Investigation of' the Kinetics of Crystal l izat ion of

Kolten Binary an5 Ternary rJxide S y s t a s

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T h i s investigation is being carried out under Contract MASW-l3Ol w i t h t h e May erials Research Branch.

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I C IACCESSION N Y M B E R ) ( T H R U )

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C A T E G O R Y )

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?hie first oxi5e sys%m. t= Le seiez '+ud ?or 5z-<esti&,%aE, z o s 5 l e r i t e 31̂ ?@-$lk:si5O18 - a tDree-Ciixerxior?al r i r i fomer, -has k e a selted s u c c e s s m y repeat e6ly ir, s eveml atmospheres and i n several ccn ta imrs Eqiiipment developed for mni to r ing the e l e c t r i c a l conductivity of t h e molten oxide sgstm as it cools has been used successf'iilly. t o zeasure t h e e l e c t r i c a l coniluctivity of the vitreous co rd ie r i t e system frm 1560 C to dynamic measurement of Young's Modulus of t h e bulk glass fi nsiskently yielded a result for glasses ia the cordierite conrpositlon f i e l d o x I& pounds per sqiime inch or 10.55 k i lopans per square centimeter. In i t ia l . experiments 3i:

t h e second oxide s y ~ t m selected for study, beni3oite or %W5i309 - a cycl ic s i l i c o n oxygen compla having discre te Si30g6- ions, have shown tk ia t this system devi2r i f ies mch mre reedi ly thaz the cord ier i te s g ~ t m .

C, Apparatus put together t o carry out the

n+ ;,ESS~S i n t h e cord ier i te glass field st;tt'sizg with 5 sicror? p a r t i c l e s i z e

_ti& plrrity s i l i c a , a h ~ i n a of 325 mesh s i z e mid 3% pxitj., and Isbmatory reagent grade m@-esk.m carbonzte r e w zaterials have been successfu.Ily rcelted. 3 e s e m t e - i s l s yield 8 w.ater-.,-hite op t i ca l grace glass f'ree of 5e&, stone, 2nd bubbles when held at a taperatme of 1% C or higher for a period of at least two hours. The glass may e i ther be grepared in the highest purity cocmmercially atrailable m y recrystallized alumina crucibles in air at tempera+,ures of 1520 C t o 15h.o C or in tungsten crucible rt either argon or vacuum etmosphems at temperatures of 1540 c a d higher. t o 99.7$, cannot be used nor can the t q e r a t u r e of 190 t o l % O C be exceeded even with t h e highest p x i t y alurnlna crucible.

crucib~es of even s l lgh t fy lower pritjr, i .e . 99.3% cf.

To study t h e e l ec t r i ca l conductivity of t he c o r d i e r i f e %sed glasses as a r j ~ c + i n n of t q e r g $ : x p , t h e &asses were r.&tej a p dcscrj.'rej E?m\rcl. orAj t h e n 'moke-, q an3 packed inzo t h e : - a s t e n crucible shw:: I n Fig. 1. crucible, which i s pictweZ at the conclusion 0." t he neesumen t , i s nade t o ser-e as a z o n h c t i v i t y c e l l by i x r o h c i n g a t u g s t e n bati, om-qtzzrter i ~ c h i n diameter, on t h e end of' a tungsten r o d i n t o t h e exact ten te r of t h e crucible and by ty ing a tungsten rod t o the outside of t h e crucible wT%h 25 nil tantalum w i r e . The whde assmbljr is then placed i n the tungsten resis tance Furnace shown i n Fig. 2 and heated until the @ass is corJpletely remelted. is then turned off and the eIectrica.3. conductivity of t h e molten oxide system i s measured conti_nuously through t h e s d i d i f f c a t i o n process as t h e m a c e cools. The temperature of the cmc ib le is neeaured at thirty-secoad intervals t o obtain t h e require6 data connecting e l ec t r i cc l conductivity with c rys ta l l iza t ion o r lack of c rys ta l l iza t ion rates

Yhis

Puwer to the furnace

P' m e a c t u a l ~easrrrm.ez? of ",e e lec t r i ca l cozdnctlvity i s z a r r l f d a ~ t by con9ectin.g e x t e r z l a l l y the "lo3 chmeter" described s c h e ~ a z i c u y i n Fig. 3 to t he two leads fron t h e t-mgsten c n c i b l e conductivity cell . Tkiese leads are

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unkn0ru.n r e s i s t o r and the sampling r e s i s to r are adjusted so that the power dissip&& i n the smq3.e is less than 500 m i c r o w a % t s , and the sample r e s i s t o r is less thsn 6.5 percen% of t h e resis tance being m e a s u r e d .

In eacb range position, a c o c s t a t q i i t u d e , 1000 cycielsec, s i c u o i d a Yoltage is applied to t he unknown ar,d the clxrent througt? it measured by a s q 1 i n g resistDr. This si-& i s p s s & throq,.!! E: series of f i l t e rs c o n s i s t k g of a b a d - ?ass f i l % e ~ ZYXZ XQ 2s XOG c ~ * c i e s / c e ~ , a twiE-tee m i c b :titer 3% EG 2;clesJsec znd a tuiil-fee r-otch f n t e r at 130 cyclesjsec ~n e ~ ~ c u ~ t ? . rmove the l a r g e muunt of rioise generate6 i r ? t h e s q l e by t h e massive (1000's of a;;;peres) &I cycle heater currer t present i n t he t.mgsten m c a c e . %her, l i n e a r l y m p l i f i e d by EL gsirded r q l i f i e r t o a l e v e l of 0.5 -Jolts p p to 50 volts p-p and used t o drive a power aqlifier. t h e guarded amplifier fion the detector. epplied t o t h e logar i tbs ic converter which puts out a d-c voltage pwport ional to t h e logarithm 05 t h e i n p t voltege. A unity gain Dperational anplifier following t h e lo,aarithTic converter provides t h e low outpat i q e d m c e necessary t o dr ive t h e s t r i p c h a r t recorder.

i 7.- -i-eze _?l.ilters ~ f _ " e c : i - ~ e ~ j i

Tkie s ~ m is

!Be power emplifier i so la tes The d-c voltage k - 0 ~ t he de t ec tm i s then

&sides t h e g l a s s nel t ixg ex-perizents and t h e mcnisoring of t h e e l e c t r i c a l ccndactivity of ;i?ese glasses 'by $he equ lpen t b u i l t and assezklea for %is prpose,. qpm-atx i KCS &so se+, 'II, f ~ r zessw:~g Ycxg's lkd-&.~s DE 3L.k @ass specli-sifens b ~ - sonic (dynaaic) c i rcu i t ry . vi3rates at a resormnt frequency deternine6 by t h e dimensions, density and Youngts Xadulus of t h e spechen. If shear a s d hertie. effects are considered, t h e formula for rectangular specimens is

A reetEIlgular o r cylindrical beam in flexure

where M = mass of sample i n g r m s a = thickness of s q 1 e i n inches L = length of s w l e ir, inches b = w i d t h of s a q l e In cent-heters f = rescrnmt freTL:eze:r of t ~ ~ l e in cjrcles/sec E = Ysung's M9dlilv-s fcr sw?le ir_ ki l sgrms Fer oo_;lwe cm.

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The res-ults obtained me in%eresting s i n c e using t h e same apparatus values for Corning Glass 6 Gasses Code (Pused si l ica) of x 10 I Code Tf@ (p-Tex) o f 9.3 x Code 7052 ( na-silica) of %,2 pounds per s Q m e lnch were obtained. The results o2taioed zse also highly concordant.

The f i m l i t e r n on which progress w a s =de during t h i s quarter consisted i n selecting the second glass fZeM t o be investigated m d preliminary tr ials at obtain-ing opt ical grade GESE ?ram t h e batches select&. The corqxxition area selected is that or' benitooite, P&'iS53Cg, whose s t r x t w e is m c h l i k e that of beryl { C e m L d ) , B+2Si6%st era is coxqrised of ring i ~ c s arrariged in sheets wl th t h e i r planes parallel but not 3 1qpr s-trcet-ne since the m e t a l Loris 3.15

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betveer? t h e sheets ~ 2 3 b i ~ d t,ogJei,t-er the rhgs 3f t5e 2lfferen$ s h e e ~ s . eqerimerts i n melting t h i s cospositicn showed that it could not be zonlairted i n high p u r i t y aLmina, mgnesia, 3r ber2U-b m d t h a t %hen melted in pIa>km, t h e izelt completely d e v i t r i f i e d presumably because of nucletxtim by c o o t x t with platinum.

Trel inlxery

In t h e next quarter the search will be continued for a su i t ab le C O E ~ E ~ ~ E Z for m e l t i q g ben l to i t e based g$lasses and a study w i l l be made of the effects of nucleating and anti-nucleating agents using both the cord ie r i t e and bexi to i te batches. Eent n ~ w at hand for measuring viscosixy ky the restrained sphere ziethoci w i l l be tested m d used fo r both types of' glass systems. ments w i l l be m d e .

The e l e c t r i c a l conductivity vill be measured i n each case and the equip-

Additional elastic moduli masure-

?ersoonel a c t i v e on this program during t h i s period were J. F. B C Q ~ principaJ invest igator and Borrrs~nn J. Chamberlain, Senior fi5rperibtental. Technician. They were aided repeatedly throughout t h e period by Louis J. Tempel, Jr. of t h e l.X(=RL Inst m e n t a t ion Section.

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klachlm, G. R., C. J. Stalego, €3. L. Tiede, A. B. Is-, and D. E. -mente ( mens-Corning Fiberaas corp,, ~ewark, Ohio) : ~ i @ ~odulus, TFazperature Glass Mbers f o r Reinforced Plastics, slrpplement 1, March 3.$1, @ADD W - 2 4 - SUppleInent 1.

McMartir,, R. Me, R. L. Tiede, F. K. Veazie (Owens-Corning Piberglas Corp., Iiewmk, Ohio): High Strength-High M ~ d u l u s Glass Fibers, Mmch l%5, AFML- m-65-90 - mt I.

Lafbertson, it. A . , D. B. ALken, and E. E. G l r a r d (TSe Car't;tcl,ran3um Co., Research an5 kvelqraent Division) : Con-kimmus Filmrent Ceramic Fibers, June ISO, %%DE TF60-244.

Girard, E, H. (The Carberundurn Co., Research and Development Division): tinuous filament Ceramic Mbers, Part 11, February lg61, WADD TR60-244.

Con-

Jkummond, W. W,, and B. A. Cash (Bjorksten Research Labs., Inc., Madison, Wisconsin): Development of Textile Type Vitreous Sil ica Yarns, Final Report, Y I C ~ 1360, wADG 59-699,

Iiagler, R. T. (Bjorksten Research Lrlbs., fnc., Y?dison, Wisccznsin) : High Viscosity Refractory Fibers, Q m r t c r l y RepGrt #1, 1 July - 30 Septerr;5er 1958, Contract BOrd-1&9, A 3 2C9;31.

D r m o n d , W. W. (Bjorks ten Research Labs,, Icc., M&dison, Wisconsin): H i g h Viscosity Refractory Fibers, &&rterly Report #2, I October - 31 Decmber 1958, NOrd-i&P, AD 210948.

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Kroenke, W. J. (B. F. !Goodrich Reseesch Center, Brecksville, Ohio) : Structured Glass Fibers, Quar te r ly Progress Report (9-1-64 t o U-30-64),

L inea r

m3(6513~sos.

i.;*oe&e, W. J. (3. F. Gocdrich Research Cen+,er, Becksvi l le , Ohio): Flexible Glass Ebers, ~ c h 1s4, m~-frz,-~~fi-6k-ii9, Contract AS^( 657) ? ~ 5 , ~ r o ~ e c ? 732C - '_"ask No. 79001.

Otto, W. H. (Namco Research & Developent Division, San Diego, Calif . 92123); S i l i c a Fiber Forming and Core Sheath Ccmposite Fiber kirelopient, Fi& S I . X E S ~ Technical Report, 3 Jmuary 1964, Navy, BuWeps, N600(19)5%07.

Otto, W. H. (Nannco Research & Developent Division, Whittaker Corp., San Diego, Calif. 9123) : Silica Fiber/Core-Sheath Fiber, Qiar te r ly Progress Report #I, 30 May 1$tC, BLiiJeps, P6ocl(19)61810.

Otto, W. If. (Narmeo Research and B v e l o p e x t Division, ' i l t taker C o q . , San Diego, C a l i f . 92123) : Fibers, Quarterly Progress Report %, 10 Fe3ruary 1905, IhWeps, IJ6UO(l~)61810.

S i l i c a Fiber/Core-Sheath Fiber/Righ-Tezperat-xe Oxide

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Scfircitz: G. K., a d A. G. Metcalfe (Solar, Subsidiary of International m s t e r CO., an Diego 73, W f . F-1: New Glasses i n Fiber Fbw. R05 l9A, RDR L a - 7 .

Exploration and EviLmtion of Final Report, 12 April l S 3 = 8RL Project 62?

I?chit,z, G. ir, a d A. 6. Mefcalfe (Solar, SLlbsidlary of In t emt io r - i a l 3arvester co., San Diego 12, Calif, gU2): in Fiber F Q ~ . through 3 l Decm3er lw, IVRL f ro j ec t 62, 305 I%, Coztract 369[00) (X) A2, 15 January 1965.

Ihvies, L. G., and 5. C, Withers. (General Technologies Corp., Materms Division, Alexandria, Virginia) : Tilamen% filaterisls by DepositLon Techniques, 1st Bimonthly Report, Jmmy 15, 1$4, Contract BOK E4-0176-E 164 1&676, Unclassified, Code 3.

Eq2ors t ion and Fraluatfori of New Glasses Binontidy Progress Report #6 (3rd contract year), 1 Xovaober

A Study of High YldLtus, R i g h Strength

Lasday, A. H. (Eoute Glass Corp.): Heat R e s i s t a n t Materials, October 1958, W N X m58-285, ASTIA I)oc. #202m, Contract AF33(6l6)-5263, Project 1340.

Development of Hi@ Modulus Fibers frox

3rossy, J, F., and J. D. Provance (Houze Glass Corp.): Modulus Fibers from Reat Resistaxt Materials? Ymch 1s0, M A E TR58-285, ?ar t 11, CLZIA %c. @3@?11 Co22ract ~~33:616)-5263, Project 7340.

Development of High

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38. Gates, L. E., arid W. E. Lent: Studies on Refractory Fiber Research, 3C October 3.960 - Contract DA-04-495-OFD-lT23 between Army Ikdistic Missile Agency, U. S. A m y Ordnance Corps-and Camponents Mvisfon, fhrghes Aircraft C-, Culver City, Calif.

39. Gates, L. E., and W. E. Lent: B v e l p e n t of Reffactory Fabrics, Fi,nal Summary Report, 8 April 1963 covering period 1 October 1960 to 2 %cernber l$z, Contract 2 3 3 8-50 between %SA, -Rorge C. ~&xrshan Spaee n i g h t Ceriter and Cloaponents & M&teriais LRbora%,ory, E.Ir;gbes :1 rzrsft, Caqrmy, CArrer City, C a l i f .

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D 910373-1 FIG. 1

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DWU313-1 FIG. 2 TUNGSTEN RESESTANCE FURNACE

l3 PROTfCTOR MECHAYISW FOR SI6441 GLASS 8 W TOP TANTALUM RADIATION W E L D S

8 0 COOLING WATER WT

@TUNGSTEFI PEDESTAL FOR CRUCIBLE @TlJM6Sl'EN cIcucl%LE @FLAT TWGSTEN HEATING ELEMENT (4) a COOLING WATER IN

4 TANTALUM RlhMATIWJ SHIELDS 5 SIDE COPPER COOLING COlLS @BOTTOM WATER COOLED ELECTRODE 8

@TOP W N E R COOLED ELECTRODE

8 '0' RING GASUET SEALS @ TOP COPPER COOLING COlLS @TOP INTERCHAWGABLE COVER FOR

@SIGHT GLASS

SUPPORT CONDUCTOR 0 7 REFLECTION SHIELD tNSERT 0 8 TO VACUUM SYSTEM 0

YEASUCIING APPARATUS 0

SUPPORT CONDUCTOR

BOTTOM PLATE FOR MOUNTING WATER Ihi BOTTOM ELECTRODE BOTTOM COPPfR COOLING COILS BOTTOM TAMALUM RADIATION SHiELDS ROTTOM lNTERCt4A)IGAfjLE COVER FOR

WATER IN TOP ELECTRODE MEASURING APPARATUS

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FIG. 3

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D9 f0373-1 flG. 4