739 or no sacrifice in bond strength after 200 hours' aging at 500F. Further increases in room temperature shear strength were obtained with higher amounts (15 to 30 phr) of the vinyl resin, but the hot strength of the unaged bonds decreased rapidly. The test results are given in Table 17 and shown graphically in Figure 5. The data for bonds to full hard type 501 steel cured at contact pressure for one-half hour at 330#F and postcured three hours at 400F follow: 15/95 E, phr Tensile Shear Strength, psi at 77F at 500F at 500F After 200 hr at 500F 0 2305 1190 825 10 3085 975 805 15 3095 595 795 20 3710 500 1125 30 4200 375 665 The effect of X-13l/Formvar 15/95 E resin ratio on adhesive bond performance was investigated for formulations cured with diaminodiphenylsulfone. This curing agent was used at the theoretical concentration (one amine hydrogen atom per epoxide group) based on the polyepoxide content of the resin blend. In two parallel series of experiments with 5/1, 3/l> l/l and 1/5 X-13l/Formvar 15/95 E resin ratios the aluminum dust filler content was used at concentrations 1) equivalent to the polyepoxide resin content and 2) equivalent to the total resin content (polyepoxide plus vinyl resins). The complete test results are given in Table 18. Poor elevated temperature strength at 500F was obtained for formulations with l/l or 1/3 X-13l/Formvar 15/95 E resin ratios. A ratio of 5/1 appeared to be about maximum for the development of any reasonable strength (640 psi) at 5Q0F. Formulations with 5/1 and 3/l resin ratios also had good resistance to thermal degradation upon aging at 5008F. Poor reproducibility, which is characteristic of current X-131 adhesives, was, unfortunately, also observed for the X-131/Formvar 15/95 E blends. Figure 6 shows the effect of X-13l/Formvar 15/95 E ratio (with 100 phr aluminum dust filler) on the shear strength of adhesive bonds at 1) room temperature, 2) 500F, 3) 500F after 8 fcours at 500F, and 4) 500F after 200 hours at 500F. The test results for bonds to half-hard type 301 steel cured at 100 psi with diaminodiphenylsulfone for one-half hour at 2408F plus one-half hour at 330F follow: WADC TR 53-126 Pt 4 12 ^ADC TH 53-126 Part 4 isd 'q;Suaa;s aeaqs ansuax 13 4200 C oncentration of F o rm v a r 15/95E, phr F ig u r e 5... E F F E C T O F F O R M V A R 1 5 /9 5 E C O N C E N T R A T IO N O N T H E S H E A R S T R E N G T H O F X -1 3 1 /D IC Y A N D IA M ID E BONDS T O 301 S T E E L l f---------------------- C u r e : o n e -h a h o u r a t 3 3 0 F w ith 4 p h r d ic y a n d ia m id e------------------------ P ostcure: 3 hours at 400 F o<M AfiS-04374 4500 isd 'm3uaa}S JBaqs ausuax W SB E- Z eO O CO Z o H-4 H < a (h J30d 6z w u % oh iJs3VC1 z o c o u w iOn' 0 o S s 05 < > s 05 o at *1* t3, i3! *O-*t :Ki J73i3 pq O 4) oC H U w <^t ma ptl pH o H 3 Vu os>* 3 U fan X-13l/Formvar 15/95 E, by wt Tensile Shear Strength, psi at 77F at 500F at 500"F After; 200 hr at 500F 100/0 83.3/16.7 75/25 50/50 25/75 2420 3555 2895 4045 4210 1100 640 345 0 0 900 1030 850 560 0 ,,: An attempt to accelerate the cure of X-13l/Formvar 15/95 E/ diaminodiphenylsulfone adhesives with a boron trifluoride complex (Curing Agent BF3-400) was unsuccessful. A reduction, rather than the desired increase in initial strength at 500P was observed for an asbestos filled 5/1 x-13l/Formvar 15/95 E adhesive which contained 1 phr BF3-400 and the normal amount (50 phr) of diaminodiphenylsulfone (see Table 19). The adhesive shear strength at each test condition was 20 to 50^ lower for asbestos-filled adhesives cured in the presence of BF3-400. Neutral asbestos fibers at a loading of 30 phr was equivalent to 100 phr aluminum dust in a single test of a 100/20 X-13l/Formvar 15/95 adhesive cured with diaminodiphenylsulfone (Table 20). Bisphenol-A at a concentration of 2 to 10 phr was evaluated as a cure promoter for a 100/20 X-13l/Formvar 15/95 E adhesive with curing agent diaminodiphenylsulfone. The. test results are given in Table 21. Small amounts of Bisphenol-A (2 to 5 phr) appeared to have no significant effect on the initial 500F shear strength. At higher concentrations (10 phr) a 60f> reduction in hot strength was observed. Strength at 50D*F after 200 hours' aging at 500F appeared to be decreased about 30$. Pertinent data are given below for 100/20 X-13l/Formvar 15/95 E bonds to half-hard type 301 steel cured at 100 psi for one-half hour at 240#F plus one-half hour at 330F with diaminodiphenylsulfone in the presence of Bisphenol-A. Bisphenol-A, phr Tensile Shear Strength, psi Original at 500F After 500F Aging for 00 0 at 77 F at 8 hr 200 hr 0 3605 1020 1505 950 5 4235 880 1285 690 10 4135 355 1080 675 WADC TR 53-126 Pt 4 15 Evaluation of Various Curing Agents Diaminodiphenylsulfone appears to be the most promising curing agent for heat resistant 100/20 X-13l/Formvar 15/95 E adhesive formulations. An exploratory study of other curing agent systems was undertaken in view of the slow rate of cure with the sulfone. The curing agents included 4 4 > jV'-triaminotriphenylmethane, melamine, boron trifluoride complexes of urea and ammonia, and BF3-400, acid salts (magnesium perchlorate and zinc fluoborate) and bexahydrophthalic anhydride. The adhesive formulations are described in Table 12 (triaminotriphenylmethane), Table 22 (melamiijie). Table 23 (BF=i-400) and Table 24 (remaining compounds). Supported adhesive tapes were prepared with solvent solutions of 100/20 X-131/Formvar 15/95 E with neutral asbestos or aluminum dust fillers and 30 phr diaminodiphenyl sulfone. Melamine and the acid salts were dispersed in the resin solutions; boron trifluoride complexes and bexahydrophthalic anhydride were dissolved. None of the compounds appeared to be as effective as diaminodiphenylsulfone (or dicyandiamide) for the production of heat resistant bonds. In addition, the thermal stability on long time aging at 500F was mediocre or poor in the limited number of tests. Illustrative data for 100/20 X-13l/Formvar 15/95 E adhesive bonds (cured one-half hour at 330F) to half-hard type 301 steel follow: Curing Agent, phr Tensile Shear Strength, psi at 77F at 500F at 500F After 200 hr at 500F 4,4',4"-triaminotriphenylmethane melamine BF3-400 BF3-urea BF3-ammonia Mg(C104)2 Zn(BF4)2-7H20 hexahydrophthalic anhydride 1430 3830 2405 2735 1635 2125 0 975 455 245 515 440 50 420 0 0 330 645 420 0 0 0 0 0 100/20/30 X-13l/Formvar 15/95 E/Diaminodiphenylsulfone Adhesive (Formulation No. 1219) One of the most promising heat resistant adhesive formulations was a glass fabric supported adhesive tape of the following composition (parts by wt): 100 X-131 + 20 Formvar 15/95 E + 100 aluminum dust + 30 diaminodiphenylsulfone. Bond performance was fairly reproducible in 16 tests of nine different batches of resin. Table 25 summarizes the shear strength values for bonds to type 301 steel cured at 100 psi for one-half hour at 240F plus one-half hour at 330F (with and without a postcure of two hours at 300-400#F). Typical data follow: VADC TR 53-126 Pt L, 16 No Postcure Postcured 2 hr at 300-400F Tensile Shear Strength, psi At -70F At room temperature At 500F, original , after 500F aging, 200 hr At 600F Bend Strength, lb 3750 840 745 - 156 3355 2710 800 850 235 no The effect of test temperature on adhesive shear strength of Formulation No. 1219 in the range of -70 to 600F is shown graphically in Figure 1. Formulation No. 1219 showed good thermal stability on type 301 steel upon aging at 500F. Figure 7 shows the effect of exposure time at 500F on the 500F adhesive shear strength of Formulation No. 1219 (average of four batches of adhesive tape) in comparison with the correspond ing adhesive cured with dicyandiamide. Illustrative data taken from the tests results in Table 26 follow: Exposure Time Tensile Shear Strength at 500F. psi at 500oF, hr Range Avg of 4 Batches 0 640-1020 8 895-1690 72 1155-1495 200 630-1030 820 1340 1355 905 The effect of postcuring of Formulation No. 1219 bonds on the initial 500F shear strength was studied in view of the improved strength (60$ increase) of specimens tested after eight hours' aging at 500F. Table 27 summarizes two series of experiments with oven postcures of 1) 2 to 8 hours at 300 to 500F and 2) 2 to 32 hours at 270 to 400F. The test results were unfortunately too erratic for interpretation. In general, however, postcures at moderate temperatures of 270 to 400F had no consistent effect on the initial hot strength of the adhesive bonds. In all cases, however, embrittlement of the bond occurred as reflected in the decrease^ room temperature shear strength values. Data for bonds from adhesive batch No. 9 cured at 100 psi for one-half hour at 240F and one-half hour at 33DF follow: Postcure hr 11 None 16 270 8 330 2 400 16 400 Tensile Shear Strength, at 77F at 500F 3630 3400 3225 2700 , i860 715 755 835 895 1090 WADC TR 53-126 Pt 4 17 ABSH0437 45 ADC TR 53-126 Part 4 isd 'JoOOS qjguaa^S Jesqs sususx 18 1600 F ig u re 7. E F F E C T OF EXPOSURE A T 500 F ON TH E 500 F SHEAR STRENGTH ------------------ O F 1 0 0 /2 0 X - 1 3 1 /F O R M V A R 1 5 /9 5 E B O N D S T O 301 S T E E L C onstant: 100 p h r a lu m in u m dust ------------------------------------------------- C u r e : o n e - h a lf h o u r a t 330 PF -------------------------------------------------- O o rsj c 00 o su3o: oIM (x o oin oo o 00 soo o ro WauWOa3x> ABI^-04 3746 The embrittlement of the 100/20 X-131/Formvar 15/95 E adhesive on elevated temperature postcuring at 300 to 400#F was also reflected in the bend strength of the bonds. A limited number of test results j lTable 28) showed a 35$ decrease in bend strength for bonds postoured eight hours at 400F. The data for bonds to type 301 steel cured at 100 psi for one-half hour at 240F plus one-half hour at 330F are plotted iin Figure 8 and are also given below: Postcure hr UL None 8 330 4 400 8 400 Bend Strength, lb 156 138 114 112 Adhesive test specimens described in this report were cut from type 301 steel panels with circular slit saws mounted on a milling machine. Several panels, however, were cut with a Do-All band saw in the investigation of postcured bonds from Formulation No. 1219. A comparison of the adhesive shear strength test results for the mill-sawed and bandsawed specimens (Table 29) indicated that the method of cutting had no appreciable effect on the initial strength at room temperature and at 5(|>0aF. The resistance of the specimens to prolonged aging at 500F was reduced markedly, however, for bonds cut with the band saw. Thermal degradation of the adhesive was probably initiated at the edges of the specimens which were badly discolored on sawing. Shear strength at 500F after 200 hours' exposure was 830 psi for the band-sawed bonds compared with a value of 1355 psi for corresponding mill-sawed bonds. Gelva C-3-V-30 Gelva C-3-V-30, a high molecular weight, carboxylic modified polyvinyl acetate resin (softening point 356F), was evaluated briefly as a flexibilizer for X-131 adhesives. It was hoped that no sacrifice in heat resistance would occur because of the possible coreaction of the resins through the carboxyl group. Supported adhesive tapes from acetone solutions of 9O/IO to 70/30 X-13l/Gelva C-3-V-30 containing 100 phr aluminum dust filler were cured with 1) diaminodiphenylsulfone (Table 30). 2) diaminodiphenylsulfone with a tertiary amine promoter (Table 31) and 3) dicyandiamide (Table 32). The preliminary experiments indicated that Gelva C-3-V-30 was inferior to Formvar 15/95 E (polyvinyl formal) for the formation of thermally stable X-131 adhesives. The toughness and extensibility of adhesive bonds with 16.7 to 25 phr Gelva C-3-V-30 was improved, but strength at 500F and resistance to aging at 500F were reduced regardless of the curing agent used. Illustrative test results follow for bonds to 301 steel cured at 100 psi with diaminodiphenylsulfone for one-half hour at 240F plus one-half hour at 330#F. WADC TR 53-126 Pt 4 19 ABS4043747 Luoz jdi am in o d ip h on y ls u lfo n e Resin, Parts by wt Tensile Shear Strength, psi at 77F at 500F at 500"F After 200 hr at 500F 100 x-131 83.3/16.7 X-131/Gelva C-3-V-30 83.3/16.7 X-131/Formvar 15/95 E 2420 3340 4015 1060 785 1285 1115 320 1095 Adhesives Based on 80/20/20 X-131/EP0N 1009/Fonavar 15/95 E Good thermal stability on aging at 500F was obtained in the initial tests of a combination of 80/20/20 X-131/EP0N 1009/Fonnvar 15/95 E cured with 24.5 phr diaminodiphenylsulfone and containing 100 phr aluminum dust filler. The curing agent content was calculated on the basis of one amine hydrogen atom per epoxide group in the combined polyepoxide resins. An extensive evaluation was made with this formulation (No. 1236) in view of the excellent 500F shear strength (1200 psi) of bonds to type 301 steel aged 200 hours at 500F. Supported adhesive tapes with good bond perfcrmanc were prepared with solvent dispersions of the adhesive according to the following procedure: 1. Prepare a solution of X-131 resin in acetone (60$ solids content). 2. Dissolve diaminodiphenylsulfone in the X-131 solution at room temperature. 3. Add EPQN 1009 solution (50$ solids in acetone). 4. Add Formvar 15/95 E solution (10$ solids in tetrahydrofuran). 5. Disperse aluminum dust (MD105) in the resin-curing agent solution. 6. Concentrate the adhesive dispersion to 58-60$ by stirring at room temperature. 7. Apply the concentrated solvent dispersion of the adhesive to glass fabric (112-Volan A). 8. Dry the impregnated fabric about one hour at room temperature and 15 min at 200F. Thickness of tape is 12-14 mils. Bonds to Type 301 Steel Adhesive bonds with Formulation No. 1236 were cured in a press at 100 psi for one-half hour at 240F plus one-half hour at 330F or only ifor one-half hour at 330#F. Some of the bonds were also postcured (oven) for periods of 2 to 4 hours at 300 to 4008F. The test results for 27 batches WADC TR 53-126 Pt 4 21 ABB-043749 of adhesive tape are given in Tables 33 and 34. In general, postcuring decreased shear strength at room temperature (4000 to 2700 psi) and increased the hot strength from a relatively low value of about 550 psi to 900 psi at 500F. The strength retention of adhesive bonds from Formulation No. 1236 in a temperature range of -70 to 600F is shown graphically in Figure 1. A sharp decrease in shear strength occurred as the test temperature was increased from 77 to 500F. The data are summarized in Tables 35 and 34 and in Table 35 (600F tests). Typical data for bonds cured at 100 psi for one-half hour at 240F plus one-half hour at 330F follow: Test Temperature -70F 778F 500F 600F _____ Tensile Shear Strength, psi No Postcure Postcure 2-4 hr at 400~F 3680 3300-4000 200-645 330 3480 2400-3400 625-870 200 The effect of elevated temperature aging of the unstressed adhesive bonds at 500F and 600*F on tensile shear strength is given in Table 36. Some of these tests results are also plotted in Figures 9 and 10 (500F exposure) and Figure 11 (600F exposure). Illustrative data follow: Tensile Shear Strength, psi Aging Condition at 500F at 600*F 8 hr at 500F 200 hr at 500F 400 hr at 500F 8 hr at 600#F 120 hr at 600F - 455 740 In a very limited study of long time load resistance at 500F, adhesive bond failure occurred after 485 and I55 hours' aging at stresses of 400 and 500 psi, respectively. No evidence of creep was observed. Long time load test data are given in Table 37 Reproducibility of the bond performance of adhesive Formulation No. 1236was disappointing. Differences in various lots of X-131 resin appeared to be one of the factors which affected the hot strength and thermal stability of bonds at 500F. No correlation between resin properties and bond performance could be made from the available data, however. The properties of various batches of X-131 resin are given in Table 38. A comparison of the performance of three batches of X-131 resin is given in Figure 12 (bonds without postcure) and Figure 13 (bonds postcured 2 to 4 hours at 400F). The complete test results for Formulation No. 1236 i WADC TR 53-126 Pt 4 22 ABS-043750 4000 c TSd `qjSuaajs JaqS ausuaj, WADC TR 53-126 Part 4 24 o(M o \<M o co (l< O DC t* O 2 W 05 tHo 05 < .u 2 *! W cso W DC IO H 2 Ol O 0) j: ooOh t at oiTl wA3Oax) H < O 2 HH o < 0< o H U w 0-1 H tvt3anp!, Oh C <2 ft 3 Si w Si c> *, -haaC> t;a, TO3 XC 5 t 8 cd ^ "O lf> acc +3 -(0 N^ 3 *. *a cd 8 ll 8 sc 33 m3 4,2 S 2O 8g, MCM o c o~ H 4-> 3 01 33 <fnv 8uo V3 Oh ABS-04375| 400 C 3800 3600 c 7> \ i 1 0 X-13 1 Resin L ot LR 199] -113 LR 3522 -147-1 LR 3522 -31 1400 I1200 1000 ll I800 1U |1 600 V- % 1400 200 0 Room Temp 1 1 500F l1 | 500F Aged 8 hr at 500 F 1 1 1 1 500F Aged 200 hr at 500 F ire 12. COMPARISON OF THE SHEAR STRENGTH OF BONDS TO 301 STEEL FROM FORMULATION NO. 1236 PREPARED WITH VARIOUS LOTS OF X-131 RESIN (NO POSTCURE) Cure: one-half hour at 330 F at 100 psi 53-126 Part 4 26 Figure 13. COMPARISON OF THE SHEAR STRENGTH OF BONDS TO 301 STEEL FROM FORMULATION NO. 1236 PREPARED WITH VARIOUS LOTS OF X-131 RESIN (POSTCURED 2 TO 4 HR AT 400 F) Cure: one-half hour at 330F at 100 psi TT WADC TR 53-126 Part 4 27 ABS- prepared with various X-131 resin lots are summarized in Table 39. The average shear strength values for bonds prepared with 5 and 6 batches of adhesive tape cured at 100 psi for one-half hour at 240F plus one-half hour at 330F are the following: Tensile Shear Strength, psi X-131 Resin Lot LR1991-115 LR3523-1%7-1 At 77F At 50OF At 500F after 8 hr at 500F At 500F after 200 hr at 500F 3950 530 1295 II65 3940 460 910 635 Corresponding test data for bonds postoured 2 to 4 hours at 400F follow: Tensile Shear Strength, psi ______X-131 Resin Lot LR1991-113 LR3523-147-T At 77F At 500F . At 500F after 8 hr at 500#F At 500F after 200 hr at 500F 2420 870 1265 1040 3110 745 745 640 As shown in the above examples, postcuring Formulation No. 1236 bonds for 2 to 4 hours at 400F decreased room temperature strength 25 to 40$ and increased the 500F strength 60 to 70$. Attempts to find postcuring conditions which would develop greater initial strength at 500"F were unsuccessful. The experimental results are given in Table 40. Illustrative data for bonds cured at 100 psi for one-half hour at 240F plus one-half hour at 330F follow: Postcure hr F Tensile Shear Strength, psi at 77#F at 500F at 500F After 200 hr at 500F None 16 270 4 330 8 400 16 400 3900 4025 3700 3015 2935 495 610 735 IO65 875 680 535 715 805 445 The embrittlement of adhesive bonds from Formulation No. 1236 upon postcuring at elevated temperature is also reflected in the decrease in the bend strength of the bonds. The effect of postcuring on bend strength is shown in Figure 8 and Table 28. Pertinent data follow: WADC TR 53-126 Pt 4 28 ABS- Q437J Postcure hr 11 None 8 330 4 400 8 400 8 500 Bend Strength, lb 186 149 133 115 48 no significant difference in the joint strength of Fonnulatian No. 1236 to type 301 steel which was prepared for bonding with four different surface treatments. These treatments included 1) sulfuric acid followed by hydrofluoric/nitric acid, 2) formalin-peroxide solution, 3) formalin-peroxide solution followed by passivation with chromic acid and 4) chromic/sulfuric acid. Shear strength was 4000 psi at roan temperature, about 600 psi at 500#F, and 1200 psi at 500F for bonds aged 200 hours at 500F for each of the treatments. The test results are given in Table 41. Figure 14 shows the effect of aging time at 500F on the 500F shear strength of bonds to 301 steel prepared with various surface treatments. No appreciable difference in joint strength was observed in a single experiment in which glass fabric carrier was replaced with stainless steel woven wire (see Table 42). Erratic bond performance precluded a valid evaluation of the salt spray resistance of Formulation No. 1236 bands to type 301 steel. Shear strength retention was 50 to 87$ of the unexposed "control" specimens after 30 days' salt spray exposure in a limited number of tests. The data are given in Table 43. . Exploratory studies were made of the effect of process variables in adhesive tape and adhesive bond preparation in order to increase adhesive strength and to reduce the wide scatter of strength values of Formulation No. 1236. These experiments included 1) use of methylal in the adhesive resin solution in place of a portion of the ketone solvent, 2) changes in the cure cycle, 3) postcuring in the press directly after cure, and 4) use of X-131 resinous primers. No appreciable improvement in shear strength or in the repeatability of adhesive performance was observed in a limited study of these factors. The test results are given in Table 44 (tape prepared with methylal). Table 45 (cure conditions) and Table 55 (X-I31 primers). The storage stability of adhesive Formulation No. 1236 at room temperature was not determined. A few spot checks of aged tape indicated that the performance of the adhesive may be altered appreciably by room temperature storage. Low strength values, especially for the 500F tests, were obtained with stored tape (see Table 47). The results of a single experiment with Formulation No. 1236 bonds to 301 steel cured at 100 psi WADC TR 53-126 Pt 4 29 ABS-043757 ADC TR 53-126 Part 4 30 F o rm u la tio n , p h r: 100 a lu m in u m dust + 24. 5 d ia m in o d ip h e n ylsu lfo n e C ure at 100 p si: o n e -h a lf h o u r at 240F + o n e -h a lf h o u r at 3308F I for one-half hour at 240F and one-half hour at 330F follow: Tensile Shear Strength, psi Age of Adhesive Tape at Room Temperature Fresh 8.2 Months At 77F 4095 3380 At 500"F At 500F after 8 hr at 500F 675 1390 305 1105 At 500F after 200 hr at 500F 1410 200 Bonds to Type 17-7 PH Steel and Titanium A preliminary evaluation of the strength of Formulation No. 1236 bonds to type 17-7 PH steel showed that the joint strength to this metal is equivalent to the strength to type 301 steel. No significant difference in behavior was noted in a single test of the bond strength for 17-7 PH which was heat treated in air or in helium. The test data for experiments with 17-7 PH steel are summarized in Table 48. The effect of aging at 500F on the 500F shear strength of bonds to type 17-7 PH steel is shown graphically in Figure 15. Illustrative data for bonds cured at 100 psi for one-half hour at 240F plus one-half hour at 330"F and postcured two hours at 400F follow: ` Type of Steel Tensile Shear Strength, psi at 77F at 500F at506*F Afte^ 200 hr at 500| F 17-7 PH (heat treated in air) 17-7 PH (heat treated in helium) 301 885 955 705 The adhesive bond strength of Formulation No. 1236 to C-110 M titanium alloy treated with chromic-sulfuric acid was mediocre (see Table 49). Shear strength values for bonds cured at 100 psi for one-half hour at 330#F were as follows: at room temperature 2275 psi; at 500F, about 200 psi; at 500 after 200 hours' aging at 500F, about 400 psi. Formulation Studies of Adhesives Based on a Blend of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E The effect of di aminodiphenylsulfone concentration on the bond strength of the 80/20/20 X-131/EP0N 1009/Formvar 15/95 E was studied briefly for formulations containing 100 and 120 phr aluminum dust as the reinforcing filler. Supported adhesive tapes were prepared with 12 to 29 phr of diaminodiphenylsulfone. Bonds to type 301 steel were cured at 100 psi for one-half hour at 240F plus one-half hour at 330F. Some of the bonds were also postcured for two and four hours at 400F. Shear strength test results at room temperature, at 500F, and at 500F after 200 hours' exposure WADC TR 53-126 Pt 4 31 A0S-O4375$ rAC TR 53-126 Part 4 1400 xsd 'j[o00S q;Suaa;s JBaqs atisuaj, 32 sWu3Oi eOfoixn< (d <u s*** H 0u) ia3on x W F ig u re 15. E F F E C T O F AG ING A T 5 0 0 F ON T H E 500F SHEAR STR EN G TH O F BONDS F R O M F O R M U LA T IO N NO. 1236 TO T Y P E 17-7P H S T E E L C ure at 100 p si: o n e -h a lf h o u r a t 330 F F..................... ....... P o s tc u r e : tw o h o u r s a t 4 0 0 .................... ................ A&S-0437 at 500F are summarized in Table 50 (100 phr filler) and Table 51 (120 phr filler). The limited test data indicated that maximum joint strength and strength retention on 500F aging was obtained with 24 to 29 phr diaminodiphenylsulfone. The application of a postcure increased the initial strength of the bonds with 12 to 20 phr diaminodiphenylsulfone; the values were less than with the higher concentrations of the sulfone, however. The shear strength test results are plotted in Figure 16 and are also summarized below: Adhesive Bonds Without Postcure Diaminodiphenylsulfone, phr Tensile Shear Strength, psi at IV? at 500F at 500F After 200 hr at 500F 12 16 20 24.5 29 1195 1050 2010 4095 4310 0 0 535 675 1010 325 325 1045 1410 1325 Adhesive Bonds Postcured 4 Hours at 400F Tensile Shear Strength, psi Diaminodiphenylsulfone, phr at 77 "F at 500#F 12 16 20 24.5 1605 1980 2610 2370 340 595 1025 940 Bisphenol-A (2 to 10 phr) was added to Formulation No. 1236 with of increasing the rate of cure of the resins and consequently of increasing the hot strength of the unaged bonds. The limited data (Table 52) indicated that small amounts of this additive (2 to 5 phr) increased 500F shear strength slightly; higher concentrations of Bisphenol-A (8 to 10 phr) decreased the hot strength. The erratic test results precluded a valid evaluation of the effect of the additive on the thermal stability of the adhesive, although it appeared that resistance to aging at 500F was reduced with 8 to 10 phr Bisphenol-A. Shear strength data follow for bonds to 301 steel cured at 100 psi for one-half hour at 240F plus one-half hour at 330F: WADC TR 53-126 Pt 4 33 ABS WADC TR 53-126 Part 4 iud 'qiSuajJS J**MS aijsuax 34 4800 F ig u re 16. E F F E C T O F T H E C O N C E N T R A T IO N OF D IA M IN O D IP H E N Y LS U LF O I ON THE SHEAR STRENG TH OF 80/20/20 X -1 3 1 /E P Q N 1009/FQ R M VAR 15/95E BONDS T O 301 S T E E L C onstant: 100 p h r a lu m in u m dust .................. C u re a t 100 p s i: o n e - h a lf h o u r a t 240 F + o n e - h a lf h o u r a t 330 F g| AB$-04 0762 Bisphenol-A, phr at 77DF at 500F 0 4155 645 2 4205 775 5 4140 785 8 4215 420 10 4065 375 The utility of several other curing agents for a blend of 80/20/20 X-131/EP0N 1009/Formvar 15/95 E was studied briefly. The compounds included 1) poorly soluble, latent curing agents, dicyandiamide and melamine, 2) 4,4% 4"-triaminotriphenylmethane, and 3) phthalic acid. Solvent spread supported adhesive tapes were prepared in the usual manner except for dicyandiamide and melamine which were dispersed in the resin solutions. The formulations are described in Table 12 (triaminotriphenylmethane). Table 24 (phthalic acid), Table 53 (dicyandiamide) and Table 54 (melamine). The hot strength of bonds cured with each of these compounds was very poor (0 to 385 psi at 500F). Bonds with dicyandiamide and melamine developed further strength on exposure to 500F, indicating a very slow rate of cure. The heat resistance of bonds cured with 4,4',4"triaminotriphenylmethane and phthalic acid was mediocre. Illustrative data for bonds to 301 steel cured at 100 psi for one-half hour at 240F plus one-half hour at 330F follow: Curing Agent, phr Tensile Shear Strength, psi at 500F After at 77F at 500F 200 hr at 500; 8 hr 200 hr 6 10 19 47.5 24.5 dicyandiamide melaminea) 4,4',4"-triaminotriphenylmethane phthalic acid) diaminodiphenylsulfone 2590 2660 3035 3925 3950 0 910 930 135 465 1055 385 835 475 130 - 305 530 1265 1160 a] Bonds postcured 3 hours at 330F. Adhesives Based on New Experimental Resins An exploratory study was made of adhesive formulations based on ten new experimental resins. These resins are characterized, in general, by greater functionality when compared with commercial EPON resins and Experimental Resin X-131. In addition, four of the new resins are liquids of very low viscosity. It was expected that the high degree of functionality and flow of the resins would result in high adhesion and good thermal resistance in metal bonding. WADC TR 53-126 Pt 4 35 ABS w The new experimental resins included the following: 1) solids similar in physical properties to X-131 (modified X-131 resin, X-141, LR2047-76, LR2047-98, and LR2047-126) and 2) low viscosity liquids (X-401-3, X-701, X-801-3 and LR2047-83 and LR2047-199). The solid resins were used in tape form; the liquid resins were used in paste adhesives or as reactive diluents for X-131 resin. Experimental, modified X-131 resin was evaluated in solvent spread supported adhesive tapes with and without Formvar 13/93 E resin and EPON 1009. The molecular weight, softening point and hydroxyl content of the modified X-131 resin are greater than the corresponding values for the unmodified resin. The properties of various batches of modified X-131 ' resin are given in Table 33. Adhesive bonds cured with dicyandiamide and diaminodiphenylsulfone are described in Table 36 and Table 57 respectively. The adhesives were characterized by poor wettability and very poor flow. The improvement in adhesion which was anticipated with the higher hydroxyl content resin was therefore not realized. Test data are cited below for adhesives formulated with 20 phr Formvar 13/93 E and cured at 100 psi with diaminodiphenylsulfone for one-half hour at 240F plus one-half hour at 330F and postcured two hours at 300F. Tensile Shear Strength, psi X-131 Resin Modified Unmodified At room temperature At 500F At 500F after aging 8 hr at 500F At 500F after aging 72 hr at 500#F At 500#F after aging 200 hr at 500F 3520 465 1225 655 1000 3615 770 1260 1290 630 Adhesive formulations based on the other solid experimental resins cured with diaminodiphenylsulfone are given in Table 38 (X-141J, Table 39 (LR2047-76), Table 60 (LR2047-98) and Table 61 (LR2047-126). The adhesive shear strengths of bonds to type 301 steel were similar to corresponding X-131 resin bonds in brittleness (mediocre room temperature strength) and in heat resistance. Modification with 20 phr Formvar 15/95 E improved the toughness of the bonds with little or no sacrifice in thermal stability on aging, but decreased initial strength at 500F. Adhesive shear strength at 600F (see Table 62) was about double that for the X-131 resin. A comparison of the bond performance of aluminum dust filled adhesives containing no flexibilizing agent follows. These adhesives were cured with diaminodiphenylsulfone at 100 psi for one-half hour at 240F plus one-half hour at 330F. VADC TR 53-126 Pt 4 36 ABS-043764 Resin at 77F Tensile Shear Strength, psi at 500F at 600#F at 500F After 200 hr at 500F X-131 X-141 LR2047-76 LR2047-98 LR2047-126 2200 2435 1705 2040 1940 1100 750 1045 1225 1330 200 460 .- 495 465 900 700 540 985 315 Paste adhesives containing aluminum dust or glass fibers were formulated with the new liquid experimental resins as follows: 1) X-401-3 and X-801-3 with a blend of pyromellitic dianhydride and maleic anhydride (Tables 63 and 64), 2) X-801-3 with diaminodiphenylsulfone (Table 65) and 3) LR2047-83 with diaminodiphenylsulfone (Table 39). The preliminary evaluation of these adhesives for steel bonding indicated that the experimental resins are characterized by brittleness and a slow rate of cure. The shear strength values at 500F and at 600#F (Table 62) were inferior to those of corresponding bonds from X-131 resin. Illustrative data for adhesives cured with diaminodiphenylsulfone follow: Resin Tensile Shear Strength, psi at 77F at 500F at 600F LR2047-83 X-801-3 X-131 2045 2080 2200 245 200 1100 - 135 200 No promising formulations were found in an exploratory study of paste adhesives cured with a combination of pyromellitic dianhydride and maleic anhydride. Shear strength at 500#F was poor (200 to 600 psi). Some of the adhesive bonds increased in hot strength to about 1000 psi after 200 hours1 exposure at 500F. Exploratory studies were also made of the utility of the liquid experimental resins as reactive diluents for X-131 resin. Hot melt adhesives formulated with 90/10 to 50/50 X-13l/diluent ratios and cured with diaminodiphenylsulfone or dicyandiamide are given in Table 65 (X-801-3), Table 66 (X-401-3), Table 67 (X-701-3) and Table 68 (LR2047-199) The best adhesive bond strength was obtained with experimental resins X-801-3 and LR2047-199- Blends containing 50# of these diluents had shear strength values of 2000 to 3000 psi at room temperature and 950 psi at 500F after 200 hours aging at 500F. WADC TR 53-126 Pt 4 37 ABS^043 Procedures for Metal Treatment and Adhesive Bond Preparation Surface Treatments for Metals Stainless Steel. Type 301 stainless steel (thickness 0.050 in.) was used in most of the evaluation work described in this report. Metal with full hard temper was used in the form of strips 1.0 in. x 4.0 in.; metal with half-hard temper was used in the form of panels 4.0 in. x 10.5 in. The entire panel or strip was degreased with trichloroethylene before the application of any chemical treatment. The metal was warmed to 150F before chemical treatment to maintain good temperature control of the bath. Eighteen panels (or an equivalent area of strips) were immersed to a depth of one inch in about one liter of the treatment bath. The pickling solutions were not re-used; the alkaline detergent solution was used for three or four applications. Heat treated type 17-7 PH steel (thickness 0.062 in. and 0.050 in.) with vapor blast finish and C-110 M titanium alloy (thickness 0.050 in.) were used for adhesive bonding in a limited number of experiments. These metals were treated in the same manner employed for the preparation of stainless steel. The metals were prepared for etching, as follows: 1. Vapor degreased with trichloroethylene. 2. Cleaned with alkaline detergent solution for 10 minutes at l60-l80F. Composition of solution: 3 oz sodium metasilicate, 1.5 02 tetrasodium pyrophosphate, 1.5 oz sodium hydroxide and 0.5 oz Nacconol NR in one gallon water. 3. Rinsed thoroughly in tap water and dried for about 5 minutes at l60-200F. The cleaned metal was treated according to the following methods. The treated metal was then rinsed thoroughly in tap water and dried for 5 to 10 min in a 200F oven. Method A (sulfuric acid followed by a hydrofluoric/nitric acid "bright dip"). Solution 1. Sulfuric acid (sp grav 1.84) Water (distilled) Nacconol NR Operating conditions 190 grams 895 " 1" 10 min at 150-l60F WADC TR 53-126 Pt 4 38 ABS-04 Solution 2. Nitric acid (sp grav 1.42) Hydrofluoric acid (48$) Water (distilled) Operating conditions 200 grams 50 11 815 it 10 min at room temp The metal was rinsed thoroughly in tap water before immersion in Solution 2. Various modifications of Solution 1, Method A were tried in order to obtain greater uniformity in the appearance of the etched metal. The treatments are as follows: Method Operating Temperature, F Surfactant A A-Mi A-M2 A-Ms A-M* A-Ms 150-160 190-195 195-200 160-170 160-170 160-170 0.5$ Nacconol NR 0.5$ Nacconol NR None 0.5$ Pluronio L62 0.25$ Pluronic L62 None Method B, formalin-peroxide solution (FPL etch). Hydrochloric acid (sp grav 1.18) 500 grams Hydrogen peroxide (30$) 20 " Formalin (aqueous 37$) 100 " Water (distilled) 450 " Operating conditions 10 min at 140-150#F Method C (formalin-peroxide solution followed by passivation with chromic/sulfuric acid). Solution 1. Method B followed by rinsing in tap water. Solution 2. Sodium dichromate dihydrate Sulfuric acid (sp grav 1.84) Water (distilled) Operating conditions 53 grams 65 1122 " 10 min at 160-170#F Method D (Franklin Institute WS-4). Saturated Na2Cr207 solution Sulfuric acid (sp grav 1.84) Operating conditions WADC TR 53-126 Pt 4 39 Aluminum. Clad 2024-T3 aluminum alloy (thickness 0.064 in.) conformed to federal specification QQA-362. The metal was vapor degreased with trichloroethylene and etched with chromic/sulfuric acid. Solution 2, Method C. The panels (4.0 in. x 13.0 in.) were rinsed thoroughly in tap water and dried for about 5 minutes at 160-200F. Adhesive Bond Preparation Adhesive bonds described in this report were single one-half inch lap joints 1.0 in. x 7.3 in. Type 301 stainless steel (0.030 in. thickness* 2B finish) which conformed to specification MIL-S-3039A (ASQ) or MIL-S-5059 was used in all of the work. Bonds from full hard metal were assembled with 1.0 x 4.0 strips and cured at contact pressure for one-half hour at 330F. Panels 4.0 in. x 10.3 in. of half-hard metal were bonded in a hydraulic press at a pressure of 100 psi for one-half hour at 330F or with a two-stage cure cycle of one-half hour at 240F plus one-half hour at 330F. The glue lines were heated to 240SF in 2 to 3 minutes, maintained at this temperature for 30 minutes and then heated rapidly to 330F and held for 30 minutes. The bonds were cooled rapidly in the press (2 to 3 minutes).' Postcuring was done in a forced-draft oven except for a few experiments in which the bonds were postcured in the press directly after the cure cycle. Seven or eight test specimens one inch in width were cut from a panel with a circular staggered-tooth slit saw mounted on a milling machine. ' WADC TR 53-126 Pt 4 40 ABSi-04 Table 1 . EFFECT OF TEST TEMPERATURE ON THE SHEAR STRENGTH OF X-131/DICYANDIAMIDE BONDS TO TYPE 501 STEEL Formulation No. 1145 (parts by wt): 100 X-131 + 6 dicyandiamide + 100 aluminum dust. Cure at 100 psi: one-half hour at 240F plus one-half hour at 330*F. Panel No.a) Tensile Shear Strength,b) psi At -70#F , At room temperature At 500F, original , after 200 hours at 500#F At 600F Bend strength at room temp,b) lb H45FJfe-l8 2525 . 2205) 420 680 - 110 II45FM4-I8 - 2180 600 - 60 a) Bonds from solvent spread supported adhesive tapes with glass fabric (112-Volan A) dried 15 minutes at 200F. b) Average of three values for one-half inch lap joints to halfhard type 301 steel (thickness 0.050 in.). Surface treatment: Method Aand A-M4. c) Average of six values. WADC TR 53-126 Pt 4 4l AB&-04 Table 2 EFFECT OF EXPOSURE TIME AT 500F ON THE SHEAR STRENGTH OF --------------- 1 X-1517dTCYANDIAMIDE BONDS TO TYPE 501STEEL Cure (contact pressure): one-half hour at 3}0F. Panel No.a) Surface Preparation Adhesive Batch No. 1145JM-16 A 16 1145JM-15 A 15 1145FC-15 C 15 1145JFS-10 B 10 1145JM-17 A 17 Tensile Shear Strength,b) At room temperature At 500F At 500#F after 500#F aging, 3 hr 8 24 48 72 120 168 200 231 500 1825 685 305 255 405 375 475 115 1730 665 315 260 335 345 330 215 1650 710 365 345 305 300 - 2105 1025 380 255 325 300 415 670 - ' 2055 855 365 115 285 115 385 440 - a) Solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200F. Formulation (by wt): 100 X-131 (lot No. 1991-113) + 100 aluminum dust + 6 dicyandiamide. b) Average of three values for one-half inch lap joints to full hard type 301 steel (thickness 0.050 in.). WADC TR 53-126 Pt 4 42 Table 3. EFFECT OF POSTCURING ON THE SHEAR STRENGTH OF X-131/DICYANDIAMIDE BONDS TO TYPE 501 STEEL Cure (contact pressure): one-half hour at 530*F. Specimen No.a) Dicyan- diamide, phr Postcure F hr Tensile Shear Strength.nsi 0rlglnal Aged 200 hr It -SOOT 77 #F 500#F 500*F IO85JF-3 -PCI -PC3 4 400 0 2310 755 4 400 1 2510 1065 4 400 3 2305 1190 730 825 825 1085JF2-4 -PCI -PC3 1145JF2-8 -PCI -PC3 4 500 0 2320 545 4 500 1 1715 660 4 500 3 1815 215 6 500 0 2505 1050 6 500 1 2135 640 6 500 3 1665 605 620 530 560 905 770 655 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 minutes at 200*F. Formulation (by wt): 100 X-131 (lot No. LR1991-H3) + 100 aluminum dust. b) Average of three values for bonds to full hard type 301 steel (thickness 0.050 in.). Surface treatment: Method B. WADC TR 53-126 Pt 4 43 Table 4. EFFECT OF DRYING TIME AT 200*F OF X-151/DICYANDIAMIPE TAPES ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL Cure (contact pressure): one-half hour at 330F. Specimen No.) 1145Jlfe- Drying Time, Min at 200 F 12 12-30 12-60 12-120 15 13-30 13-60 15-120 15 30 60 120 15 30 60 120 Tensile Shear Strength,) psi Original Aged 200 hr at 500#F 77 F 500 F 500F 1940 1875 2115 2350 815 920 1015 1130 425 445 445 465 1935 1940 2270 2595 595 575 695 835 410 350 375 415 a) Bonds from solvent spread supported adhesive tapes with glass fabric 112-Volan A. Formulation (by wt): 100 X-131 (lot No. LR1991-H3) + 100 aluminum dust + 6 dicyandiamide. b) Average of three values for bonds to full hard type 301 steel (thieloiess 0.050 in.). Surface treatment: Method A-lfe, WADC TR 53-126 Pt 4 44 Table 5. EFFECT OF DICYANDIAMIDE CONCENTRATION ON THE SHEAR STRENGTH OF X-131 BONDS TO TYPE 301 STEEL Cure (contact pressure): one-half hour at 330F. Specimen No.) Dicyandiamide, phr 11U5JM-17 1146JM-2 1203JM 1204JM 1205JM 6 8 10 12 14 Tensile Shear Strength,psi At room temperature At 500"F At 500F after 500F aging, 8 hr 48 72 120 168 200 2055 845 365 115 285 115 585 46o 1935 585 385 95 245 380 320 350 1815 525' 460 195 525 620 320 455 1915 535 475 505 555 1025 795 790 1665 60 595 595 540 535 630 295 a] Aqueous-acetone spread supported adhesive tapes (glass fabric 112- Volan A) dried 15 min at 200*F. Constant ingredients (by wt): 100 X-131 (lot No. LR1991-113) + 100 aluminum dust. b) Average of three values for bonds to full hard type 301 steel (thickness 0.050 in.). Surface treatment: Method A. WADC TR 53-126 Pt 4 45 Table 6. EFFECT OF ALUMINUM FILLER CONCENTRATION ON THE SHEAR STRENGTH OF X-131/DICYANDIAMIDE BONDS TO TYPE 501 STEEL 1CoMA IOIAAJ O VIIAAO O s O 8 O s O IA vJlAor VroHO A r 1 1 1 1 CIIAOA i 1 CICAOM HoCMt aOIA5 -AAd ab 0 O Oir>ki 1 1 1 1 IrrHHA i 1 VCQOM -Cod-- OlA -AOd fH 1S Ia A +> 3 + CO (Xf ft 1 1 1 1 CCIAOM i 1 O$J CM 3IA JCSM> CO xco: UN CO IS 1 1 1 1 IrrHHA i 1 VorHO ICOAM VIIOAA ACA-- f 0) 1 | 1 1 1 VIIOAA i 1 CrOHO IOAv JIIAjA- CAQO KO a IIIAAA V-I=OAt Vot--O VtO--O GxIAOt <AIXA> VIt--OA I0OA\ CIAAD ItO--A A VO CO (Cao4>O. +0 VOIrAOH IA CM ICCCAMM- O 8CM IA 8CM ItCIAAAM A C2M1 OrIrHA-- IIrrA--AH IA 8rH A &rH co 1 o VO Jr VO VO Jr VO VO VO VO VO 0) QH O, 3 |P P 8 8 8 21A A A O A g cvi cm a ccm CO H z0 CM1 AI <-h -a ^ ^ ^ -- || 09 8 > 1 a # < jJ mill 8 S ` A'J xIA`t Rinn vOk ^ 3 21 21 21 25 CO WADC TR 53-126 Pt 4 46 M AB$-04B77^ Table 7. EFFECT OF COPPER 8-QUINOLINOLATE ON THE SHEAR STRENGTH OF X-131/DICYANDIAMIDE BONDS" TO TYPE 301 STEEL" Cure (contact pressure): one-half hour at 330#F. Specimen No.a) Copper 8-Quinolinolate, phr 1145JM-17 1210JM 0 0.5 1211JM 1.0 1212JM 2.0 Tensile Shear Strength,b) psi At room temperature At 500F At 500*F after 500#F aging, 8 hr 48 72 120 168 200 2055 845 365 115 285 115 385 460 1455 510 ' 260 270 310 345 400 425 1260 485 335 305 240 305 305 505 1675 415 220 280 315 440 270 505 a) Solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200#F. Constant ingredients (by wt): 100 X-131 (lot No. LR1991-113) + 100 aluminum dust + 6 dicyandiamide. b) Average of three values for bonds to full hard type 301 steel (thickness 0.050 in.). Surface treatment: Method A. WADC TR 53-126 Pt 4 47 ABS-0 Table 8. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM X-151 ADHESIVES WITH k-6 PHR CURING AGENT E Cure: one-half hour at 310F at contact pressure. Specimen No.>) Urln|h^ent Postcure at 400F, hr Tensile Shear Strength.b) psi Original Aged 200 hr at 500F 77 F 500*F 500F 1186TF; -PCI -PC3 4 4 4 0 525 0 1 2335 305 3 1845 700 810 685 1187IF3 -PCI -PC3 6 6 6 0 2195 485 1145 1 1930 930 1025 3 1875 1200 1000 Bonds from solvent spread supported adhesive tapes (glass fabric 112- Volan A) dried 15 minutes at 200F. Formulation (by wt): 100 X-131 (lot No. 1991-113) + 100 aluminum dust. b) Average of three values for bonds to full hard, type 301 steel (thickness 0,050 in.). Surface treatment: Method B. 1 WADC TR 53-126 Pt 4 48 ABg-043770 Table 9. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-131 ADHESIVES WITH 15 PHR CURING AGENT Cure at 100 psi: one-half hour at 240F plus one-half hour at 310-330*F. Postcure (oven): three hours at 300*F. Panel No.) Surface Treatment Method Cure, min/F Type of Adhesive^) Formvar 15/95E, phr 1232E%-P33 A-M3 30/310 Hot Melt None 1229EM4-P33b) A-M* 30/330 Tape None 1231FM4-P33C^ A-M* 30/330 Tape 20 Tensile Shear Strength,) psi At room temperature At 500F, original At 500*F, after 500F aging, 24 hr 48 72 120 200 1670 565 .210 515 of) 145 570 1285 485 200 210 25of) 215 315 1905 215 370 515 400f) 455 165 i : i a) Constant ingredients, phr: 100 aluminum dust + 13 Curing Agent (2,6-diaminopyridine). b) Test results for panel No. 1229Etyj-P33 cured one-half hour at 310#F: Shear strength at room temperature, 1660 psi (avg of eight values), c) Test results for panel No. 1231Eife-P33 cured one-half hour at 310F: Shear strength at room temperature, 1900 psi (avg of eight values). d) Adhesive bonds prepared with glass fabric 112-Volan A. Adhesive tapes were prepared from solvent dispersions of the adhesive and then dried 13 minutes at 200*F. e) Average of two or three values for one-half inch lap-joints to halfhard type 301 steel (thickness 0.050 in.). f) One value. WADC TR 53-126 Pt 4 49 AB$ Table 10. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-151 ADHESIVES CURED WITH BENZIMIDA20LYL GUANIDINE Cure (contact pressure): one-half hour at 550#F Formulation No.aJ Curing Agent, phr 1200JM 1202FM; 1145JM-16 10 BIGC) 20 BIG0) 6 dicy) Tensile Shear Strength,d) psi At room temperature At 500*F, original 1175 530 1425 110 1825 685 At 500CF, after 500 *F aging, 8 hr 48 72 500 540 . 510 135 95 240 305 255 - 120 610 540 405 168 715 200 595 420 415 375 475 a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 minutes at 200F. Formulation (parts by wt): 100 X-151 (lot No. LR1991-113) + 100 aluminum dust. b) Cure: One-half hour at 240 F plus one-half hour at 530#F. c) "Dicy" is dicyandiamide. "BIG" is benzimidazolyl guandine. d) Average of three values for one-half inch lap joints to full hard type 501 steel (thickness 0.050 in.). Surface treatment: Method A. WADC TR 53-126 Pt 4 50 ABB-0 % Table 11. SHEAR STRENGTH OF X-151/PIAMINODIPHENYISULFONE BONDS TO TYPE 501 STEEL Formulation (parts by rrt): 100 X-131 + 100 aluminum dust + 30 diaminodiphenylsulfone. Cure at ICO psi: one-half hour at 240F plus one-half hour at 330F. Panel No.) 1^bf" 1201FE-4 1201FE-5 1201FE-6 X-131 Resin lot No. LR- 1991-H3 1991-U3 3523-147-1 3523-115 1991-113 Tensile Shear Strength,d) psi At room temperature At 500F, original At 500F, after 500F aging, 8 hr 48 2255 1075 1095 710 l84oe) 905 - 28l5e) ll4o - 2l4oe) 1280 2420 1060 - ll65e) - 1150e) 72 785 - - - 1220e) 120 690 - - - 1075e) 168 200 At 600*F, original 670 - - - 780 870 830 835 1115e) - - 195 - - a) Bonds from solvent spread supported adhesive tapes with glass fabric (112-Volan A) dried 15 minutes at 200F. b) Bonds to full-hard type 301 steel cured at contact pressure for onehalf hour at 330F and postcured two hours at 300F. Surface treatment: Method A. c) Adhesive tape stored for two months at room temperature before testing. d) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. e) Average of two values. WADC TR 53-126 Pt 4 51 ABB Table 12. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-131 ADHESIVES CURED WITH 4 >1, V1 -TRIAMINOTRIPHENYLMETHANE Cure: one-half hour at 330#F and 100 psi Panel No.) X-131/EP0N 1009 Ratio,b) by wt Formvar 15/95 E, phr Triaminotriphenylmethane, phr 1326JE 100/0 23.5 1327JE 100/0 20 23.5 1328JE 80/20 20 19 Tensile Shear Strength,0) psi At room temperature At 500F, original At 500F, after 500*F aging, 8 hr 865 1^30 525 ' 1*55 605 h-20 3035 385 835 120 730 510 795 200 375 350 1*75 a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 minutes at 200#F. Constant ingredient, by wt: 100 aluminum dust. b) X-131 lot No. LR3523-64. c) Average of three values for one-half inch lap Joints to half- hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. d) Average of two values. WADC TR 53-126 Pt 4 52 ABS-043 Table 15. EFFECT OF X-151/EP0N 1009 RESIN RATIO ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL CURED WITH DICXANDIAMIDE Cure (contact pressure): cne-half hour at 330 *F with 6 phr dicyandiamide. Specimen No.a) X-131bV EPON 1009 Surface Treatment Method Tensile Shear Strength,c) pgi Original Aagetd520000.Fhr 77F 500F 500F 1145JFd) 1195JF4-2 II96JF4-2 1197JF4-2 IOO/O 90/10 80/20 70/30 B 2290 1145 675 B 2865 1045 830 B 2785 1020 1075 B 2455 855 880 1145JM<0 100/0 A 1930 770 680 1195 JMb-2 119&nfe-2 1197JMs-2 90/10 80/20 70/30 A--M2 A-Ms A-Ms 2225 2205 2335 755 585 655 635 1235 780 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112Volan A) dried 15 min at 200#F. Constant ingredients, phr: 100 aluminum dust + 6 dicyandiamide. b) X-131 resin lot No. LR1991-113. c) Average of three values for bonds to full hard type 301 steel (thickness 0.050 in.). d) Test results given are the averages for six adhesive batches. e) Test results given are the averages for eight adhesive batches. WADC TR 53-126 Pt 4 53 Table 14. EFFECT OF X-151/EPCN 1009 RESIN RATIO ON THE SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL CURED WITH DIAMINODIPHENYLSULFONE Cure at 100 psi: one-half hour at 240F plus one-half hour at 330F Postcure (oven): two hours at 300*F Panel No.a) X-131/EP0N 1009 Ratio, by wt Diaminodinhenylsulfone. phr 1201JM- 1235Fife- 1234FM5- P23) P23 P23 IOO/O 90/10 80/20 50 _ 27 _ 24.5 1235FM3P23 70/30 21.5 Tensile Shear Strength,.15) psi At room temperature At 500F 2255 1075 2315 750 2255 775 2640 785 At 500F after 500F aging,d) 8 hr 1095 855 550 590 48 710 420 500 580 72 785 760 760 610 120 690 720 760 590 200 780 900 700 885 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200*F. Constant ingredient: 100 phr aluminum dust. X-131 lot No. 1991-113. b) Average of three values for 0.5 in lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method A-M3 c) Bonds to full hard type 301 steel (thickness 0.050 in.) cured at contact pressure. Average of three values for all tests. Surface treatment: Method A. d) Average of two values. WADC TR 53-126 Pt 4 54 AB3-04 Table 15. EFFECT OF DRYING TIME AT 200F OF X-151/ EPON 1009/PICYAKDIAMIDE TAPES ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL Cure (contact pressure): one-half hour at 330F Specimen No.a) X-131/EP0N 1009 Resin Ratio*5) Drying Time, Min at 200F Tensile Shear Strength,0) psi uOnriggminaail Aagt e5d0200F0 77F 500F 500F 1195JM2-2 -30 -60 -120 90/10 t . It It 15 30 60 120 2225 2435 2730 2745 755 895 865 935 635 605 395 415 II96JM2-2 -30 -60 -120 80/20 11 It It 15 2205 585 1235 30 2235 635 960 60 2690 745 *35 120 2700 1025 415 1197JM2-2 -30 -60 -120 70/30 tl It It 15 2335 655 780 30 2575 585 370 60 2500 735 260 120 2405 770 460 a) Bonds from solvent spread supported adhesive tapes with glass fabric 112-Volen A. Constant ingredients, phr: 100 aluminum dust + 6 dicyandiamide. b) X-131 resin lot No. LRI99I-H3. c) Average of three values for bonds to full hard type 301 steel (thickness 0.050 in.). Surface treatment: Method A-M2 WADC TR 53-126 Pt 4 55 aBs-o I Table 16. SHEAR STRENGTH OF BONDS TO TTFB 301 STEEL FROM X-131/ EPON S34 HOT MELT ADHESIVES CURED WITH DIAMINQDIPHENYLSULFONE Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F Panel No.a) X-131/EP0N 834 Ratio,) by wt Diaminodiphenylsulfone, phr 1298FE 50/50 25 1299FE 60/40 26 1300FE 70/30 27 1201FE-4b) 100/0 30 Tensile Shear Strength,psi At roan temperature At 500#F, original , after 500F aging, 8 hr , ) 120 9 200 1560 1945 3215 375 0 555) 550 375 120 v 570f) 525 no 55 625) 445 2815) 1140 830 a) Bonds prepared with hot melt adhesives and glass cloth 112-Volan A reinforcement. Constant ingredient: 100 phr aluminum dust (MD201). b) Solvent spread tape dried 15 min at 200#F. c) Experimental resin X-131, lot No. LR3523-147-1. d) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. e) Average of two values. f) One value. WADC TR 53-126 Pt 4 56 Table 17. EFFECT OF FQRMVAR 15/95 E CONCENTRATION ON THE SHEAR STRENGTH OF X-131/DICYANDIAMIDE' BONDS TO TYPE 301 STEEL Cure (contact pressure): one-half hour at 530F Postcure: three hours at 400F Specimen No.a) 1085JF-3PC5 1182JF2-PC3 1183JF2-PC3 1184JF2-PC3 1185JF2-PC3 Formvar 15/95 E, phr 0 10 15 20 30 Tensile Shear Strength,psi 0rigeriinnaoll AIgted520000Fhr tTf 500F 500F 2305 1190 825 3085 975 805 3095 3710 4200 595 500 375 795 1125 665 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200F. Constant ingredients (by wt): 100 X-131 + 100 aluminum dust + 4 dicyandiamide. b) Average of three values for bonds to full hard type 301 steel (thickness O.O5O in.)* Surface treatment: Method B. WADC TR 53-126 Pt 4 57 Table 18. EFFECT OF X-131/FORWAR 15/95 E RESIN RATIO ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL CURED WITH PIAMINQDIPHENYLSULFONE Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330#F Panel No.a^ X-13l/Formvar 15/95 E Ratio, by wt Al Dust/Total Resin Ratio, by wt 1219FF-5 1248FF 1249FF 1250FF 83.3/16.7 75/25 5O/5O 25/75 _ 5/6 3A 1/2 .. iA. Tensile Shear Strength,b) psi At room temperature At 500F, original , after 500F aging,0) 8 hr 48 72 120 200 3555 640 I690 1545 1390 1490 1030 2895 345 1385 1500 1425 1200 850 4045 0 1010 1100 790 855 560 4210 0 160 95 60 no 0 Panel No.a) X-131/Formvar 15/95 E Ratio, by wt Al Dust/Total Resin Ratio, by wt 1251FF 1252FF 1253FF 1254FF 83.3/16.7 75/25 5O/5O 25/75 _1/1 1/1 1/1 1/1 Tensile Shear Strength,*5) psi At room temperature At 500F, original , after 500F aging,0) 8 hr 48 72 120 200 4015 1285 1530 1490 1405 1230 1095 3725 1265 1490 1605 1215 1265 925 3665 0 620 460 400 500 100 2070 0 465 120 0 0 0 a) Bonds from solvent spread supported adhesive tape (glass fabric 112Volan A) dried 15 min at 200F. Constant ingredient: 30 phr diaminodiphenylsulfone. X-131 resin lot No. LR1991-113. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method B. c) Average of two values for all aged bonds. WADC TR 53-126 Pt 4 58 ABS-043788 Table 19. EFFECT OF BF,,-40Q ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM 100/20 X-131/Formvar 15/95 E ADHESIVES CURED WITH DIAMINQDIPHENYLSULFOKE Cure at 100 psi: one-half hour at 240F plus one-half hour at 330F. Postcure (oven): two hours at 300F. Panel No.a> Curing Promoter,k) phr Tensile Shear Strength,0) psi At room temperature At 500F, original , after 50QF aging. 8 hr 9 48 9 72 9 120 a; d) d) 9 200 1237JM*-P23 1 BFs-400 2285 430 695 725 855 460 285 1238FM4-P23 None 2655 680 1165 1010 1315 1010 830 a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 min at 200F. b) Constant ingredients (parts by wt): 100 X-131 (lot No. LR1991-H3) + 20 Formvar 15/95 + 3 neutral TC asbestos + 30 diaminodiphenylsulfone. c) Average of three values for one-half inch lap joints to halfhard type 301 steel; specimens cut with Do-All band saw. Surface treatment: Method A-M4. d) Average of two values. WADC TR 53-126 Pt 4 59 Table 20 . COMPARISON OF THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM 100/20 X-131/F0HMVAR 15/95 E ADHESIVES WITH ASBESTOS AND ALUMINUM FILLERS Cure at 100 pai: cue-half hour at 240F plus one-half hour at 330F. Postcure (oven): two hours at 300F. Panel No.) Filler,phr Tensile Shear Strength,) psi At room temperature At 500F, original , after 500F aging. 8 hr 48 72 $ 120 i 200 1238FJ4-P23 30 TC Asbestos 2655 680 U65 1010f) 1315*) 1010f) 830 1219FM4-4P23 100 A1 Dust 2740^) 670) 830 a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 min at 200F. b) Constant ingredients (parts by wt): 100 X-131 (lot No. LR1991-113) + 20 Formvar 15/95 E + 30 diaminodiphenylsulfone. c) Average of three values for one-half inch lap joints to half-hard type 301 steel; specimens cut with Do-All band saw. Surface treatment: Method A-M*. d) Average of nine values. e) Average of six values. f) Average of two values. WADC TR 53-126 Pt 4 6o ABS Table 21. EFFECT OF BISPHENOL-A ON THE SHEAR STRENGTH OF 100/20 X-151/FQHMVAR 15/95 E BONDS TO TYPE 501 STEEL Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F Panel No.a) Bisphenol A, phr Tensile Shear Strength,bj psi Original At 500aF After 500"F Aging ForJ 77F 500F 8 hr 48 hr 72 hr 120 hr 200 hr 1219FE-6 0 3605 1020 1505 1415 1495 1115 950 1260FE 1220FE-2 1261FE 2 3765 545 1520 1025 760 660 625 5 4235 880 1285 1270 920 1050 690 8 4010 530 1520 1320 U55 1275 610 1262FE 10 4135 355 1080 1010 880 425 675 a) Bonds from solvent spread supported adhesive tape (glass fabric 112Volan A) dried 15 min at 200F. Constant ingredients (parts by wt): 100 X-131 (lot No. LR1991-115) + 20 Formvar 15/95 E + 100 aluminum dust + 30 diaminodiphenylsvilfone. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. c) Average of two values for all aged bonds. WADC TR 53-126 Pt 4 6l ABS-04 Table 22. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM 100/2Q X-13l/F0RMyAR 13/95 E ADHESIVES CURED WITH MELAMINE 1 H 43 & N 8 O01 8 I 4 vo tO tA & CM ITV _ O tA rA O tA IA frAt -CM I VO d lA 8>f HI -=t JSA C QQ Si S "rA *Sr tA rA II a tA _ CO - rA S I 3 lrAA rA \IA 8 saad> 2 tA * 3 AOn & + M 3 % 3 3OJ cvT + g IA ft & IA HO rA Si IA 83 * Ia |0Pr}l4 ((AA T HrA rH 4. 8s O IA a Si tA O IA 15 Sft.g a"- tA tA IA 3ft '& CM H CO Vo OH h3 Ma p.Sop peon *H a HH13 OOP_ rf-a*od 8,^ ^43 I a 58 a Vm lAH! O ph a.a C3VO *3 0) o 0) O $ Vo 8 S rAVi p 0o0t Q TO O S .rss* 50 p *<3 00 CO P2m c i||l zO pho3 a 4) & IVSi l 3 fa M WH 5 i--< pH <5d frHo (S >< 2 Id *h Vo PW fVfii -0H0 j5 u tsS (DM5 *> > 43 fa CO Q 8 a> rH ft, HWcH P< -*P3 >w8 SPco f10t 5g r9l 3fi H t > p g. rol P o .(3..IA. P Vj Vo IAO 3 00 8 p P O JH- . CM Vo H CO Vm 3 P O CO O Vo 31 I o ,- h < 43 O WADC TR 53-126 Pt 4 62 ABS Table 23. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-131 ADHESIVES CURED WITH CURING AGENT BF-W Cure: one-half hour at 330#F Panel No.aJ Hardness of Steel Cure Pressure X-131/EP0N 1009 Ratio, by wt Fornrvar 13/93 E, phr_________ Tensile Shear Strength,) psi At room temperature At 500F, original , after 500F aging, 8 hr 9 48 9 72 9 120 9 168 9 200 ' 1199JM Full Hard Contact 80/20 0 1221Flfe; Half-Hard 25 psi 100/0 20 545*) - 555 160 390 305 555 450 2405 515 . 395e 370 320e 650) - 42Qe) a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 min at 200F. Constant ingredients, phr: 3 BF3-400 + 30 TC neutral asbestos. X-131 resin lot No. LR1991-113. b) Bonds precured one-half hour at 240F at 25 psi. Surface treatment: Method A-M3. c) Average of three values for one-half inch lap joints to type 301 steel (thickness 0.050 in.). Surface treatment: Method A. d) Shear strength for bonds precured one-half hour at 240F: 395 psi at 500F. e) Average of two values. WADC TR 53-126 Pt 4 63 ABS-043791 Table 2k. SHEAR STRENGTH OF BONDS TO TYPE ^01 strict, from 100/20 X-151/F0RMVAR 15/95 E ADHESIVES CURED WITH ACID-TYPE CURING AGENTS Press cure at 100 psi for one-half hour at 2kOF plus one-half hour at 330F Panel No.) I242FF EPON Resins, Parts by it 100 x-131 Curing Agent, phr Filler, phr Tensile Shear Strength, osib) ,, 0r,,,BBl Aged 200 hr At 500*F 77*F 500*F 500'Fc> 3 Magnesium perchlorate 100 Al 2125 420 ob) I245FF l244FU4d) I243FF R 9 Zinc fluoborate heptahydrate RR broke on handling a 3 8F3 * ammonia RR 1635 50 0 3 BF3 urea RR 855 0 45 I247FF-P333) R. 0I 30 TC Asbestos 2735 440 0 I240FU4-P333) I239FM4-P333) a 75 Hexahydrophthalic anhydride*) g) t if) I246FF-P333) 80/20 X-131/1009 I267FF-P333) 0 47.5 Phthalic acid 1 f) R R R R 975 0 490 0 3925c) 130 1965 55 0 0 305b) 285 a) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 ein at 200*F. Constant ingredient, phr: 20 Formvar 15/95 E. Experimental resin X-I3I, lot No. LRI99I-I13. b) Average of three values for bonds to half-hard type 301 steel (thickness 0.050 In,). Surface treatment: Method B. c) Average of taro values. d) Surface preparation: Method A-M4. e) Bonds postcured for 3 hours at 330*F. f) Formulation contained 2 phr dimethyl ethanolamlne as a cure promoter. g) This formulation without Formvar 15/95 E resin. Table 25. SHEAR STRENGTH OF 100/20 X-151/FQHMVAR 15/95 E BONDS TO TYPE 301 STEEL (FORMULATION NO. 1219) Formulation (parts by wt): 100 X-131 + 20 Formvar 15/95 E + 100 aluminum dust + 50 diaminodiphenylsulfone Cure at 100 psi: one-half hour at 240F plus one-half hour at 330F Panel No.8) Surface 1219- Treatoent Adhesive Batch No. X-131 Lot No. IR JU|-P23C) FU3-2P23 FU 4-2P23 FU3-3P24 FB4-3P24 FB4-4P23) FM4-4P23) F4-4P24 FF-4P23 -4P24 FF-5 FE-6 -7 -8 -9 FE-9P233 -9P24 A-M, A-U3 a-u4 A`3 a-u4 a-b4 A-II4 A-M4 B B B C C C C C C 1 1991-113 2 3523-64 2 3523-64 3 1991-113 3 1991-113 4 1991-113 4 1991--113 4 I99I-II3 4 1991-113 4 1991-113 5 1991-113 6 I991-113 7 3523-147-1 8 3523-115 9 3523-147-1 9 3523-147-1 9 3523-147-1 Postcure hr/*F 2/300 2/300 2/400 2/400 2/400 2/300 2/300 2/400 2/300 2/400 --1 -- -- -- -- 2/330 2/400 Tensile Shear Strenoth.) osi aOriig.inal1 Aged5(2)000.F hr 77-F 500*F 500*F 2720 3615 3295 . 2480*> 1865**/ 2740*) 2725*) 1655 3205 2380 850 770 610 900 990 670*) 635*) 695 835 935 3555 3605 3870*> 4080d| 3630**) 3160**) 2700**) 640 1020 905 930 715 780 895 1015 630**) - 975 . 1225") 830 1355 1020 820 900 1030**) 950**) 415 555 765 675 700 a) Bonds froe solvent spread supported tape with glass fabric (112-Volan A) dried 15 ein at 200*F. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thicknesa 0.050 in.). c) Bonds to full hard type 301 steel cured at contact pressure for one-half hour at 330*F. ` d) Average of two values. e) Speciaens cut with Oo-AII band saw. f) Average of five to nine values. Table 26. EFFECT OF 500 P EXPOSURE ON THE SHEAR STRENGTH OF 100/20 X-151yFQRWAR 15/95 E BONDS TO TYPE 501 STEEL (FORMULATION NO. 1219)" Cure at 100 psi: one-half hour at 240F plus one-half hour at 330*F Panel No.a) 1219- JM1-P23b) FM3-2P23C) FF-5 fe-6 Surface Treatment Adhesive Batch No. Postcure, hr/300#F A-Mi 1 2 A4^ 2 2 Bc 56 00 Tensile Shear Strength,d) psi At room temperature At 500*F, original At 500#F, after 500#F aging. 8 hr 48 72 2720 850 895 920 1155 3615 770 1260 1215 1290e) 3555 64o 1690 1545 1390 3603 1020 1505 1415 1495 120 1355 1380 1490 1115 168 1035 - - - 200 1015 630 1030 950 a] Bonds from solvent spread supported adhesive tape with glass fabric (112-Volan A) dried 15 min at 200#F. Formulation (by wt): 100 X-131 (lot No. LR1991-113) + 20 Formvar 15/95 E + 100 aluminum dust + 30 diaminodiphenylsulfone. . b) Bonds to full hard type 301 steel cured at contact pressure for one-half hour at 330*F. c) X-131 resin lot No. LR3523-64. d) Average of two or three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). e) One value. WADC TR 53-126 Pt 4 66 ABS Table 27. EFFECT OF POSTCURE ON THE SHEAR STRENGTH OF 100/20 X-131/FORWAR 15/95 E BONDS TO TYPE SOI STEEL ~ ( formulation no. 1219V Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330#F X^OAiCX ilU t AUU601VC 1219 Treatment Batch No. Tensile Shear Postcure (oven) Original Aged 200 hr at 500#F hr *F 77 F 500F 500 8F EM4-4P23 -4P43 -4P83 -4P24 -4P44 A-M fl ft tl ft -4P84 -4p5 -4P15 -4P25 -4P45 ft II ft If If FF-4P23 -4P83 -4P24 -4P84 -4p^5 -4P45 B If It It fl ff FE-9 -9P427 -9PI627 -9P3227 -9P233 C If If ft ff -9P433 -9P833 -9P24 -9P84 -9P164 c It , tl It II 4c) It It If M 4) II tl II It - 4) ft II If If If 9d) II If It II 9<1) If ft ft fl 2 300 2740 670 4 II 2325 395 8 It 2275 540 2 400 1655 695 4 tt 1535 670 8 400 1560 720 0.5 500 1705 685 1 II 1340 . 775 '2 It - 1675 740 4 It 975 485 2 300 3205 8 If 2900 2 400 2380 8 If 2280 0.5 500 2130 4 tl 735 635 825 935 1055 385 . 840e) 0 -- 3630) 715 4 270 3805) 740 16 If 3400e) 755 32 If 3335] 640 2 330 3l6oe) 780 4 330 3470] 845 8 ff 3225e! 835 2 400 2700] 895 8 tl 2460) 1225 16 If i860) 1090 825 890 800 1020 1025 1035 585 715 1035 795 820 465 900 935 960 765 765 615 505 480 675 685 550 700 46o 410 a) Bonds from solvent spread supported adhesive tape with glass fabric (112-Volan A) dried 15 min at 200F. Formulation (by wt): 100 X-131 + 20 Formvar 15/95 E + 100 aluminum dust + 30 diaminodiphenylsulfone. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). c) Experimental resin X-131, lot No. LR1991-113. d) Experimental resin X-131, lot No. LR3523-147-1. e) Average of two values. WADC TR 53-126 Pt 4 67 ABS Table 28. BEND STRENGTH OF X-1S1 ADHESIVE BONDS TO TYPE 301 STEEL Cure at 100 pal: one-half hour at 330*F Panel No.*) X-I3I/EP0N 1009 Ratio, by wt Foravar 15/95 E. phr Curina Agent,) phr Postcure, hr/*F Bend Strength, lb Range Avge) Shear Strength at 77*F,C) psi II45FU3-I8 1160FU3-4P24 I2I9F3-3P24 I2I9FE-9 -9P833 100/0 II (1 Cl 6 dicy None 106-116 110 22I5<0 20 2/400 98-107 102 22 40d) 8 30 DADPS 8 103-109 105 2480d) 8 88 None 145-163 156 3630) 8 88 8/330 103-156 138 322S*) 1219FE-9P 44 -9P84 I236F3-2P23 I236FM4-2P85 I236FE-9 100/0 II 80/20 0 n 20 30 DA0PS 4/400 103-133 114 8 8 88 6/400 97-106 102 8 24.5 DA0PS 2/300 117-123 120 a aa 8/500 42-57 48 a 88 None 181-198 186 - 2460 2780d) 1245 3900) I236FE-9P833 -9P44 -9P84 -IOP44 1236JE-19P aP 44 80/20 a a 0 3 20 24.5 DA0PS 8/330 135-170 149 3560) 8 88 4/400 126-139 133 - 8 a8 8/400 98-146 115 3015) n a8 4/400 108-198 150*) 2845 a au 8 91-101 94 1870 I236JE-20P44 -20Pb2P44 -20Pc|P44 -20Pc2P44 80/20 H n 8 20 24.5 0A0PS 4/400 n 88 8 aa 8 n n8 8 68-81 57-96 81-94 91-101 75 80 88 91 2135 1575 1985 2015 a) Bonds froa solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 aln at 200*F. Constant ingredient: 100 phr aluainua dust. b) "Oicy0 is dicyandiaaide; "DAOPS* is diaainodiphenylsulfone. c) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). d) Average of six values. e) Average of two values. f) Average of four values. WADC TR 53-126 Pt 4 68 4BS-Q437 Table 29. COMPARISON OF THE SHEAR STRENGTH OF TYPE 501 STEEL ADHESIVE SPECIMENS CUT WITH A DO-ALL BAND SAW AND A MILL SAW Formulation No. 1219 (100/20 X-lJl/Formvar 15/95 E) Cure at 100 psi: one-half hour at 240F plus one- half hour at 550F. Po8tcure (oven): two hours at 500F. Panel No.a) Method of Cutting Specimens FI219FM4AP25 1219FM4-P25 Do-All Band Saw Mill Saw Tensile Shear Strength,psi At room temp, average , range , No. of specimens At 500F, average , range , No. of specimens 2740 2550-2960 9 670 440-850 6 2725 2180-2940 8 655 450-740 5 At 500F after 200 hr at 500F, average , range , No. of specimens 850 760-900 3 1555 1260-1450 5 a] Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 min at 200F. Formulation No. 1256, batch 4 (parts by wt): 100 X-151 (lot No. LR1991-115) + 20 Formvar 15/95 E + 100 aluminum dust + 50 diaminodiphenylsulfone. b) Shear strength for one-half inch lap joints, one inch in width, to half-hard, type 501 steel (thickness 0.050 in.). Surface treatment: Method A-M4. , WADC TR 53-126 Pt 4 69 AfiS-0 Table 50. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-13l/ GELVA C-3-V-50 ADHESIVES CURED WITH DIAMINODIPHENYLSPLFONE Press cure at 100 psi for one-half hour at 240*F plus one-half hour at 330F Panel No.a) X-13l/Gelva C-3-V-30b) Resin Ratio, by wt Diaminodiphenylsulfone, phr 1201FE-6 lOO/O 30 1255FE 83.3/16.7 25 1256FE 75/25 22.5 Tensile Shear Strength,) psi At room temperature 2420 . 3340 3715 At 500F, original , after 500F aging,d) , 8 hr 48 1060 1165 1150 785 510 495 545 460 640 , 72 , 120 1220 665 430 1075 580 380 , 200 1115 320 0 a) Bonds from solvent spread supported tapes (glass fabric 112-Volan A) dried 15 min at 200F. Constant ingredient, by wt: 100 aluminum dust filler. b) X-131 lot No.: LR-1991-113. Gelva C-3-V-30 is a carboxylic modified polyvinyl acetate resin. c) Average of three values for one-half inch lap Joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. d) Average of two values for all aged specimens. WADC TR 53-126 Pt 4 70 ABS Table 51. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM X-15l/ GELVA C-3-V-30 ADHESIVES CURED WITH DIAMINODIPHENYLSULFQNE AND BENZYLDIMETHYLAMIHE PROMOTER Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330#F Panel No.a) X-131/ Gelva C-3-V-3O Weight Ratiob) Curing: Agent) DADPS, by wt Benzyldimethyl- amlne, by wt Postcure at 400*F, hr Tensile Shear Strength,d) psi Original Aged 6 hr at 500#F 77 F 500 *F 500"F) 1301FE -P24 90/10 II 26 It 0.45 ft 0 3130 890 2 1890 920 865 935 1304FE -P24 1255JE-2e) 83.3/16.7 1? It 24 II II .41 II - tl 0 2320 420 240 2 3125 585 .365 0 3240f) 385f) 1035 1302FE -P24 80/20 II 23 II .40 It 0 1890 260 2 2030 525 220 270 1303FE -P24 70/30 It 20.5 11 .35 It 0 2290 160 2 2630 225 185 200 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112Volan A) dried 15 min at 200F. Solids content of adhesive dispersion used for coating: 75-8o$w. Constant ingredient (by wt): 100 aluminum dust filler. b) X-131 batch No. LR3523-147-1. Gelva C-3-V-30 is a carboxylic modified polyvinyl acetate resin. c) DADPS is diaminodiphenylsulfone. d) Average of two values for bonds to type 301 steel (l/2 H), thickness 0.050 in. Surface treatment: Method C. e) Cure: one-half hour at 330?F. Shear strength at 500F after 500F aging: 120 hours, 1355 psi: 200 hours, 605 psi. f) Average of three values. t WADC TR 53-126 Pt 4 71 ABS-0fl379 Table 52. SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM X-151/QELVA C-5-V-30 ADHESIVES CURED WITH DIC7ANDIAMIDB Press cure at 100 psi for one-half hour at 330*F Panel No.) X-13l/Gelva C-3-V-30 Ratio, by wt ll45JM-17b) 100/0 1307JE 83.3/16.7 1308JE 70/30 Tensile Shear Strength,0) psi At room temperature At 500#F, original . , after 500F aging, 8 hr , 120 , 200 2055 845 365 115 460 3005 615 395 965<0 490 3565 545 425 895d) 45 a) Bonds from solvent spread supported adhesive tape (glass fabric 112Volan A) dried 15 min at 2008F. Constant ingredients (by wt): 6 dicyandiamide + 100 aluminum dust. b) Bonds to full hard type 301 steel (thickness 0.050 in.). Surface treatment: Method A. c) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. d) Average of two values. WADC TR 53-126 Pt 4 72 ABS-q Table 53. SUMMARY OF THE SHEAR STRENGTH OF BONDS TO TYPE FROM FORWJLATION NO. 1256. BATCHES 1 THROUGH H stout Formulation No. 12j6 (parts by art): 80 X-131 + 20 EPQN 1009 + 20 Formvar 15/95 E + 100 aluminum dust +24.5 diaminodiphenylaulfone. Press cure at 100 psi for one-half hour at 33OT. Panel No.*) Surface 1236- Treateent X-131 Lot No. IR- Adhesive Precure Postcurs Batch at 240*F, at 400f. No. hr hr Tensile Shear Strength .b) 08 i Original At 500*F After 500*F Aging 77 F 500f 8 hr 120 hr 200 hr FL'3-P24 FH4-P24 -2 -2P24 FO-3 A-3 1991-113 A-(J4 ft 1 ft ft a 0a 1 2 9 3 1/2 11 2 27800 905 1145 ft 2440 865 - - 1350 0 4200O 615 1280 1450 1360 2 2370 940 . 0 3875 350 1135 1425 1220 FE-3 FF-3 FE-S -6 -7 c 1991-113 B9 Ca 3 ft 5 ft 3523-147-1 6 II 7 1/2 ft ft > ft a 0 4095 675 1390 1440 1410 ft 4015 695 1370 1370 1190 ft , ft 4155 685 1330 835 645 4155 645 - 535 V 4020 750 - - 660 FE-8 -8P24 -8P44 -9 -9P24 FE-I0P44 F0-I0P44 Fy4-IOP44 -IIP34 FD-IIP34 FE-IIP34 PE-IIP34 FE-12 -13 -I3P34 c 3523-147-1 i ft A ft 0 ft C 0 A-M4 a 0 c a . i 3523-147-1 a a A a 3523-147-1 f a 0 a 8 9 A 9 ft 10 9 II 9 l< 9 12 13 ft 1a/2 n ti 1/2 0 ft ft ft 1/2 ft ft ft ft 0 4275 630 735 670 2 3335 825 970 840 4 3405 830 935 595 0 3900 495 _ 680 2 3435 835 - - 675 4 27650 895 800 _ 660* ft 3410 ft 1710 . 3 1570 . ft 3310 - - - - 3 2645 . . a 2750 585 735 775 645 0 3870 460 985 735 765 a 3870 390 . 455 3 2850 425 - - 535 JE-13 -I3P44 c 3523-147-1 13 ft It ft 0 ft 0 3310 235 1050 505 4 2620 710 790 - 745 a) Bonds from so I van tspread supported adhesive tapes (thickness 12-14 ails) olth glass fabric (112' Volan A) dried (5 Bin at 200*F. b) Average of two to four values for one-half inch lap joints to type 301 steel (thickness O.OSO in.). c) Average of six values, d) Exposure period 248 hr. WADC TR 53-126 Pt 4 73 ABS-0 4380 Table *>k. SUMMARY OF THE SHEAR STRENGTH OF BONDS TO TYPE ^01 STEFT. FROM FOFtMJLATION NO. 1256. BATCHES Ik THROUGH 27 Formulation No. 1236 (parts by wt): 80 X-131 + 20 EPQN 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 24.5 diaminodiphenylsulfone. Press cure at 100 psi for one-half hour at 330#F. Panel No.8) Surface 1236- Treats ent X-131 Lot No. LR- /tussive Batch No. Precure at 240f, hr Postcurs at 400*F , hr Tensile Shear Stirength.b) psi Original At 500*F After 500*f Aging 77-F 500-F 8 hr 120 hr 200 hr JE-14 C 1991-113 14 0 0 3635c) 3I5C) 1200 1530 1240) -I4P24 ft ft 8 2 2610 870c) I290) 1460c) 945) -15 3523-64 15 ft 0 3955 340 1075 1325 975 -I5P24 1 8 n 2 3465 685 910 835 735 -16 ft 3523-147-1 16 a 0 4200 350 965 995 825 JE-I6P24 C 3523-147-1 16 0 2 3635 840 725 595 620 -I8d) 8 3523-64 18 8 0 2330 165 1070 1110 .; JHS-I8<0 JE-I9P44) A-U5 8 C 3523-31 8 19 a a 3715 170 820 865 ' 4 2465 635 925 990 900 JE-20 8 8 20 a 0 4030 170 940 960 1105 JE-20P44 c 3523-31 20 0 4 2730c) 590c) 805c) 1020 990) FE-20 8 ft 1/2 0 4190) 280c) 970 1190 980) JE-21 ft 3466-106 21 0 0 3795 180 1035 1200 935 -2IP24 9 ft ft ft 2 3085 665 945 880 760 -22 9 3466-109 22 D 0 915 0 945 575 295 JE-22P24 C 3466-109 22 0 2 2665 485 920 765 625 J5-23P24 A-5 3523-31 23 ft ft 2205 585 705 790 705 JE-24 C 24 ft 0 1010 0 1065 750 490 FE-24 a 8 ft 1/2 II 3885 245 - . 1310 -24P24 9 0 ft ft 2 2230 760 1100 1145 1090 FE-25 -25P24 -26 -26P24 -27 -27P24 0 1991-113 a ft ft 3523-31 -- 8 a 98 25 ft 26 0 27 0 1/2 0 3325 345 1235 1115 975 V 2 2265 770 1215 1110 800 ft 0 3785 335 1090 1120 895 ft 2 2315 580 825 1055 805 ft 0 3370 615 1235 1220 1035 1 2 2195 625 1200 1120 865 *) Bonds prepared with solvent spread supported adhesive tapes (thickness 12-14 nils) with glass fabric (112-Volan A) dried 15 sin at 200*F. b) Average of two or three values for one-half inch lap joints to type 301 steel (thickness 0.050 in.). c) Average of five or six values. d) Tape dried 30 sin at 200*F; thickness 26 ails. 1 WADC TR 53-126 Pt 4 Ik ABS-Q438C Table 55. SUMMARY OF THE 600F SHEAR STRENGTH OF BONDS TO TYPES ^01 AND 17-7 PH STEEL AND TO TITANIUM FROM X-151 RESIN ADHESIVES Cure at 100 psi: one-half hour at 330*F. Panel No.*) X-I3I/EP0N 1009 Ratio, by wt Formver 15/95 E, phr Curing Agent,") phr Hetal Postcure,c) hr/*F Tensile Shear Strength at 600*F, psi Range AvgOJ 120IFE-4 I2I9F4-4P24 -4P43 -2P23 I286FE -P34 100/0 1 a a 8 n 30 OADPS 301 20 a a 8 2/400 n qa 8 4/300 a t0 8 2/300 a 35 a - a 8 fl 8 3/400 0-330 0-200 170-200 310-380 140-210 0-200 195 125 185 335 175 95 l236FU4-2 a n -JE-14 (1 80/20 a a 8 20 24 DADPS a a 8 88 D a 8 08 301 8/500 8 200/500 0 ' 8 8/600 250-380 520-690 520-580 270-350 420-490 330 635 445 320 455 I236JE-I4 n -FE-24P24 -JE-20P44 I287FE 80/20 a 0 n n 20 24 DADPS 0 aa a a 8 08 a 29 0 301 120/600 fl 200/600 8 2/400 11 4/400 0- 660-790 0 200-310 140-270 360-400 740 0 245 185 375 1236J0-20 80/20 20 24 DADPS Titanium -20P44 n ft a 1 0 4/400 -J5-23P24(H) a D a0 17-7 PH 2/400 II45FU4-I8 116OFU4-2 100/0 - 6 Dicy a 20 0 8 301 0 - - 0 0-60 410-520 40-70 80-110 0 30 i 470 55 95 I275FE-P34 I276FE-P34 -PE-P34 I277PE-P34 100/0 8 _ 10 Uelanine 301 20 8 8 11 0 10 0 80/20 a 8 0 0 3/400 fl 0 8 0-140 60-120 0-200 0-170 115 90 140 165 607FU4-834 (Adhesive 422) II - 1650-1900 1810 5a^gsasgagB asassssaasBaaaegaaBasgaagsasa^iaaasaaaaaasaasaL --.m^jssssafsassaasss^ssasssssssss a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan) dried 15 sin at 200*F. Constant ingredient: 100 phr aluminum dust. Oetails of cure conditions and .natal treataents used are given in tables which summarize X-I3I foraulations cured with I) DAOPS, 2) dicyandianide or, 3) melamine. b) "DAOPS" is diaainodiphenylsulfone. "Dicy* is dicyandianide. c) The data include tests results for specimens aged for prolonged periods at 50O*f and 600*F. The aging is designated as a "postcure" to simplify construction of the table. d) Average of three values for one-half inch lap joints. Thickness of metal adherends: 0,050 in. WADC TR 53-126 Pt 4 75 Table 36. EFFECT OF ELEVATED TEMPERATURE AGING ON THE SHEAR STREMfiTff OF FORMULATION NO. 1256 BONDS TO TYPE 501 StwT; Formulation (by wt): 80 X-131 + 20 EPON 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 24.3 diaminodipheny1sulfone Cure at 100 psi: one-half hour at 330*F Panel No.^) Adhesive Batch No. X-131 Resin Lot No. LR- I236FM4-2) 1236JE-14 1236JE-1^ 2 14 180) _1991-113 1991-113 3523-64 Tensile Shear Strength,d) psi At room temp, original , after 500F aging. 8 hr 9 200 At -70F, original , after 500#F aging, 8 hr At 500QF, original , after 500F aging, 6 hr 48 9 72 9 120 9 168 9 200 9 300 / 400 ) 500 ; 600 At 600F, original ; 700 9 800 , after 500F aging, 8 hr 9 200 , after 600F aging, 8 9 120 9 200 4215 1245 1800 3680 1480 620 1280 1345 1335 1450 1345 1360 890 1090 905 440 145 0 330 635 . 545 * 3970 - - 320 1335 1530 1350 - - -- -- 320 - 455 740 0 2330 * -- - 165 1070 1110 _ 815 520 - -- - _ - ' : a) Bonds prepared with solvent spread adhesive tapes (thickness 12 mils) with glass fabric 112-Volan A dried 15 min at 200F. b) Bonds precured for one-half hour at 100 psi and 240F. Surface treatment: Method A-M*. c) Adhesive tape dried 30 min at 200F; thickness 26 mils. d) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. WADC TR 53-126 Pt 4 76' ABS-0 Table 57. LONG TIME LOAD STRENGTH AT 500* F OF X-151 ADHESIVE BONDS TO TYPE 301 STEEL Press cure at 100 psi for one-half hour at 240F + one-half hour at 330F Exp No. Specimen No.a) x-131/EPON 1009/ Farmvar 15/95 2 Ratio,b) by wt Postcure at 400F, hr Load, psi Time to Failure. hrc> 11 1201FE-4 lOO/o/O 0 240 215.4 (no break) ld l8d) 26d) 27d) 1219FMi-4P44 It -4P84 II If 100/0/20 It II II If 4 240 215.4 (no break) II 400 25.5 8 400 280.8 (no break) II 500 257.2 (no break) II 600 208.6 22 1236FE-10P44 16 It 23 n 17 11 80/20/20 II II It 4' 400 484.2 (no break) tt 500 9.6 If 500 155.8 II 600 55-4 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200#F. Constant ingredients: 100 phr aluminum dust + 24.5 to 30 phr diaminodiphenyl sulfone. Bonds were one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. b) X-131 resin lot No. LR3523-147-1. c) No evidence of creep was observed. d) Surface treatment used with Formulation No. 1219: Method A-M. X-131 resin lot No. LR1991-113. WADC TR 53-126 Pt 4 77 ABS-043E Table 38 PROPERTIES OF EXPERIMENTAL RESIN X-131 Resin Lot No. LR- Epoxy, eq/100 g Hydroxyl, eq/100 g Chlorine, Mol Wt Durran Softening Point, F 1991-H3 3523-20 -31 -64 -115 -147-1 3466-106a) -109a) 0.485 .485 .502 .489 .466 .464 .465 499 0.113 .092 .086 .102 .143 .130 .092 .048 0.57 .77 .56 .70 1.23 1.29 1.31 .47 667 677 663 721 823 696 640 732 170 160 155 170 174 160 156 176 a) Laboratory scale preparation. WADC TR 53-126 Pt 4 78 ABS-0 1 Vi (A 0) it 8l T3 I*?3 i58 w 3 H *CJ Is? Vi GH fa CO 0 Q S3 lA ri--lt t<A0 00 -P sI 3 + .s wp 3CVJ o\'c Hi* tp S Vi C3 l -rl + to 8* 4! + 8 to H jSs ooONn+) (0 iH 3T S 3 2 o to 6*9. rs CO + Oh III 8 to 4^ Ik *- % Ik "* s: % O '8 -- <o O) o --m s no n -- CO -- -- III m tp inAr C(ip/O) uoCO">! 22 O P"-- g S a-rt-- mctSmn iie^mp IAUIOO NN 80 mInO oNMloNccnn icnn >o mIIoIo m in ^ swo5? be o o n in e m ^ cv oi m <p i iT O w w> p (v* <n ^ wm-- -- ssss Cl cn CCOl CCOl 8 ttnnI CcnMn o_I c. i cn 8 cn cn cn cn e s? m to in CM CO N. in to in m o i ais ctoo uki5 15 8 g a C- 8 2 |S 2 SS3M* -- cm cn om fi cn cm cn i 88 28 O cn cn o s c Ot fe &K 58 CM m** C bS o .e ** 5l j= O 4 i8 % ** s &s'4?-* 8i n c (. a 3 sir fc i -5 -8 J-S 3 ^ CD I X --J c* rv ci in in to cm m- to -- to __ cn fi. to cn t cn cn cn Ol CM CM CM m mm cn cn cn _ cn to cn i-- cn cn i cn o> CM CM CM Ol m in m cn cn cn O tt be a +t+o a U --4c^ aC c ** t. g a e cl u ax a x x ax -si L _ SL>X 3 4O X -C -- * -- a a t- U 3C o o 3 4 4" - o L. O aO o cn c-- 9 a ?a C- a > > *< .0 O WADC TR 53-126 Pt 4 79 Table 40. EFFECT OF POSTCURE ON THE SHEAR STRENGTH OF 80/20/20 X-151/EPON 1009/fCRMVAR 15^95 E ADHESIVE BONDS TO TYPE 301 Sim (FORMULATION NO. 1236)aj Press cure at 100 psi far ane-half hour at 240F plus one-half hour at 330F Postcure (oven) hr F Tensile Shear Strength, psi15) Original Aged 200 hr at 500F at 77"FC) at 500F at 500#F None 4 16 32 2 4 8 2 8 16 270 II It 330 II It 400 ft 11 3900 4250 4025 3860 3670 3700 3560 3435 3015 2935 495 585 610 670 675 735 775 835 1065 875 680 650 535 530 875 715 640 675 805 445 a) Formulation No. 1236, batch No. 9 (parts by wt): 80 X-131 (lot No. LR 3523-1^7-1) + 20 EPON 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 24.5 diaminodiphenylsulfone. Bonds prepared from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15-min at 200"F. b) Average of three values for one-half inch lap joints to half-hard type 301 steel. Surface treatment: Method C. c) Average of two values. Table 41. EFFECT OF METAL SURFACE TREATMENT ON THE SHEAR STRENGTH OF 80/20/20 X-I31/EPON 1009/F0RMVAR 15/95 E BONDS TO TYPE 501 STEEL Formulation No. 1236 Cure at 100 psi: one-half hour at 240 F plus one-half hour at 330F Panel No.&J Surface Treatment**) Tensile Shear Strength,) psi At room temperature At 500F At 500^) after 500F aging, 8 hr 48 72 120 200 1236FM4-26) 1236FD-3 1236FE-3 A-Mg__________D C 4215 620 1280 1345 1335 1450 1360 3875 350 1135 1330 1570 1425 1320 4095 675 1390 1480 - 1400 1440 1410 1236FF-3 B 4015 695 1370 1240 1420 1370 1190 a) Bonds from solvent spread supported adhesive tape (glass fabric 112 ' Volan A) dried 15 minutes at 200F. Formulation No. 1236, Batch No. 3 (by wt): 80 X-131 (lot No. LR1991-H3) + 20 EPON 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 24.3 diaminodiphenylsulfone. b) See the last section of this report for description of methods of surface preparation. c) Average of three values for one-half inch lap joints to half-hard, type 301 steel (thickness O.O5O in.). d) Average of two values except for Panel No. I236FM4-2 where three specimens were tested for each test condition. e) Formulation No. 1236, Batch No. 2 was used for bonding. WADC TR 53-126 Pt 4 81 Table 42. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM AN 00/20/20 X-151/EP0N 1009/FORMVAR 15/95 E ADHESIVE TAPE WITH STAINLESS STEEL CARRIER Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F Panel No.a) Formulation No. 1236, Batch No. Type of Carrier 1236FF-3 3 Glass Cloth 112-Volan A 1236FF-4 .4 Stainless Steel11) Tensile Shear Strength,) psi At room temperature**) At 500F, original**) , after 500F aging, 8 hr 48 72 120 200 4015 695 1370 1240 1420 1370 1190 3500 305 1105 1265 1295 905 955 a) Bonds from solvent spread supported tape dried 13 m-in at 200F. Formulation (by wt): 80 X-131 (lot No. LR1991-H3) + 20 EPON 1009 + 20 Formvar I5/95 E + 100 aluminum dust + 24.3 diaminodiphenylsulfone. b) Woven wire, type 304, 30 mesh; wire diameter O.OO65 in. c) Average of two values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method B. d) Average of three values. WADC TR 53-126 Pt 4 82 ABS-0 4 Table k3. EFFECT OF SALT SPRAY EXPOSURE ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM FORMULATION NO. 1236 Press cure at 100 psi for one-half hour at 24-0 F plus one-half hour at 330 *F Panel No.3) Adhesive*11) 1236 Batch No. 1) FE-I0P44 2) ' 1) FE-IIP34 2) * 1) F0-I0P44 2) * 1) FD-IIP34 2) 1) FM4-I0P44 2) 1) FU4-IIP34 2) " 10 " II n 10 ' II 10 n II Surface Treatment Method C (FPL) formalin-peroxide followed by passivation ! Method 0 (Franklin Institute) I chromic-sulfuric acids Method A-U4 sulfuric; HNO3-HF itcure 400*F, hr Tensile Shear Strength at Room Teao. Dsi Original After 30 Days' Salt Sorav Ranoe Avqc) Ranoe Avad) 4 2400-2560 2480 2540-2920 2715 fl 2920-2930 2925 1800-2370 2110 3 1960-3 ISO 2570 980-1560 1255 R 2510-3120 2815 960-1850 1395 4 2390-3490 2940 1610-2000 1850 n 3040-3890 3465 1420-1980 1670 3 3 250-3400 3325 2140-2700 2430 fi 3240-3350 3295 2140-2640 2465 4 1480-1660 1570 760-1340 975 a 1740-1960 1350 880-1390 1180 3 1530-1740 1635 650-920 7S0 R 1410-1590 1500 840-1260 1060 a) Bonded panels (10.5 x 9.0 in.) with one-half inch lap-joints; half-hard type 301 steel (thickness 0.050 in.). b) Bonds from solvent spread supported adhesive tape (glass fabric 112-Volan A) dried 15 a in at 200*F. Formulation No. 1236 (parts by wt): 80 X-I3I (lot No. LR-3523-147-1) 20 EPON 1009 20 Formvar 15/95 E 100 aluminum dust 24 diaminodiphenyl sulfone. c) Average of two values. d) Average of five values. WADC TR 53-126 Pt 4 83 ABS-04381 Table 44. COMPARISON OF THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM FORMULATION NO. 1236 ADHESIVE TAPES PREPARED WITH METHY1AL AND ACETONE Press cure at 100 psl for one-half hour at 240F plus one-half hour at 330F Panel No.a) 1236FE-12 1236FE-8 Methylal, parts by wt Acetone, parts by wt 1/9 MEK/THF,*>) parts by wt Tensile Shear Strength, psi) At room temperature At 500F, original , after 500F aging, 8 hr , 72 , 120 , 200 ' 53 25 200 3870 460 935 920d) H40d) 765 0 53 200 4275 630 735 -- 670 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried one hour at room temperature and 15 min at 200F. Formulation, parts by wt: 80 X-131 (lot No. LR3523-147-1) + 20 EPON 1009 + 20 Formvar 15/95 E + 24 diaminodiphenylsulfone + 100 aluminum dust. Solvent concentration based on 80/20/20 X-131/EP0N 1009/Formvar 15/95 E. bt MEK is methyl ethyl ketone; THF is tetrahydrofuran. c) Average of three values for bonds to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. d) One value. WADC TR 53-126 Pt 4 84 ABS-04 Table 45 EFFECT OF METHOD OF BOND PREPARATION ON THE SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL Panel No. 1256PE-11P34 1236PE-11P335 1236FE-10F44 Adhesive batch no. 11 11 10 Cure at 100 psi 75 to 400eF in 30 min 75 to 350F in 30 min 30 min at 240F 30 min at 330#F Postcure, hr/F Press - 3/400 Press - 3/55 Oven - 4/400 Tensile shear strength,b) psi Range Avg Range Avg Range Avg At room temp 2230-3100 2750 3560-3880 3665 2110-3410 2845 At 500F, original 500-660 585 580-740 655 700-1000 895 , aged at 500F, 8 hr 650-850 735 680-790 745 720-890 800 , 72 hr) 500-740 615 730-1120 925 - -. , 120 hr) 660-890 775 36O-67O 515 - - , 200 hr 610-680 645 550-700 605 - - , 248 hr - - - 650-670 660 a) Bonds from solvent spread supported adhesive tapes (112-Volan A glass fabric) dried 15 min at 200F. Formulation, parts by wt: 80 X-131 (lot no. 3523 147-1) + 20 EPON 1009 + 20 Formvar 15/95 E + 24 diaminodiphenyl sulfone + 100 aluminum dust. b) Test results for three bonded specimens to half-hard type 301 steel (thick ness 0.050 in.). Surface treatment: Method C. c) Test results for two specimens. WADC TR 53-126 Pt 4 85 ABS-0438 It e Ottoo CO +> fc. 8o r-J CO J ra a> s 82 " C0PH3k Oh O O CPO O 03 8V (0 8o m -p bl S| 0-i Ol. < c -- CD t c9 & 5 SI 9 sO 9w 9 O __ Mm Nn o CD CO CV V- g)R v- w JS ao uo r00 in CM 07 uo fr-- O CO 0 0ao UO r*- * 1 ID CO in CO CO uo uo 0in <0 uo 0u0o 8 UO Q. OC (O H--- CesOj 9 o* =*= & *5 5; s sa p- 3 Ee ^5 u. uCMo c 9 u<a0> u 9 T<90 Vfp--- 0 00 in in C**Or r-- in CM "" u00o o> uo 8 0n CD 9 >* C*- 0 oU t . v feig c. CZ" CS - = S CM -- -- *9 "8 * &I Lfc. OIDl 8S CJ ocon. -- to CO N o..e. CgJ .o21 co *>* --9o 9 u CO <0 L. ^ I X 9 --e -9oH9co </o < S . S8 > 8 a. CNI 9 ja u O 9- O Q. a. 0. a. a. Q. z CD 07 8 0 8 O *9 11 CM CM C ** 9 CO CO a. CO CO CM CM 5 Eo S tu .C9 O 5 o, 18 t- Sa. 9 UJ -c5 o 8 S c CO 1? CO CM c UO 0 CO OaL. QC 9c -C i C 0O 9 J9 * 9 J M- CO CM 9 L. CM 9O 9 O 9 M- 9 9 z fe. M-* e Xc S 99 9 J 9 Sc g 9 9 9 C * >O. 9 2 C -- TO JC J3 X uO 8O CO O (. 9ox*(0 -h* So a. -9 a. * *5 oH- o J5 CJ 9 9 9 > 9> c. -c * a*:(/) OtJ 9O * o *>(0 * O OQ> CO rO B< *0 O WADC TR 53-126 Pt 4 WADC TR 53-126 Pt 4 Table 47. ROOM TEMPERATURE STORAGE STABILITY OF X-131 SUPPORTED ADHESIVE TAPES WITH DIAMINQDIPHENYLSULFQNE tA Sia ii II ii II o ir\ IA ON co -4- Ul ' l o= 8= OrOAJ aL* IOcJAuiJ) O7 ABS-0k381 Table ^8. SHEAR STRENGTH OF 80/20/20 X-131/EP0N 1009/FQHMVAR 15/95 E ADHESIVE BONDS TO TYPE 17-7 PH STEEL (FORMULATION NO. 1256) Press cure at 100 psi for one-half hour at 330F Panel No.#) 1236- Steel b) _________ _ Surface I . rT Thickness, Etchant ,t f. Type "" Tensile Shear Strength,d) psi n, . - At 500*F After SOOT tA,ollMr f7l7i*pF f5n0A0a*PF f8i lh_r l1e2A0 lh._r o20aa0 hr F-13) -I3P348' J-I3P34 -I4P34 JE-18 17-7 PH fl 301 0.062 1 9 .050 None 1 0 9 C 0 3880 270 515 3 2370 535 - - 0 3 2520 610 1005 205 285 3 - 815 1070 - 460 0 2330 165 1070 1110 JE-18 -I8P84 JII5-18 -I8P84 -18 17-7 PH 9 ff 1 301 .062 1 0 .050 c 9 A-5 f 9 0 4425 230 1095 1340 8 - 575 - - 0 3815 180 1105 1060 8 - 685 - - - 0 3715 170 620 865 - J5-23P24 -23P24(H)f) -23(H) -23P24 17-7 PH > Heat 17-7 PH treated rin heliua 301 J .062 .050 i A-1I5 9 9 9 2 3505 915 1250 1220 885 2 3205 810 1280 1100 955 0 2505 255 - - 730 2 2205 585 700 790 70S a) Bonds froa solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 ain at 200F. Foraulation No. 1236, batches 13, 14, 18 and 23 (parts by t): 80 X-I3I * 20 EPON 1009 20 Foravar 15/95 E 100 alualnua dust 24 diaainodiphenylsulfone. b) Araco 17-7 PH steel, condition TH 1050, with vapor blast finish. Half-hard type 301 steel with 2B finish. . c) Oven postcure at 400*F (no pressure), d) Average of two or three values for single one-half inch lap joints, e) 8onds "procured* at 100 psi for one-half hour at 240*F. f) Shear strength at 600*F: 470 pal. WADC TR 53-126 Pt 4 88 ABS Table 49. SHEAR STRENGTH OF BONDS TO TITANIUM (C-110 M ALLOY) FROM Bo/20/20 X-131/EPON 10Q9/F0RMVAR 15/95 E ADHESIVE (FORMULATION NO. 1256) Press cure at 100 psi: one-half hour at 330F Panel No.a) Metal (thickness O.05O in.) Postcure, hr/F 1236JD-20 1236JD-20P44 1236JE20-P44 Titanium*5) Titanium15) 301 Steel0) 4/400 4/400 Tensile Shear Strength,^) psi At room temperature At -70F At 500F, original , after 500F aging, 8 hr Bend Strength, lb } 48 } 120 ) 168 ) 200 2275 1465 165 695 525 565 565 395 114 770) 625 215 335 355 265 295 385 35 1830 - 550 715 905e) - a) Formulation No. 1236, batch No. 20 (parts by wt): 80 X-131 (lot No. LR3523-31) + 20 EPON 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 25 diaminodiphenylsulfone. Bonds prepared with solvent spread supported tape (112-Volan A) dried 15 min at 200#F. b) C-110 M titanium alloy. Surface treatment: Method D. c) Conforms to MIL-S-5059; Micro Rold, half-hard, condition C, composition D. Surface treatment: Method C. d) Average of three values for one-half inch lap joints. e) Average of two values. . WADC TR 53-126 Pt 4 89 Table 50. EFFECT OF DIAMINQDIPHENYLSULFONE CONCENTRATION ON THE SHEAR STRENGTH OF 80/20/20 X-151/EP0N 1009/F0BMVAR 15/95 E BONDS TO TYPE 301 STEEL Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F Panel No.a) 1257FE -P24 -P44 1258FE -P24 -P44 1259FE -P24 -P44 1236FE-5 -3 . -P24e) 1269EE 1287FEe) Postcure at 400F, hr 0 2 4 0 2 4 0 2 4 0 0 0 2 0 0 DADPS,*) phr 12 tl If 16 II H 20 It II 24.5 If It If 29 It Tensile Shear Strength,psi Original *%*$* 77F 500F 500 F H95., 2780d' 1605 0 70 340 325 - - 13 137^) 1980 0 350 595 325 - - 2010 3360d) 2610 335 865 1025 1045 - - 4155 4095 3900 3435 4310 4100 645 675 495 835 1010 535 645 1410 680 675 1325 % 635f> a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200*F. Constant ingredient: 100 phr aluminum dust filler. X-131 resin lot No. LR1991-H3 b) DADPS is diaminodiphenylsulfone. c) Average of two or three values for one-half inch lap joints to half-hard type 501 steel (thickness 0.050 in.). Surface treatment: Method C. d) One value. e) X-131 resin lot No. LR3523-147-1. f) Exposure period at 500F was 248 hr. VADC TR 53-126 Pt 4 90 Table 51. EFFECT OF ALUMINUM FILLER AND DIAMINODIPHENYLSULFQNE CONCENTRATIONS ON THE SHEAR STRENGTH OF X-151/PQHMVAR 15/95 E BONDS TO TYPE 301 STEEL i i Sn i i 11 1 1 1 UN 1 KN 1 81 NO NO +.Sa>-i ^O j1 < m 4 bi 0 -V \i i_r\oC* pj w a JC9O I H HSV a tj-a O IfN IfN UN KNVO 1 C-- On o t~- t- q r-i H O SjIfNvJUO*N MU^NOvQOKU^NN 8, KN NO o *?no o 5 1 R0 H fH rn 8 KN& 1 8- t-COr^ /Is f-- UN "8 UNUN& Ch 1 KN NQ ONO IfN tH HH O Q O UN t--IOC- 1 H KN KN On H i--9 H ' UN IfN O UNO IfN UN UN UN UN UN UN UN ON O 3 knS NO t- C--NO CO CVl NO CU J- KN or-i in c^ ow UNO O IfN IfN IfN KN KN UN H IfN NO COCO O KN KN KN KN J- UN UN QQ O % Q O UN UN UNO KN H O UN t-rH CVJ On CO KNHO CVJ Jt-4- KN KN -d- 3 bo \Sl8H = = H8 = = 8H rcH 8H =8i-l lfN UN OIA = KlfNN = O ~ ~ ~ 8" J p,, llsll H r-ii KN t-- m KN f- . 3H -d; <--1 r--j <--9 --(--1 rl H s = ii KN rH KN i-l KN 1111 1 II _ +a2 -c ,o -*g T) 9) V4 Q H KN r-i KN r-l KN KN KN rH kn (0 *H bp A && H KN 8 CVl pv CVl CVJ Ol UN ON UN UN UN Ov CVl ON IfN iH KN i-9 KN KN KN H KN lRa*4) T3 O O +> ON 8 O* KHN H *+r>l p7 f Z rt >5 X o as xij w fEO.NMEOMNEgMgEHt cd oS a Si IcfvNj HH HHH CVJ Un8 (7\ wtwilwlw w 5S b IfN K\ KN KN KN CVJ CVJ CVl CVl KN HHHHH Iff vssfi HHH aJ -P o <u C:3> ^c-8 IJjll 43 fit S p Oa o -h <h O + VO, -P , litLi t=o0)> 8S , . CsO ofc OQ Q3 Q sP> V(SS 5 91 bdp wo <30 CQ OJ = ^ CO a) ,a o xJ fl) H WADC TR 53-126 Pt 4 91 ABiS-04381a Table 52. EFFECT OF BISPHENOL-A ON THE SHEAR STRENGTH OF 60/20/20 X-131/EP0N 1009/FQHMffAR 15/95 E BONDS TO TYPE 301 STEEL Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F " Panel No.a) Bisphenol- Tensile Shear Strength, psip) A Original At 500F After 500"F Aging ForCJ phr 7777Fr 500 4F H8 hlTMr 4liH8 hhnr T7O2 hr 1lQ2f0t hr 02/0V0\ 1h- r 1236FE-5 1263FE 1264FE 0 4155 645 1330 1120 950 835 645 2 4205 775 1485 1230 1155 850 845 5 ' 4140 785 1365 1115 890 1130 1025 1265FE 8 4215 420 900 780 535 540 300 1266FE 10 4065 375 1275 6O5 820 735 460 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 minutes at 200F. Constant ingredients (parts by wt): 80 X-131 (lot No. LR1991-113) + 20 EPON 1009 + 20 Formvar 15/95 E + 100 aluminum dust + 24.5 diaminodiphenylsulfone. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. c) Average of two values for all aged bonds. WADC TR 53-126 Pt 4 92 ABS Table 53. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM 80/20/20 X-151/EP0N 1009/FQRMVAR 15/95 E ADHESIVES CURED WITH DICYANDIAMIDE DISPERSED IN THE RESIN SOLUTION Press cure at 100 psi for one-half hour at 240F plus one-half hour at 330F Panel No.a) Postcure (oven), hr/#F 1272FE None 1272EE-P34 3/400 Tensile Shear Strength,psi At room temperature At 500F, original , after 500F aging,<*) 8 hr ) 48 } 72 ) 120 200 2590 0 910 690 1175 885 930 3790c) 200 - - a) Bonds from solvent spread supported adhesive tape (glass cloth 112-Volan A) dried 15 min at 200F. Formulation, phr: 100 aluminum dust + 6 dicyandiamide. Dicyandiamide not dissolved but dispersed by trituration with the resin solutions. b) Average of three to four values for bonds to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. c) Average of seven values. d) Average of two values for all aged specimens. WADC TR 53-126 Pt 4 93 ! 8 d> a TJ 4CO) 1&0 + 0) 09 w 024 kM CO U 83 1 CO Ui aO a a 9 fe ao 4. 8 k o- CO CM O CO CO 8s o CO c o 1 CO CO a s Ui -- ru fs- CO s o CO CO CM o CO o + CO 9 a a s Ui a 8: ao 8 k a. CO CM o "" CO o CO CO CO o r CO CO c a uu 4 > u. CO o r*r- 9 CO CM CM o <o 8 *3* CO CO M* CO CO 8 co <5a. o i 4 a CO CO UJ u. CO 9 CO u CM CM o CO L. c a a W J8 u. 4 c -- C a. a k a 3 k -c <0 a o. oaa a SB c a s*-- a u9 a 44 S a. 3a* y <5 ae 3705 8 1g CO FS Wo aa 1 m in co CM CO un to CM in in 8 CO CO in CO CO s8 8 a CM X<_I -- c CnM --O %on T5 CM -- O O 4^ O k-- S s<* -- s 8 c u* CM 00 jkC o in tn m CO CO m CO CM o GO _ a S' o. 8* JC U. 44 a O' c fa a 44 c u 4on4 a k 9 fa a 44 fa cx k O a a oJaCn 44 a * u. * o a ko Qa 8 44 a s-s CO -- 4^ a ck a 3 a 8- 44 a C in a -C .g 3 u --a cc a *"' ar O. CO k u. afa 8-- n -S 8 .= ~ 4< I X OC O--)' au X --aoe> aa ? =i a u^ JC ? . 8 CO 44 _ o 3 g*. * -- S 'S O 44 * -- CM LOO 3 JLZ +* 5 *8 a CD o e" M- -8 *? o8 --c s L S 7 fe r o o 4O- 4L4 s' ok 4w-. Sfc m- a o a !1 a nk WADC TR 53-126 Pt 4 9^ ABS 0438 ! b0fc Co rl C* II oo CO P* I--I oo 3t-- r*l o j* rrH sl in ir\ CVI r-1 (ON CM v8*= Ne^O Si 3 t ' HM 88 1% K 00 8 w&<<<Dy H &s OH Si Si O in in rH in t-- CO 00 m CM 11 t- m mjo fOv H& CL, 3 atC\ H rHii 8 NO 11 11 ON tOI1 m11 -=if NO11 rH k\ ON CM -* CM R CO 3 &ON in ri m KN WADC TR 53-126 Pt 4 95 i i i ..i ABS-04382 0 A oCm Vi O r-l KN Ja1)S+0^ 8S G2 5Vl A rHa VHgl P*X5 8 r-\ O 13 9 9h X\ o 83 8* pm a ffcl'8 I Om 2 *a<3 3% jHSfifo<MTMJ 55 ^8 ib tj OJ G CSMiHQ aCOSQOS itno ^ CVi si Cm 0 |s W 5 VO o 5 32 ae a> Q) 0)0) ir\o O IA tAO ON (OH HJJ ON a- IA I CM 0) 0) IfN O tfN IfN <M W KNrl IfN KN i--t a- KN 0) IfN a t~ lb & IfN lf\ O O O IA IfN UN KN-tf- C.a rfN ONrH -it 3 VO KN K*N a- IfN VO vO 8 0 IA IfN IfN UN IfN KN C-- O_N. Ol W O I -S' OJ r-t ` iC-Mt KN KN a> CD s ICD O a iH s a CD O KN .3 3 Vi 0 Cm i0 3 G KN a> P rl -ri fi 1 o aa.ss CM. T* 2o ao 5a 01 c i- CM ^ W*- II s! Is<t). 26 HV HKN * T0J) iVHrti 0_p) G0>o) CO'- i--I 0) RN <u ir\ o ON 'fllfN H T) G oG h a QH UO, cog CM OCO t- CM VO (0 bo G CM H b0o Ini 2 5 G 00 S'3 aco 2. afa Oo 2^ CO P + HG<u *< <Jj _ +> G0. Vi 0,0 G0 3*3* IA O 3 m <H a co 0 a o tj 0 WADC TR 53-126 Pt 4 96 ABS-043824 Table 57. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM EXPERIMENTAL MODIFIED X-131 RESIN CURED WITH DIAMIN0DIPHENY1SULFQME e) Average of two values f) One value. UIt %-- Q --> (0 *0 O CD iCnO tCnO o-- ^ (O O CO in tn 0C0O cCO- u--o *C---oJ "s- M- CM iofitn^No CO -- a> m tn cm r^> CO O) 8 oo zCO I otOtoo U^J -- 8o^i8 o3*ro S Si -- n-M* l/> .I GO CO CO CO .I 0s0 sK * CO o c JC, u .8 O N O) cn -- *. -- 8^8 3 gii 28 s -s L. 1 4* fc -C u oj O __ a SS28mcn?-- Oo S SI <0 h. M N N 88 CO (0v ^-- CM o O --- mQi CM C .8 --L s2 5 8.- C 8 1-0 ---u- oCIM_ >---o* oM D s CO -- g CM CO in "~O -- CM " CM CMI Stn m tn m tp cm c-- uo in ? N OH0 8- i i 1 5. *u 8* -2 S < 8 s CM x c5 ft JC am u .c "SK Rg b & xo: oc 0 b> u O 03 c. -C o. 8 5 u. Is .c lco ^ -- s co 'f* e --o co _ QC 3^ ^-- .cL. , C7> -- o0 >c cQ> 1 U-- > --* C JC. O --O ofZl- "OO- .'w z oe 2 o ^ c n-- n--1 -- ^0 a. xx a a. ocac>. <u3+^ ----c mo c_ c. o CO <. aa -- ol G> M" * -C U. ^ oo -2 8 % o o_ L. am> oc L. ft **-=5 -e8 o oc 00 -- " -e8 o CD -81 to S' 8 C. M ;b < co JO u WADC TR 53-126 Pt 4 97 A$S-04382; Table 58. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM EXPERIMENTAL RESIN X-141 CURED WITH DIAMINODIPHENYLSULFONE Press cure at 100 psi for one-half hour at 2lt-0F plus one-half hour at 330F ~ Panel No.15' X-141/EP0N 1009 Resin Ratio, by weight Forravar 15/95 E, phr Diaminodiphenylsulfone, phr At room temperature At 500F, original , after 500F aging, 8 hr , 139) , 248) At 600F Tensile Shear Strength,6^ psi 12fl2FE I283FE 12o4fE 100/0 100/0 80/20 0 20 20 33 . 55 27 2435 750 845 920 515 460 5270 815 865 1180 770 475 3045 185 895 880 385 125 a) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. b) Bonds from solvent spread supported adhesive tapes (glass fabric 112-Volan A) dried 15 min at 200F. Constant ingredient: 100 phr aluminum dust. c) Average of two values. WADC TR 53-126 Pt 4 98 ABi S Table 59. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM EXPERIMENT&T. | RESINS LR2047-76 AND LR2047-83 CURED WITH DIAMINODIPHENYLSULFONE Cure at 100 psi: aae-half hour at 240F plus one-half hour at 330F Panel No.B> Resin Diaminodiphenylsulfone, phr Adhesive Form 1270FE LR2047-76 38. Tape13) Tensile Shear Strength,) psi At roam temperature At 500F, original , after 500F aging,d) 8 hr 00 , 72 , 120 , 200 1705 1045 1080 1480 1295 890 540 1201FE-6 X-131 LR1991-U3 30 , Tape") 2420 1060 II65 1150 1220 1075 1115 1271FE LR2047-83 31 Hot Melt 2045 245) 495 200 355 220 0 a) Bonds with glass fabric, 112-Volan A. Constant: 100 phr nlnm-tnnrn dust filler, b) Solvent spread tape dried 15 min at 200"F. c) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. d) Average of two values for all aged specimens. WADC TR 53-126 Pt 4 99 ABS Table 60. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM EXPERIMENTAL RESIN LR2047-96 CUBED WITH DIAMINODIPHENYLSULFONE Press cure at 100 psl for one-half hour at 240F plus one-half hour at 330*F Panel No.a) LR20U7-98/EP0N 1009 Ratio, by wt Formvar 15/95 E, phr Diaminodiphenylsulfone, phr Postcure, hr/#F 1278FE 100/0 0 30 None 1278FE-P44 100/0 0 30 4-/400 1285FE 80/20 20 24 None 1285FE-1 80/20 20 24 2/400 Tensile Shear Strength,13) psi At room temperature At 500F, original , after 500F aging, 8 hr 159) 248) At 600F 2040 1225 820 955 9Q5 495 1230 890 480 - 3800 945 1155 350 840 400 2635 905 1155 730 420 445 a) Bonds from solvent spread supported adhesive tapes (glass fabric 112Volan A) dried 13 min at 200aF. Constant ingredient: 100 phr aluminum dust. b) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness O.O30 in.). Surface treatment: Method C. c) Average of two values. VADC TR 53-126 Pt 4 100 AflS-0 I Table 61. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM EXPERIMENTAL RESIN LR2047-126 CURED WITH DIAMINODIPHENYLSULFONE Press cure at 100 psi: 30 min from 80F to 400#F plus 3 hours at 400F LR2Q47-12fe_ No.*) / by wt phr 1295PE-P34 1293PE-P34 100/0 11 0 20 -2P34 t! 11 1294PE-P34 -2P34 80/20 11 It if Tensile Shear Strength^) psi --I Original At 50bkF After 500#F Aging 77QF 300*F 600F 8 hr 200 to" 55 1940 1530 465 1460 315 11 3010 285 320d) 1280 395 11 2725 265 - 1245 390 28 3180 295 510 1040 935 11 2420 210 - 1025 775 a) Bonds from solvent spread supported tape (glass fabric 112-Volan A) dried 15 min at 200F. Constant ingredient: 100 phr aluminum dust. b) "DADPS" is diaminodiphenylsulfone. c) Average of two or three values for one-half inch lap joints to half- hard type 301 steel (thickness O.05O in.). Surface treatment: Method C. d) Range of values: 140 to 660 psi. WADC TR 53-126 Pt 4 101 ABS-0 i- Table 62. SUMMARY OF THE 60QF SHEAR STRENGTH OF BONDS TO TYPE 501 STEEL FROM NEW EXPERIMENTAL RESINS Cvire at 100 psi: one-half hour at 330 F with diaminodiphenylsulfone. a) Panel No.*5) Resins. by wt Experimental X-131 EPON 1009 Formvar 15/95 E, phr Postcure, hr/F -- -iri r Tensile Shear Strength at 600F. psi Range AvgJ 1279JE-P333 1280JE-P333 -P333HM 1281JE-P333 129OPE-P34 100 X-801-3 II II II II 80 l 10 It 0 II II 11 72 1291PE-P34 1292PE-P34 1282FE 1283FE 1284FE 40 60 X-80tt 1-3 100 JU141 II II 80 II 48 32 0 ft 11 1278FE 1285FE -P24 1293PE-P34 1294PE-P34 100 LR2047-98 80 It II II 100 LR2047-126 80 It 0 tt 11 II II 1295FE-P34 1329JE-2 1330JE-2 1331JE-2 607JM5-IH2 100 LR2047-126 0 10 LR2047-199 90 30 It 70 50 ft 50 (Adhesive 422) 0 It It 20 18 12 8 0 It 20 0 20 ft II II 0 II II II 3/330 90-170 135 20 It 0-110 55 II It II 11 0-75 60-80 50 >5 - 3/400 30-100 65 -- 3/41100 130-170 0-80 if50 l10 -- .-- 370-540 40 20 444-540 475 It - 110-160 lb 430-580 4< 20 11 -- 2/400 340-430 420-490 460 4f5 tt 3/400 140-660 320 It II 460-600 5}.0 .. 3/400 300-580 4<>5 - - 120-270 1' r0 -- -- 50-90 6>5 -- -- 60-180 1Cp - 1530-1670 161 5 one amine hydrogen per epoxide group. Filler was 100 phr aluminum dust. b) Bonds prepared with glass fabric (112-Volan A). Details of bond prepar ation including adhesive form, cure and complete formulations are given in the tables which summarize the formulations containing the experimental resins. c) Average of three values for one-half inch lap joints to half-hard type 301 steel (thickness 0.050 in.). Surface treatment: Method C. WADC TR 53-126 Pt 4 102 A$S mtn in O *n CO in m m SI CO CO in > CO j=oS> c V OO L"a. s_ "S' to fc. _io to lO CO CO -- <0 s CO So cm tn cm in SN- 8M C 2 9 ou (A to 8 : 8Ol *** 2 S s 32 g 12 S 8 S-- in CO in co in CM sCM 8 r CO CO CO CO a 9 CCJ -c CO n o woa o o (., -9c'-s. o*9u ^ o CO CO CO -- CO CO . s ttoo c. a. o -- ---- CO Ol uc L. UJ > in t- 2^ om <0 8 8 3 *o >o 3 8 CO CO CO -1 J. J. 8I X 8I 8I XX 8 Jt I X 8 8 8 oo CMI UJ oc CO CM in O) CM CM CM n. CO CO CO CO o T X o T 8 n(o- u 4. --- o. tn 12 oa CD CJ CM CM CCMO CO CO CO WADC TR 53-126 Pt 4 103 c) d) e) f) PUDA is p y ro a e lIitic dianhydride (du Pont Co.); HA is aaleic anhydride. PUDA was dispersed in a solution of the resins and HA. Average of three values fo r one-half inch lap jo in ts to half-hard type 301 steel. Surface treataent: Method C. The adhesive contained I phr phosphoric acid as a cure proaoter. VCOE is vinylcyclohexene dioxide (Carbide and Carbon Cheaical Corp.). ,BS-<p438 Table 64. SHEAR STRENGTH OF BONDS TO ALUMINUM FROM RESINS CURED WITH COMBINATIONS OF PYRQMELLITIC DIANHYDRIDE AND MALEIC ANHYDRIDE Panel No.a) Resins, Parts by wt EP0N 1009 Cab-0-Silb) Fitler, by wt Curing Ai^ent. phrP PU0A UA Type of Adhesive Tensi le Shear^) Strength After 16 hr at 350*F, osi at 77`F at 500*F 1310 I3l4e) I3l5e) 100 X-I3I 100 X-I3I 80 X-I3I - 20 0 20 18 Tape 915 115 0 20 18 Tape 1195 200 0 16.5 15 Tape 1235 215 1311 100 EP0N 828 - 1316 80 EP0N 828 20 10 23 20 Paste 1135 340 5 21 19 Paste 1435 so 1312 100 X-401-3 - 1317 80 X-401-3 20 10 36 32 Paste 1090 0 5 31 28 Paste 1355 300 1313 100 X-801-3 - 1318 80 X-801-3 20 10 39 35 Paste 885 365 5 34 31 Paste 1335 345 a) Bonds to 0.064 in. ciad aluminum alloy 2024-T3 with glass cloth reinforcement (grade 112Vofan A). Constant ingredient (parts by wt): 100 aluminum dost filler. b) Colloidal silica (Godfrey L. Cabot, Inc.). c) PMOA is pyromel litic dianhydride (do Pont Co.); MA is maleic anhydride. PilQA was dispersed in a solution of the resins and MA. d) Average of three values for one-half inch lap-joints. Surface treatment: chromic- sulfuric acid etch. e) Formulation also contained 20 phr Formvar 15/95 . WADC TR 53-126 Pt 4 104 & Table 6 5 . SHEAR STRENGTH OF EXPERIMENTAL RESIN X-601-3 ADHESIVE BONDS TO TYPE 301 STEEL CURED WITH DIAMINODIPHENYLSULFONE Sf i 8^1 uo -4<* JZ JC O uCOo o-- UoO uo 'M* CM CO -- GO UCOO ,. 2 , 'H CO -- CM 3n. h- rsj n N -- U (O ^ 9 , ^ S JC -- GO N N N uo CO 1 1 UO I CO CO 8 uo o o CM CM ^ CM O WO O UO UO O to o> m 2 ue 8S8SS SSSSeSO 0 <0 m -- frOtv 8N N (M ^ O) co cm o -- o NNNNN s Q> O -C U- 3 a> v a cd U? o f uo 4^ CO . 1 CO <0 CO CO C%O & OQO_ -uC 9 " to Pc 0> oCIO I 8 >e mo) rl + o uo a as ooo> o 09 to & c6u 9 9o e B CM g . s 2 9 s? <c0 >01 CM -CM --3 -,LC CM -- O co j0c. 57 8 = s o> c 0> Q. 2 .2 Q. "O i4- > -uc cl in ao cm __ GO U. 3 -L >, c c*. S < 2 uo 25 CO 4c^ Q3C -H o U C L CaO o --O jC Jti5 Cj CM b > a M- *4- CO CO CO CO CO CO CO CO CO CO aCO. ^ cl aCO. Q_ cm CO cl 1 T 1 i s CM CpOo 4COCO o* 4" ^ CO ^N CaO. CQO. OCO. C-O t *">0-0-0. S ' -- Q --' CM GO O) Gl 0> CM CM CM CM o> T> OOCD -- e --<3Q <0 CO jLOO Q9OCL O' 2* --> CO> 4^ aa> <> r <*p .n wj a uk M- CT -C WADC TR 53-126 Pt 4 105 4BS-Q438 Table 66. SHEAR STRENGTH OF X-131/X-4Q1-3 ADHESIVE BONDS TO TYPE 301 STEEL Press cure at 100 psi for one-half hour at 240 F plus one-half hour at 330F Panel No.) Ba13) x-i3i/ X-401-3 Resin Ratio Curing Agent,0) phr Tensile Shear Strength,1^ psi OriginDall A*Jgted520000.phr 77F 500F 500F 1222PM3 1222FM3-3 1222FMq-2 II6OFM3-4 1223FM3 A 85/15 6 dicy 2665 105 B C It M It It It M 2690 2540 85 65 C 100/0r' II tl 5635 385 G 85/152) 4.5 dicy 2965 275 525 , 475e) 230 610 170e) I228PM3 1230Bfe-P23h), 1230B^-2P2311) 1219FM3-2P23*1) 'F A C C 85/15 ft It 100/02) 4.5 dicy 30 DADPS It II tt It 3115 3410 2025 3615 ' 165 330 30 770 225eJ 350e 230) 630e) a) Bonded with hot melt cast unsupported adhesive tapes; constant ingredients, phr: 20 Formvar 15/95 E + 60 aluminum dust. b) See Table 55 for identification of resin batches. c) "Dicy" is dicyandiamide; "DADPS" is diaminodiphenylsulfone. d) Average of three values for 0.5 in. lap joints to half-hard type 301 steel (thickness O.05O in.). Surface treatment: ) Method A--M3 e) Average of two values. f) Solvent spread supported tape (112-Volan A glass fabric) with 100 phr aluminum dust. g) Adhesive contained 10 phr Formvar 15/95 E. h) Bonds postcured two hours at 300F. WADC TR 53-126 Pt 4 106 Table 67. SHEAR STRENGTH OF BONDS TO TYPE 301 STEEL FROM X-151/X-701 ADHESIVES CORED WITH DICYANDIAMIDE Cure (contact pressure): one-half hour at 330F Specimen No.&) U45JMd) 1172JM! H73JMX 1174JMx ' Tensile Shear Strength,psi X-13l/X-701ab)) c) d) Resin Ratio 77F 500F 500F 100/0 1930 770 680 90/10 2055 565 305 80/20 2285 560 470 70/30 2220 425 420 a) Bonds from hot melt impregnated supported adhesive tapes with grade 112-Volan A glass fabric. Constant ingredients: 100 phr aluminum dust (MD201) + 6 phr dicyandiamide. b) X-131 resin lot No. LR1991-H3. c) Average of three values for bonds to full hard type 301 steel (thickness 0.030 in.). Surface treatment: Method A-Mx. d) Solvent spread supported adhesive tape. The test results given are the averages for eight adhesive batches. fct o 0to to G) 1 I-1 M 8 IN w CoO. o o p CO 0) g 8 i o ^ CM VC to lO to o to rto \_t to ve CM nt o to On CM -a R o t-- to p WO ^ tO o\ to o to I' -Oan 'V o ts rH Oi ITv ON o VO CM On kv to P W4 OrH * aON U VM ft to IO NO* to > Pg x: Pt v 0) p CD c o Cm G rH o On z On 3 CO rH H x: >> I oc t-a p 03 0) x: oX zo CM <V > Oi o H sCO H 0) 0) A CO I T3 H CL, X < o to tJIfN t-- R 3 to O IfN %" O p C CD Pra G to IO o o O -a ON VO o CM p X) to to to at ON ON 1 1 o to *o -a P -a & to lA lf\ t- VO to g &O to to to to CO On VO to CM to CM TJ o to to c-- IO lO On to to CM 1 to o i to f-- CM 0) a H H 0) 3 pH bO 0) XS p o CD P G tant G H C CO rH * CM CD ICD et X! P P a> CD p a O IO <D +> T5 & ? CM rt CD .C a p G IfN O IfN CM CD CM CM CO VO CM O 8 CO CO -a- to CO O ON o CM IO O H H CM *v v fc H bO ca C p, H bo 03 o WK (^4 XZ 0 8p at bO G rH G 3 CO to at P 3 G CD *H G p G bo at W at *H p & u Cm G E O CD CD at at p v G u w E0 oQ at p O Cz-t P' 8 p G IT\ VO p CO P -P P G<< at < E- oo P CM CM CD Xi o o c/t p CD CD Vi P a s P 0) Pb0 T) js i I .. Ph "GH M.aj.> G O P Gat CO rH to 0 p <1> CO CM Vt CD > to at a sH 8 to co G CO p a> rH CO xx rH at at TJ CO 0 3 CO 0 > CD P Otz 0> G at > + +3 0) 3 CO > O G CO O CD X> P pG * P< P V C P Q p 0 P CD Vi O Vt O a> at C Cm rt g at P at TJ bo bO CO <D P CD O CO 0 to U to G 3 O mp O1 at 0 > at > 03 iH x ; 0 <! jr"s^o--s CO X3 O o WADC TR 53-126 Pt 4 103 ABS-Q438 Table 69. COMPARISON OF THE SHEAR STRENGTH OF X-151 ADHESIVE BONDS TO CLAD ALUMINUM ALLOY AND TYPE 501 STEEL Panel No.) Formvar 15/95 E. phr Curing Agent,b) phr Variable, phr Hetalc) Tensile Shear Strongtha) n.. . "n,,"sl Aged 200 hr it roof 77 *F 500-F 500 *F 1145J-16 1145JU-I6 6 dicy - a9 Alclad 1475 695 625 - 301, FH 1825 685 475 I205J I205JU I209J I209JU 1I60J-2 1I60J-2P238) 1160JU j-2P23c) - 14 dicy av Alclad 1565 460 - 301, FH 1665 60 r 6 dicy 200 Al dust Alclad 1350 770 - ga 088 301, FH 1925 675 20 6 dicy a a8 0 a8 _ Al8clad 2025 620 1755 570 - 301, FH 2310 640 790 295 595 685 665 695 710 935J-2 935JU3-2 15 10 dicy \ 10 TAT-0-2129) Alclad 1650 500 a ab } Hot melt 301, I/2H 1935 80 310 305 l2l8J I2l8j-P23'f' - 4.5 dicy - no l2l8JU|-P238)f) - an Alclad 1525 555 545 0 1425 465 635 - 301, FH 1665 635 645 I223F-P23) I223F9) !223FH39) I222F-P23) l222Fh) l222F3h) 10 4.5 dicy \ Alclad 1845 225 (i fl O 0 2530 410 a 20 aa 6 dicy /s 60 Al dust. Hot melt 301, I/2H 2965 Alclad 2745 275 400 Ja a a a .. 8 2245 301, I/2H 2665 380 105 120 275 170 625 590 525 I2I9J I2I9J-P23) I2I9JU|-P23) 20 30 0A0PS 0 aa * as Alclad 835 555 700 . 0 2135 605 915 - 301, FH 2720 850 1015 I220J I220J-P23) I220FE-2 20 a 30 0A0PS aa 5 Bisphenol A 08 Alc8 lad 2615 545 2455 685 8 8a 0 Q 301, I/2H 4235 880 830 950 690 I236J-I3') I236JE-I3') 208 248 OAO8 PS Alclad 2315 301, I/2H 3310 225 235 710 505 a/ Bonds froo solvent spread supported tape (glass fabric llZ-Volan A) dried lb rain at ZuU*F. Con stant ingredients (parts by at): 100 X-I3I * 100 aluainun dust. Cure: One-half hour at 330*F. b) *0icy" is dicyandiamide; "DAOPS" is diaainodiphenylsulfone. c) Aluminum alloy clad 2024-T3, thickness 0.064 inch; type 301 steel, thickness 0.050 inch. d) Average of three values for one-half inch lap joints. e) Bonds postcured two hours at 300`F. ' f) Adhesive contained experimental modified X-I3I (D). g) TAT-0-212 is triethanolamine titanate N-oleate (du Pont). h) Adhesive based on a blend of 85/15 modified X-I3I (G)/X-40l-3. i) Resin base: 80/20 X-I3I/EP0N 1009. WADC TR 53-126 Pt 4 109 ABS Table TO. IDENTITY AND SOURCE OF MATERIALS EVALUATED IN HIGH TEMPERATURE ADHESIVE FORMULATIONS EKX Adhesive TI is a pests-like, proprlatary confound mad as a htSiding (at, particularly in tbs ai- jraft industry. It is praparad by simple aixlag of gPQf 63k rmala, Tinyllta AXAF (polyvinyl acetate resin), asbestos, allyl glyeidyl atbsr (MX), tiCU, aad Aoetasrtnr Orange (a dya). With tbs transfer of its pro duction tram Abell DsveLopasnt Co., BneryrlUe to Senear s narked increase In tbs riscoelty of the final product has occurred. fbls in turn has censed cost mar ecagialnts because of the inexrased difficulty in handling the notarial. Ooo- ssifntly. an investigstion of the cause for this change vas undertaken. Laboratory piloting of Adhesive VI nsnufaeture bee indicated that eons, as yet unknown, property of the DQi 83b reeln Itself la the naln variable affect" ing the vieooelty of the final adhesive. Traces of alkalinity introduced with tlu> asbeetoe also incresss the viscosity significantly. Ranoval of this alkali (with rseulting rsduetlon in ndbaalve vlacoalty) waa acoas^llihed in the laboratory by a wstar waab but this is not consldsred practical for plant operation. OnsBparieon of tbs Denver and bsryville nethods for producing adbeelves shows that the ftssiyvllle nethod euploying shorter adzing tine definitely result# in n loser vlacoalty product. Bowever, it ia oondudsd that the coohined use c-f the Becryrille proccsi and alkali-free aSbeetos will not always belgpce the unknown, undesirable property of oertaln legs of M 83^. ' [ . - It if reooasamded tbst e safflcisnt Quantity of Danver KPQg 83k stocks (1-er fi druse) bs transferred to fcaTyvina to pendt Shell Sevelopmnt to ukke e pUst batch of idhesivo VZ la their sgilpnant aad by their technique. Vurthar aotie^ upald ssedt the rasalte of this test, - ^- - -................................. . ABS- 043839 Laboratory Mcanrandu* Bo 163 BEST AVAILABLE COPY lMmjutxrim The Initial aanufactur* of XPOH Adhesive VI wsa carried out by Shell DevsLopeent On., teeryvlll*. They developed the fonsuia and supplied Market Developnaot gmntltlee of this naterlal until the details of its Manufacture were finalised. Cuetc--r acceptance, and consequently specifications, were based on the Material, as produced by esryrlUe. After transfer of its aanutaett re to Dsneer it was found that the Dearer protect was acre viscous than the tern ji 111* Material sod excaadad ths spacifleatlon for this property (aaxlmai of 1 Ml csntlpolsaa at 77*7). teetlrga were held between interested parties tram lead Office, tartr, Shell Developnent Ccageny (Bneryvlllc), and the San PimmoIsoo Marketing Offloe to dlscuse the prablaa. The Meeting resulted in an extensive pilot paqgraa at Danvor. 9ns report n--rises the results of the woe's to date on Adbsslv* 71. dll mMIm of IRS 63b ussd in this work ware obtained froa feuston althar aa 1 peoductloo or special laboratory ouplu. These included the XTQi froa aonsal tear pleat stocks. dll other Materials were froa Denver plant stocks: Allyl glycldyl ether (kl), asbestos, titanlvm dioxide. Vinylic AZAT, end Acetaaloe Orange (dye). The original teavyrina procedure for preparing Adhesive VI hot. been Modified In the plant to fit sore closely the opeiTttlng situation at Drawer. Both Methods are described in the Appendix. Laboratory preparation of adhasiv* used a three-quart Rasd-Otandard slpm blade blender, closely duplicating the plant blender of the seas type end Manufacturer. Where pre-airing was suggested (Baaryvllle procedure), laboratory glassware was used. Vlsooelty was Measured on a Brookfield Vis roaster. Model HB7. All sa^iss were placed in a 77*7 water bath for a Minimal of 16 hours before tasting. This tlsm Interval was found adequate for attaining t mgs return ofulllbrlun. Alkalinity aaesuraaaat* on the TO resin ware aade by diluting 50 g of the TO with 150 al of aostane and pouring Into BOO nl of distilled water. The resultant water aoetoos phaae was titrated with 0.0B 0 HJSOl to pH 7 and the alkali nalrwleted as |gM PaCi. 9m alkalinity of the aSBestos floats was dstsndaart by shaking 25 graaa adbaetoe with IDO al water, and filtering and saMsg with another IDO al wetar sadar ration. The ctelmd filtrate aad washings wave checked far pi, them titrated to pB 7*0 with 0.02 I w Infrared scans of throe cables of TO (Lots 3BL, *H59, 6BL53) sa ate oa the Model 1, Psrtda-Slaer BpertjnofhoC emst ar after dlletloa with OCL to facilitate handling. ABS-043840 Laboratory randun So. lB3 BEST AVAILABLE COPY Page 3 A method vu devised for determining AGS contact of the product since It was fait that Loss of this. Its cost volatile component, could be responsible for high viscosities. Using a pilot batch of Adhesive VI which had been very carefully prepared to contain the correct asotint of AGS (lO.80w) a snail snount of the adhesive was spread on a iwssl 1 glass piste in s layer about l/&i `rch thick, weighed to determine the sample else, and placed in a vacuus oven to nssst'^e loss in weight. After investigating various conditions It was determined that a loss In weight euulvalaat to the AGS content occurred aftar one hour at 12C*C end 10 as Hg- Applying this test to plant batches of Adhesive VI /1th high viscosities, about lO.Spw voletlies wore removed. It woe concluded that ' no significant loss of AGS takes place durlnc plant production of the adhesive. Table 1 shows the results obtained vlth the two different mixing pro cedures and with variations in the AGB content. It is apparent that, the hnery- vllle process with shorter olxlng tlste produces 1. lower viscosity adhesive than does the Denver process. Ifewever, the BseryvlU- process (using our raw materials) did not oaks an adbaalva with a viscosity bei 1 MM CP 4 77" F. Although In sasw eases adhesive viscosity shows onanaloua behi.ior with high AGB content It is obvious that a HitItih of 120* AGS would be needed (colored to LO.Ojtw called for in the fanatic) to reduce the viscosity belcw l Ml CP. tensile sheer strength of adhesive with high AGB content (Batch P-17) see 351/ pel at 77*? end 1725 pel at 100"F. These values pees shear specifications and are In line with shear volnae of adhesive containing tba normal amount of AGS. II deals with the offset of alkalinity Introduced with the asbestos. Bonsai asbestos washed with neutral woWr will produce a wash water of pH 8-11. Ibi rsaorval of these traces of reduced the resultant adhesive viscosity from 1.8 to about 1.3 Ml CP. The addition of P.JJk water to the formula was avoa sore affective, reducing viscosity to 0.8 Ml CP. The effect of water on product per formance Is not known. The addition of 0.10* acetic acid (HAc) appeared, detrimental, to vleeoalty while 10w water woe Ineffective. y-hie III llluetrstse the variation of adhesive vlocoslty with the Vd resin used, hws faces dote it le concluded that traces of si kali In the resin end the sigei eit resin vlsooelty hove no nasi lug on the final adhesive viscosity. However seas property of the resin appears to have a significant effect an adhesive viscosity. Ossgilss of the KPOB resin (Lots 381* kR159* 8QJ3) vend srameil la the lnfxered but wero found to give identical spectra. Table IV lifts the analytical dote obtained by iwetoa and forwarded with tbalr reels esplsr'. It le to be pointed out that Bun P-25 using TO 63fc supplied from BesryrUla stocks did oaks a specification vlsooelty adhesive (O.96 Ml CP). Table f shows how viscosity aassurseeats of Adhesive VI tend to In crease with storage time, lbs prise excels Is lberyvlllo Batch 2<S0b-7 which looreeesd from O.89 to l.*<0 Ml CP over e period of ten we sire. The Ansyvllle Laboratory bos been advised of this and will investigate other saaples of their ABS-0438| Laboratory MranrsTuliiB Bo. 163 best . AVAILABLE COPY J .. page 4 All of adhesive enadned appear ' o "mat out" a reddish Uadd on ttaa auxiaee of eatwgpeS kMw. Bote' > M4, M6, WB, P-19, r Bit, Mlf MS* and MJ ears stirred tgr hand prior to tbt six day viscosity MMMMMtc aad, ae steaa la Able V. the vlaooelty w radnood. 4MBBmQBaErBnBaaBpSUB4UUaJS - bmo4 ob the data contained la this report it la cooeluded that the Aarpllla process doea Bake a loaar vlsooslty Jdhaaln TX than doaa the Denver ratted. fen tteuah ao oedfleatlan adhealve boa been Bade froa realm ob head, other than that supplied by Banyvllle, It la evidaot that Denver prodaetioB ahoeld toe and* vlth the ahortaet tlaata^sri*turs process to lower adhesive vlaooelty ao mob aa possible. Ae addition of other eo^oranta aoeh aa voter, addltlooal MB, etc. la not lam--Mlail, aim though thay do loner viscositybecause of poaaible effects Although traoaa of alkalinity In the e-baatos are drtrtaantal to the vlaooelty of the final protect, eater vaahlng of the aabeetoe i* sot considered practical far pleat operation. Vtartter, the siqppller (Jbh&s-Munmie) atatea that ao other grade of adbeotoe (referring to alkali eoetaot) la aeda by than. Other aouroaa of adtsetae vlll be investigated. . Aa aeriain niant of vlaooelty la thla Banner (Brookfield Vlaoaneter) la ohvloaaly not a preelee taat. ftooo thaaa adhesives are paoudo-plaatle the actual raaulta obtained era not traa vlaooelty. harar, aa Long a* the torque (erasure1 la terra of the vlaooelty eeale) thick raaulta during the test la repeatable aad correlates vlth mietnrar acceptance the test la satisfactory for evalaatlag the adhesive. Ae free rat test appears to bo repeatable to vithla about 19. FSW81WE It la raooarandad that ora or too drrae of Denver EPOV 83k stooke be transferred to lharyvITlw to pendt Shell Developrant to sake a plant betoh of SAralve ?1 la their eqplpneot aad by their ratted, da observer froa Denver should be present. Ala reals vouLd rapraaaul aatarlal vbich, vtea used at Deover, both la the plant nod Laboratory, failed to aate spaoifleation adhealve. Should this reds produce high viscosity adteel/e at Aar/vine further dietmaalona vlth horaton vould be la order. Bata by* 8. Savin, J. A. gtradah, B. M. Berry Bafereooe: Ach. Beoord tel. lB, pp *>-53, tel. lB9, pp 3, 10-13, 15, 23 if# is* xmyii K. B. Ntrple (2) aBs-o Laboratory > o. lB3 - AFBTOg PCS ADBE31TE VI HW3FACTUR1 Mfp owmmo PRocrouRE (otised) Faa 5 At least 24 hours before a batch of Adhesive VI la to be alxed, i tvo ftruw of SFGi 834 should be pieced In the hot box to liquefy the resin. The adhesive is prepared by nixing by weight In the blender aa follows: 1. Allyl glycldyl ether (AGE), 177 lb. 2. Acstealne orange, 147 grans 3. Tlnylite AIAP, 94 lb. 4. T1tanas, 8 lb 2 os. Mix ten ntmitee, turn on stean, and add 5- EKM 834, 500 lb (1 dnas). 6. Asbeetoo floats, 353 lb. This should be added In 100 lb Inc; eeelm that each addition is atrad in before adding nors. DECT AVAILABLE COPY 9 7. Whan asbestos has alaost all bean pulled into the air, atop the blander, scrape down the walls to the. point where the blades reach, nix again for a few adnotee to be sure all tbs akbestoa baa bean worked in, than add 8. EPOS 834, 500 lb. Allow to nix overnight, reversing the direction of agitation occasionally. Inspect to soe that no unaired resin renal ns on top. If there is such, work it in with the scraper by hand. 9. Whan batch is randy, bolt down the blender lid, sat up the scale and pour the adhesive into cans aa specified. Containers will be 1-gallon, holding 8 potmds, or 5-gallon, holding 40 pounds net. Label each can with de signation "72" and batch nuMbnr. About at the nlddle of the batch, take two 1-plat ssagilee properly labeled, shlch ere delivered to the labora tory. . 10. Upward the and of the packing, it will be necessary to ra the blander in the proper direction to posh out the bulk of the adhesive. Tbs lsst of the contents will have to be screed out. If another batch of the sens adhesive le to be node, the blender need not bo ecraped clean. XT another type of adhesive will be node next, scrape out as snob of this bstoh as ABS-04384 mm masBL mmmgm HOCTO Uiiii *8 100/0 9m jdjrfiqA iciitrti (mr) is dissolved in AGE by stirring it la at %fC tor %-U> hr. 9m solution is osde to contain 1$ ports AGB sad 009 sod. to this solattso is addsd stout 0.03 ports dps* Vs Sand aiaMr is ctogrt with 0$ ports 001 63b sad this is hsotsd T0*C by stooo. Add 0 ports sstostoo floats sod 0.7 Ports titoaliM amt tfto total nftasd tor 2 hr at 10-73*0. Os tbs 11$ ports at W AdMlis is oddsd tto 23 ports of f-dTIT and blondlag noUnost tor 0 aiantos. BEST AVAILABLE COPY 3 3! *\ lf\ A {Sin* I i } ! li S * * 1 * Ililhlf**! E * I e 5, d J* Oi H <0 P 8 * g H H 9 9 8 d S H OI O CM 01 % * % * * * P 8 ft H 01 O 01 H St n nil in if in It 8 a a a a a a a a j in Hi mu BEST available COPY AElS-04384(f Laboratory IWnnHw Bo. IB3 Pa 10 Lot go. Vleooelty, Oerdaer Color, CnrOner VFB Hater, V Chloride, 0* -nr puma or pcb 834 ubp you JB52L43S2L!! !2*2 *2 5 851 212. l 297 2SL 2 2k6 *2 1 830 assil *2 3 art C.10 0.01 0.01 0.01 0.01 O.fll 0.87 0.21 0.18 0.53 asjl! V* 8-3 2%3 0.03 0.25 a) kff* Wk/M snA far aoooodery eeaetic addition b) Modified mm fe8 proeoo* o) Prqmd via mpontlT* cooling during ronctloo BOB: Thooo data atvplled by Bovotoa laboratory; coo tbelr ltr. of <7tOy 19, 199% to B.O., Ntg.-OBor. BEST AVAILABLE COPY i i ABS-Q4384 Laboratory N to. 183 fetch to. >-9* N9b M* P-7b P-1A P-l6 P-17 P-8* P-lfl P-19 P-80 P-81 P-88 P-3 260*-7*^ TABLE V VAKIATIOI or vxboobxr toAWWMBrrs Viscosity 0m CP 77*8)# at Tias After KLxiae 1 fear um usa LSss. 2*JS 1.82 1.22 1.22 1.60 90 V 1.15 1.79 1.76 1.01 -- 9m 1.17 1.5* 1.76 1.26 -- mm mm mm -- l.*0 1.6$ m 1.33 -- 1.87 -- --- mm 1.0* 1.22 -- 1.2* 1.26 0.79 l.*9 m 1.98 -' -- -1.69 0.91 2.02 1.12 1.99 1.71 1.55 1.63 1.11 1.27 l.*l 1.30 l.*7 1.26 1.11 mm l.*0 1-36 1.67 1.** m l.*3 1.91 0.96 o.dsfi -- 1.23 - 1.12 1.09 1.27 mm ) Pleat aftaeJv* pvapared aod mmMured at lesij rtlla BEST available COPY