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Wt w p 'u t h i s s w j u ii w*twriNumNRWy* > --'--i-Vr-'-- w LIA224 76 AZI-LIA EXPANDED RESEARCH PROGRAM '< Axouan Zin c In s t it u t e , In c Le a d In d u s t r ie s As s o c iat io n SCHEADE r. RADTXl .~J DImic l * wiirA 60 EAST 42ad STREET NEW YORK 17, N. Y. NO I.MU m 'WffW o 'Jr July 1, 1959 To All Members of the American Zinc Institute sal the Lead Industries Association Gentlemen: 3he second Quarterly report of the AZI-LIA Repealed Research Program la attached. Ve hope that the firat report met with your approval and baa been uaeful to you. It la our dealre that you be kept fully evare of the progress and nature of the way Individual project* aa veil as the over-all direction of the total program. Tour additJetal research contracts have been Initiated In the laat Quarter and several existing programs have been extended. The objectives of these are suaaarlzed In the respective Lead Research and Zinc Research sections. Hie format of the resume has been changed so that the report may be readily separated Into lead and zinc sections vlth Individual tables of contents, end the Individual programs have been categorized Into Metallur gical, Chemical, and Electrochemical disciplines. Oils vas done to facilitate the use of the report by reviewing personnel, and vs hope you find that these changes Increase utility of the report. Ve look forvard to receiving your ccements end suggestion*. *---Sincerely yours, s\ attachment 1 i uuum ?r o 1 1 3 o ; ! i J ,s 1 1 0 4 i : i WJ.*'. . IWJUSIg .iicii a x i-l ia comma) r es ear c h pr o g r am Ah : lcn Xlne Institute Lead. Industries Aisocistlc* Quarterly Report Vo. 8 July 1, 1959 1 r N 1752.01 M q j j w h w p iuwiiqu uweqspnsprew yi *i1*W*WWW",WWWilTW%Zi!qqggr<%^rarBMi<^^ ? LIA22478 -r '- ->-a.--- - -.-i-- Second ftiarterlr Beport AZI-LIA EXPABDEP KESBAKCB FSOORAM oai cr ccarcrre z nrewjcucTif ZX UUU> HBSARCH ISOCBUtf A Program* Recently Initiated 1. LP-&-59 fundmental Investigation of Load tarter Metallurgy 2. LP-2<>-59 Investigation of Method for Producing Load Co*tod Steal B. Active Metallurgical Program* 1. LP-15-59 Continuous Extrusion of Lead C*hla Sheathing 2. LP-1-59 8tudjr of Lead Baae Alloy* 3. LP-9-59 Plbar-Relnforeed Lead k. LP-16-59 High Spot Investigation of Lead for Sound Attenuation C. Active Chemical Program* l. L?-10-59 Lead Chemical* 2. LP-11-59 High Emission Leal Compound* 3. Lead In Ceramic Material* - Fellowships a. LP-19-59 * Effect* of Lead Oxide In Porcelain fnaaela b. LF-20-59 - lead Glare* for Ceramic Vhltevsre Bodies e. LP-12-59 - Wettability of Lead Glare* Upoa Structural Clay Bodie* d. LF-lV-59 - Phase Relationship A Propartlaa of Selected Ceramic Systems LP-21-59 - Development of Ultra Lov-Loe* Ceramic Dielectric* f. LP-22-59 * Fundamental Behavior of Load in Glasses ( LP-23-59 - 8tudy of ferroelectric* Containing Lead Compound* u rrrrw u uummn Ptg 1 1 6 6 7 7 0 mm - eu m LIA22479 ' 1 > ' i. * Becood ftiarterlr Report AZI-UA DTPAJCDED RESEARCH HtttBlAM i nsRococnqi Bill Becood ftiarterly Report of the American Zinc Institute sal the lead Industries Association Expanded Research Progrsa briefly turner1tea the progress that ha been aade oo the aany reeearch prograas la the period April 1, 1959 to July 1, 1959- During thle period four nev programs hare been Initiated, end the objectives of these are outlined. Extensions of severe! existing prograas have also been aade and are noted In the suaaai7 of the appropriate projects. To facilitate the use of the report by the personnel of the sponsoring coapanles, the fornat has been changed so that the report nay be readily separated Into lead Research Prograa and Zinc Research Program sections vith a separate table of contents for eech. dhe Prograa sumarles have also been Classified Into Metallurgical, Chealcal, end Electrochemical disciplines, depending oo the nature of the Individual Investigations. By this arrangement, the Expanded Research P-ogrsa hopes to achieve surlmia utility of the report by the Program's sponsors. * UtiMMWvm n LIA22480 r. -> --^w. .. rt>-at,wn>^ ...Mjrs-. ... 8econd Quarterly Report AZX-UA TXPtXOBD RESEARCH HlttffiAM 11 - IXAJ) RESEARCH CTOCHtAM A. FROgRAMS RECEHTLT IHITIABP 1. ycndnacntal Investigation of Lead Powder Metallurgy (LP-8-59) (Rensselaer Polytechnic Institute. Dr. T. V. Lend) A program to Investigate the fundamentals of lead powder metallurgy w Initiated June 18, 1959 for ooe-year period. Rensselaer vaa chosen to perfora thie Investiga tion from the four reeesirch organisations who submitted proposals In respoae to the Expended Research Program's lnvltatlm to hid. Sr. Lenel has heen associated vlth the science of powder Metallurgy for sane tine and therefore brings a broad background of experience with him to apply to this research program. the primary objective is to investigate dispersion hardening techniques for pro* dueIn* stronger and more creep-resistant wrought lead products. The first part of the project will be to determine the relationship between the degree of dispersion of a second phase in a lead natrlx and the strengthening effect thus produced. This study will be made by extruding alloys made up from a series of compounds, including lead oxide, and lead powders of different particle lire. Powders of lead alloys which have Improved creep strength will also be incorporated Into mixtures with a second disper sion phase to determine the extent of additional strengthening Obtained. Another recently developed method of obtaining very fine second phase dispersions in lead powders will be investigated. This consists of atomising a lead alloy in which the alloying eleaent Is soluble in the liquid phase but practically lnsolublm la tha solid phase. This method produces a powder In which the alloying eleaent is distributed In the fora of a very fine dispersion. The creep properties of a wrought product fabricated in this way will be investigated, as well as tensile and corrosion performance. As a result of these initial studlas. It is anticipated that techniques will be developed for producing wrought lead alloys possessing tensile and creep strengths superior to the known alloys of lead. 2. Investigation of Methods for Producing Lead Coated 8tccl (LP-26-59) (Expanded Research Program Supervision) A program has been initiated to evaluate the various methods for producing leadcoated steel. An lsaediste objective Is to determine the most economic method of pro ducing lead-costed can stock for nonfood containers. Supervision of this project will be handled by the Expanded Research Program ataff which will let feasibility study and sample production contracts to organisations that have particular akllls in the various techniques. Initially it has been proposed that tha techniques of vacuum metallisation, direct cladding by powders, foil or sheet cladding, electroplating, and hot dipping will be investigated. A contract has been let to Rational Research Corporation to produce lead-clad steel by the vacua metallisation process. Lead lends Itself well to this technique and advances is production equipment are making this method of deposition cosQWtltlva to older processes in certain areas. If no difficulties are encountered in vacuum metallisa tion, delivery of the coated steel should be made la the near future. srtr LIA22481 UBkfiu -*r- !( * 9 Other organisations her* b*n approached for the procurement of lead-coated eteel by the other proceeeea. the materiel* produced by the various metipds vlll be evaluated by a major container organisation. B - ACTIVE METALmBOICAI FPOORAX3 1. Contlnuou* Extrusion of Lead Cable Sheathing (Lf-15-59) (John Robertson CompenyT Three additional lead cable sheathing alloys hare been extruded on the Robertson machine since the last report period. Bre operating characteristic* of the mm*h1ns have been determined for the antisocial alloy, tellurium alloy, and Eablrloy. fits** alloys vers shovn to be ertrudshla cn the modified continuous marhlne of Robertson vlth varying degrees of ease depending on the alloy. The Halted runs performtd are believed to be asrpl* Indication that they can be continuously extruded into cable eheathlng on a coosserclal bad*. Metallurgical evaluations of these elloys are being performed by Mr. Snyder of the Anaconda Wire and Cable Company's Laboratory. future vork vlll Include the preparation of a technical brochure to sum up the operating characteristics of the machine end the metallurgical evaluation of the sheathing produced from each of the alloys. This vlll include a discussion of coeserclally pur* lead, f-3 arsenical alloy, Eablrloy, tellurium alloy, copper* bearing alloy, and the antlaonlal alloy. 2. Study of lead Base Alloys (LP-k-59) (Amour Research foundation, C. R. Sisco*, Supervisor) This Is a fundamental study of t>* recrystalllcation kinetics of binary lead alloy* Involving approximately 15 high purity alloy systems and a total of scat 60 composition ranges. Xssertlally, dl the chosen composition* have been Belted, cast, end prepared for the recryetallication studies. The procedure chosen to study recrystalll tatloo kinetics involves cold pressing prepared Ingots at -110y and then measuring hardness changes vlth a specially developed hardness tester as the eamples vara to room temperature. Die cold vorked samples vlll also be up-quenched and held at various temperatures to sake Isothermal hardness measurements. Preliminary measurements Indicate that the recryrtalHiatlc- temperature of 99-9999% lead is -6oF. Initial results of the lead l antimony alloy have ahovn the competing processes of softening due to recrystalHsatlon end hardening due to aging, phenomena vhlch are expected In several of the alloy systems. The lov recryatallltatlon temperature! and hardness of the high purity alloys have necessitated the development of apeclal techniques. Bov that successful procedures have been vorked out, the recryatallltatloo measurements vlll be rapidly carried out. future vork vlll consist of alloying the remaining fev systems and performing and analysing tha O {-crystallisation studies. Consolidated Mining and siting Co., St. Joseph Lead Co., and American belting and Refining Corp. hay* contributed much to this program by supplying high purity lead and alloylhg additions end technical data to Armour.  yii'. i ar 11 .1 i .j i iii- iiipjpm.uy .mu m-j u t --' WgP.uwL'iw p -. >3 .. ---- ----*--- -Ilf) IIT M n ~ ril M ||-| W3 3. flber-Relnforced Lead (LP-9-59) (Amour Research Foundation, R. 1. Reed, Supervisor) Development of method* for producing self-supporting lead product! by reinforcement vlth metal fiber Matte* 1* the object of this project. A atudy of lead infiltration condition* leading to impregnation of a phosphor- bronze fiber atructure o' varying de&aitlea ia being performed by imeralng the fiber matte* in molten lead vlth and vlthout tray* to minimis* lead run out. Conditlon* found to promote impregnation are high lead bath temperature, tin addition* to the lead, pre fluxing of the nattea, and mechanical vibration of the lead bath. 80 to $0 Infiltration of the matte voids vas obtained by immersing vine chloride-ammonium cblorld* fluxed wttas into a 750T lead bath for three minute* vlth attendant 60 cycle vibration of the lead bath As-fabricated composites of various lead-tin alloy* exhibited tensile strengths ranging froa 3lb0 to 6b00 pal ccapered to the component strengths of lb80 pal for a 20 danse phosphor-bronze fiber structure and 2230 to A900 pal for 99-9f lead and 90^ lead - 1Of, tin alloys respectively. Si* strength of the composites vas essentially equal to the additive strengths of the components. Thle is less than theoretical calculated strength --a fact attributed to Incomplete bonding between the fiber and matrix phase* and to the formation of a brittle Internets! ! 1c phase, believed to be CupSng- The internets! 11c phase vas alao believed responsible for the surface cracking of these eoiposltes vhlch resulted froa cold sorting by pressing and rolling. Per cent reduction possible before cracking occurred varied froa 23 to 75$. Bie higher ductilities vere shovn by the lower density fiber mattes. future vork will consist of modifying the lead allays to minimis* Intel-metallic phases, developing techniques to improve infiltration efficiency, and preparing steel fiber-lead compositive. b. High Spot Investigation of Lead for Sound Attenuation (U-lt>-59) (Bolt Beranek A levnan, Inc.) Ells project entail* a feasibility study for employing lead product* in architectural structures for sound Isolation. It le to be exploratory in nature; intended to give direction to further development in the promising area of lead as a sound isolation medium. Si* investigation is expected to be completed prior to the next quarterly report. C. ACTIVE CHEMICAL PROGRAMS 1. Lead Chemicals (U-10-59) ^Arthur D. Little, Inc., Dr. C. B. Morgan, Bupervleor) Si* current areas of research in this program are a study of the ccmpound dlcyclopentadlenyllead, th* preparation of p-*tyrenyll*d and bexaphenyldilaad moooners and their polymers, and a continuing literature search of current organoleed chemistry. P-styrenyltrletylleed monomer has been Isolated and polymerised to a bard, transparent plastic. Si* aonoemr, vhlch contains 53 vt- lead, vas produced by th* reaction mt trlettiyllead chloride and a etyrecyl Orlgnard reagent. It vas Isolated by room togeraVurehl(Ji vacuum distillation. On standing at room temperature, in th* absence of Inhibitors, the monomer became viscous aad on exposure to high intensity ultra-violet light, it polymerised. A new monomer, p-styresyltrlphenyllead, has been prepared by reaction of trlphe&yllead chloride end styrenyl Orlgnard reagent but it has not a* yet been polymerltcd. Ed* monomer contain* 38.3 vt - $ lead. */ mw>a "T"" V J i<rti M* k 9 A study of the compound dicytlopentadlenyHead (DCL) Indicates that It forma aa adduct vlth neleic anhydride. SCI. la of interest because of lta restively good thermal tability compared to previously known divalent organolead compounds, aad it vlU be atudlad further. Hexaphenyldllead - maleic anhydride addueta hare been prepared aad a preliminary atudy of lta esterification vlth ethylene glycol made. Analysla of the addueta do oot agree vlth a previously reported structure. Before additional work oo coDdeaaatloo polymerisation of the addueta la carried out, the structure must be established. - Is the future these compounds vlll be Investigated further and greatly lacreeaed effort vlll be directed towards application research oo available chemicals A. 0. Little end others have prepared. Bile program ham been supported by the eooperatloe of Rational Lead Costpany aad Khtyl Corporation vho have furnished bibliographies on organolead chemistry aad samples of organolead compounds. 2. Hlrti Emission Lead Compounds (LP-11-59) filev Tork University, Professor I. B. Cedoff. ftiperrisor) A fundamental study of the thermal and spectral cmlaalvlty of lead compounds la being carried out on thla research investigation. Thla program. Initially coctrmcted for the academic year 1953-1959, has recently been renewed for the academic year 1959*1930. Work has been concentrated on obtaining the room temperature emission properties of lead tellurlde, the compound vhleh la expected to have the highest emlaslvlty In the series being Investigated, vhleh consists of PbSe, PbS, FbO, and FtTo. To avoid absorption, refraction, aad reflection at grain boundaries, measurement* are being made using PbTe single crystals vhleh have been prepared. Preliminary emission data hare been obtained on R>Te samples. These have shown that reflectivity Is nearly Independent of vave length vlth a slight minim at shout 9 microns. The absorption values Indicate that the sample must be approximately 500 microns chick to absorb all tha Incident radiation and therefore have emlaslvlty properties of the bulk materiel. Materials sued as surface costings mist be quite substantial In thickness to coaq>letely mask the properties of tha underlying material and have diffuse rather than spectral relfectloo. 3. Lead in Ceramic Materials Research on ceramics la being carried out by means of fellowships in seven univarsi ties . Recently all the fellowship programs were extended to Include the tmodealc year 1959-1960. The reports of progress sines the last report period are suamarlsad belov. (a) Affects of Lead Oxide In Porcelain Enamels (LP-19-59) TUnlversity of Illinois, Pr. A. I. Andrews, Supervisor) The investigation Is being continued 00 the effects of leal oxide on the roerystalllna tion of crystalline opaclflera in ensmela, and tha reduction of reflectance produced by mill-added pacifiers due to eolutlon In high lead enamel glasses. (b) Lead Olaies for Cer*ic Whitevare Bodies (LP-20-59) (Ohio State University, Dr. R. Russell. Jr., Supervisor) The object of this fellowship is to determine the relative effects of varying compo- HUI I J ?! M gHHi.WJLgn sewn'MlI lijUJ 1' LlA22A8A : -'t- --^V~ W5 altlcns on the properties of typical land glut! when tasted as glut asplas--the results to be used la the formulation of glares haring certain desirable properties when applied to typical ceramic whitevare bodies. Bie fallow performing the investigation on this progrea was unable to continue the work after April, 1959 and no replacement va* available until July, 1959* At this tine yellow Edwin L. Rogers accepted the L1A fellowship and will continue the Investigation for the academic year 1959-1960. (c) Wettability of Lead Planes upon Structural Clay Bodies (L?-lP-59) (Gleason Agricultural College, Professor 0- C. Robinson. Supervisor) This program entails a study of wettability of lead glares upon structural clay bodies with respect to clay body composition, lead composition of the frit, and firing atmosphere. A thesis by yellow X. X. Macyarlane written In partial fulfillment of the require ments for a Master of Science Degree has been received. It covers the Investigation he has performed In 1956-1959 academic year on the LXA fellowship. The general conclusions of ths effects of ttui variables studies on wettability are sumriaed: Initial liquid formation of a glass vns relatively Independent of the firing atmosphere and the clay body composition, end Initial wsttlng occurs at a considerably higher temperature than required for liquid formation. It tr*s dependent on firing atmosphere end body and glass composition. A slightly oxidising atmosphere promoted vetting of the evaluated bodies and glasea, and a reducing or oxidising atmosphere containing water vapor ralaed the vetting temperature. Seducing atmospheres were specifically disadvantageous for leaded glares because they tended to reduce the oxide to BMtalllc lead, causing spotting and reducing the flux content of the frlasa. Lead oxide substituted for other fluxes In the glare definitely lowered the melt ing end vetting temperature of the glare due to the better fluxing properties of ItoO. j An Increase In silica content of the body caused a alight lowering of the wetting temperature In dry air and moist air atmosphere and had llttlw effect in reducing atmos phere. An Increase in celcium content lowered the vetting temperature in all atmospheres and generally the high calcium contest bodies were the most easily vetted. B>e vvttlng range, however was decreased In those bodies by the rapid penetration of glare into the body. Any effect eeueed by the change In Iran content was offset b7 the effects of the fluxes and silica, the compositions of which were proportionally Increased whan Iron was reduced. Iron displayed its --xlmia effect under e reducing atmosphere, demonstrating that as the oxidation state of iron was decreased, the wetting temperature was decreased. In general, body composition affects wettability by the promotion or retardation of the solid-liquid Interfacial reaction. r sepwn* wpmbiy j*juuic if; ' inwwWBPf^?**' " ngsmrps >j .'> L1*Z2`,85 ry r ittmnriaitaim.vii J*c 6 i 4' -i i' (d) Phase Relationships g Properties of Selected Ceraalc Systems (U-lk-59) rfgnngylruila Sut University, Professor P. A. Humael. Supervisor) Investigation of the physical properties of the lead silicate, lead phosphate, lead borate, lead phosphate-silicate, lead alualnun-elllcate, sad lead borate-silicate com pounds are being carried on concurrently vlth a study of ths phase relationships of the ternary systems PbO - XmgOj - SiOj* The compound JrtjO-2SiOp has been suggested. An attempt to verify Its axlstenes by X-ray 'diffractloo patterns did not show that It vas present. Samples prepared by both solid state reectlan and devitrification of glase ahoved only mixtures of 2AO-S109 and FbO-BlOj. 8lx lead phosphate compounds and one leed phosphate-elllcate ternary hare been prepared and are under study. Cbe lead borate-silicate and four leed borate compounds are aleo being Investigated as are three lead-aluminum silicate ca^ouzda. Ths ternary syst<m, IbO-La^O^ - 8i02f is being investigated In the lov silica region since this Is vbere the elx binary compounds are thought to exist. Present vork has Indicated that one ternary caapound exists. It seems highly probable that several ore vlll be found. A nev leed compound, % PbO - loo3 vhlch may here Interesting dielectric properties has been found. These properties vlll be investigated at a later date. (e) Development of Ultra Lov-Loss Ceramic Dielectrics (LP-21-?9) {Rutgers UalverTlty-Pr. J. E. Xocnlg. Supervisor) Ths successful development of ultra toe-loss cerssslc dielectrics baaed on lov loss glass binders and fused quarts crystalline components ss reported In the last quarterly report Is being augmented by a study of dielectrics Incorporating alumina os the main crystalline compound. Using an alumina crystalline phase end the lov-loes silicate glosses containing lead, barium, bismuth, and calcium vhlch vert previously developed In the fused quarts studies, several dielectric bodies vere Investigated, firing of these bodies prt'd difficult. Anomalous dielectric properties and vster absorption valuea vert obtained depending on the firing conditions. Conditloaa vhlch produced good dielectric properties caused high vmter absorption because the bodies did not vitrify. An Increase In firing temperature end time produced vitrification but the dielectric properties vere markedly Inferior. An Investigation of the causes for thle vas mode, and it vas found that poor dielectric properties vere accompanied by the recryetolllsatloo of the alumina Into large grains, from an examination of the system It vas found that after the lead frit malted, further heating caused ths glass to gradually dissolve the alumina crystals. The Initial firing conditions, 2160 to 2200P, no soak at temperature and fast cooling, gave bodies contain ing alpha alumina and lsad aluminum silicate crystals having good dielectric properties but poor vitrification. Soaking at Z200T for one hour caused considerable solution of the alumina vhlch reurystalliaed Into large alpha-alumina crystals on slov cooling. Vhen e these large crystals formed, no lead-alumlzzum silicate crystals vere present, Indicating that the glass composition bad shifted Into the corundum field of the AljO.-SiOg-PbO system due to the solution of alumina. Several possibilities vere proposed to explain the poor dielectric properties In the presence of the large rec ryetalllied alpha-alumina crystals. A study of these possibilities vlll be undertaken. -w v* 0 suim saq^sw 'JJ1 mg. WPJU11 -- JI V" ! w mm i u tfwajiwig^BBmg 111 lip JOT LIA22486 ---- ---. --- ---- - -- - -'-- ^-- ------------------------------------------------------------------------------------------------------------- -------- t **< 7 (f) fundamental Behavior of Lead In Glass (LP-gg-59) {Alfred University, Professor C. Preen*, ftjpenrlsor) Oils Investigation of the fundamental behavior of load la a (lui systea la being carried forward V a study of the IbO-KpO-EiOp aytea. Apparatus for producing the glasses under controlled condition* have been constructed and 18 compositions hare been prepared. She thermal cxpanalon of 13 uteriala have been measured In the temperature range, 0-300C by us* of a dllatcmeter, and It haa been found that In the area of the system from which aanageable glasses can be obtained, the coefficient of ezpanalon appeara to be a linear functloo of the compositions. froa thla the coefficient* for the three components say be calculated and theaa calculation* art being carried out. (g) Study of Ferroelectrica Containing Lead Compound* (LF-23-59) (University of California, Professor J. A. Peak. Supervisor) The angnetle ferrite* hare been developed only recently and hare shown a combina tion of vary uaeful electric, dielectric, and magnetic propertlas. The leal ferrltea subject of this progras, have found extensive use In permanent aagnats because of their high intrinsic coercive force aid relatively high renanence. They are derived fros magnetite by the substitution of lead atoo* In the sagnetlte cubic crystal. A literature survey of the lead ferrltea has disclosed considerable divergence of opinion as to ccopound* forsed In the ferric oxide-lead oxide systea. In view of this, the initial area of lmreatlgatlon of the progras Is to deterslne which lead ferrites do exist. O Lead ferrites are being produced by sintering chealeally pure mixtures of JtoO and PcpO, powders which have been pressed into cylindrical slugs. Ihe (lugs are sintered at fixed temperature* for known times and rapidly air quenched. IXu-ing sintering, exothermic and endothermic reactions ere recorded by differential thermal analysis, tine sutereo slugs arc ground and then analysed by X-ray diffraction techniques. Lead lose during sintering it measured. Using these techniques on a powder mixture of 1:A molar ratio of fbOt TpO,, It was found that; (l) at 705 sintering temperature, only elpha-Fe-O* aad 2FbO-f#.jO-. are present; (2) with Increasing temperature PbO-fiPe-Oj begins to form (8000 C upward); (3) at 8AOC and 875C, Pb0-6Fe20v PdO-2T*?Ov and Fein arc present, and (A) at 910C - 915C, the compound Rj0-6Feo0j 3 la still present but . X-ray peak Intensities are decreasing, possibly dus to the vaporisation of IbO. The** results ara not in fall agreement with those of other Investigations, lbs possibility of the occurrence of solid solutions will be Investigated In the continuing study of the lead oxlde-lrom oxide systea. 1 J i jjuwur~w T --yijg JiWiil'lW I j `JP.IW * (I --wry atka im.' mn ii.'yw j *3, h i iin j s *a i\m y fa a. ------>' ifafa Second Qierterly Report AZI-UA ECPA1CED RESEARCH RtOORAK zn sue MCSEARCB pr o g r am TABUS CT COWgTS ises. 8 A. Progrene Recently Initiated 1. ZP-lb-59 Cathodic Protection of Crab Pot# 2. ZP-17-59 Fundamental Iuveetigetloe of Zinc Powder Metallurgy 8 8 8 B. Active Metallurgical Program* 1. ZP-5-59 Development of Improved Zinc Die Casting Alloy* 2. ZP-i-59 Improvement of Zlac Lithographic note* 3* ZP-18-59 Development of Improved Dry Cell Battery Asodee V. ZP-JD-59 Dolled Zinc la Architecture 9 9 9 10 10 C. Active Chemical Prograna 1. ZP-22-59 Evaluation of Zinc Oxide Exterior Souse Point* 10 10 D. Active Electrochemical Program* 10 # 1. ZP-12-59 Pinlthing of Zinc Die Carting* 2. ZP-20-59 Corrosion of Hot Veter Storage Tania 10 12 3. ZP-ll-59 Vet Storage Stalnlrga of Galvanised Sheets 12 k. ZP-35-59 Expo*ur of Galvanised end Ccopetltlv* Steel Sheet 13 5. ZP-13-59 Zinc Anode Znstslletloos for Karine Tknfcer* 13 *1 **/ o l e v-uy1 yF*H" U'lilHHiM' I pMij w b WiUMiPjUfWgP mim n ppjn-mM,www iw> LI A22488 r JM** 8 Secood Quarterly Report AZI-LIA ECPAHISD RESEARCH PROGRAM HI - ZUK RESEARCH PROGRAM A. pr o g r ams racnrmr inHAgp 1. line Anode for Protection of Crab Poti (ZP-1&-59) {Virginia Institute for Scientific Research, W. R. Buck, Supervisor) An applied program to Investigate the uae of tine anode* for protection of galvanised vlra crab pot* used In the Chesapeake Bey area vu Initiated on May 18, 1959 with the Virginia Inatltute of Scientific Reaearch. The Virginia Fisheries Laboratory Is an equal co-sponsor of the prograa, and the special tine anodes to be used In the prograa vers furnished through the courtesy of the American 8melting and Refining Coapany. Corrosion of galvanised Iron crab pots la ertlmated to cost helf-alllloa dollars annually In the Chesapeake area alone, and although soae crabbers hare used tine anodes to extend pot life, no study has been Bade of the anode site, lifetime, fouling, protec tion achieved, nor the effect of the anodes on the crab catch. The purpose of the prograa Is to supply this Information through laboratory experiments and field vork so that It can be widely disseminated to the crabbing Industry. Che progrea is expected to be completed prior to the nd of the year. 2. Fundamental Investigation of Zinc Povder Metallurgy (ZP-17-59) (Bcneelae~Polytcchn!c Institute, Dr. F. V. Lenel, Supervisor) A progrea to study the fundamental characteristics of tine powder metallurgy vas Initiated at Rensselaer oc June lfl for e period of one year under the preaent contract. Dr. Leuel, who Is to supervise the Investigation, has been associated for aany years In the field of povder metallurgy and has s broad background of experience to apply to this research. Bie Initial objectives of this prograa are to Investigate suitable methods of consolidating nine powders into scssl-fabrlcated products for further working to the wrought condition and of directly coaverting povder to wrought products. These studies will be preliminary to the main objective of finding technique* for producing tine base alloys having finely-divided, insoluble second phases to Impart superior strength sod creep properties than tu-e currently available In alloys fabricated by conventional methods. This will Include s study of the available comerclal and laboratory grade* of sine powders with regard to their oxide content and fineness. The effect of addition of sine oxide and other compounds to tine powders will be determined to find combinations producing dispersion strenthened alloys. A recent develojraent for producing very fine dispersions of practically insoluble lntsrmetallle compounds In powders will be evaluated as to Its applicability to tin: powder metallurgy. The method consists of stoaltlng an alloy of the matrix metal with an alloying element which la almost insoluble In the matrix meted, ut ambient tenpersturs but soluble 'Sv in the molten state. Rapid solidification produces s finely precipitated dispersion In the povder. Zlnc-nlckel alloys are e candidate for this procedure. In the evaluation of the alloys developed, particular attention will be paid to creep. Other mechanical properties and corrosion resistance will also be evaluated.  i'.in imj ' 11 a \ u. * wjty* mmjm ^6q p*x 9 o B. ACTIVE KKALLUHOICAL BROgWO 1. Development of Improved Zinc Die Casting Alloys (ZF-5-W) (lev Jersey Zinc Company. Mr. E. A. Anderson, Supervisor) The Initial phase* of the die casting alloys program are searing completion and work vlll soon begin on the casting and mechanical evaluation of high alualnua-tlnc alloy compositions. Design of the experimental die, which Includes a round and flat tensile bar and an impact bar, has been completed. Fabrication of the die has begun and Is expected to be completed In July. A selection of elements to be considered as ternary additions to the tine-aluminum binary system has been Bade, considering such factors as solubility, toxicity, cost, availability, oxidation rate In the melt, and tendency to promote Intergranular corrosion. Frua these Initial considerations, It v s l s decided that the first experiments would Incor porate copper, magnesium, silicon, titanium, zirconium, vanadium, molybdenum, tantalum, chromium, tungsten, manganese. Iron, cobalt, nickel, antimony, end possibly hafnium. The liquid solubility of many of these elements was screened In Zn-8^ A1 and Zn - lty A1 alloys by performing melt analysis of samples taken 50C above the binary llquldus. The quantity of each element retained In solid solution and as a finely precipitated compound after slow cooling was measured. Only In the cases of copper aod silicon did the amount held In liquid and solid state appear to be approximately the same. Iron, o manganese, titanium, zirconium, vanadium, molybdenum, cobalt, nickel, and tantalum all shoved a sharp drop In solubility during alloy solidification at alow rates. L. Future work will Include a study of the Interaction of a combination of selected elements to determine which will form compounds between themselves rather than with sine or aluminum during solidification. The slllcides In particular will be Investigated. 2. Improvement of Zinc Lithographers' Flates (ZP-k-59) ( Lithographic Technical Foundation, Hr. H Bruno, Supervisor) This Investigation, since Its initiation In March, has been proceeding along m*ey lines concurrently. Its goal la to Improve the characteristics of zinc lithographic plates. Creep end banding tests have shown that a titanium-copper alloy plate possesses mechanical characteristics far superior to regular zinc plates, and a few sunsce treat ments have shown promise of Improving the water-receptivity of these zinc plates. Co-spoosors of the program furnished titanium-copper alloy materials for evaluation, and ont of these materials shoved markedly Improved creep resistance over conventional zinc plates, which often exhibit objectionable creep during long runs. The superior alloy contained O.lktf titanium and 0-35% copper and was beat treated at U8oF. Extensive press runs indicated a negligible amount of creep, amounting to only 0.02^ compered to approximately 0.2% for regulei zinc. The bending characteristics of the alloy were equivalent to those of the conventional material. Attempts to brush grain the zinc alloy plates, method for producing a very fine grain, have shown that this process ten0* to polish the alloys (as It does regular tine plates) Instead of producing a fine grilned surface. The plates could be tub-grained successfully, however. 0 The llthogiaphlc properties of the alloy plates were Investigated In view of their superior mechanical performance, and no detrimental characteristics ware found in asking either albumin or deep-etch Images. 81r different desensitizing treatments were compared (treatments that produce water-receptivity In the nonprinting areas), anl of these the Fost-Eltal treatment In conjunction with cellulose gum proved superior and gave better scuamlng resistance to the alloy than to regular zinc plates. V/ 90 o a* i / n i i i [TTin i r-i'T1-1^^--.- ...---- ----- ' page 10 - Investigation of aurfae* traatments to derelop better water-receptive surfaces without destroying the excellent lnk-receptivlty of slxtc vere carried out by measuring, aa a screening teat, the contact angle of vater on the treated line eurface la air and the contact angle of oleic acid on the eurface In vater. A l40y acid bichromate solution treatment followed by a lUoF oxalic acid solution treatment shoved promise of producing a lasting olecphoblc treatment. 3. Development of Improved Pry Cell Battery Anodea (ZF-18-59) (Cooperative Program) A performance test for rating pinhole perforation of aloe battery cens la under evaluation by the cooperating participants In the program. The test procedure, vaa sub mitted by Bright Bter Industrie* and consists of determining the perforation rate of battery cans in a heated solution of tine and ammonium chlorides. To determine If the test vill give reproducibility of results, each pertlclpeat vill conduct the test on battery cans furnished by Ball Brothers. The cane sent the various participants vere manufactured from the same lot of alnc to reduce the possibility of material variation. After the testing procedure is etanderdlted, the chemical end metallurgical aspects of battery cans relative to perforation vill be investigated. , - V. Boiled Zinc in Architecture (ZP-3D-59) (Cooperative Program) i The over-all object of this program is to evaluate the performance of various rolled o tine alloys In exterior architectural applications. Rolled tine products have enjoyed relatively large market* in many European countries for roofing, flashings, downspouts, and gutters, and an evaluation of ltc performance In the varied climatic conditions and atmos pheres In the United States la being carried out on a cooperative basis by the rolled tine producers, building contractor*, and the All. ZSoC alloy gutters and dovnapouta for private homes are being fabricated and Installed at Daytona Beech, Florida end Syracuse, lev fork. The alloy* being used for fabrication J of the component* are the titanium-copper alloy* and the Cu alloy. Standard galvanised steel components are to be Installed at the same location* to serve as performance control*. It la anticipated that the original Installation vill be completed in August. C. ACTIVE CHBCCAL FROGRAXS 1. Exposure Tct on tine Oxld> Containing Exterior House Paint* (ZP-2g-59) (Cooperative Program) The outdoor exposure test oo numerous formulations of tine oxide exterior bouse paint* Is continuing. Ksny factors are being studied In these test*, Including vehicle*, extenders, substrates, and tine oxide content. Panel* are being evaluated vlth respect to checking, cracking, peeling, chalking, tint retention, and mlldev resistance. Panels have been oo exposure for approximately one year and recent Inspections bavt Indicated that significant performase* dlffarences between the many formulation* are being manlfeeted. The data obtained 1* now in the process of analysis and results vill be reported In the naar future. D. ACTIVE ELECTROCHEMICAL FBG3UMB 0 1. Finishing of tine Die Casting* (EP-12-59) (Battelle Memorial Intltut7 Mr. V. H. Safranek, Buparrior) ftirlng th* last quarter, further work has been carried out to determine the effects imifi WWI wjlllll eaeiunsimsaSiauanSi nmsm wu of U^urltles on chromhm plate continuity. Preliminary studies on direct plating of chromium on tine casting vere made. Evaluation of th outdoor exposure pacala and accelaratod-corroalon studies on plating systems vaa alao performed. An evaluation of dual chroalua alactroplatea vaa alao lnltlatod. Trlvnlant chromium vaa found to b< a beneficial Impurity In high-temperature, high-ratio batha employed for producing bright crack-free chromium. Porosity and bllaterlng during Corrodkota teatlng vaa reduced In depoalta from batha containing 0.5 to 1$.grana per liter of trlvaleot chromium. fine aa an Impurity vaa found to have very little influence 00 plete quality, and copper end nickel Induced poroalty aa datemined by eleetrographlc printing and cocfiraed by Corrodkota teatlng. A typical automotive part vaa plated directly vlth chromium followed by bright nickel end regular chromium to determine corroaloa performance in the ahaeace of the normal Initial copper depoalt uaed In conventiooal plating systems, the objective being the elimination of the cyanide vaate disposal problem attendant vlth copper plating, The Initial results Indicated that tUe chromium-nickel-chroedua system vaa more corrosion resistant than the copper-nlckel-chromlum on*, The appearance of the parts vaa good except that nodules tended to develop at the edges. This plating system vlll be evaluated further in light of thea* Initial results. Evaluation of outdoor exposure panels Incorporating various plating systems has abcnm that after 23 veeka of weathering at Eure Beach, Detroit and Columbus, the panels having .025 to .075 >11 of bright, crack-free chromium (high temperature, hlgh-ratio bath) over bright nickel vere in good condition. Panels haring regular chroalua over duplex nickel vere nearly aa good. Earlier panels plated vlth bright, crack-free chroalua deposited from e self-rcgulmtiag bath, nov on exposure for TO veeka et these sltbs, are still In good condition. An Initial evaluation of the dual chromium plating system vaa made. This system consists of copper, bright nickel, and two layers of chromium deposited from two different self-regulating batha. Coed resistance to copper-accelerated salt spray vaa obtained from the system end it vlll be evaluated further. The Battalia program, which voder the preeent contract terminated July 31, 1959s la being extended to December 31, 1999, under e nev contract to Investigate recent development* and continue the inspection of outdoor exposure penels. Among the phases to be studied are: e. Evaluation, by accelerated end outdoor exposure, of systems involving duplex nickel and bright, crack-free chroalua froa high-temperature, blghratlo baths. Nobile exposure tests vlll alao be conducted on trucks. b. further evaluation of the chroacum-alckal-chroadum system. c. further evaluation of the dual chromium system. d. Evaluation of the practicality of plating bright,crack-free chroadum la cold bath* (at 90y and lover). e. Study the effects ef cyclic heating end cooling on cracking of nlckel- 9 chroadum deposits cm time die castings. f. Investigate electropollshlng and leveling electroplating ef time die castings as a practical procedure for eliminating buffing. <M i1 n m TV "ET"I^V .immmsL1 *>.' LiA22A9Z . - ... ,-------------V. .-.. .. - rfilrmi H r t I i*e* 12 2. Corrosion of Hot Water {Storage Tanks (ZP-20-59) (Cue Institute of Technology, Dr. R. C. WeastT Supervisor) Bill investigation is proceeding sloog three Bain lines in s study to determine the mechanism of end overtone the premature failures of galvanised hot vater storage tanks, they are: a. Determination of the electrical potential of sine in aqueous sytaas under pressure. b. X-ray studies of corrosion filsu formed on corroding sine. c. Use of cathodic protection to inhibit corrosion of galvanised hot vater tanks. Many measurements have been mole to detect the change of sine potential in distilled vater and dilute solutions at various temperatures and under pressurised oxygen end nitro gen atmospheres. In distilled voter preswurlted to 30 pslg vlth oxygen, the actual sine potential vas approximately 0.7 volt vlth reference to a calomel half cell. Normally, uzxler atmospheric pressure, sine exhibits approximately 1 volt potential to this rexerencc, tod reversal vlth respect to iron is considered to be in the 0.6 to 0.7 volt range. A 0.1 I XCL solution under this pressurlsation caused negligible sine potential loss, but potentials in or belov the reversal range vere found in saturated solutions of CaCOj vlth additions of 10 ppm S0^" 25 ppn 80^* and 30 ppm Cl". Increasing the solution temperature caused a reduction in the tine potential, and vhen oxygen vas replaced by nitrogen in 10 pirn SO," (Sat. CsCCO solution, the potential is time returned to the normal value, indicating that even with a ZoO film, reversal vlll not occur in the absence of oxygen. These experiments show that the effect of oxygen concentration Is a significant influence on the reversal phenomenon of sine. Tbs mechanism by which oxygen causes this effect vlll be studied further. further clarification of the corrosion products of 99-999$ sine in oxygenated distilled vater shoved that from 0 to 10C sine hydroxide and very small amounts of oxide formed at temperatures of 25 to 70C the proportion of oxide markedly increased; and above 68C only ZoO vas detected. Between 70 and 90C two layers of ZoO formed vlth the inner layer being such more miherent than the outer, although X-ray analysis Indicated no difference between them. At 100C a dense adherent black layer forms after corrosion has occurred for a month or sore. Tests cooducted to learn if the conversion of Zd (0H)j to ZoO in vater is purely a thermal effect vere affirmative. Mo meaaureahle corrosion of tint occurred in vater through which nitrogen was bubbled. Tests to determine the minimm current density necesuary to protect galvanised steel are being conducted using platinum anodes, Cleveland tap vater, and 1**0, 160, and 180T temperatures. Initially, a current density of 12 allllaspere per square foot has afforded complete protection. She current density vlll be reduced until the mintmim for protection is found. Other vater* vlll then be tested by the same procedure. 3. Vet Storage Staining of Celvanlted Sheet (tP-11-59) (Southern Research Institute, Dr. V. B. Wilcox, Supervisor) Three phases of this progrsa were pursued during the last quarter. The evaluation of several protection coatings for inhibiting vet storage staining of galvanised sheet has been carried out as veil ns additional evaluation of the effectiveness of coatings used by covaerclal galvanised steel producer*. Developments In testing procedures for determining the susceptibility of vet storage staining hare also lead to a new and rapid method which Is being correlated with existing test procedures.  m mi--i I --SWilli 1-- piwgn1j V-l W 13 O Preliminary results have shown that citric acid additions to tannic acid greatly lscreaaad the protaction effectiveness of tannic acid. A further investigation of citric acid alone ahoved that by itself It vu ineffective In Inhibiting vet storage staining. A propriety corrosion inhibitor, Anco C-203-1 "surfactant film", vas evaluated and found to give protection equivalent to the best organic coating tested thus far. However, the recooaended dllutent Is toluene, and the acceptability of the material would be seriously Halted because of Its reco--ended application frea a flasmable solvent. A satisfactory Beane of continuously measuring the progress of vet storage stain ing has been developed through uee of light reflectance froa the surface of the sheet under test. The apparatus consists of s colllasted beaa of light passing parallel to the surfaces of a galvanised panel In J. stilled vster. She formation of vhite rust Is detected by scattering of light which is picked up by a photodiode and continuously recorded against tins by a recorder. At the beginning of a test the output of the photodiode Is adjusted to produce a siro reading. Results obtained by this Method show good agreement vlth those froa other tests developed for determining the susceptibility of galvanised sheet to vet storage staining. The light reflectance method, like the industrial stack test, gives s more exaggerated distinction between good and bad sheet than either of the velght loss Methods. Its advantages are rapidity, objectivity, and simplicity; all three suggesting an attractive production quality control method. The correlation of this test to actual vet storage staining susceptibility vlll be evaluated more thoroughly. V. Exposure of Galvanised A Competitive Steel Sheet (ZP-35-59) o (Cooperative Project - Formerly Zf-1-59) Outdoor exposure of the penels and tenalle specimens Is continuing. The condition of the galvanised panels has changed little since the last report but some evidence has been reported that localised rusting of the aluminized panels is still occurring and In one instance the coating Is peeling svay around these localised areas. Sufficient corrosion has not occurred to begin the testing of tensile specimens that have been exposed concurrently vlth the panels. The material has been on exposure since March, 1958 la four locations. 5. tine Anode Installations for Maine Tankers (EP-13-59) (Cooperative Program) The anode Installation In Mo. 9 cargo tank of Texaco's tanker Bull fo. V566, "0. 8. Maine", has been completed and the ship Is nov in service for approximately two months. The completed installation Included 222 type 2-30 sine anodes conforming to KIL-A-lfiOOl, Type 0. Elve sine reference electrode* are also Installed at various locations la the tank, and these vlll be monitored by the crcv of the "Maine" at various Intervals to determine the degree of protection afforded by the system vhen the tank Is in ballast. Tha initial results of the installation should be reported soca. --e KM* v isw; _