UNCLASS I Fl ED

AD_ 297322

ARMED SERVICES, TECHNICAL INFORWATON AGCYARLINGTON HALL STATIONABLINGT 12, VIRGINIA

UNCLASSIFIED

NOTICE: When government or other drawings, specifications or other data are used for any purposeother than in connection with a definitely relatedgovernment procurement operation, the U. S.Government thereby incurs no responsibility, nor anyobligation whatsoever; and the fact that the Govern-ment may have formilated, furnished, or in way

supplied the said drawings, specifications, or otherdata is not to be regarded by implication or other-wise as in any er licensing the holder or anyother person or corporation, or conveying any rightsor permission to manufacture, use or sell anypatented invention that may in any way be relatedthereto.

S:: I (111111 II)a!E:NEiRAL ,DYNAMiCS :CO NVAIR

Report No. 8926"0O01

Material Adhesives - High Temperature Ceramic

Literature Survey &nd Tensile Strengths

D. S. Pratt, J. E. Shoffner, E. E. Keller

2 March 1959

Published and Distributedunder

Contract AF 33(657) "8926

Post Office Box 1950, San Diego 12, California CYpress 6-6611

Material Post Office Box 2071 BRoadway 3-8000 1 Accounting Post Office Box 510

C/) 4,,EmNERAL DYNAMICS CONVAIR

Report No. 8926 O0i

Material - Adhesives - High Temperature Ceraic

Literature Survey and Tensile Strengths

cD. S. Pratt, J. E. Shoffner, E. E. Keller

2 March 1959

Published and Distributedunder

Contract AF 33(657) "8926

Post Office Box 1950, San Diego 12, C alifornia CYpress 6-6611

Material Post Office Box 2071 BRoadway 3-8QO I Accounting Post Office Box 510

UUENNNAL bVINAMIC.8 I CoNAIRM PAGE

-~~--- ------- --PO 1

Report No.i 8926m09l

Material Adhesives - High Temperature CeramicLiatu -e Sur'vey and Tens ile Strengths

Abst-aC-t

A literature survey pertin~ent to high temperature cetri adhesives Wasconducted. Seven literatur'e refer-ences ar given in the body of thereport. Appendix 1 Of the report gives 101 refer0-nces taken from thetechnical literature and Appendix !I cites 9 references taken P'rom~ wADcTR 58m8 4 , August 1958. Tensile tests were mrade with Univdrsity ofIllinois U-1067 COffiposition With indifferent results.

Reft renCe:t Prt D. Se, Shoffner, J; Es, Keller. 2. E.,I",High Tempeature~ ceraic Ad-hesivesi" GeneralDyftm1ic/covair 'Report MP 58dI.75, San Diego,California, 2 March 1959. (Ref'erentce attached).

c 0 N V A I R -REPOR Ti --------A r.ti~oN 60 GENERALODYNAMICS CORPmORAT ION

DATE 2 arh 959-SANI DIEGO -08

MODEL RA73

T.N. ~7038)

TITLE

140J N. IW-58-4&75

1IH =9 A OUAICC AMBIVUS

IAREPARED BY GROUP Watrials & Processes Lab,

CUCKI Br REFERENCE__ -

CHECKED BY ' ' 6 ..- APPROVED BY APChief of Structures&MtiasL .

CUCKID BNO. OF9 PAGES 1

NO. OF DIAGRAMS-2

Group h-gieer________REVISIONS

NO. DATE By CHANGE PAGES AFFECTED

PORM ISMA.4

ANALYSIS C 0 'N V A I R PAGE1IflEPARED &V D. Sj Pratt A DIVISION OIF GINIAL DYNAMICS COMPORATION REPOdRT No. bd-58-475s.-IECKIED BY W. M. Sutherland SAN 0190O MOEL REA-670 3BkEVISEDY yDATEC 3--59

Now high speed aircraft Ad Missiles now Oft the drawibg boards will- have hig - urf,

temipera-tures when in service. The suraces must be smsooth in order to keep thistemperature as low as possible. Mhesives offer a methodof achieving this -by

*keeping irregularities to a minimum. Organic adhesives have a teMersature limdita-tion of approximately 6006F, but since ski temperattres are expectd tors bve60O06P, they can t be considered for lonbg time operation.,

Ceramic materials, well known for their -ability to withstand hi gh temperature, off'.possible source of high temperature adhesives. Various types of ceramic adesivc

i-e., sodium silicaite, sodium aluMihate, magnehium oxcychioride, aluminum phosphate.,and potas~ium silicateihave been in use for years.6 These materials fail under conel-tions of heat and/or humidity and are not suitable for conditions found in highspeed Aircraft. (7 ) Therefore, other c~eramic coMpOsitions must be inivestiga~ted fora Possible high temperatur hdhesive.

LITRAURASRVY

In the course of a three year investigation by Spriggs (2) (7), Over 10 ifrnformulations were tried as a high temperature adhesive for types 302 and 17-7 PH

.adnless s-teel. These fonrmlations included ceramic-xd glassy bonded cdatinetccermets with siatered metal bonds, air setting temp~erature resistaint silicates,aluminates, oxychiorides, oxygulphides, and ceramic oxide resin bonded materials.Those specimens requiring heat for curing were fired for twenty minutes under a501 psi loading at temperatures from 1000P* to 2000-P. Tensile testingwsdn atroom temperature, 6000P, 8000F, and 10000P on a TJinius Olsen testing machine. Spt-states that some glassy bonded adhesives, when imdified with Vsidered metal additiot'..develop over 1000 psi tensile strength from room temp~erature to 1000"PF. These valv(were obtained using a stainless steel screen carrier in the Joint area.

The Boeing Airplane Company has developed a metal to metal ceramic adhesive. TheNarmo Company is licensed for sale of this itua, Ibat at last report cember 10,1958, was not ready to release somles for study. Mr. Roger Lonjg of the NaalucResearch Group, Sap Mego, state ta eeivdthupeliiof the adhesive

woldbeabut8o~7Whwever,. the values at that temperature would be over 1000 pzr2'(3)

Besides the 10-eing adhesive, the Nanaco laboratories are working on a WAXC coatractAP 33(616)"MT6 aid Navy Ro;ero contract NOms58-587C. The W=W work is a follo-upon, the University of T-linois workc, while ithe Navycnrt is on the deeomnof an exothermuic adhesive.

The Aeronca Comaney, Middletow, Obo, is also workid on further development ofthe University- oQ- Illinis research. -This work is being dow nd ier WAXC contract

AP33(616)-5538.1

DISCUSION OF LITEAURE SURVEY:

Throughout the Unversity of Illinois investigation it is stated that the best ad-herence will be achieved when the coefficients of expansion of the metal and theceramic adhesive are closely matched. However, one or fin al, cmoitionsdeveloped, UI 1067, has A very low coefficient, 06.1*0l cm/0C. Thi0seadhsive

---- ------

ANA LYSIS -C 0 N V A I R PAGE 2PREPARED fY D.S. Art IVISION OF GEERSAL DYNAMICS CORPOATION REPORT NO. IW-58-475CHECcKED by W.,M. Sutherland *AN 6196O MODEL MZ-7038REgVISED by DATE -- 9$

DISCUSION O IAU SUV:(oninued)

is as favorably reported asanother which has an expansion factor of 42W-- 0-7cm/cm/*'Ce Stail."ess Steel all-oy, type -302 has a, coefficient of 61x0 c/C.This laboratory is unable to explain why this formulation VAS considered for investi-.gation or why it functions as it does.

The function of the Stainless Steel car~rier is unexplained. it wa proven to be anaid in achieving bond, but just how it does was not d-iscussed. A fiberg-lass carr~ierin organic adhesives localizes shrinkage, maintains a predetermined joint spacing,Nand prevents the propagation Of cracks. Does the stainless steel calzvier functionin the same manner, or IS there a Union of Metals at the carrier-metal interfacethat gives added Strength?

Some work was done Vith the addition of adherence 0xides to the adhesives,. bat thisline Of investigation Was limited. No foliulations were tried with cobalt oxidewhich is known to contribute greatly to the bonding of porcelain enamel to metal. (4)

Nearly all of the University of illinois work was done on metal roughened by sandblasting or other mechanical means. Another method of metal preparaton, nickelPlating, wa" investigated to a Smaller extent.

Adhesive i rprto The University of M-- inois composition u! W067 wasfavoably repoirted by -Sprgga.- (7) %is formuila was used to coMound a tt florthe initial laboratory study.

Adhesive Frit Oxide Comosition, Frit Batch C uosition'mert by !eight __Parts-by Weight

S10 2 38.0 Quz214.8-aO5.0 Sodium Nitrate 9.0

V-O3 57.0 Boric Acid 66.2

The frit was ball1 milled with silica, and water until the residue on a 200 meshScreen was less than 2% of the weight of a 50 Cc sanqle.

Adhesive ftit 401 Mill Yo- laPart byWeigh

Frit wl67 100Colloids! Silica 14Water 28.2

ANALYSIS C 0 N V A I R PAGEL 3PIREPARED av D.S. Pratt A DIVISION OF GIEMAt bVNAMiCS CORPOKA4ab EOR O.?.81yCHIECKED MY W.M. Sutherlwid SA IOIMODEL M-7O3jo

£Ivisgo mY ATE -25

TNITAL ABOATOY SUDYO~'UNIVRSIY O IL~hOS MTERAL:(Continued)

Adhesive Slip eaion a&d Cu Sandblasted specimiens of type 32-1 stainles;steel were sprayed with the idheuive Slip until a dried thicknaess of 7-10 mils was

acievd.They were dried at 90007 for one hu.The specimens wr smldtgive a net contact area of 1.3 in 2 . They were pressed together as tightly as possiuzby means of a. 1/2" nut and bolt aragmnand tired at 1750 - for twenty minutepwithout the application of additional pressure.

Adhesive l1,ine

___ Stainless

Steal Type 32J.

Method of fastening specimens

:Up1l Shear Test Reuta Of the eight joints compressed amd cured, only tbzcrsurvived the disassemlin ofth -t and bolt. Die oxide scale formd between the*;iut and bolt made the disasanbl very difficult. The specimens were pulled on aTinius Olsen tensile machine at room temperature. Thelaigrt m 0 0lsper nute. Telaigrt a M±10ls

Joint No.TeilVau

1 Broke on Disassembly2 i t

3 215 pal4 -529 psi5 Hoke on Disassembly6 W 0psi

7 ftoke on Disassembly8 I

Average 358 Poi

ANALYSIS C 0 N V A I Rt PAGS 4PIREPARED0 NY D. S. Pratt A SOMON S 01Euuu AMS a~uuGDOAY.N IMPORT No. Z.0-5&475CHiEKkD my U .8t@lM MODECL FMn-to038REIMED By DATE 3- 2-59

The average tensile value of 38psi is lower than the 545 psi obtained by theWU. versity of Tfim cis; however, -the conitions were not the aem. The Wiveisity

of 0l-1-Incs aplied- a 50 pei loading during the curinog and ooolIr-, and used a 98mesh stainl es steel screen as ant adhesive aiier. Our initial evaluation seemsto indicate that the values reported by Spriggs (?) can be obtained If ll conditionsare duplicated. ftlication wLl- require the devemlagmmnt of a fixture to lyw thenecessary loading during firing Mnd utililifg 28 gaugs staI10ess9 steel 6000e610g.

MLC - PonO5aF , a -P!MOUMM:

A4 The -first effortsb shounld -be t4 check the reprodicibility Of the UivesityOf IllinoiOs Investigation. In addition to checking with staLess steielalloys 3D2 and 17&7 PR,, superslloys of the lens 1.1 and Hastefloys W35 or-

25(L605) types would be used. The latter allo0r are Ones belag ooftideredfor the fabrication of new high pe6mc aircraft en- vissiles, and theadhesives mast be epplicble to them. Other ffit opSWAiMs should bestudied.

13. The types Of bond achieved would be studied by mealopqii, zarayp andelection microtscopi-c methods. After determining the meoemim of bniga study should be moe of possible changes in the fozLUaa to laprove the,adhesive character of the bond.o

0. An investigation should be made into various methods of metal preparMan.The introduction of another strata Into, the system, i.e., metal plating,may bidge the difference In qansIO Ubween the mtal "a the SeI~MASDto a degree vwee It would be loes critical. This strata also nd.At providea better bonding surface for the cead6hesive.

D. After developing a ceramic adheive that woul give the desired resutsione type of testing, I 90.0 tensile shearing, on i0Nuetato should

be mad. of other possible dodog pausmterse Vlues would be obtainedfM twt, peel, oaressiom - pat "Wpe ofret~.Zbto

of thIs type woul be- of wine to deidp aid oswo Va t would havetheasd to ]wthe int"4mi properte of Poe4" 46001s.

ANALYSIS C 0 N V A I R PAGE 5 - -161EPAREDb BY D. S. Pratt A DIVISION OF 6111SAL DYNAMICS CORPORATION RIEPORT NO. I-867CHECKED DY W6 Me Sutherland SAN DIEGO MODEL REA-7038

EVISED Doy DATE 3-2-59

1. gagles, A.E., "A Surv-ey of the Theories ContcerniAg Ceramic to Metal Adhesives",IWAMC 'A 5841, August 1958.

2. Lefort, 9L,4., SPriggs, R.M., be nttP D.G.J. ",Research on Elevated TW-qertUreResistant Ceramit Strucotural1 Adhesives", 'WADC TER 55491 Part1I2I, January 1959.

3# Long, Ri, Narfco Researeh LAb., Sea, Diego, PNrsonal Commication.

41. Wore, D.G.,, Pitts, J.W., Richmond, J.C., Ikurvison, W.N., "Galvanic Corrosion"Wroy for Adherence of Plorftelh EA3el- Ground Coats to Stel-J.i Am . Cer. SoC, 37, 1 (1954).

5. Reiz~t, ?1 W., "Surrvey of Adhesion and T y-pes of 2boms involved in Adhesionand Adhesives ,Pud~utas ad Practice", Clark, Rutzler, sidSavage, Edltors, Wiley em Sons$ 1954, N..ep 9-15

6. Shoffner, Jig., "FnaetlSuyo anlAhrneMtlic Mill1- Add-itionsto Replace Adherence Ox ides in Sta --ard 1. m1 Ground Coatal",Ford Mtri, Co., Scientific Lab. Report 2-48, dated 1-27-F56.

7, Spriggs, X.M., Wflianis, C.NO, Lefort, Rio., benett, D.G. "Bese1"rch on1Zlevtted Teoqerature Resistaat Structurl Ahesives", WPMC

TE55-.491, Part 1I2, Dec. -1957e

PC"S lt"

ANALYSIS C 0 N VA I RpAocE5 APREPARED BY D. S. Pratt A V'IVISiob or 091aIIAt oDYwaMC caoSA*?Io REPORT NO. MP-58475CHECKCD (BY W.M. Sutherland 4SAN DIEGO) MODEL REA-7038REVISED By DATE 3-2-59

The effectiveness of a high tez~efatufe ceiiamic adhesive will depend Onthe union achieved between the adhesive and the Metal. Following is abrief sumary of factors affecting ceremic to metal3 adherene and thefive Main theories as to why boading occurs. (1)

A. Factors Affectin Aftftez~

1 Cofficin tpaso The coefficients of expansion Of theMetal and adhesive-should be as close together as possible. Ifthe adhesive's Coefficient is greater,, it ill- tend to Pop offwhen cooled to room temperatture.

2 - -c"tng Composaitionq The composition of a ceramic Controls Itomelting point. It would be ve~r desirable to have the meltingtemperature of a ceraic adhesive the same as a, temperature uuddIn the heat treatuent or aging opeaino temtl

3 4 SurfaWetting & Me ceramic adhesive Muast Vet the surfaed* ofthe Metal.- If -wetting doe no cu, the adhesive My be unableto fore a reaction bond, or to obtain a mechanical grip on themetal.

4 -Reaction Time - The time at the maturing temperature is importan~t.03e time mas be long enough to complete all the desired reaction.Excessive time might produce several undesirzable results: (1) de-

vitifiatin,(2) adhesi -ve flowing frut the joint, (3) excessiveinterface reaction, or oth, an-hudb avoided.

5 Adhesive Thickness -The cohesive strength of the ceramc adhesivem e telitn fator of theJit The thicker the adhesivethe greater the opportunity for the production of Into-ZIAl fatsthat could lead to failure A minimam thckesmas t be imitalnedto insure the presence Of eough adhesive to complete* the bondin-g.

6-Effect- of Adherene (Oides Certain metalic Oxide are luvwn toimprov the ad eece betwen Porcelain onel a the bae etal.

Perhaps thsom effect vii]. bund in cer~c adesives.

7 metal, Paration - Zia will involve not only metalc clening torem~vesoiliAnoides, but Could ,iclude the deposiino

thin coatng of an adherence pronoting oxide or mother mterial.

FORM 1812.A

ANALYSIS C 0 N V A 1 tPG 6PREPARI-ED my De B. Pratt A SIVISIOM OF 694MAL DYNMICS tO.P600?IO REOR N. -r58-475CHIECKIED BY Wim. Sutherland @AN DIEGO MDLRA73

REVISIED my DATE C 5

A. Patr -fifecitIng- here-nce (Cotintied)

8-fvltoo ae S mnall quantities of 3ae Or ga roduders, ike,

N, N, or C are trapped in Most Metals Upon solidification. These afeeither in the nlecula~r coi~osition or ameitrrnla.Uo eti-49, these gases tend to boil to the surface of the metal. If thecera5mic adhesive forms a glaesy sur-face before most of these gaseshave escaped, discobtinuities in the fornu of micro bubblzes vilz cuin the adhesive and/or at the interface. Gases may also originatein the medium used to carry the Ceramic adhesive frit.

9 I n porcelain enameling it is generally agmeed. that adegree Of metal oxidation occurs during the firing, SM this Metaoxide contributes to the adherence. The metals used in aircrafthave high Oxidation resistance, And it may be necessa-ry to prnomteOxidation at the adhesive line in order to achieve satisfactoryadherence.

10 Firin moper ~st investigators believe the -besat ceramic tometal adherence Is obtained in an oxidising at-msphere. This c~ition would present some problem, ifwnlybdenulm were the meta beingbonded.,

Bo Theoae -of-C-er ci-o Mtal Adherence

Tbday, five theories are accepted for ceramic to metal adherene:

1. Mtallic Dendrite-Fozution Wr~ning the fusion period, the metaland constituents of the ceramic unite to form interlocking crystaswhich are firmly bonWe in the ceramc and to the metal.

J7 Ceramic

Keta

go Ceramica constituentM~ Metal contuen

2. Oxcide Layer FozuatIon Thisa theQy states that %he cei"de to metaladhrene i dii ~ te izutio ofthn layer of Metal wdides at

the interface.

ANALYSIS C 0 :N V A I t PAGE 7P1REPARED My D. S. Pratt Amiis. 61IO o OIN -9AL DYKANU CO TOmNs RHEPORT NO. tU"-58-4CHECKIED MY W.-M. Sutherland sAN 646GO MODEL REA.103fRVISED By DATE .2.5

Be Thoiso4emPoaAdherenCe (Continued)

3., Galvfnic -C~oftoiob There is some evidence that an electrolytic re*Action occUrs- at the ceramic-Metal interface., This Action seems toprodluce Pitting And surface irregul-arities that permit the ceramicto "toebal" itself Onto the metal. See Figure 1L

I&. chaunical Grip -- i -This is the same type of bonding As is foundin the galvanic Corrosion theory. It is hefe assmed the surfaceirregularities are fozrned by pick-ling Or 5sarblating Prior to theapplication of the ceramic.

5.Chemial --- nd-in- Here the bonding is claimed to come from theMutual sharing Of an oxygen bond between the metal and the ceramic.As the Metal tries to Oxidize at the higher te~eratures~j itsuccessful-ly borro or shafts mo with the adherene oxides inthe cezraI6, thus a chemical bond Is forund between the two.

ANALYSIS C 0 N V A I R PAGE 8PREPARtED my D. S. Pratt SAN 01900 REPORT NO, M4P-58-.475CHECKED BY W. M. Sutherland MODEL RFA-7038REVISED By DATEs 3-2-59

DIFFERENCES IN THE CORROSIVE ATTACK ON IRONBY COBALT FREE AND COBALT BEARING GROUND COATS

Enamel Enamel Eae

Iron Corr"hion - .Iron Corrosion

Ironron ~ Iron

(1)(2) (3)

A) No Cobalt

(1) 2 min6 after entering furnace(2) 4 tot(3) 6"I

EnamelEnamel

IroIron

B obaltBearing

Schematic drawing illustrating the differences in the corrosiveattack on the iron by cobalt-dtree end Jsobalt bearing ground coats. hefiring time increases in both sets of diagrams from left to rightl the firstdiagram in each case indicating the interface condition shortly after

the enamel fuses, From Moore, et el (4)

Figure 1

-0mg e~gJ

ANALYSIS C 0 N V A 1 PAGEK 9PORMEAR&D MY D6 So Pratt $AN DIEGO REPORT No. -84>CmfttKEDt by W. M. Sutherland MODUb M&A7036PEirmreD ow- DAT 3-2-59

'm .0 43

4A

I.4 43343 w'0'42

U~ 0. 4-3

0 .4 10 0

F4 48-4 0

,.-G 4 0 0 4

E-4 121-4 41

a Nbr

44

P00W lose ,% ----

ANALYSIS C 0 N V A I it PAGEC N.PREPARED 1EY D. S. PfttA £mIyboVeS01,1tkiiAL WMANICS CORPORAION REPORT NO. NT5S- 5CHECKED MY W. M- SutherlandMC "AN Dirac MODEL 1TE-Mu3REVISED MY DATE 3-2-59

The bibliography from "ftuamental Study of &MOl A dherencemetallic Nil11 Additions to Replace Adherence Oxcides in Stabl-

ard~aelGround Coats,7.E Shoftner, Ford Motor CoayScientific Laboratory Report Nov 5-1e8, dated Ja y 27, -1956 (6)

Wals bibliography is presented to makie aval~ble to the reader a listingOf pertinent references on aftesionw

FORM lei&

ANALYSIS C 0 N V A 1 it PAGE

PREPARED BY D. S. Pratt A 61ISION ,.,IIAL DYAMICSUOSAIOU REKPORT NO. Wc58-475cmmeCKE my W. M. Sutherland GAN bite MODE[L REA 7038REVIORED my DATE 3-2-59-

CO0P Y Report No. 248

-BI&ORAR

1. Amberg, C.). Prior, 9. DO, and RichuwnajC. "Adhesion Of 2000elstoSteel Produced by the M.eatte Pogilton4-f 3&, oil theSel,JoU-r. Am.s Cerfti. Soc., 013 0)

26 Amn, "Porcelain hfamel Adherence tet", Am., Boc. Buill., 27 (2) 67 (19w.).

3. Bakeri R. W. and Joublanco J. C., "Progress Report on the Study~ Of Gabes.in Dumeling Vron"', Jour. Am- Cerft. Soc, -16 (9)4371.1~ (I1933).

4. Beg, M. and Immik, . "A Contributidn to the Ibor f erence",Am Ceram., Soc. Bu., 331 (9) 329- 31 (1952).

Doeyerleia, K.,J- "Action of Adhesive ajoxi :in Ground Cost Aels", cermiAbotte 12 (1)8(13)

6. Carter W. K.and fn R. N.j "Ibamai-c of Sil Adhor"mae: Pa~t IIIamels on Coppr3 %he Nature of 2m.i1 Adherenoe"j, Jour., Am. corm,Soc., 14 (1)W8894 (19U1)

7. Chu, PAK., KerJA6, and Davis, HM,"A Study of Ga inP elainmlng" Jour. AM. CeraMm. Soc., 36 (2) 1.-9(1953).

8. Chu, P. Y., Magor, a. K., 0 nd Dovis, H. M., "Some Influences of Carbon-in Enamling of Steel" Jour. Am. Ceram. SOc., 37 (9) 391-1.01 (1911)

9. Clawoon, C.D., "A Study of Adherence of Ground Coat. to Sheet St C" C ima

WId. 13 (W 164 (1929).

10. Cooke, B. D, Enme Syzosim: Making and Firing of Sheet Steel GroundCoats", Jour. Aim. Ceram. So09, 10 (6) 454.-55 (1927).

11. Cooke, R. A., "El~fect of Furnace Amupheres on the* Firln of Enamel"JoUr. Am. Ceram. Soc.,s 7 (4) 277"61 (199-4).

12. Cress, W. C., "Proposed Test for Adherence of Moinm' to Cast Imw", Am.Cezam. S-c. 23 (3) 123-5(94)

13. Deringer, W. A., "Relation of Hydrogen to Adherence of Shet-Steel EnMels"Joaw. Am. Ceram, Soc., 26 (5) 15L-59 (1943)e

14. Dietzel, A. and iHeUres, K., "Reactions ij~ortan fr aencWhnfrg

Ground Cosa Containing No Adherence PctigOxides", Jour. Am.Cerame Soc., 18 (2) 35-;37 (1-935).

15. Dietze, A. and Mures, K. "Ad e __ _ justuent o ftenaels to Mxet Steel," ja~w.Am. Coram Soco, BA ( 37-38 (13)

(2). mi1930

ANALYSIS C 0 N V A I Rt PAom12PREPARED SY D. S. Pfttt £A svis.Om 0 euliiaUm bOn~ REtouls 4PORT NO. *W-58-475CHEMCED SY W. M. SutherladdNOIG MODEL ftA-7038REVISED BY IDATEt 3-2-59

C 0Py Report No. 2-4e8

16. Dietzel, A.,0 "zol mion of the Pftblm Of Sheet-1ron Romel Adherence",Cera- Abstr6 114 (5) 107 (1935).

17. Diettel, A., "Adherence in Sheet-Iron ftemelvare". Cermm. atte, 15 (5)107 (1935).6

18. Dietzel, A., "Iblybden in aei" Ceame Abstr., 20 (10) 2-32 (1941).

-19. Dietzel, A., "Possibilities of Replacing Cobalt and Nickel as Adheringodde&', Ceram. Absttr. 2s (9) 156 (194.6).

20. Dietzel, A, "M1eoty of Adherence of Maeo on zzoon", Ceramu. Age, 62 (6)17425 (1953).4

23.4 Doglas, .. at adz .. -ay Study of the eactions at the Steelurace ihen, Titania hamel is Applied Directly, 'Jour. Ant. Ceram.

Soc.,) 35 (1) 5-1 (1952).

22. Ebright, A. 2. andi MIntyre, G. e X, "Effect Of Water Vapr on Porcelain Dur~ingFitin g", Emai list, -10 (6) 11413 (1933).-

23. Ebright, H. E., McIntyroo G.H., AMd Irvin, J*T.,* "A Study of FurnceAtmspheres and Temperature Gradients and Their Effect on Porcelainhae-11ling", Jour. Am. Ceram* gocs., 18 (10) 297-3D3 (1935).

24. Ellefuon, B.S. mad Taylor, N.W., "Surface Properties of Fused Salts andGlaoe: Part I, Sessile-D=o Method for Dtieaiuin Surface

Tension and Density of viscous Liquids at High Tuu~ertures", jour.Amer. Cer. Soc., 21 (6) 193-413 (1938).

2. Ellefeen, B.S. and Taylor, N.W., "Surface Propertion of .used Salt andGlasses: Part II, Contact AMUl as -oko deIononolamd PlatInn in Various Amspheres", Jour. Am. Cerm, Soc.., 21(6205-13 (1938).

26. Fr'eemean, $4E. and Melocke, U. Me., "1icro-Gas Analysiso a roWpedi

Vitreous hamelsa on 0elin Iron b-Ariumn X iM",jol Jo ca r=*em.SOc., 18 (4) 123-25 (1935).

27. Geisinger, e E. McrsotcSuy of Gromd Coat and Cover Coat Reactionas",Jour.- Amer. coe. 50c. 5 (6) 322-37 (1922) o

20. Greaves-Walker, A.M., and Xing, RJ4., "Mechanics of Minel Adherence: Part 1V,Some Studies on the Adherence of Xamel a to Cast Iron", Jour. Am.Cera. Soc., 15 (9) 476-.8(1932).

29. Harrison, We N., Richmon, j. C., Pittoit, We andhnr . . AMbisotope Study of Cobalt in Porcel~ain Rasmling"s Jour. AM. CpeSOc. 35 (5)- 113-120O (195k).

A NALYSIS 0 N V A IR PAGEC13PREPARIED BY D. . ttt A urns... ~oi Gjzju. DYNAMICS cCpO.*MPoT RE"OT NO. *aP-58-475CHE.CED BY W- M4. Sutherlxid SAN DIEO MODELM REA-03REVISED BYDAE325

CO0PY y Pport No.2-1.48M,.IGRP (Continued)

30., Healy, J6 H.4 abd Abdfews A16, "The Cobalt-Reduction Theory for the Ad-hetencC of Sheet-.Iron Orumd Coats" Jor-m ea.Sc,31()207.-2MU (1951).

31.6 ealy, J. 16 and Aadrevrs, A.,K., "The Elemens of the ird, Fourth, andFifth Series as Possible Mdhei ce-Ptowting Iftter-ial- tot Sheet-Iron amels"l, Jour. Am. Cerem. Soc.-, 34 (7) 214-9-19 (1951).

3 2. Heal1yj J. H. 6M Andrews, A.11. "Cobalt Reduction T-heory of S-heetmironbmelis", Piftish, 7 (12) 22i-23 (1950).6

3-3. Hetimer, F.,,"Atomic Hydrogen and mmeTing", Ceram Abtr., 18 (1) 9 (1939).3400 HOU010y, W.L., and King, Re Me,, "Mkechanics of- Zamel- AMeec:Pr

Appliation of 'Theory of enritic Adherence to the Deeoment ofWhite Gound Coats for Sheet Steel", Jour. Aft. Ceft. Soc., 1.8 (10)319---2 (1935).

35a goire, Xf. E.0 "'Aherence Pheim of Sheet-lron Groubd Costs", !Letter~menating, 9 (9) 13-19 al938).

36. Howe, E. E. AMd Fello-ws, Ro L., 'Effect of bleagabese, Nlickel and Cobalt 0cideUpon the Adherence of Reboiling Praories of a Ground Coat hmanel",Jour. AM. Ceram. Soc., W~ (10) 3159-24 (193 -)

37. Johnson, L. A. and Howe, L. E., "Factors Govfting Adherence of hNaelsApplied to Sheet Iron", Jour. As. Cerm. Soc., 29 (10)296-301 (191.6).

38. Kautz, K., "Further Data on Ume1 Adherence", Jour. Am. C ern. Sc, 19(93-108 (1936).

39.- Kautz, K.,0 "Effect of Iron Surface Preparation on hm l AUheeoc", Jour.Am. Ceram. SOc., a0 (9) 00-93- (1937).

40O. Kautz, K., "Discussion of J. 0. Lord's Paper", Jaw-* Am Cezug-. Soo., 2D (14)115-M2 (1937).

41. Kautz, K., "Random ~cErie on~u1Ahrence",ou.A.CamSo,21 (-) 30-37 (1938)0

1i2* Kautz, K., "Observations on Functions of Adherence-Piumiotig OWde in GOmmu-00at DMI0ls", Jour. Am. CeOM. Soc., 22 (8) 250*54 (1939).

43. Kautz,, K. "Oxide Film Between Fired Orow cost Rmis and iron", Jour.Am. Cern. soc,, 2 (8) a47"53 (1939).

4-4. xhutz, K, , "observations -aOn Function of Afherencem-- -- ting Oxdes In GroUh4-coat ftEMels" Jour. Am. COM~. SOO., 22 (8) 250-55 (1939)e

Pam 16.&A

ANALYS1iS N V A I R PAng 14PREPARED MlY De S. Prtt A 61INONo 00 SiIAL SYSAUICS 662ouTOuNo REPORT No. H..5b-475CHEC0KED my Wi. 14. SutherlAMd GAN DIZ66 MODEL M-A.7038REVISED0 Mly, T

C or y -~~BIT P~ (Continuied) BeotN.24

45. Kautz, K., "Ml'lybdenzn in Inamels:. Part 1, Adherence Produced vithW'lybdenum Compound3s ", jour. As. Ceram. Soc., 23 (10) 988-87 (19W0).

46. bautt) K. , 1641bdenum in Roamels: Part 11, Aherence Produced with SolubleA n- boluble Iblybdatesi', Jour. Am. Ceram. Soc., 25 (6) 160-68

474 Keeler, J4 H,) Chur, P.L*, and Dvid, 9. 14., "On Role of NickelI in PosvelaInhaxweling", Jour.o AS. Ceram. Soc., 35 (3) 7'2-75 (1952).

1.8. ft-UeI, RI., a6M Cook, !RL,"ators Ifluencing Oxdation Of Iron aringFiring of Grouna-Coat, ftsels", Jour. As. Ceram. Soc, j33 (2) 57-.62

49o King, it. 14., "Mechanics of bowl Adherence: Part VIII, A) Apparatus forFiring inzes under Acecurate Control of Tawerature)-Pressure,and Amsphere wim B9) Stu&1.es in Firing under Reduced PrYessures,IIjoure Am. Ceram. Soc., -16 (5) 232-38 (1933).

500 King, R. M., "Mechanics of -Amel Adherence: Part X,1 Iron Oxide in Sheet-Steel Ground Coats", lour. Am. Ceram. So-C., 17 (7) 215-19 (1934).

51. King, R. M., "Mechaftics Of &eMel Mbherence: PatXI A Chemical and X-Rsay19;amination of Metallic Precipitates from Xwmls Containi .g ronandi Cobalt Oxides", 1or i Crm o . 9 (9) 2146-49 G.936)o

52. King, R. M., "Mechanics of Eftael Adherence: Part XV, Influence of Cobaltand Nickel Oxides on Metal Precipitation at Ground Coat - - Iron

Intrfae",Jour. Am. Cer'am. Soc.,, 26 (10) 350-360 (1943).

53.- King, R. o, "Nature of bowel Adherene", Finish, 4 (9) 37-38 (1917).

54. King, R, 14., "Mechanics of Bwame Adherene Par XII A Reviev Of the

Theoretical Explanations for Formation of Metal- Particles iuCobalt Ground Coats md Powe Pertinent Experiments", Jour. Am. Ceram.Soc., 2) (2) 53-55 (1937).

55. Kang, B. x., "Mchani__cs of Uowel Adherene: Part XXV, 1) EBole Of CobaltOxide in Metal and Oxide Precipitation Dulrig the Ground Coat FiringCye - - 2) DetemmIna-tio Of the Teqieratur em i nevlof Precipitation", Jour. Am. Ceram So. 26() L114. (1913).0

56. King, R. No, "Mechanics of Enamel Adherence: Paut XVI, Influence ofManganese Dioxide on Metal Plecipitation at Ground Coat - - IronInterface", jour. Am. COMinu Wo. 27 (U) 350-51 (19-44).

PC"u set"

ANALYSIS C 0 N V A I R PAGE 15PREPARED 03Y D. s. twatt A DIVISION OF 691191L DYNAMICS CONF64AsnOM REPORT NO. MP 53- )75

CHCKDS VW 14. Sutherland SAN 61166 MoDEL MEA703bIREVISED0 BY DATE 34&59

Co0P y Report go. 2&48

5. Knapp, W.J., Shah, C.C., and, PlasmT .,"etn Pr ede of Som57i Eamnel Glasses and Relation to Impact Resistance", Jour. Am. Ceram.

Soc., 33 (8) 258-2 (19q50).

583. LoDrJ. 0. and Rueckel, W.C, "Mechanics ot Eamel Adherence: Fart I,-Technique 0±' Preparing Xnamel Metal Sections f'or Ii11croscopic Analysis)Jour. Am Ceram. Soc., -14 (10) 771-81 (193-1)

59. Lo rd, J. 0., "A Sunmiaa'y of the Observations and Facts concerning the Phenomenonof Reboiling", Tour-. ---. Ceram.i Soc., 16 () 442"46 (1933).

60. Lord, J. 0., "Critical Analyi of Som tatements and Experimnents of theAdherence of Sheet - Steel Ground Coats", Jour. Am.* Ceram* Soc., 20(4) 111-14 (1937)6

61. Lucian, A. N., and KAutz, K., "Ptirther Progress Report on the Study ofGases in Enameling Iron", Jour. As. Ceram- Soc, 17 (6) 167-72 (1934).

62. Markert, F.S., "Function of Manganes Dioxide in Ground Cots", Enamelist,3 (i) 929 (1925).

63. Martin, W. G., "Oxidation Control in Firing Ground-Coat Enwneis" Ceram.Ind., 25 (1) 60-64 (1936).

64. Martin, W. G., "Enaml Defects Prev ented by Firing in Inert Gas Atmosphere",Ceram Indl., 25 (1) 20-21 (1935).

65- McLaughlin, J.L., 'Evaluating Adherence of~ Blue Sheet-Iron Ground Coats",Jour. Am. Ceram. Soc., 32 (5) 166-70 (1949).

66. Miller, G. E. and Sweo, B. J., "Some Observations on Reactions of Enainelwad Ir'on", Jour. Am. Ceram, Soc., 33 (3) 107-110 (1950).-

67. More, D. 0., Moson, M.A., And Harrison, W. N., 'Relative importance ofVarious Sources of Defect-Producting HydrenIt'de noSelDu~ring the Application of Porcelain EnaesJoure Am. Ceram, oce.,35 (2) 33-41 (1952).

68. Moore, D. 0., and Mason, titA., "Investigation of Gases Evolved During Firingof Porcelain Enaels", Jour. Am. Ceram. Soc., -6 (8) 241-49 (1953)1.

69. Moore, D. G., Pitts, J. W., Richmo~nd, j C.,sn a'ioW ."aviCor-rosion Theory for Adherence of Porcel in Rnazbel Ground Coate toSteel", Jour. Am. Ceram. Soc., 37 (1) 1-6 (1954).

70.1 P44k, J. A., "Adherence of Glass to Metal",. Better Enameling, 20 (11) 0-7(1949).

FORM IIII.A

C 0 N V A I it A k

FAMPARZOD my D. S. Pratt SAN 61160 REPORT NO. 1vr.58-475,.Fircxub ey W. Mo Sutherland MODEKL A-738WE~ihIE WYDAE 3-2-59

CILOGAH (cotined Report No. 2-48

71. Patrick, . F.,P- Porst, E.., and Spencer a-Stronhg, G. ., "Study of Some

Phenomena Associated with the Adherence of Sheet-Iron Ground

'79 Planhieh h W. J., and Andrevs, A. I., "Ibduction Firing in, The Study of IFurnace Atmospheres", Jour. Am. Ceram. Soc,)3 (3) 69-75 (1953).

73. Porter, F. F. and Nead , . H, "Charateristics of Iron ad Steel forPorcelain ~aeigJour. Am. Ceram, Soci., a- (i) 9w!6 (1L938).

74. Richmbd,) J.C., M.ore, Di 0., Kirkpatrick, H.B., and Harrison, Wi V.$"Relation between R1oughness of Interface and Adherence of Porcelaingnam l to Steel", Jour., Am.i Ceam. Soc., 36 (12) 410-416 (1953)4

75. iker R. . n ie .. "Survey of Adhesives ard Adhesion', N.A.C.A..

Tech.__NoteNo. 989, August, 1954.

7 6. Rueckel, W. C. and King, B. M., "Mechanics of -rael1 Adherence;: Prxrt Ii,9ffect of Coq0sition and Firing Ativapheres on the Adherer ce ofGround-Coat Enamels", Jour. Am. Caroam. Soc., -14 (10) 782-86 (1931).

77. Schwartzwaider, K. and King,0 R. M.- "Mechanics of Enamel Adherence: PartVI, A Petrographic, Metallographic, andXM a Study of Ea~ci-MetalContact Zones", Jour. Am erm oc., 15(j93 483-86 (1932).

78, Simoxns, J. B., "Titania Anme -ietto Titaniumu Steel", Fns,7t.56-62 (1950).-MecFnsh 4

79. Sirovy, G. and 'Czol o, E P , "hanel Chippin : Re a i n ip o Gr d

Coat Adherence to ThicImess and Yield Value of S-heet Steel", i'

Cerszn Soc. Nil., 17 (4) 160-17o (1938).

80. Spener-Strong, G. H., Lrd, J. 0,and King, R.d., "Mechanics of Rome1Adherence: Part VUI, Further Studies of Enamel - etal Contact Zoneby MicrO8ospic aX4 Met $orepblc MethodO", Jour. Am. Ceram. ki.15 (9) 486-490 (1-932).

81. -pencer-8Strong, G. H., and King, R. M., "Mechanics of Enml Adherence:Part v, Stud AZn of Eamel " Metal Contac Zoey Chemical MthoAJour. Am. Ceru~n. Soc., 15 (9) 48D-483 (1932).

82. Spencer-strong, GeH., "Effects of Frnace Gaes onl Physical Proprties ofetPrces Cast Iro _wue s, Jour. Am. Ceram. Soc., 22 (8)

2-55"60 (1939)o

8. SPener-Strong, G. H. and King, R. Me, "Mechanics of Haumel Adherence:Part IX, Equilibriu Studies in Some Systems of Enuml 01.s. andCobelt, Nickel, OWd Iron 091408".. Jour., Am. Ceram. Soce., 17 (7) 208-14 (1-934).

ANALYSIS C O0 N V A I PqAdE 17PREPARED By De . Pr att A 61Vion Of' GKONAL ONMAVICI CoaOVO. REPORT NO. MP-58475CHECKED BY w4 M. Sutherland JOAN 09900) MODEL R-7038REVISED 13Y D -A TE -3-2-59

CO0P y Report No. -48

84. Staley, 9. F., "glectrolytic ResactionB in vitreous hunels and gieir Relationto the Adherence of ae1s to teel", Jour. Ann. Ceraft Soc., 17(616-647 (193)

8%. Stavemn A. 3., "molecular Forces" Chapter 2 -in "Adhesion and Adhesives",lasevier Publishing Coiiany, Houston, 1951.

86. Viellhaber, L.,' "BehAvior of Metal Obkideg in drownd Coats on Sheet Steel",-Coem Abtr., 4 (6) 156 (1925).

87. Vicihaber, Lo, "Oases in bahmeJls"i Cerun. Abtr., U6 (3) 84 (1937)o

88. Wainel', E. and baidvin W. J. , "Nfickel Flashing and its Relation to hMOM!Mdherende", Jour.4 Am. Ceram. Soc., 28 (1-) 217-26 (19545).? 1

89. wre, 0., "Adherence Teets for Porcelain fthmels Mn Hig Temperature CerdaicCoatings: Part I, Discussion of Destructive T-ype Tests and CompleteInformation on the Porcelain MAWI Institute Standard Adherence Tee.,;IFinish, 11 (1) 3 -35 04IO (1954).

90. waen do., "Adherence Tests for Porcelain ~Immele and High Tbapertare Cerud(i'.Coatings: Part II, Application of Standard P.E.I. Adherence Test to~High 5eprre- Coati gs", inish, U (2) 53-54 (1954).

91. Weyl, W. A. and Zerfoss, So., "Discussion of Paper by C. A. Zspfee and C. B.S11=1",. obur. Am. Ceram. Soc., 23 (10) 91 (19140).

92. ittL. ad Kg, R. M. , "Adherence of Sheet Steel GrounCotasIfeceby Titania Mill Additions", Finisch. 7 (1) 28-29 (1950).

93 acaV. F., VdtcheliJ, D. W., Mitoff, So P., and Pask, J. A., "FuzM-amntalsof Glass to Meta1 Bonding: Part I, Wttablity of Some Group 1 00MGroup'I easb Sodli Silicate Glass", Jour. Am Ceram. Soc.

06() 84.8 (195)

9-4. Zavfte, C. A. and Sims, C. Z., "Rielation of Defects In Mml coatings OnCast Iron", Jour. Am.u Cerun Soc., 24 (9) 249--53 (194.1)-

95. ZpfeeC. A. Bad Sims, C. E., "RelatUon of Defects in Mme-l Coatig -to

HydrogniSel" Jor. Am. Ceram. Soc., 23 (7) 107w219 (1940).

96 Zpfee, C. A., "Cause of Defects In E~nel Fir-ed on Cast Iron at Temperaturesabove 725C.," Jour. AM.- Ceram, Soc., 25 (7) 175-180 (1-942).

97. ZePfee C. A. and Yarns 6J. L., "Scratch Misters", Jour. Am. Corm. S90c., 25(T) 180-190 (9 )

FORM 1gliAA

ANALYSIS C O0 N V A IR PAGEI 18P-REPARED Ey D. S. Pratt A DIII1 Of GENCIAL DYNAKICS CONFOSATIOM REPORT NO.W-&'!)CHIECKED BY W. M.i Sutherland (SAN IDISSO) MODIEL PyA-7038REVISED Fly D C3-&5

co0p y Report No. 2m-48

BlI(IRP(ContinW.,ed)

98., Zapfee-, C. A. and Yarne, 3. L.0 "Relation of SLrface oxidation to, CertainDfects in -am1 Coatings on St..1l", Jour. Am Ceram. Soc., 25($191-sm194 (1942).

99 . Zapfe C. A. em-d Yarne, j- L- "1Chips, Fish ScOAles, AM' d iners", jour. Am,Cer-m. Soc.., 2-5 (7) 1 M-25 (1942).

100. Zapfee, C. A. and SiMa, C. E.,"Fu±rthek Considerations of Hydrogen as a Causeof Ebaae1 befects", Jodur. Am Ceram. Soc., 25 (7) 9054-15 (1949).

101. Bryanmt., E. 9. & Anmno MG., "eeinton f Compressive Stress Prxesent inPorcelain - -me on Sheet In"Jour. AM CeramSoc. 31. (1)29-30,(191.8).

FORM 10111.A

'.S5C 0 N V A I R PAGE9 19f-'EPARKD by DO . *Pratt A DIVIION OF 41161RAL DYNAMICS C.OMBATION EPORT No. *.58-475C.HICKED mY W.l M. 'Outher1Wn (ANDI*O MODEL it-67OSSREVISED SIY DATE 325

Selected references fM "A Survey of the TheoriesCoceduig Ceramic to Metal Adherence",f A.Z. Begles,

UW TRB $8-8&, August 19$8 (1)

EUbmaks, A6 0. and D. 0. Ibore, "Wtect of Oxyge Content of Furnace - 1~eron Adherence of Vitreous Catings to Iron", Je Am. Cer. Soc., 38 226,

2. Kembel, C. "Thnteri lecula~r Porces and. Stregh of Adhesive J0ints", in Adhesionand Adhesives, FUndamentals atid Practice, Clark Ruttle? and Savage,.1-itors, Wiley AM Sons, 1954,. N.Y. pp. 69-f!.

3. King, 1B. Wo, H. P. Ttipp, and W. Hi Duckworthp "ie Nature of Adherence ofPorcelain ftamels to Mtal', Cero Industry, 69, 101 (1957).

1j. Mobore, D. 0. AM A. 0. Subanks, "Influence of Copper Ions on Adherene 6fVitreous Coatings to Stainless Steel", J.Atm Cer. Woc. 39, 357 (1956)-

5. 0' timcn, t.S6, "Rypothesid of Adherence Of Porcelain Mmmls to Metals m ATreatise of Published Works", M1orp~hed. byr Mttelle Mmrial Insti-tute, Columbus, Ohio.

6. fosenber- J.L Dvlpmepts in Gr'ound Coat MommelaCrmi iuty34, 414 (191.0).

7. St+ll, R. P., Jr., "A Study of the 0ddation of Steel Pl.ate as -elatd toWettability And Adherence of Porcelain Mel", ftll Am* Coro Soc.37, 22 (1958).

8. White, J, "Oxidation of Iron anid Adhesion of Mmmn", Pouniry Trades J, 59, 114(1938).

9. Za~er, j. M., "Belatione Detee c_ Ice Deposit aMAdherene" Better swl-INS, U, 10 (110) Ceu. Abs. 9) 32 (9.)