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Influence of oxygen on the interfacial reaction between sapphire and copper. Misra, Surya Kumar 1964

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INFLUENCE OF OXYGEN. ON THE INTERFACIAL.REACTION BETWEEN SAPPHIRE AND COPPER by SURYA KUMAR MISRA A THESIS SUBMITTED IN. PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED. SCIENCE . IN THE. DEPARTMENT OF . METALLURGY We a c c e p t . t h i s t h e s i s as conforming t o the standard r e q u i r e d from candidates f o r the degree of MASTER OF APPLIED SCIENCE.. Members of the Department of Metallurgy. THE. UNIVERSITY OF BRITISH COLUMBIA • A p r i l 196^ In present ing t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f the requirements f o r an advanced degree at the U n i v e r s i t y of B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r reference and study. I f u r t h e r agree that permission f o r extensive copying of t h i s t h e s i s f o r s c h o l a r l y purposes may be granted by the Head of my Department or by h i s r e p r e s e n t a t i v e s . It i s understood that copying or p u b l i c a t i o n of t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be allowed without my w r i t t e n permiss ion . Department of M e t a l l u r g y , The U n i v e r s i t y of B r i t i s h Columbia, Vancouver 8, Canada. A p r i l 23, 19& • Although- the e x p e r i m e n t a l . i n v e s t i g a t i o n was considered acceptable as. the requirement f o r the Master ' s degree programme, the w r i t t e n form< as submitted by Mr.- S K . • Misra. was n o t . . T h i s . i s - t h e f i n a l form, of the t h e s i s a f t e r i t has been correc ted and e d i t e d b y M r s . • A . • M . • Armstrong and Dr.- A . C . D. -Chaklader . i i . •ABSTRACT : The i n f l u e n c e of oxygen on the wet t ing of sapphire . ( ^ - A l 2 0 - 3 ) by l i q u i d ' copper was i n v e s t i g a t e d u s i n g the s e s s i l e drop, technique i n vacuum at 1230°C. For addi t ions , to copper of c u p r i c oxide , v a r y i n g from 1 - 72$ of the copper w e i g h t , . c h e m i c a l r e a c t i o n at the l i q u i d - s o l i d i n t e r f a c e r e s u l t e d i n spreading of the l i q u i d and a r a p i d decrease of the contact angle to a steady s ta te v a l u e . A d i r e c t r e l a t i o n s h i p between the f o u r t h power of the b a s a l radius of the molten C'.drop and, the oxygen present was observed. The product of the i n t e r f a c i a l r e a c t i o n was found to be CuA10 2 , Phase diagrams of the systems CuO-Al 2 C>3 and C u 2 0 - A l 2 0 3 were d e t e r -mined experimental ly u s i n g X - r a y d i f f r a c t i o n techniques f o r i d e n t i f i c a t i o n of the phases. The aluminates , Cu(A10 2 . ) 2 and-CuAlG 2 were i d e n t i f i e d and t h e i r ranges of s t a b i l i t y i n a i r e s t a b l i s h e d . i i i . ACKNOWLEDGEMENT The author acknowledges, the help and guidance of D r . A . C D . Chaklader and Professor W. M. • Armstrong f o r h i s encouragement and i n i t i a t i v e i n the whole metal-ceramic research p r o j e c t . . The author, i s g r e a t l y indebted to M r s . ' A . M. Armstrong, f o r her help i n i n t e r p r e t i n g the experimental d a t a . Thanks are due t o M r . . . R . . G . B u t t e r s , Mr. R. R i c h t e r and Mr.- A r v i d L a c i s f o r the t e c h n i c a l help and a s s i s t a n c e . . The author wishes t o express h i s gra t i tude to Professor. F . A . Forward f o r g i v i n g him the opportunity to 'Come t o the U n i v e r s i t y of B r i t i s h Columbia f o r higher s t u d i e s . The work was f inanced by the Defence Research Board of Canada by research grant 7510-32 through t h e . U n i v e r s i t y of B r i t i s h C o l u m b i a . . i v . TABLE OF CONTENTS Page I . INTRODUCTION . . . . . . . 1 A . General D i s c u s s i o n 1 B. The S e s s i l e Drop- Technique . . 3 C . . Review of Previous Work on C u - A l 2 0 3 System . . . . . . . 6 D. Aim of the Present I n v e s t i g a t i o n . ' 9 I I . . • • EXPERIMENTAL ' 10 • A . M a t e r i a l s . Used f o r the S e s s i l e Drop Experiment . . 10 1 . Aluminum Oxide 10 2 . Copper, Cupr ic Oxide and Other A l l o y i n g Elements . . . . 11 . B . M a t e r i a l s Used f o r Phase Diagram-Study' . . . . . . . ' ' 12 . C . -Apparatus f o r the S e s s i l e Drop Experiment . . . . . . 1 3 1 . Furnace 13 2 . Vacuum System 13 3 . . O p t i c a l System . . • 16 D. Apparatus f o r Phase Diagram Study 16 • E . Specimen Preparat ion . . . . . . 17 1.. Sapphire Discs . . 17 2 . Copper Buttons . 18 F . Preparat ion of Specimens f o r Phase Diagram Study . 18 G. Experimental Procedure 19 1 . S e s s i l e Drop Experiments 19 . 2 . Phase Diagram Experiments 19 3 . X-Ray D i f f r a c t i o n . : , . 2 1 k. Meta l lographic Observation 2 1 I I I . - EXPERIMENTAL RESULTS AND CALCULATIONS 22 A . S e s s i l e Drop Experiment Results 22 1 . Sapphire-Copper System 22 2 . S a p p h i r e - C o p p e r - S i l v e r System 22 3-- Sapphire-Copper-Titanium System 22 k. Sapphire-Copper-Oxygen System 23 V . Table of Contents Continued Page B. Photomiorographic Study . • 28 C . X-Ray Study 31 • D . . Phase Diagram Experiment Results 31 I V . DISCUSSION • .37. A . S i g n i f i c a n c e of A l l o y i n g 37 • 1 1. - S a p p h i r e - C o p p e r - S i l v e r System . . . - . 37 2. Sapphire-Copper-Gupric Oxide-Ti tanium System . 37 3. Sapphire-Copper-Oxygen System 37 J a) Recovery of Oxygen 37 b) . Formation of CuA10 2 38 c) L i q u i d - S o l i d I n t e r f a c i a l Energy kO d) Spreading . . . • k2 B. . Phase Diagram D i s c u s s i o n . hk • V . CONCLUSION k& . V I . RECOMMENDATIONS FOR FURTHER WORK i+9 V I I . APPENDICES . . 50 . VIII . REFERENCES • 82 LIST OF FIGURES No. Page 1. Surface Tension Forces A c t i n g on a S e s s i l e ; Drop k-2. S e s s i l e Drop Parameters ' . 5 5 3. Surface Energy of Copper as a Funct ion of Temperature . . . 8 ^2 4. L iquidus Curve of C u 2 0 - A l 2 0 3 System . . . . . 8 5. P i c t o r i a l Representation of Sapphire L a t t i c e ( a f t e r Kingery) 10 6-. Photographs of Apparatus Ik 37 7. Schematic Diagram of Apparatus 15 8t Schematic Diagram.of V e r t i c a l . F u r n a c e 17 9. Sample Specimens and Susceptor Assembly 20 10. Contact Angle as a Funct ion of Oxide A d d i t i o n 2k 11 T-I . S e s s i l e Drop Photographs 25 11-11 S e s s i l e Drop- Photographs 26 12. Contact Angle as a . F u n c t i o n of Time 27 13. Oxygen Recovered versus Oxygen Added . . . . . 29 Ik. Photomicrographs of the Interface 30 . 15. • D i f f r a c t o m e t r i c Graph of the Interface 32 16. Phase Diagram of C u 0 - A l 2 0 3 and C u 2 0 - A l 2 0 3 . 34 17-I .Photomicrographs of Phase Diagram Specimens . 3 5 17-II.Photomicrographs of Phase Diagram- Specimens 36 18. Copper-Oxygen System 39 19. The I n t e r f a c i a l Energy as a Funct ion of Oxygen Present . . . hi 20. Fourth Power of B a s a l Radius as a Funct ion of Oxygen Present i n the Drop v i i . . LIST OF APPENDICES Page I . Theory of Spreading . . . . . . . . . . . 51 I I . C a l c u l a t i o n s f o r Monolayer Formation- 53 I I I . Bashforth and Adams Method 56 IV. Resul ts of the S e s s i l e Drop Experiment 6Q V . Phase Diagram Observations 6k V I . : D i f f r a c t o m e t r i c . G r a p h - R e a d i n g s 68 D i f f r a c t o m e t r i c Graph f o r C u ( A 1 0 2 ) 2 69 . D i f f r a c t o m e t r i c Graph f o r CuA10 2 , 7 0 V I I . - Debye-Scherrer Powder Patterns Readings 7^ A . S . T . M . Standard Cards f o r CuO, C u 2 0 , A 1 2 0 3 , . C u ( A 1 0 2 ) 2 . . . and CuA10 2 8 0 INFLUENCE OF OXYGEN ON THE INTERFACIAL. REACTION • BETWEEN SAPPHIRE AND:COPPER ..I.•INTRODUCTION A . . .General D i s c u s s i o n The e x c e p t i o n a l l y good c reep- , c o r r o s i o n - and h e a t - r e s i s t a n t A. p r o p e r t i e s of the S . A . P . a l l o y s and var ious other types of metal-ceramic -combinations have l a t e l y s t imulated a widespread e f f o r t among i n v e s t i g a t o r s . Most s tudies have been made to develop new mater ia ls which could have the d e s i r a b l e p r o p e r t i e s of metals and ceramics incorporated . in to a . s i n g l e body. However, very l i t t l e i s yet c l e a r as to why these mater ia ls combine such u s e f u l p r o p e r t i e s and so f a r the art. of prepar ing cermet, bodies i s far. i n advance of the s c i e n c e . • To. have the most e f f e c t i v e admixture of such heterogeneous composites, i t i s of prime importance t o consider the fundamental nature of bonding between.the metal and the ceramic phases. The problem may be approached from a c r y s t a l l o g r a p h i c p o i n t of view, which suggests that a gradual t r a n s i t i o n from i o n i c . t o m e t a l l i c type of bonding must e x i s t across the i n t e r f a c e . An a l t e r n a t i v e approach i s through i n t e r f a c i a l energy c o n s i d e r a t i o n s , s ince wett ing of the ceramic by the metal i n f l u e n c e s to a large extent the d i s t r i b u t i o n of the m e t a l l i c phase i n the poly-phase composite and determines the e f f e c t i v e n e s s . o f bonding. A S i n t e r e d Aluminum Powder - 2 --The study of metal-oxide "bonding involves the knowledge of 1 2 c e r t a i n fundamental f a c t o r s , such as wett ing ' which may be d e f i n e d i n terms of the contact angle formed at a g a s - l i q u i d - s o l i d i n t e r f a c e . The f a c t o r s ^ which a f f e c t the wett ing of a s o l i d by a l i q u i d are t h e i r respect ive surface energies; and the i n t e r f a c i a l energy between them. The l a t t e r i s s t r o n g l y dependent on the extent of chemical i n t e r a c t i o n •between the two phases. I n t e r f a c i a l energy i s d e f i n e d as the work : required t o enlarge the surface of separat ion of two phases by u n i t a rea . 5 The work of adhesion i s def ined as , the decrease i n energy i n b r i n g i n g together a. u n i t a r e a . o f ' e a c h of two phases t o form a u n i t area of the i n t e r f a c e , w h i c h , . i n other words, i s the work required t o p u l l a u n i t area, of the i n t e r f a c e apart to give c lean surfaces of the o r i g i n a l phases. This i s a measure of the a t t r a c t i o n between, the two phases. 5-12 A number of p o s s i b l e i n t e r f a c i a l reac t ions has been suggested which can e f f e c t the b o n d i n g . i n a metal-oxide system. There can.be s o l i d s o l u t i o n by d i f f u s i o n , product ion of d e f i n i t e chemical compounds at or near the metal-ceramic i n t e r f a c e and so on. T h e s e ; r e a c t i o n s lower the i n t e r f a c i a l t e n s i o n between the two phases as w e l l as change the surface f ree energy of the s o l i d . Besides these c o n s i d e r a t i o n s , s ince there are two or more d i f f e r e n t mater ia ls i n v o l v e d i n such cases , t h e i r thermal^mechanical and s t r u c t u r a l p r o p e r t i e s should be considered i n formulat ing a good workable cermet system. - 3 -B. .The S e s s i l e Drop. Technique The s e s s i l e drop technique has been s u c c e s s f u l l y used by 5 , 13-19 • '. many workers f o r w e t t a b i l i t y and surface t e n s i o n measurements at high,temperatures s ince the experimental.method i s ra ther simple and at the same time the r e s u l t s can be i n f o r m a t i v e . Kingery, 1 Eremenko and t h e i r co-workers have used t h i s method e x t e n s i v e l y f o r the study of metal-ceramic bonding, s i n c e , by simple c a l c u l a t i o n s from the experimental data both the l i q u i d surface t e n s i o n and the i n t e r f a c i a l energy can be determined. In a d d i t i o n , the' drop, provides a convenient i n t e r p l a n a r surface to permit study of the r e a c t i o n products . and, the various s t resses developed dur ing the process . ..The shape of .aumolten drop. (Figure 1) on a s o l i d surface depends on the e q u i l i b r i u m between the forces of surface t e n s i o n tending t o form a surface of minimum area and forces of g r a v i t y tending to f l a t t e n the drop. C o n s i d e r i n g a small drop, the e q u i l i b r i u m contact angle can be s a i d t o be dependent on the f o l l o w i n g three f a c t o r s . 1. "YG, r^ surface energy of the s o l i d 2. VTIT-J surface t e n s i o n of the l i q u i d 3 . * Y s L > s o l i d - l i q u i d i n t e r f a c e energy. ' 1 ' 20 The f o l l o w i n g r e l a t i o n s h i p was f i r s t g iven by Young and l a t e r extended by D u p r e ^ that = Y ^ ^ . - y Cos 0 (0 being the e q u i l i b r i u m contact a n g l e ) . . The work of adhesion, - W S L = < Y L V + Y s v ) " Y S L = VLV + C O S ° ) can be obtained by measurement of the e q u i l i b r i u m contact angle 0. - k , VAPOUR Figure 1. Surface tension forces acting on a sessile arop. I f Y SL i s l a r g e r than Ysv *he contact angle i s l a r g e r than 90° and i f the reverse i s t r u e 9 0 is, acute . Further r e l a t i o n s h i p s and t h e i r p h y s i c a l s i g n i f i c a n c e are given i n Appendix I . Since d i r e c t measurement of the contact angle i s not accurate 22 f o r angles of more than 9 O 0 , Bashforth and Adams , developed a method, f o r c a l c u l a t i o n of 0 and ^fT„ from the drop dimensions•in systems where wett ing i s . l i m i t e d . The estimated e r r o r by this .method i s l e s s t h a n * ' 2 $ . The method developed by Dorsey f o r . t h e same purpose i s much s i m p l e r , but the e r r o r may be as h i g h as. ±. 5 $ . I t was s ta ted that the most accurate r e s u l t s could: be obtained by t a k i n g measurements a l l around the drop per iphery to f i n d the average value of 0. For contact angles of l e s s than 90° > the above method.of d e t e r -N / 23 mining Y^y cannot be employed, but E l l e f s o n and T a y l o r suggested t h a t , i f the drop i s assumed t o be a .. .spherical segment (Figure 2b.) the contact .angle w i l l be given by 0 = 2 tan — o r . t a n 0/2 = ^ . This was found • 2k to introduce a-maximum-error of 2° i n the 0 v a l u e , even though the assumption of a s p h e r i c a l segment may not be s t r i c t l y v a l i d . - 6 -C . . Review of Previous'-Work on the G u - A 1 2 Q 3 System Grant , Z w i l s k y , • P r e s t o n , S a v i t s k y and others have worked on the Cu-Al 2 C>3 system, p r i m a r i l y t o develop, d i s p e r s i o n - s t r e n g t h -ened, m a t e r i a l s of engineering i n t e r e s t , e i t h e r by i n t e r n a l o x i d a t i o n or by powder mixing . The work of Grant and Zwilsky i n d i c a t e d that copper-alumina powder compacts (up to 10$ AI2O3) had at l e a s t three times the strength of that of pure copper at ^ 5 0 ° C . S . C . P . (Sintered Copper Powder) ?8 a l l o y s have r e c e n t l y been s tudied by Savi tsky and V l a s o r who have shown the s u p e r i o r s t rength of these bodies compared.to pure copper. I t was a l s o shown t h a t , among a ; v a r i e t y of oxides-used f o r t h i s purpose, AI2O3 produced the best r e s u l t s . •During. the study of s i n t e r i n g , g r a i n growth and r e c r y s t a l l i s a t i o n - 2Q i of A 1 2 0 3 , i t was found that some a d d i t i v e s enter i n t o s o l i d s o l u t i o n i n AI2O3 and s t r a i n the l a t t i c e s u f f i c i e n t l y to increase m a t e r i a l t ransport g r e a t l y , whi le other a d d i t i v e s produce a glassy phase which increases 3 0 , 3 1 the surface d i f f u s i o n . C u 2 0 , B e O , • F e 2 0 3 e t c . .were found t o f a c i l i t a t e the formation of a l i q u i d (glassy) phase which s t a b i l i s e d the g r a i n growth 32 of A 1 2 0 3 . .Noboru and Grant found t h a t , i n the presence of excess•oxygen dur ing the i n t e r n a l o x i d a t i o n treatment o f mixtures of Cu .and A l 2 0 3 , alumina formed a complex phase which was found t o be qui te r i c h i n copper. The presence of t h i s phase increased the rate of t ransformation of * / t o 0C - A l 2 0 3 . This s o - c a l l e d . " X oxide" was r e l a t i v e l y unstable at higher temperatures. A l l e n and Kingery^ measured the i n t e r f a c i a l energy between copper and-AI2O3 u s i n g s i n t e r e d alumina plaques as the ceramic support . For the - 7 -c a l c u l a t i o n s , the surface energy of alumina .was taken to be 905 e r g / c m 2 at l 8 5 0 ° C ( t h e temperature c o e f f i c i e n t being - 0 . 1 e rg /cm 2 per degree C ) . The v a r i a t i o n of the surface energy of copper w i t h temperature i s shown i n Figure 3. . .Their value of the surface energy f o r copper at 1100°C was 1 2 2 0 e r g s / c m 2 and dY had a normal -ve value of - 0 . 3 0 6 e r g / c m 2 / d e g . C . dT .The i n t e r f a c i a l energy between copper and alumina at 1100°C 2. was found t o be 22^5 ergs/cm . I t was a l s o shown that the composition of the l i q u i d d i d not change a p p r e c i a b l y during the experiment, i n d i c a t i n g the absence of an i n t e r f a c i a l r e a c t i o n . 33 3 -^Two patents ' claimed t h a t s i l v e r ^ c o p p e r a l l o y s , c o n t a i n i n g ; 35 1 to 10$> copper, would wet and bond t o ceramic m a t e r i a l s . Baxter found that the presence of oxygen was e s s e n t i a l f o r bonding. Copper oxide was observed t o spread.over the surface and penetrate i n t o the body of the alumina p e l l e t s used. Since cuprous oxide i s the s table oxide of copper above I0.OO°C, i t i s evident that i t must p l a y an important r o l e i n the wet t ing and bonding process . Work-on other systems, such as N i - A l 2 0 3 , C r - A l 2 0 3 , • F e - A l 2 0 3 , i n d i c a t e d that wherever wett ing was found, i t was due to s o l i d s o l u t i o n , formation of a compound, change i n .structure '.or some r e a c t i o n i n which 1 2 e i t h e r the metal or an a l l o y i n g element were i n v o l v e d . Pincus s tudied the M n - A l 2 0 3 and the M o - A 1 2 0 3 systems and found the i n t e r f a c e l a y e r t o be a s p i n e l which formed from the g l a s s y mel t . - 8 -w.. 2 0 0 0 L _ I J L _ 1 0 0 0 1100' . 1 2 0 0 . 1 3 0 0 1 4 0 0 . 1500 Temperature ( ° C . ) Figure 3« Surface Energy of Copper as a , F u n c t i o n - of Temperature^. I - 9 -So f a r there has not been any systematic phase equ i l i b r i u m study of the copper oxide-alumina ..systems* However, the l i q u i d u s of k. 57,58-36 Cu 20-Al 203 has been reported to follow the curve shown i n Figure k Copper oxides with A12G3 form two aluminates, Cu(A10 2) 2 and GuA10 2 Their c r y s t a l structures' have been determined, but not t h e i r s t a b i l i t y range s. D. Aim, of the Present Investigation The work of Baxter and others had.clearly suggested the influence of Cu 20 i n forming a strong bond with A l 2 0 3 . The superior strength of S .C .P.. materials produced by i n t e r n a l oxidation supported t h i s view.. The basic purpose of t h i s i n v e s t i g a t i o n was therefore to study the i n t e r f a c e r e a c t i o n and bonding between sapphire (;;£ single c r y s t a l alumina) and various copper a l l o y s by the s e s s i l e drop method and to • .investigate the fundamental r o l e played by oxygen i n these systems. I t was also e s s e n t i a l to study the phase diagrams f o r copper oxides and alumina i n order, to i n t e r p r e t r e s u l t s obtained i n the wetting•study. - 10 -I I . EXPERIMENTAL A. M a t e r i a l s Used f o r the S e s s i l e Drop Experiment 1. Aluminum Oxide S i n g l e c r y s t a l s of h i g h p u r i t y (99-99$ A 1 20 3) sapphire suppl ied by the Linde A i r Products L i m i t e d and A . M e l l o r and Company, Rhode I s l a n d , i n the form of rods and windows r e s p e c t i v e l y were used throughout the experiment. .The rods and a few of the windows were of c o n t r o l l e d and known o r i e n t a t i o n . In the hexagonal c lose packed s t ructure of sapphire (Figure 50 the oxide ions are very near ly i n a c lose hexagonal packing with the aluminum ions occupying the octahedral s i t e s . Due to the l e s s number of aluminum ions one t h i r d of the octahedral s i t e s remain vacant . The arrangement of the occupied and vacant s i t e s i s however ordered. Fig. 5 • Structure of A1203 showing two layers of large oxygen ions with hexagonal array of A l 3 + and vacant octahedral interstices. Slip directions and Burgers' vector b for basal plane slip are indicated, ( a f t e r Kingery^6) - 11 -The sapphire rods used f o r the work were O . 8 9 cm i n diameter wi th the rod ax is or ien ted at 6 0 =1- 5° t o the crystallographies ' c - a x i s . . Plaques, when cut perpendicular to the rod a x i s , provided a .working surface approximately p a r a l l e l to the ^ 1 0 1 2 ^ p l a n e . A few of the windows used had t h e i r working surfaces e i t h e r perpendicular or p a r a l l e l to the c r y s t a l l o g r a p h i c - Cr - a x i s . D i f f e r e n t l y or iented planes were used to i n v e s t i g a t e . t h e e f f e c t of o r i e n t a t i o n of the s o l i d on the contact a n g l e . < .The surface energy of s o l i d alumina i s known w i t h reasonable / 2 15 accuracy and has a value of 905 ergs/cm at l 8 5 0 ° C . with, the d Y =. dT - 0 . 1 e r g s / c m 2 / d e g . . Therefore at 1 2 3 0 ° C , Y . = 9 7 0 • e r g s / c m 2 . D V 2 . Copper, Cupr ic Oxide and Other A l l o y i n g Elements High p u r i t y copper ( 9 9 - 9 9 9 $ ) s u p p l i e d ; b y Johnson-Matthey and Company L i m i t e d i n the form of rods of 7 mm i n diameter and 15 cm long was used, f o r the experiments. The c u p r i c oxide powder used was reagent grade, s u p p l i e d by the General Chemical Company of New-York. S i l v e r i n the. form, of smal l bars was obtained from Cominco, .Canada, and. t i t a n i u m hydride was obtained from Metal Hydride Incorporated. The chemical analyses of these mater ia ls are given i n Table I . - 12 -Copper • TABLE. I . Chemical A n a l y s e s . o f the M a t e r i a l s Impurity ppm Pb 2 Fe 2 S i 2 Ag 2 Na 2 Cd l e s s than one Mg l e s s than one Tjtanium Hydride Element $ • T i 95 Zr 0 . 1 H 2 3 - 5 . N 2 0 . 2 Cu 0 . 0 5 Mg 0 . 0 5 A l 0 . 1 S i .0-1 C u p r i c . O x i d e Insoluble i n HC1 0 . 0 5 $ Carbon • Compounds (as. C ) 0 . 0 2 $ . c i " 0 . 0 0 5 $ S 0 4 0 . 0 3 $ N 0 . 0 0 2 $ ,. B. - M a t e r i a l s Used f o r the Phase Diagram Study For, the phase diagram study the same cupr ic oxide powder was used together w i t h ' L i n d e " B " high p u r i t y alumina abrasive powder (type O .O58, Lot No. 7O6). C . Apparatus for, the S e s s i l e • Drop; Experiment The apparatus, designed f o r s e s s i l e drop measurements by 39 kO previous workers was used w i t h very minor a l t e r a t i o n s and. i s shown i n Figures 6 and. 7. 1 . - Furnace The i n d u c t i o n u n i t used f o r the power • supply f o r heat ing was a . L e p e l (Model T-10-3) high frequency i n d u c t i o n generator . Heating was done through a water -cooled.copper c o i l f i t t i n g exac t ly the outer surface of the Vycor tube used as the vacuum.chamber. The dimensions of the susceptor and. the r a d i a t i o n shield were as f o l l o w s : : Length Diameter Thickness Susceptor 2.5 cm 1.7 cm O.O5O8 cm • R a d i a t i o n S h i e l d 10 cm 5 cm 0.0127 cm Temperatures were measured through a pyrex window at one end which was f i t t e d t o the elbow l e a d i n g t o the vacuum system, wi th a Hartmann and Brown d i s a p p e a r i n g - f i l a m e n t o p t i c a l pyrometer. The window kO absorpt ion c o r r e c t i o n f o r t h i s apparatus was found to be 23 C . E m i s s i v i t y c o r r e c t i o n s were not necessary. A l l the experimental runs were made at 1233 * 5°C and f o r a p e r i o d of 15 minutes. .2. .Vacuum- System • The pump used "was a Speedivac iiprcury d i f f u s i o n pump (Model 2M2A) . T h i s pump i n conjunct ion w i t h a mechanical fore pump, was able to produce a vacuum of 1 X 10" 5 mm.Hg i h a f a i r l y short time as.measured by a . W . R . C . i o n i z a t i o n gauge (type 507)• Figure 6 . Photographs of Apparatus 03 fl P cf-O O M l p. C+ 01 2 1 C o o i n g * To vacuum system OPTICAL SYSTEM (1) Ground (taaa or (*»ot o r n a t e p U U . (2) Vertical adjuataant KTW. (3} Horlsontal adjustaant track. (M Vocuulnr K m . (?) MJuatabla b*lt<M. (6) Ocular Una. (7) 0 b > c l l » » UM, ahuttar and trim dlapfcrw. (0) Vartical adjuataant acrav. vc (91 (10) ( u l H.Wr-eool.4 optical f lat . I h t a M t o M braaa f l t t lnf . Kafnatlc abutter. FURNACE ASSEMBLY Tjrcor tab*. Induction c e l l . Baattnf f U a M t , n d u t l o n abUld anj «paclaan. Ionization ftuaja. d u lnlat central. .8) Ylaalm •lndo*. 91 B n n f l t t lnf* . [3D) Optical ifrOMt«r . [21) Llfbt aourca lntarcbanfaabla »l tb pyrr—tar . vn i - 16 -3 - O p t i c a l System The image of the copper but ton-on. the alumina plaque could.be pro jec ted-on a ground glass screen and focuss ing could be done by a d j u s t i n g the s l i d i n g b e l l o w s . . For t h i s purpose a beam of l i g h t was focussed on the drop through the same window used f o r t h e pyrometer. However, t h i s a d d i t i o n a l l i g h t source was unnecessary f o r photographing .the mOlten drop because of i t s own incandescence. The specimen dis tance .from, the camera.lens could be e a s i l y adjusted to give s u i t a b l e m a g n i f i c a -t i o n t o the s e s s i l e drop image. .Because of the extremely r a p i d change of the contact angle wi th time a P o l a r o i d : Land camera wi th u l t r a , h i g h speed s e l f - d e v e l o p i n g f i l m (3000 -ASA e q u i v a l e n t , Type k^) w a s employed to take p i c t u r e s i n quick success ion . -An exposure v a l u e , of l / 5 0 second at f.64 was used. . .Since the developing time necessary was 10 seconds, a.sequence of 5 , 1 0 , 2 0 seconds, 1 minute 15 seconds, 2 minutes 15 seconds, 5 minutes 10.minutes and 15 minutes was chosen. With . the help, of var ious screw-thread and s l i d i n g arrangements the apparatus could.be e a s i l y a l i g n e d and l e v e l l e d . • D. Apparatus f o r the Phase Diagram Study A Leco carborundum r e s i s t o r furnace and a . v e r t i c a l res is tance furnace of r e c r y s t a l l i z e d alumina tube wound with molybdenum.ribbon were u s e d . f o r f i r i n g the compacted powder specimens i n the phase diagram study. . F i g u r e 8 shows a schematic diagram of the v e r t i c a l furnace . A continuous stream of cracked ammonia was^maintained through the i n s u l a t i o n (A]_^)Jfalumina powder) t o p r o t e c t the molybdenum ribbon from o x i d a t i o n . Water-cooled copper c o i l s at both ends of the tube were f i t t e d to copper - 17 -bellows t o a l l o w , f o r expansion and a l s o . t o act as a . s e a l f o r hydrogen. - A.platinum-rhodium, thermocouple i n s i d e the furnace was used f o r automatic,temperature c o n t r o l . An a d d i t i o n a l thermocouple was used with a potentiometer f o r accurate measurements, of the temperature of the specimen. •E . •Specimen Prepara t ion • 1 . Sapphire Discs Discs of roughly O.h cm t h i c k were cut from the sapphire rod , p e r p e n d i c u l a r t o i t s own.axis , w i t h a . F e l k e r " D i - M e t " diamond t i p p e d wheel saw. • For convenience i n c u t t i n g the. r o d w a s , f i r s t mounted.in p l a s t e r of p a r i s . The cut alumina, d i s c s were mounted.in Luei te and. given a p r e l i m i n a r y rough p o l i s h on a. r e v o l v i n g cast i r o n d i s c us ing coarse carborundum powder kl i n water suspension. P o l i s h i n g was then done on a v i b r a t o r y p o l i s h e r r Platinum Wire Insulator•' / Fig. 8. SCHEMATIC DIAGRAM OF FURNACE 5 - 18 -s u p p l i e d , b y the Syntron Company. The base of the p o l i s h e d bowl consis ted of a h e a v i l y etched copper d i s c . The. specimens were gripped- i n , heavy brass mounts and l e f t i n a kerosene-suspended f i n e carborundum powder f o r 2k hours at a c r i t i c a l adjustment of the v i b r a t i o n a l frequency. -The specimens were hand p o l i s h e d with 1 Ja and l/k yx diamond paste smeared on s i l k c l o t h over a;.glass p l a t e . The e f f e c t of even minor surface.roughness .on the contact a n g l e 2 demanded a very good surface f i n i s h on the alumina d i s c s . The p o l i s h e d d i s c s were washed i n concentrated^ HNO3, r i n s e d w i t h water, carbon t e t r a c h l o r i d e and a l c o h o l j u s t before use . 2 . -Copper Buttons . The ..high p u r i t y copper rod was i n i t i a l l y machined down to 0 . 3 2 cm i n diameter and cut i n t o d i s c s . o f equal thickness wi th a j e w e l l e r ' s saw. Smal l c a v i t i e s were then d r i l l e d - i n t o . t h e specimen.to h o l d a l l o y i n g m a t e r i a l s . The bottom surface was p o l i s h e d . t o give maximum contact w i t h the alumina s u r f a c e . Before use, these buttons were r i n s e d w i t h 50$ HNO3 t o remove surface contamination, washed with water and a l c o h o l and d r i e d immediately w i t h a b l a s t of c o l d a i r . F . Prepara t ion of Specimens f o r the Phase Diagram Study The c u p r i c and aluminum oxide powders were weighed:.!, i n the required p r o p o r t i o n s and ground together i n a l c o h o l i n an agate mortar . The powder mixture was then d r i e d and compacted i n a c y l i n d r i c a l d ie of 1 .3 cm diameter , at a pressure of 2 0 T p i i n a h y d r a u l i c p r e s s . For the determinat ion of the l i q u i d u s l i n e , t h e buttons were p r e f i r e d at 1000°C f o r 5 hours , powdered and made i n t o cones u s i n g as a b inder 10$ p o l y v i n y l a l c o h o l suppl ied .by . the Shawinigan Chemical Company under the name " G e l v a t o l " . - x9 -G. Experimental Procedure 1. S e s s i l e Drop Experiments ..The specimens were weighed to 0 . 1 mg with the required-amount of a l l o y i n g mater ia ls i n i t s c a v i t y . The sapphire d i s c was p l a c e d on Lhe p l a t f o r m i n s i d e the susceptor and the copper button placed at the center, of the d i s c . (Figure 9 . ) . The susceptor was then p o s i t i o n e d , i n s i d e the Vycor tube. The whole furnace was c a r e f u l l y l e v e l l e d to prevent the copper button from s l i d i n g o f f the sapphire d i s c because of the s l i g h t v i b r a t i o n of the tube caused by water c i r c u l a t i o n i n the c o a l i n g c o i l . The furnace tube was pumped-down t o a pressure of 1 ji of Hg •before s t a r t i n g the mercury d i f f u s i o n pump, which subsequently took about 10 minutes to b r i n g . t h e vacuum down to I X 1 0 ~ 5 mm of Hg. The temperature was s lowly increased i n stages t o 1230 C ± 5°C. The time f r o m . i n i t i a t i o n to completion of mel t ing was found to be k seconds. • Using a t i m e r , p i c t u r e s of• the drop were taken i n the sequence noted above. The drop dimensions were measured.fromthe photographs as w e l l as from the p r o j e c t e d image . f o r contact angle and surface t e n s i o n , c a l c u l a t i o n s . 2 . Phase Diagram Experiments . T h e pressed compacts i n r e c r y s t a l l i z e d alumina c r u c i b l e s were f i r e d twice f o r 12 hours at each temperature, and a i r quenched. They were then used f o r metal lographic and x - ray d i f f r a c t i o n study. The f o l l o w i n g procedure was used f o r the determination of the l i q u i d u s l i n e . Cones prepared from the p r e f i r e d mater ia ls were mounted on the base of an alumina c r u c i b l e which was. then lowered i n t o the furnace wi th plat inum w i r e s . - 20 -Figure 9- Sample Specimens and Susceptor Assembly (Sapphire rod, Sapphire d i s c mounted f o r the v i b r a t i o n p o l i s h e r , polished samples, susceptor and r a d i a t i o n shield.) 21 -The temperature of the furnace was r a i s e d g r a d u a l l y u n t i l the t i p of the cones bent and tloudhed the base. Since i t was not p o s s i b l e t o reach a temperature of more than l650°C i n t h i s furnace , the liq.uid.us beyond 20$ AI2 .O3 could not be reached. • 3 . - X-Ray D i f f r a c t i o n The copper drpp adhering to the A1 20 3 plaque was . t reated with concentrated-'HNO3 u n t i l just a t h i n l a y e r at the i n t e r f a c e was l e f t . In some cases the drops were cut o f f . The i n t e r f a c e . m a t e r i a l was scraped o f f w i t h a diamond needle or sapphire r o d . The powdered m a t e r i a l thus obtained was used . t o determine the ... Debye-Scherrer powder p a t t e r n . The alumina d i s c s , a f t e r removal of the. metal drops, were put d i r e c t l y i n the d i f f r a c t o m e t e r f o r surface l a y e r i d e n t i f i c a t i o n . ' The same method was fol lowed f o r the i d e n t i f i c a t i o n of the phases i n the f i r e d buttons prepared from, mixtures of CuO and A1 20 3. h. M e t a l l o g r a p h i c . O b s e r v a t i o n The copper drop, on the alumina, d i s c was sect ioned v e r t i c a l l y through the center , mounted, p o l i s h e d and the i n t e r f a c e examined micro-s c o p i c a l l y a f t e r d i s s o l v i n g the metal components w i t h HN0 3 . In a l l cases representat ive photographs were taken. The f i r e d powder compacts were p o l i s h e d and examined m i c r o s c o p i c a l l y . - 22 -I I I . EXPERIMENTAL:RESULTS AND CALCULATIONS A. S e s s i l e Drop Experiment Results 1. Sapphire-Copper System The required, dimensions of the s e s s i l e drops (x, x 1 , z, z 1 i n Figure 2) were measured:on the photographs taken at d e f i n i t e i n t e r v a l s of time a f t e r complete m e l t i n g . • Results are tabula ted i n Appendix IV. •The surface t e n s i o n ( ^^ y) of pure copper and i t s contact angle on p o l i s h e d 22 sapphire were determined u s i n g the Bashforth and Adams method (Appendix I I I ) . The e q u i l i b r i u m contact angle was 1 6 3 ° The ft ^  f ° r pure copper was found t o be 1172 e r g s / c m 2 . -Taking . the surface energy of s o l i d alumina ( ^gy) a s 9 7 ° ergs/cm at 1230°C , the i n t e r f a c i a l energy (0 gjO between / 2 copper and alumina was c a l c u l a t e d to be 2129. ergs/cm . This value compares 2 5 f a v o r a b l y w i t h the value of 22^5 ergs/cm obtained by Kingery and A l l e n . . 2 . • Sapphire -^Copper-Silver System Measurements were made w i t h 5$- and 2 8 . 2 $ ( eutec t i c composition) of s i l v e r i n copper ( r e s u l t s i n Appendix . I V ) . The a d d i t i o n of s i l v e r , to copper d i d not i n f l u e n c e s i g n i f i c a n t l y the contact a n g l e . This i s i n conformity w i t h a . s t u d y by B a x t e r - ^ w h o found that very l i t t l e bonding was developed i n s i m i l a r systems i n the absence of oxygen. 3 . •  Sapphire -Copper-Titanium- System 5$ t i t a n i u m was added t o copper. Although there was some e f f e c t , f u r t h e r work was discontinued, as the e f f e c t of oxygen was taken as the major f i e l d of i n v e s t i g a t i o n . Resul ts are given in\Appendix ' IV . - 23 -k. Sapphire-Copper-Oxygen System • Oxygen was added t o the system i n the form of c u p r i c oxide . The a d d i t i o n of even 1$ c u p r i c oxide reduced the contact angle to about 93° from 1 6 3 ° . With f u r t h e r a d d i t i o n s the r e s u l t a n t angles were a l l acute , and thus "VLV c o u 1 ^ not-be c a l c u l a t e d u s i n g , t h e Bashforth method. The contact angle 9 was then determined from the r e l a t i o n s h i p 0 = 2 t a n - 1 . Z X (Appendix I I I ) . •Varia t ion of the contact angle 9 wi th oxide a d d i t i o n s i s shown i n Figure 1 0 . The e q u i l i b r i u m contact angle of 1 6 3 ° f o r pure copper was reduced to 2 1 ° by a d d i t i o n of 72$ CuO (percentage of copper metal by weight ) . Further a d d i t i o n of CuO was not p o s s i b l e s ince the c a v i t y was l i m i t e d i n s i z e and the r e a c t i o n v i o l e n t i n . nature . The e f f e c t of oxygen i s i l l u s t r a t e d i n the s e s s i l e drop photographs, i n F igure 1 1 . •For the a d d i t i o n of major amounts of copper oxide, the e f f e c t of s i z e of the s e s s i l e drop was evaluated . This was done by use of drops of three times the s i z e normally used. The corresponding s e s s i l e drops were f l a t t e n e d and the shape d i d not correspond to the segment of a sphere. A p p l i c a t i o n of the. u s u a l geometric r e l a t i o n s h i p s gave low. values of B, For t h i s reason, the volume of the specimens was kept very n e a r l y constant 17 throughout the s e r i e s . I t was found by K e l l o g g 1 that r e s u l t s w i t h minimum e r r o r could be obtained w i t h an X / Z ;.ratio.i:'of , 1 .8k. The v a r i a t i o n of 9-with, time f o r a l l concentrat ions of oxide i s shown i n Figure 1 2 . I t i s apparent, from these data that the e q u i l i b r i u m contact angle was reached w i t h i n about 5 seconds a f t e r complete m e l t i n g , and the time taken t o reach that angle was almost independent of the oxide CD H O O s d-P> o d-p 0 0 o , c+ o o O X > M-<+ H-o 0 10 20 30 40 WEIGHT % CuO ADDED 50 60 70 i ro Pure Copper b . Copper with 1$ CuO. F l a t drop: showing s i z e e f f e c t Copper with 5$ CuO Drop h a l f molten Copper with 5$ CuO Drop f u l l molten Figure 11*1. S e s s i l e Drop Photographs e. Copper with 1$ CuO f . Copper with 10$ CuO 27 -•o-§ ' • 8-o. 8 J I L Q JO. • o -A / — O -0 — / V — O -• O — A / — Q -O - w — O -Q — A c — O -W — o -A / — O A/ — O • J L 1 0 20 40 60 80 100 120 TIME IN SECONDS, AFTER COMPLETE MELTING. 600 Fig.32. Contact angle as a function of time. - 2 8 -concentra t ion . Resul ts are tabulated i n Appendix IV. Because of t h i s v i r t u a l l y instantaneous attainment of e q u i l i b r i u m , i t was not p o s s i b l e t o f o l l o w the i n i t i a l r e a c t i o n r a t e . When sapphire c r y s t a l s with d i f f e r e n t o r i e n t a t i o n s were used, keeping a l l other experimental condi t ions i d e n t i c a l the v a r i a t i o n of the contact angles.was found to be w i t h i n ± 2 ° , which could be due t o experimental e r r o r . The a c t u a l oxygen content of the drop at the end of each run was measured. . This was done by determination of the l o s s i n weight on reducing- the specimen i n hydrogen f o r kQ hours at rJOO°C. A graph of the recovery of oxygen v s . . oxygen added i s shown i n Figure 13. A separate experiment was conducted t o s tudy. the i n t e r f a c i a l r e a c t i o n between Cu and AI2O3 i n a i r . Under these c o n d i t i o n s , the copper o x i d i z e d and complete wett ing was- obtained. Baxter has reached the same c o n c l u s i o n . B. Photomiorographic Study The s o l i d i f i e d drop attached t o the sapphire c r y s t a l was t rea ted with concentrated n i t r i c a c i d to remove the metal l a y e r completely . - A f t e r removal of the metal a t h i n l a y e r of a grey c r y s t a l l i n e phase was found adhering t o the i n t e r f a c e and t h i s could not be removed by f u r t h e r a c i d treatment. Under the microscope t h i s phase appeared as w e l l developed n e e d l e - l i k e c r y s t a l s growing i n a r a d i a l d i r e c t i o n . f r o m the drop per iphery towards the center (Figure ika,.). I n . one specimen a . smal l bubble was trapped at the. i n t e r f a c e . The needles were found t o be more pronounced around i t , growing i n a r a d i a l d i r e c t i o n away from i t s p e r i p h e r y (Figure lkb a n d - l k c ) . A v e r t i c a l s e c t i o n through the drop and the sapphire c r y s t a l showed .a t h i n i n t e r f a c i a l l a y e r of a . d i f f e r e n t m a t e r i a l i r r e g u l a r l y p e n e t r a t i n g i n t o both the metal and the ceramic phases (Figure l k d . . and i k e ) . - 29 -O 2L\ I L _ ! i L i _ J i l i l i 1 0 l 2 3 k 5 6 7 Weight $ Oxygen Added Figure 13. Oxygen Recovered versus Oxygen Added a. R a d i a l growth of needles X800 b . Needles around the a i r bubble X 8 0 0 e. Same as " d " X1100 Figure lk. Photomicrographs, of the Interface - 3 1 -- C . X-Ray Study Debye-Scherrer powder pat terns were taken of the m a t e r i a l obtained from the scraped i n t e r f a c i a l l a y e r . The l i n e s i n the x - ray d i f f r a c t i o n p a t t e r n produced d-values which completely, corresponded with those of e < - A l 2 0 3 and GuA10 2.. The r e s u l t s are i n c l u d e d ' i n Appendix V I I . •After the removal of the m e t a l l i c part of the drop, the i n t e r -f a c i a l l a y e r was a l s o scanned i n a x - r a y d i f f r a c t o m e t e r . . The r e s u l t i n g graph (Figure 15) showed f o u r peaks. Three of these peaks corresponded e x a c t l y t o the r e f l e c t i n g planes of 003,,'006 a n d - 009 of CuA10 2 and the f o u r t h to the 123^ plane of o < - A l 2 0 3 . •D'. Phase Diagram Experiment Results The r e s u l t s obtained from.the s e s s i l e drop experiments i n d i c a t e d that a . s t u d y of the phase r e l a t i o n s h i p between copper oxide andcx* -Al 2 0 3 was necessary. Compacts of about 5 gm i n weight made from the w e l l blended const i tuent oxides (CuO and A 1 2 0 3 ) wi th proport ions ranging from 2 to 70$ A 1 2 0 3 separately f i r e d : a f t e m p e r a t u r e s from 6 0 0 ° C - t o I l 6 5 0 ° C . They were r e f i n e d and. then a i r quenched from the respect ive temperatures. These specimens were used f o r X - r a y and microscopic study t o i d e n t i f y the phases. Copper oxide and A 1 2 0 3 were found t o form two d i f f e r e n t aluminates C u ( A 1 0 2 ) 2 and CuA10 2 . Both.these compounds have d i f f e r e n t temperature ranges of s t a b i l i t y . The compound C u ( A 1 0 2 ) 2 was found t o be formed at about 800°C presumably, by the s o l i d state r e a c t i o n , as no l i q u i d was encountered at t h i s temperature. •This phase was s t a b l e . u p to a .maximum, temperature of 1 0 0 0 ° C , where i t was converted i n t o CuA10 2 , which was found to', be s table up to about , 1 2 5 0 °C . \ - 32 -Figure 15. D i f f r a c t o m e t r i c Graph of the Interface - 33 -- For the mel t ing point determination the cone f u s i o n method was •k-2 employed. The advantages of t h i s method as used by Ibrahim and Br ight over the quenching method developed by the Geophysical Laboratory , Washington D.C . , are that quenching from high.temperature i s experimental ly d i f f i c u l t and. from low. temperature g e n e r a l l y r e s u l t s i n d e v i t r i f i c a t i o n of the melt . Cones prepared according to the procedures a l ready given were used t o determine. the l i q u i d u s . The temperatures of complete bending of the cones were taken as the melt ing p o i n t f o r the respect ive composi t ion. Due t o the very high mel t ing temperature, of compositions r i c h i n alumina, i t was not p o s s i b l e to determine the mel t ing p o i n t of mixtures having more than 20$ of AI2O3 . The experimental observations are given i n a t a b u l a r form i n d i c a t i n g the composit ion, phases present at d i f f e r e n t temperatures and. the l i q u i d u s temperatures up t o 20$ A l 203 i n Appendix-V. The phase diagram i s shown i n Figure .16. A very gradual change i n the microstructure of the compacts was observed over the whole heating rangej From about 800°C to 1000°C i t was ' found from.the X - r a y data that the compound C u ( A 1 0 2 ) 2 w a s present and the powder compacts looked.reddish .brown i n c o l o u r . The s t ruc ture was changed s i g n i f i c a n t l y at 1000°C w i t h i n c i p i e n t formation of a granular s t ruc ture as shown i n Figure 17-1. This was changed on f u r t h e r heat ing at higher temperatures i n t o completely w e l l d e f i n e d needles as shown i n stages i n . F igures 17-Ib. and 17^IId. I t was found however, that there was an optimum composition between 30 to 35$ o f A l 2 0 3 f o r the best development of these needles . A c a r e f u l observat ion o f the needlesshowed that they were not s i n g l e phase. At higher m a g n i f i c a t i o n d i s c o n t i n u i t i e s were e a s i l y d i scer nable and i n dark f i e l d i l l u m i n a t i o n more than one phase could be seen as shown i n Figure 1 7 - I I f . 1800 • _ Liquid 1600 — % • • • • • • — 1400 / Liquid + A l 2 0 3 Liquid+oT , • • • . • _ Cu 2 0 / ' . • • •*/• • / • • • ( C ' " 1200 jl • 9 • • • Jflo Liquid+#Cu A I0 2 * • • • • • • • -1000 >••••• I I 65°C • Cu-O+CuAIOj," * CuAIO, + . A , 2 ° 3 • l l 1 • • — • —A ct z> r -< £ cu 2 o Ii 900 UJ H 800 CuAI0 2 i • A l 2 0 3 • CuO + Cu(AI0 2 ) 2 • I I I CutAIOggfAlgOj • 700 - . . 6 0 0 l i i i CuO+ A l 2 0 3 • • • 0 20 40 60 CuO Wt. % A l 2 0 3 80 100 A l 2 0 3 F i g u r e .16 . Phase diagram of C u O - A l 20 3 and C u 2 0 - A l 2 0 3 b . F i r e d at 1100°C c. F i r e d at 1200°C X 8 0 0 X 8 0 0 Figure 1 7 - 1 . Photomicrographs of Phase Diagram Specimens f . Only Needles X 1100 IV. -.DISCUSSION •A. S i g n i f i c a n c e of A l l o y i n g 1. Sapphire - C o p p e r ^ S i l v e r System A d d i t i o n of s i l v e r t o copper r e s u l t e d i n a s l i g h t decrease i n the contact angle i n comparison w i t h the pure copper-sapphire system. - For copper and s i l v e r w i t h sapphire the % values were found by Kingery to be 22^5 and 1770 e rgs /cm 2 r e s p e c t i v e l y . The ^ values of copper-^silver a l l o y s were SL lower than those values p r e d i c t e d by the l i n e a r mixture law. This could be due t o the minor i m p u r i t i e s i n the s i l v e r (99-9$) o r t o the adsorpt ion of s i l v e r at the i n t e r f a c e . 2. Sapphire-Copper-Cupric Oxide-Ti tanium System 39b Previous work i n s i m i l a r systems showed: that t i t a n i u m adsorbed at the alumina-metal i n t e r f a c e to f o r m , T i 2 0 3 . This r e s u l t e d i n reduct ion of t h e • i n t e r f a c i a l t e n s i o n i n the N i - T i - A l 2 0 3 system. In t h i s case a l s o i t was found, that the a d d i t i o n of 5$ T i reduced, the l i q u i d - s o l i d i n t e r f a c i a l energy from 2129 t o 1700ergs / cm 2 . 3- Sapphire-Copper-Oxygen-System a) Recovery of Oxygen -Oxygen was added t o the copper metal i n the f o r m . o f C u O . Since the l a t t e r i s . u n s t a b l e at the experimental temperature (1230° ) , . loss of oxygen may be expected to occur during heating a n d . d u r i n g , t h e p e r i o d of observat ion at temperature. The f o l l o w i n g reac t ions may occur : . C u O + C u — - i . C u 2 0 (1) CuO s. l/2 Cu 2 0- + l/h 0 2 (2) CuO v Cu + 1/2 0 2 (3) C u 2 0 i. 2Cu + l/2 0 2 (k) - 38 -Under standard c o n d i t i o n s , r e a c t i o n (1) i s favored : thermo-dynamically over the other three at t h i s temperature. However, under reduced pressure , , the f ree energy changes f o r ( 2 ) , ( 3 ) and ( 4 ) become considerably more n e g a t i v e . • A l s o , under t h e « ^ x p § r ' i m e n t a l condi t ions used, the a c t i v i t y of CU2O was decreased by r e a c t i o n w i t h AI2O3 to form the compound CuA10 2 which would favour r e a c t i o n s . ( 1 ) and ( 2 ) . Although •nominally, the system was at 1 0 ~ 7 - 10~ 8-atmospheres t o t a l pressure , i t i s probable that c o n s i d e r a b l y h i g h e r oxygen pressures e x i s t e d i n the immediate v i c i n i t y of the s e s s i l e drop, at l e a s t d u r i n g the i n i t i a l stages of r e a c t i o n . As a r e s u l t , the a c t u a l p r o p o r t i o n of oxygen l o s t from: the system would be governed t o a . c o n s i d e r a b l e extent by k i n e t i c phenomena and could not be p r e d i c t e d .on thermodynamic grounds. E x p e r i m e n t a l l y , i t was observed. (Figure 13) t h a t , . o v e r the e n t i r e range of oxygen a d d i t i o n s , the r a t i o of oxygen remaining i n the system to that a d d e d . o r i g i n a l l y was remarkably constant at 0 . 6 . T h i s i n d i c a t e s the r e p r o d u c i b i l i t y of the experimental procedure and suggests that r e a c t i o n ( 2 ) may predominate under the condi t ions used. b) Formation of CuA10 2 < As. a l ready noted> CUAIO2 was found to be present at the copper-alumina., i n t e r f a c e f o r ' a l l a d d i t i o n s of oxygen. The phase diagram of the Cu 20-rAl203 system constructed I n t h i s i n v e s t i g a t i o n (Figure 16) i n d i c a t e s c l e a r l y • t h a t , at the experimental temperature, l i q u i d Cu 2 0 w i l l d i s s o l v e A 1 2 0 3 t o form a s o l u t i o n of CuA10 2 i n G u 2 0 . Whether or not- s a t u r a t i o n w i t h subsequent p r e c i p i t a t i o n of CuA10 2 i s , r e a c h e d at temperature depends on the rate of t h i s c o r r o s i o n r e a c t i o n . --39 -However, from the phase diagram of the copper-oxygen system. (Figure 18) i t i s apparent t h a t , under e q u i l i b r i u m c o n d i t i o n s , a , l i q u i d Cu 2 0 phase should not separate u n t i l the l i q u i d copper contains about 2 weight per cent oxygen. The f a c t that CuA10 2 was formed even at the lowest oxygen a d d i t i o n (0.18$ oxygen) suggests e i t h e r that the a c t i v i t y , of oxygen • i n copper i s s u f f i c i e n t l y h i g h at t h i s concentra t ion t o permit the. formation of CuA10 2 at the i n t e r f a c e or that' the C u 2 0 formed by decomposition of the CuO a d d i t i o n had not" completely d i s s o l v e d i n the. copper -metal. Since the • compound CuA10 2 decomposes at I260°C, • the standard f ree energy of formation at 1230°C must be s m a l l . I t may therefore be i n f e r r e d that an e q u i l i b r i u m s o l u t i o n of oxygen-in copper was probably not achieved- i n the i n i t i a l stages of the r e a c t i o n . 1400 1200 1083' 1000 800 600 400 200, Atomic Percentage Oxygen 10 20 30 40 50 L,i 1 SJ3J I20C - i i-y G + Lt +Lo 6 + -fo39 1065* IO£ IIIO' 0f5*— a+L, -a -y y + y~ +--G— o ifi a + 7y • -2200 1800 1400 1000 600 Weight Percentage Oxygen Figure 18. Copper-Oxygen System ^ 3 - ko -c). L i q u i d - S o l i d I n t e r f a c i a l Energy ' In s e s s i l e drop experiments, measurement of the contact angle permits c a l c u l a t i o n of the l i q u i d - s o l i d i n t e r f a c i a l energy through the ^ 20 21 Young-Dupre equation ' (page 3) provided a n d "jfgy a r e k n ° w n . In . the present case i t was .poss ible to measure ^ ^y from the drop shape only f o r . t h e lowest oxygen a d d i t i o n (1$ CuO). This showed that the surface t e n s i o n of l i q u i d copper had changed from 1172 dynes/cm. f o r no oxide a d d i t i o n t o 1022 dyaes/cm f o r 1$.CuO. •The change of 13$ i s w i t h i n the s t a t i s t i c a l s c a t t e r observed f o r s i m i l a r measurements.in.the Fe-MgO s y s t e m ^ 9 , and. i s therefore not considered to represent a s i g n i f i c a n t change. Provided, the system.has been p e r m i t t e d . t o come to e q u i l i b r i u m i n each case the f i n a l value of K^ y should' not change . throughout the s e r i e s . of oxide a d d i t i o n s o r , i n other words, the f i n a l concentrat ion of oxygen i n the drop should remain unchanged. The t e r m i n a l oxygen p a r t i a l p r e s s u r e , i n the v i c i n i t y of the drop, w i l l be determined, b y the CuA10 2 saturated s o l u t i o n at the i n t e r f a c e and, i n the whole system, by leak r a t e s , o r by the molybdenum '• susceptor . T h i s undoubtedly represents a..steady state c o n d i t i o n not a t rue e q u i l i b r i u m . . O b v i o u s l y , , the conclusion as to constancy of f i n a l ^ .^y values w i l l not be v a l i d - i f surface a c t i v e i m p u r i t i e s other than oxygen are i n t r o d u c e d - w i t h the CuO a d d i t i o n . The l i q u i d - s o l i d i n t e r f a c i a l energy was c a l c u l a t e d f o r each of-the oxide a d d i t i o n s , assuming Y^y t 0 be 1022 dynes/cm and $ s y , 970 e rgs /cm 2 at 1230°C. These are p l o t t e d i n Figure 19 as a f u n c t i o n of the: logar i thm of the weight per cent oxygen (measured value) present i n the copper drop. •Figure 19. The I n t e r f a c i a l Energy as a Funct ion of Oxygen Present . - 42 -The p l o t resembles i n form the Gibbs> adsorpt ion equat ion. However, i t i s important to recognize that the l a t t e r i s not a p p l i c a b l e i n the present case, although i t has been used by others f o r s i m i l a r s t u d i e s " ^ . The apparent adherence to t h i s f u n c t i o n may be f o r t u i t o u s , .and serves, t o i n d i c a t e that erroneous conclusions can be drawn u n l e s s . t h e condi t ions on which the G i b b s ' equation i s based are f u l f i l l e d i n the o r i g i n a l experiment. d) Spreading '\i£. j. •.... From a p r a c t i c a l point of view, i t i s important t o consider the q u a n t i t a t i v e r e l a t i o n s h i p between the increase i n spreading and the amount of oxygen present i n the system. I f i t i s assumed that spreading i s due predominantly to the format ion of l i q u i d Cu 20 at the i n t e r f a c e , then"a d i r e c t r e l a t i o n s h i p would be expected between x (x^—:basal radius of the drop) and the amount of oxygen present i n the system f o r a f i x e d drop s i z e . However, experimental l i q u i d - s o l i d i n t e r f a c e areas were not as large as p r e d i c t e d by t h i s p a r a b o l i c r e l a t i o n s h i p . • E m p e r i c a l l y , i t was found that the experimental r e s u l t s obeyed a power law of the form: x ' 4 = Constant X amount of oxygen present (as shown i n Figure 20) . .. This discrepancy may be due t o d e p l e t i o n of Cu 20 by r e a c t i o n with AI2O3 at the i n t e r f a c e , which occured simultaneously w i t h spreading . A l t e r n a t i v e l y , the p a r a b o l i c r e l a t i o n s h i p i s an o v e r s i m p l i f i c a t i o n because i t neglects the increase of l i q u i d - v a p o r i n t e r f a c e area accompanying the spreading. - ^3 -0.5 1.0 1.5 2,0 2.5 3.0 Amount of Oxygen Present (weight $>) Figure 20. Fourth Power of Basal Radius as a Funct ion of Oxygen present i n the Drop - .kk -B. Phase Diagram D i s c u s s i o n To construct a phase diagram i n v o l v i n g copper oxides and alumina one should i n v e s t i g a t e the te rnary system C u O ^ C u 2 0 - A l 203 under d i f f e r e n t p a r t i a l oxygen p r e s s u r e s . . For the sake of s i m p l i c i t y and without the involvement of elaborate experimental procedures however, two phase diagrams can be constructed e x c l u d i n g . t h e range of temperature i n which both CuO and C u 2 0 coexis t i n a i r . I t was found i n the present i n v e s t i g a t i o n and a l s o reported by other workers that CuO and C u 2 0 coexis ted w i t h i n therange of 9 0 0 - 1 0 5 0 ° C - The phase diagram of CuO-Cu 2 0 reveals a e u t e c t i c at 0.k2 mole f r a c t i o n of Cu^O mel t ing at 1080°C and below t h i s temperature both oxides can e x i s t i n a i r . But i t has been reported, that CuO becomes unstable above 900°C and d i s s o c i a t e s at a very, fas t rate to form C u 2 0 and oxygen between 1 0 0 0 - 1 1 0 0 ° C . The k i n e t i c parameter c o n t r o l l i n g , t h i s d i s s o c i a t i o n process makes the coexistence of CuO and C u 2 0 p o s s i b l e between these temperatures. In v i e w . o f t h i s , , the phase diagram was s p l i t i n t o two par ts omit t ing the temperature r e g i o n of 9 0 0 - 1 0 0 0 ° C . , . a l t h o u g h : t r a c e amounts of CuO were detected up t o 1050°C and s i m i l a r l y , . t race amounts of G u 2 0 were found t o be present even at 9 0 0 ° C . The r e s u l t s are given i n Appendix V . Another d i f f i c u l t y one encounters i n c o n s t r u c t i n g a phase diagram i n v o l v i n g phases, none of which has g lass network-forming a b i l i t y , i s the absence of any g l a s s y phase i n the quenched melt which can be used f o r i n v e s t i g a t i o n at room temperature . . U s u a l l y i n a l l these cases the quenched product ended as the const i tuent c r y s t a l l i n e phases at room temperature. I t was always necessary to e x t r a p o l a t e . f r o m the study of the l i q u i d u s curve t o a s c e r t a i n the existence of one or more l i q u i d phases at h i g h temperature. - k 5 -Compositions having more than 20$ of A 1 2 0 3 i n the mixture were f i r e d at d i f f e r e n t temperatures from:1250°C t o l650°C. Although i n t h i s way the l i q u i d u s curve c o u l d be e s t a b l i s h e d the quenched product was f o u n d . t o be a simple mixture of C u 2 0 and AI2O3 as .expected . (due t o the non-glass• forming, character of the mix ture ) . The x - ray powder pat terns obtained i n a l l these cases showed only the C u 2 0 and A 1 2 0 3 l i n e s . There were s l i g h t •l ine s h i f t s and changes i n the r e l a t i v e i n t e n s i t i e s p a r t i c u l a r l y w i t h the p<-alumina.lines. However, the e f f e c t was not consis tent and very i n s i g n i - ' f i c a n t . I t ' c o u l d be assumed with some c e r t a i n t y that at these h i g h temperatures there was d e f i n i t e l y a g l a s s y l i q u i d phase which u l t i m a t e l y was d i s s o c i a t e d on cool ing : t o the const i tuent , components. • S i m i l a r behaviour has been observed kk by other workers who constructed phase diagrams w i t h components having no g lassy forming a b i l i t y . The micros t ructures of these powder compacts f i r e d at high-temperatures showed a. w e l l - d e f i n e d n e e d l e - l i k e s t r u c t u r e . . I t was found that i n a d d i t i o n , to the matr ix , c e r t a i n par ts of the needles were at tacked with d i l u t e HN0 3 (see Figure l 6 l l ) . This i n d i c a t e d that the needles were aggregates of both ^<-AI2O3 and C u 2 0 , formed by p r e c i p i t a t i o n and agglomeration of the C K . - A I 2 O 3 wi th C u 2 0 during' the c o o l i n g - p r o c e s s . The needle-shaped s t r u c t u r e s . o b t a i n e d i n t h i s case were a l s o obtained k^ -by Baumann ^ and others i n the Mg0^Al 203 and M n 0 - A l 2 0 3 systems. They found that the needles were oc. - A I 2 O 3 c r y s t a l s and concluded t h a t , when heated beyond the s t a b i l i t y temperature of t h e magnesium .or manganese aluminates , the oi.-A.l2O3 c r y s t a l s were exsolved.along, the c r y s t a l l o g r a p h i c d i r e c t i o n of the s p i n e l s and. thus the p r e c i p i t a t e d alumina had the appearance of a c i c u l a r c r y s t a l s . In a d d i t i o n , as i n d i c a t e d i n the phase diagram both the aluminates Cu(A10 2 )2 and CuA10 2 were formed by the s o l i d state r e a c t i o n * -M6 -•1. CuO + A 1 2 0 3 > C u ( A 1 0 2 ) 2 2. C u 2 0 + A 1 2 0 3 i 2CuA10 2 The exact e u t e c t i c composition i n the C u 2 0 - A l 2 0 3 system, was d i f f i c u l t t o determine by the cone f u s i o n method, because of the very viscous•nature of the l i q u i d product at the melting, temperatures. . However, . the e u t e c t i c composition was•found, t o be about .5$ of ^K. - A 1 2 0 3 ' i n . t h e C u 2 0 - A l 2 0 3 mixture .•'WithJ..ithe^.existing.equipm'ent i t was only p o s s i b l e t o determine the l i q u i d u s temperature up t o l 6 5 0 ° C , i . e . at a composition c o n t a i n i n g 3 0 $ by weight of A 1 2 0 3 . T h e " r e s u l t s are given i n Appendix IV. • According t o t h i s phase diagram 5 6 .2$ , o f A 1 2 0 3 was supposed to react w i t h CuO to f o r m . o n l y C u ( A 1 0 2 ) 2 which-was s table w i t h i n . t h e range of 8 5 0 ° C . t o 1 0 0 0 ° C . But x - ray invest igat ion•showed,that there•was always some f ree C u 2 0 and A 1 2 0 3 present i n t h i s system. T h i s could be explained by the u n c e r t a i n t y of 2CuO ^ > C u 2 0 + l / 2 0 2 . d i s s o c i a t i o n r e l a t i o n s h i p . As soon-as the required-mixture was heated to a temperature above 900°C some of the CuO converted t o 1 C u 2 0 . ' Although'CuO would.react wi th A 1 2 0 3 t o form C u ( A 1 0 2 ) 2 , C u 2 0 d i d not react with A 1 2 0 3 to form CuA10 2 as t h i s was not s table at that temperature ( 9 0 0 ° C ) . • This presented some d i f f i c u l t y , i n . drawing an accurate boundary l i n e . However, i t was assumed that under a h igher p a r t i a l pressure of. oxygen when a l l the copper oxide could be expected to be present as CuO, formation of 100/o C u ( A 1 0 2 ) 2 from the mixture.would.be expected. A c c o r d i n g l y the boundary, l i n e was drawn at t h i s composit ion. - k 7 -- The x - r a y powder patternsas w e l l as the d i f f r a c t o m e t r i c readings of the aluminates obtained i n the present-study•• were i n good agreement wi th the values given i n - t h e standard A i S . T . M . " c a r d s . In c e r t a i n cases , however a s l i g h t l i n e s h i f t - a n d a s l i g h t - d i f f e r e n c e i n the r e l a t i v e i n t e n s i t i e s were observed i n the 0< - A 1 2 0 3 l i n e s . T h i s . c o u l d be a t t r i b u t e d t o . t h e e f f e c t of e i t h e r s o l i d s o l u t i o n or d i s t o r t i o n i n the alumina l a t t i c e but no s p e c i f i c i n v e s t i g a t i o n was c a r r i e d . o u t . i n t h i s . r e s p e c t . - k& -v; CONCLUSIONS The s e s s i l e drop, technique has been used to study the i n f l u e n c e of oxygen on. the wett ing of s i n g l e c r y s t a l alumina by molten copper i n •. vacuum at 1230°C. The a d d i t i o n of copper oxide t o copper, metal i n amounts of f r o m . l to 72$ of the metal weight caused a decrease i n contact angle which v a r i e d w i t h the oxide a d d i t i o n . The lqlwering of i n t e r f a c i a l energy was due i n every case t o a chemical r e a c t i o n at the i n t e r f a c e which r e s u l t e d i n the formation of CuA10 2 . K i n e t i c a l l y the r e a c t i o n was extremely r a p i d , the major decrease i n contact angle o c c u r r i n g w i t h i n 10 seconds a f t e r m e l t i n g . Subsequently, an extremely slow.decrease was observed, which could be a t t r i b u t e d to s o l i d s tate d i f f u s i o n of CuA10 2 i n t o sapphire . The degree of spreading ; of l i q u i d o n . s o l i d was found-to be dependent on the amount of oxygen added t o the system. A l i n e a r r e l a t i o n s h i p was observed, between the f o u r t h power of the radius of the s o l i d - l i q u i d i n t e r f a c e and the oxygen a d d i t i o n . The s t rength p r o p e r t i e s . o f SCP a l l o y s a f t e r i n t e r n a l o x i d a t i o n may be expla ined .by the formation of CuA10 2 as an intermediate phase at the C u - A l 2 0 3 i n t e r f a c e . The strengthening e f f e c t may be due . to the decrease of i n t e r f a c i a l energy and/or to the increase of t o t a l and s p e c i f i c contact areas between the two phases. . Phase diagrams f o r the systems C u 0 - A l 2 0 3 and C u 2 0 - A l 2 0 3 were constructed f o r the temperature range of 600-l600°C i n a i r . The l i q u i d u s curve f o r the l a t t e r was determined by the cone f u s i o n technique. The compounds C u ( A 1 0 2 ) 2 and CuA10 2 were i d e n t i f i e d and t h e i r regions of s t a b i l i t y e s t a b l i s h e d . -k9 -. V I . RECOMMENDATIONS FOR FURTHER. WORK Although the s e s s i l e drop technique has been used very e x t e n s i v e l y t o study the i n t e r f a c i a l reac t ions between metals and ceramics, i t has severe l i m i t a t i o n s . In g e n e r a l , . t h e smal l s i z e of the s e s s i l e drop does not permit p r e c i s e i d e n t i f i c a t i o n of a l l r e a c t i o n products or of the exact c o n f i g u r a t i o n ' o f the i n t e r f a c e . . Data .obtained by t h i s technique should be supplemented.by c o n t r o l l e d t e s t s on a l a r g e r scale i n which the complica -t ions of geometry are absent . The present procedure cannot be used convenient ly to f o l l o w the sequence of r a p i d r e a c t i o n s . However, i n c o r p o r a t i o n of a movie camera. into the apparatus may improve t h i s s i t u a t i o n . Instead of oxygenaddition as. an oxide, atmospheres of c o n t r o l l e d oxygen p o t e n t i a l should be used. This w i l l require m o d i f i c a t i o n of the furnace design t o a v o i d . t h e presence of the molybdenum susceptor . Only under c o n t r o l l e d environmental c o n d i t i o n s , w i l l i t be p o s s i b l e to analyze the experimental data q u a n t i t a t i v e l y . VII.•APPENDICES APPENDIX I .Theory of Spreading - 51 -APPENDIX I A comprehensive-theory of the spreading of l i q u i d s has been worked out by Harkins .The f ree energy, of a .substance at constant temperature, pressure and concentrat ion i s d e f i n e d as ( 'OF/'QC )<ppj^  tf = f ree surface energy/cm 2 where F, = f r e e energy of the substance (f = i t s surface a r e a . This leads to the statement that the c o n d i t i o n f o r spreading to occur i s t h a t , f o r the e n t i r e system' dF < 0 f o r non spreading, dF ^ 0. I t i s assumed that i n the course of spreading of a l i q u i d " b " on a surface " a " the f o l l o w i n g area r e l a t i o n s are obtained d ^ = d s~ab = " d <r* then (XJF/ocr)' = V b + tf TP b ° ab 0 a Hence, the spreading c o e f f i c i e n t i s s b,/ a l = - - D F / b c = * a,- ( *b.+ Xa,b.) pressure and temperature being constant , and the surfaces are mutually saturated as designated by the primes. The work of adhesion i s the work r e q u i r e d at constant T and P to p u l l . t h e i n t e r f a c e "ab" apart t o give c l e a n surfaces of a and. b f o r u n i t area of i n t e r f a c e . W A tfa + tfb ~ V a, b» - ^2 -I f a monolayer of " b " i s present on the surface of " a " the surface pressure of the f i l m i s d e f i n e d as 77"= V - if "i f = surface t e n s i o n of " a " when covered w i t h a monolayer of " b " . I t i s apparent that " ^ a , = ^ ( e q u i l i b r i u m value f o r "Y ) and therefore \</a - ~ " T e Where 77~e i s the pressure of the monolayer i n e q u i l i b r i u m with a lens of " b " . With o i l i n water the f i n a l spreading c o e f f i c i e n t i s always negat ive , t h e r e f o r e , the f i l m pressure i s always l a r g e r than the s e m i - i n i t i a l c o e f f i c i e n t S ^ M e h has general ly the value very near ly the i n i t i a l c o e f f i c i e n t S^^& For a l i q u i d " b " on a s o l i d " a " S L / S = Vs "( "V L + ^ L ' S ' ) i n i t i a l S L ' / S = L ' * ^ L ' S ' ^ s e m i - i n i t i a l f i n a l Since i t i s d i f f i c u l t t o measure V and *Y d i r e c t l y , the 6 S' 0 S ' L ' work of adhesion can be computed by measuring the contact angle . W A ( S L ) = V L ( 1 + COS 9 ) So as a primary guide the c o n d i t i o n f o r spreading can be taken as V s > V L APPENDIX II C a l c u l a t i o n s f o r Monolayer Formati APPENDIX II C a l c u l a t i o n s f o r Monolayer Formation from the G l o b ' s Adsorpt ion Isotherm r - S L S L RT d i n C Where J"1 = excess i n t e r f a c i a l concentra t ion ,mole /cm 2 (X. = a c t i v i t y of the solute C = b u l k concentrat ion of the solute T = absolute temperature R = gas constant VSL ^ O R on^y 1 a n < ^ 2 $ CuO was p l o t t e d against l o g (CuOg concentrat ion) and the slope W S L was taken from the p l o t , ^ l n C • S L ( w h - e r e t t L e contact angle was $2°kV f o r 1$ CuO a d d i t i o n ) was determined by the Bashfor th method and found to be 1011 e rgs /cm 2 as against 1017 ergs/cm^ i f c a l c u l a t e d by t a k i n g . Y^y v a 3 - u e to be constant . The d i f f e r e n c e was not s u f f i c i e n t to introduce any ser ious e r r o r f o r 1 and 2$ of CuO a d d i t i o n i f ^jjy i s taken as a constant f o r c a l c u l a t i n g The slope S L = > l n C 390 2.303 x 0.81+51 V i n these ttwo cases. = -200.7 T = 1503°K R = 8.314U x 10^ ergs/deg/mole. Therefore p = 200.7 = I.606 x 10"^ moles/cm 2 8.31M+ x 10'( x 1503 Avogadro's Number = 6.06 x 1023 atoms/mole Therefore J1 = I.606 x 10'9 x 6.06 x I O 2 3 = 9.8 x lO^BS 10 x l O 1 ^ atoms/cm 2 55 -T h e o r i t i c a l C a l c u l a t i o n s : Basal radius of the drop at 1 to 2$ CuO = x' = 2.32 cms M a g n i f i c a t i o n = 7 times Therefore the a c t u a l r a d i u s = 2-32 = 0-331 cm 7 Therefore "basal area = 7 T x ' 2 = 0-3^5 cm 2 Ionic radius of C u + = O.96A0 Therefore area occupied by one C u + i o n = 5-^8 x 10 cm Ionic radius of 0"" = 1 . 3 2 A 0 . Therefore area occupied by one 0 " ~ i o n - ;' . ' . ." ... = 5-^8 x 1 0 l 6 c m 2 Therefore , approximately the area occupied by two C u + ions and one 0 ~ " i o n -.16 2 = 11.3 x 10 cm Then.' the t o t a l number of these i o n groups (2Cu + + 0~~) present at the i n t e r -face = 0-3>5 ... 11.3 x 1 0 " l b Therefore the t o t a l number of ions present at the i n t e r f a c e = 0-3k5 • x 3 11*3 x 1 0 " 1 6 = 9.3 x 1 0 l l + i o n s . The c a l c u l a t i o n shows that 9>3 x 1 0 ^ ions of C u + and 0~~ are r e q u i r e d t o -gether fco» form a monolayer of CUgO"" at the a v a i l a b l e i n t e r f a c e . Experimental ly lk 1 2 i t was found to be 10*0 x 10 atoms/cm which seems to be i n f a i r l y good agreement between the experimental and c a l c u l a t e d values ( d i f f e r e n c e by a f a c t o r of 3)• APPENDIX I I I Bashfor th and Adams Method - 57 -APPENDIX I I I Bashforth and Adams Method The f o l l o w i n g are sample c a l c u l a t i o n s f o r the contact angle and l i q u i d surface tens ion from the s e s s i l e drop dimensions us ing the Bashfor th and Adams t a b l e s . For d e t a i l s r e f e r to E l l e f s o n and T a y l o r 2 ^ . Example 1. For Obtuse Contact Angles Taking pure Copper and Alumina the f o l l o w i n g drop dimentions were measured d i r e c t l y from the photograph. From Figure 2 x = 1.8 x'= 1.025 z = 1.65 z'= 2.82 Therefore x = 1.091 Now us ing the Bashfor th and Adam's Table I f o r 0 = 90° the value of j3 w a s found to be 0.5- Taking the value of B = 0<5 the values of » and z were ' b b determined from Table I I . x = 0.9328 z = 0.85k9 b b Knowing x and z from the measurements, b was c a l c u l a t e d separately f o r both the cases i e b = x = I.9296 and b = z = 1-930 0.9328 0.85^9 Taking the average value for b s I.9298 b 2 = 3.72k Now from the relationship fl = g p b 2 r y L V x where g- = acceleration due to gravity = 980.7 cm/sec J = density of copper at 1230°C =7.82 gms/cc M = drop magnification = 7 times ^ Ly i s calculated as V L V = (980.7) x (7.82)-x (3.724) = 1172 ergs/cm2 (0.5) x (7) 2 To obtain the contact angle the erverse procedure was followed: ie x' = 1.025 = 0.531 and z' = 2.82 = 1.462 b I.9298 b . I.9298 Now Table II was again used for these values of x' and z' at R b b Theraverage /value of 9 was found to", be 163° • From these values of T^_,y: and 9 Y S L was calculated ( ^  S L = Vsv " ^ L V C O S ^ using.. V SV = 9 7 0 e rS s/ C f f l 2 a t 1230°C. From this V S L = 2129 ergs/cm2 - 59 -E l l e f s o n and T a y l o r Method Example 2. For Acute Angles Taking copper w i t h 5$ CuO on Alumina I t was assumed that the drop was small enough A that the shape was that of a s p h e r i c a l segment. Again from the photographs the drop dimensions x and z were measured See Figure Z x ' =. 2.775 z = 2.2 Then 9 = 2 tan" 1 z = 2 tan" 1 (0.7935) x or tan 9/2 = 0.7935 9/2 = 38°26" 9 = 76°52' APPENDIX IV Resul ts of the S e s s i l e Drop Experiments TABLE I. A c t u a l Number 9 at d i f f e r e n t times ( s e c . ) a f t e r Average C o s O ^ L V " ^ S L Wt.$ of 0 2 of complete mel t ing of the drop Value . of weight Run of G a f t e r ergs/cii? e rgs /cm 2 of copper • 5 10 15 30 75 135 • 300 75 sees 0.00 1 2 3 167° 16U°8' 163°k3' 163 °2k' 163°6' 163° 163° 162°57' l62°7' 162° 162°42' l62°5' 161°57' 163° -0.9563 1172 2129 0.18 1 2 3. k 110° 108°7' 9k0 93°50' 93 0 k2f 93° 92°k0' 93° 92°8' 92° V7' 92°ko' 92°16' 91°2' 92° 8' 91°56' 92°ko' -0.0U65 1172 1022 ft 1017.75 l O l l . 75 . i t 0.50 1 2 3 108°6' 98° la' 88° 8k°k3' 82°52' 82°50' 82°5k' 82° 6' . 82°2' 82° 8l°55' 82*52' ,0.121+2 1022 81+3 - A O.56 , 1 2 3 1+ . 109°3' 77*56' 80° 4' 79°52' 78° 771 •• 76°30' 77° 2' 76°3k' 76^9' 76°22' 76° 76° 6 ' 75°50» 75052. 76°3k' 0.2323 1022 733-5 A 1.28 1 2 3 98°57' 69°1+0' 68° 58' 69° 68° 2 ' 68°3l' 67° 142' 67°k6' 67°52/ 67°3/ 66°5' 67°k6' 0.3781+ 1022 583 ' 1.99 l 2 3 i l l 0 7 ' 57 °' 53°30-52 036' 5 k°3 / 52°22' 52° 52° 20' 5l°52' 51° 6' 5l°3' 50°56' 52010' O.613I+ 1022 31+3 1 1+7° i+i+°38' 43° 8' ky'- 42° ki' 1+3 ° 8' 0.7298 1022 255 continued. A c t u a l No. 0 at d i f f e r e n t times (sec . ) a f t e r Average Wt.$ of 0 2 of complete m e l t i n g - o f the drop Value Cos 0 VLV OSL of weight Run of 0 a f t e r ergs /cm 2 e r g s / c m 2 of copper 5_ 10 15 $0 75 155 300 75 sees  2.85 1 2 3 101° 41°57' 43° 4l° 4i°52' 4l°50' '39° . 39°2' 39°12' 39° 38° 2' 38°17/ 38° 39°^' O.7698 1022 "182 4.75 l 2 99°58 28°16' 28°20( 27°4o' . 27°10' 27° 26°3o' 26°47' 27° 6' 0.8902 1022 60 1 25° 23°2' 21°14' 20° 6' 21°14' 0.9321 1022 17 A l l o y i n g A d d i t i o n s t o Copper 5$ Ag 1 2 l4l°2' 142° 13 9° 10' l4o° 139° 139°22' 139° 138° 17' 139° -0.75^7 1172 1855' 28.1$ Ag 1. " 2* 137° 133° 133° 2' 131°18' 131° 130° 56' 131° 131°. -0.6572 1172 1741 yjo T i 1 ,130°7' 129° 128°37 ' 128° 128°37' -0.6241 1172 1702 5$ C u O t 1$ T i 1 87°23' , 8 4 ° 83° 20' 82°56' 83° 20' 0.1146 1172 835.2 A Indica tes the ca lcula ted , values of & S L , t aking the value of V L V o f C u a f t e r 1$ a d d i t i o n of CuO. ( i . e . V = 1022 ergs/cm 2 ) QLV - 63 -..TABLE. I I . 1°. CuO of the $ Cu 20 of the Average value A c t u a l Amounfe Average Value Weight of Cu T o t a l Weight of $ 0 of t o t a l of 0 2 i n Wt.$ of x' .= b a s a l x'4 A d d e d Added Weight Added as Present by H 2 r a d i u s . i n cms.. ( i O 2 ) CuO Reduction 1 0.891 O.I99 0.18 0.275 O.572 2 1.765 0.39^9 0.296 0.290 O.706 5 4. 305 0.9594 P.563 • 0.348 1.466 10 8.25 I . 8 3 O I.276 0.419 3.08 20 15.25 3.318 I.987 O.490 5-76 30 21.1 4.64 2.826 O.525 7-59 j - 6k -APPENDIX V Phase Diagram Observations !-65 -APPENDIX V Experimental observations used f o r the c o n s t r u c t i o n of the phase diagram of CuO - A120~, system. (Phases i d e n t i f i e d at room temperature by a i r quenching from respec t ive temperatures. Composition Temperatures i n Degrees Centrigrade r a t i o CuO:Al 202 600 700 800 85O . 900 * 98:2 AC AC AE AE AB ' E 95:5 AC AC AE AE A B ' E 93:7 AC AC AE AE AB ' E 90:10 AC AC AE AE A B ' E 80:20 AC AC AE AE A B ' E 70:30 AC AC AE AE A B ' E 60.95:39'-05 AC AC AE AE A B ' E 50;:50 AC AC A C E A C E A ' B ! ' C E 43.8:56.2 AC AC A ' C ' E A ' C ' E A ' B ' C ' E 40:60 AC AC '. CE CE B ' C E 30:70 AC AC CE CE B ' C E Compositions above 70$ A l g O o c o u l d not De A = B = CuO Cu 20 s t u d i e d . C = AlpO-> D = C u A l 0 2 E = C u ( A 1 0 2 ) 2 Primes A ' , B ' e t c . represent phases i n t r a c e s . * Not i n c l u d e d i n the phase diagram. - 66 -b . For Cu^O and AlgO^ system. Composition Composition r a t i o of r a t i o of CuO-.AlgO^ CUgOiAlgO^ 1000 # 1050 1100 1200 1250 1300 1600 98:2 97.82:2.18 A'BD BD BD BD BD BC BC 95:5 9 k - k 7"5-53 AlBD BD BD BD BD BC BC 93:7 92.29:7.71 A'BD BD BD BD BD BC BC 90:10 . 89:11 A'BD BD ' BD BD BD BC BC 80:20 78.22:21.78 A'BD BD BD BD BD BC BC 70:30 67.7 k:32.26 A ' B ' D BD BD BD; : BD BC BC 60.95:39-05 58:1+2 A ' B ' D D D D B ' D C BC BC 50:50 l+7«k:52.6 A ' B ' C ' D CD CD CD B'DC BC BC k3-8:56.2 1+1.2:58.8 A ' B ' C D CD CD CD B'DC BC BC 1+0:60 37.5:62.5 B'CD CD CD CD B'DC BC BC 30:70 27.9:72.1 BCD CD CD CD B'DC BC BC A = CuO B = Cu 2 0 C = AlgO^ D = CuA10 2 E •=:-Cu(A102)2 Primes A ' , B ' e t c . represent phases i n t races * N o t . i n c l u d e d i n the phase diagram M e l t i n g p o i n t s determined by cone f u s i o n method. Composition r a t i o Composition r a t i o Temperature i n C u O : A l 2 0 3 C u 2 0 : A l 2 0 3 98:2 97.82:2.18 I I 8 0 95:5 9 k - k 7:5.53 1165 93:7 92.29:7.71 1195 90:10 89:11 1365 ! 85:15 83.61:16.39 l k 50 80:20 78.22:21.78 151+5 APPENDIX VI D i f f r a c t o m e t r i c Graph Readings - 6? -I •••i-x 8 = 8 S 8 « ! ij j | s D i f f r a c t o m e t r i c Graph of Cu (A102)2 (Scanned from'2 0 = 30 - 70% Each d i v i s i o n 6 ° ) ! - 70 -APPENDIX VT D i f f r a c t o m e t r i c graph reading of specimen with 39-05$ AlgO-, and 60-95$ CuO, f i r e d at 850°C f o r 12 hours . . Readings: o :ak No. R e l a t i v e Peak height 29 d(A) Correspondin; 1 5 25.6 3.476 A 1 2°3 2 60 31.47 2.839 C u ( A 1 0 2 ) 2 3 5 32.55 2.752 CuO 4 45 35.56 2.522 CuO 5 100 36.95 2.428 C u ( A 1 0 2 ) 2 6 ^5 38.8 2.318 CuO 7 5 43.3 2.087 A 1 2 0 3 8 15 44.85 2.018 C u ( A 1 0 2 ) 2 9 10 48.87 1.861 CuO 10 15 55.75 1.649 C u ( A 1 0 2 ) 2 l l 5 57 A 1.603 A 1 2 0 3 12 5 58.3 1.581 CuO 13 30 59-45 1.553 C u ( A 1 0 2 ) 2 14 5 61.6 1.504 CuO 15 5^ 65.3 1.427 C u ( A 1 0 2 ) 2 16 5 66.3(hroad) l.4o8 &l2°3> C u 0 17 5 68 .2(broad). 1.31k Cu(A102)2,i 71 -Diffractometrlc Graph of CuAlO, (Scanned from 2 G - Ik - 70°) D i f f r a c t o m e t r i c graph readings 60.95$ CuO f i r e d at 1100°C f o r 12 hours Readings: Peak No. R e l a t i v e ..29 Peak height 1 30 15.75 2 80 31.68 3 90 36.75 k 100 37.86 5 50 1+2.3 6 20 kQ.35 7 15 52.8 8 50 57-2 9 60 65.3 10 15 66.1 11 35 66.78 12 30 7^.38 13 25 78 Ik 10 80.81+ I - 72 -specimen with 39«05$ A l Oo and o d(A) Corresponding to 5.618 CuA10 2 2.821 CuA10 2 2. ¥ + 2 CuAlO 2 2.37 k CuA10 2 2.13U CuA10 2 1.880 CuA10 2 1.732 CuA10 2 1.609 CuA10 2 1.1+27 CuA10 2 1.1+12 non i d e n t i f i e d l i n e 1.399 CuA10 2 I.27I+ CuA10 2 1.223 CuA10 2 1.1879 CuA10 o I - 73 -Readings from the d i f f r a c t o m e t r i c graph of the i n t e r f a c e are t a b u l a t e d . (The photograph i s given i n F i g . l 4 ) . o L i n e No. R e l a t i v e 29 d(A) h k l Corresponds Peak height to 1 35 15-74 5.625 003 CuA10 2 2 100 31-3 2.820 006 CuA10 2 3 35 48.4 1.879 009 CuA10 2 4 20 66.25 1.409 12§4 - A 1 2 0 ^ The f i r s t three peaks represent, a set of s i m i l a r planes ; of the CuAlOg c r y s t a l s which form at the i n t e r f a c e as a r e a c t i o n product . They are ; o r i e n t e d i n a p a r t i c u l a r manner wi th respect to the 1234 plane of the AlgO-, which i s the a c t u a l plane of sapphire used. Further i n v e s t i g a t i o n i s necessary to e s t a b l i s h the o r i e n t a t i o n r e l a t i o n s h i p between the new c r y s t a l phase and the sapphire s u r f a c e . APPENDIX VII Debye/fecherrer Powder Patterns' Readin, i - 75 -APPENDIX VII Readings from the Debye^bcherrer powder patterns and the A . S . T . M . Standard Cards given f o r r e f e r e n c e . 1. 39-05$ A l 0 and 60-95$ CuO , f i r e d at 850°C. 2. 39-05$ A - 1 ^ ^ a n d 60.95$ CuO , f i r e d at 1100°C 3. Scraped i n t e r f a c e . 1. 39'05$ AlpO^ and 60.95$ CuO, F i r e d at 850°C. o Line No. I / I l . .. , dA Corresponding 1 10 3-^75 A 1 2°3 2 3 2.839 C u ( A 1 0 2 ) 2 3 5 2.752 CuO 4 . 50 2.528 (broad l i n e ) CuO, AlgO^ q 5 100 2.425 C u ( A 1 0 2 ) 2 6 50 2.318 CuO 7 20 2.087 A 1 2 0 3 8 80 2.018 C u ( A 1 0 2 ) 2 . 9 10 1.861 CuO 10 80 1.647 C u ( A 1 0 2 ) 2 l l 20 1.603 A l 2 03 12 5 1.581 CuO 13 100 ' 1.553 C u ( A 1 0 2 ) 2 14 10 1.504 CuO 15.: 100 1.427 C u ( A 1 0 2 ) 2 16 10 1.409 (broad l i n e ) A 1 2 0 3 CuO 17 30 1.370 (broad l i n e ) C u ( A 1 0 2 ) 2 , A l 2 0 18 50 1.274 C U ( A 1 0 2 ) 2 19 50 1.231 CU (A1 0 2 . ) 2 20 40 1.218 C u ( A 1 0 2 ) 2 21 50 I.I65 C u ( A L 0 2 ) 2 22 30 1.134 C u ( A 1 0 2 ) 2 23 50 I . O 8 5 C u ( A 1 0 2 ) 2 24 60 1.049 C u ( A 1 0 2 ) 2 Continued Line No. 0 dA Correspondin 25 X X X 26 X X X 27 0.9312 C u ( A 1 0 2 ) 2 28 Uo 0.8^57 C u ( A 1 0 2 ) 2 29 60 0.023 k Cu(A10 2 ) I-..78 -2 , 39-0^ '4 A l 203 and 60-95$ CuO, f i r e d at 1 1 0 0 ° C . L i n e No. I / I l 0 dA observed Corresponding to 1 Uo 5.6l8 CuA102 2 75 2.821 C u A 1 0 2 3 75 2.kk2 C u A 1 0 2 k 100 2-37 k C u A 1 0 2 5 50 2.13k C u A 1 0 2 6 25 1 . 8 8 0 C u A 1 0 2 7 15 1.732 C u A 1 0 2 8 50 1.609 C u A 1 0 2 9 50 IA29 C u A 1 0 2 ' 10 30 1-399 C u A 1 0 2 11 ko 1.275 C u A 1 0 2 12 30 1.223 C u A 1 0 2 13 10 I.189 C u A 1 0 2 Ik 2 0 l.lk2 C u A 1 0 2 15.' X '. X 16 X X 17 35 1 . 0 0 C u A 1 0 2 18 2 0 0-9753 C u A 1 0 2 19 5 0.94l6 C u A 1 0 2 2 0 10 0.9295 C u A 1 0 2 2 1 15 O.9U7 C u A 1 0 2 I- 79 -3« Scraped i n t e r f a c e o Line No. ,dA Corresponding to 1 10 5.625 CuA10 2 2 60 3A76 A12°3 3 25 2.823 CuA10 2 4 100 2.557 A 1 2 0 3 5 20 2.439 CuAlOg 6 50 2.379 (broad l i n e ) (CuA10 2 + AlgO^) 7 20 2.134 CuA10 2 8 100 2.089 A 1 2 0 3 9 5 1.880 CuA10 2 10 50 1.747 A120~,, CuA10 2 11 80 1.609 A 1 2 0 3 , CuA10 2 12 10 1.519 ALpO-, 13 10 1.427 CuA10 2 14. 50 1.408 AlgO^ + CuA10 2 15 60 1.379 A 1 2 0 3 16 20 1.274 CuAlOg 17 30 1.241 A 1 2 0 3 18 5 1.223 CuA10 2 19 15 1.190 A 1 2 0 3 , CuA10 2 20 X x ' X 21 X X X 22 X X X 23 10 1.079 A 1 2 0 3 24 15 1.039 A 1 2 0 3 25 20 0.999 A 1 2 0 3 , CuA10 2 26 5 0.972 CuA10 2 d 2.47 2.14 1.S1 3.020 CUgO vu 100 37 27 9 C O P P E R OUS OXIDE C U P R I T E 5-0667 TT" RadCu Dt*. VI, A 1.5405 Cut off ruur Con. doorr.ab*.t Bat, SaAMSON AND FuTAT, NBS CIRCULAR 8>a.CiMie a, 4.2696 h . • 0 Bat I B I D . 7 R O . OM - P N S U A C Z 2 B O * Color S A M P L E P R E P A R E D i t THC N B S . S P C C T . t U L . I < If C A . S I ; « 0 . 1 « A L . W B ; < 0 . 0 n A S , 9 , 3 A , F I , T I I < O . 0 O t « Ikt.Pa.SM. X - U T P A T T E R N AT 26%. R«PLACta 2-1067. *-<X1i. 3-08*8 d A 3.020 2.465 2.135 1.743 1.510 1.287 1.233 1.0674 0.9795 .9548 .8715 .8216 I / I . 9 100 37 1 27 17 4 2 4 } J 3 hid uo 111 200 211 220 311 222 400 331 420 422 511 Irl ktt 5-0661 d 2 . 5 2 2 . 3 2 2 . 5 3 2 . 7 5 1 CuO * I / I i 100 9 6 49 12 COPPER IC OXIDE T E N O R I T E R a d C u A 1 .5405 F i l te r D i a . Cut off C o U . I / I i d corr. aba.? B « £ S»AN80H AKD TATGE, NBS CIRCULAR 5 j j » ( ^ ^ ' Sy*. MDNOCLINIC a. 4 . 6 8 4 b, 3 . 4 2 5 a t 9 9 ° 2 8 ' R e t I B I D . S.G. C 2 H - C 2 / c c, 5 .129 A 1 .368 C 1 .498 y Z 4 JV Ret. DD0 Dx6.51 mp Color Sign SAMPLE FROW JOHNSON M A T T V E T AND C O . A N A L . I F A I N T T R A C E S OF F E AND M G . X - R A T P A T T E R N AT 26°C S P E C T . 3 - 1 2 6 3 R E P L A C E S 1 - 1 1 1 7 , 2 - 1 0 4 0 , 2 - 1 0 4 1 , 3 - 0 8 6 7 . 3 - 0 8 8 4 , d A 2 . 7 5 1 2 . 5 3 0 ) 2 . 5 2 3 ) 2 . 2 . ! . ? 2 3 ) . : . 3 l 2 ) 959 86G 778 714 581 505 418 1 .410 1 .375 1 .304 1 .265) 1 .262) 1 .1961 I / I . h k l 12 110 49 002 100 111 96 111 30 200 3 112 25 202 2 112 8 020 14 202 20 113 12 022 15 311,310 19 220,113 (311,512 (221 7 6 004 7 222 2 304,114 d A 1.1697 1.1620 1.1585 1.1556 1.1233 1.0916 1.0737 1.0394 1.0178 1.0074 0 . 9 9 2 1 .9808 .9576 . 9435 . 9 3 9 0 . 9332 . 9 2 0 9 . 9 1 0 0 .9039 I / I . 5 3 2 4 2 6 2 <l 3 4 t l 4 . 3 <1 4 2 2 2 1 d 2.09 2.55 1.60 3.479 a-AlaOg * I/I. lOO 92 81 74 A L P H A ALUHINI m O X I D E CORUNDUM HadCu A 1.5405 Filter Dta. Cut off CoU. I / I . dcorr.aba.1 B C L S M N S O N AND F U T A T , NBS C I R C U L A R 5|g, y o ^ ^ I 87a. HEXAGONAL a. 4.758 b . • * B a t I B I D . S . G . D , D e. 12.991 A T Z 6 R3c C2.716 la * V Rat Dx3.987 mp Color S A M P L E FROM U A L L I N C K R O D T CHEW. M I R K S . S P E C T . A N A L . • «0 .1» K , N A , S I | < 0 . 0 l « C » , C U , F E , M G , P B | <0.or B , C R , L I , U M , N I . X - R A T TERN AT 2 f ° C • * P I d A I / I . hid d A M . hU 3.479 74 102 1.0781 7 314 2.552 92 014 1.0426 13 226 2.379 42 110 1.0175 1 402 2.16S <1 006 0.9976 11 1.2.10 2.085 I X 113 .9819 2 044 1.T40 43 204 .9345 3 138 1.601 81 116 .9178 2 229 1.546 3 121 .9076 12 234 1.510 7 108 .9052 3 1.0.14 1.404 32 124 .8991 6 410 1.3T4 48 300 .8804 4 413 1.276 2 028. .8698 2 408 1.239 16 0.1.10 .8580 12 3.1.10 1.1896 6 220 .8502 4 3.0.12 1.1601 <1 306 .8303 22 416 1.1470 4 223 .8137 4 1.1.15 1.138S 1 311 .8075 11 0 .4 .10 ' . .1255 5 / 132 2.0.10 0 . . ' .12 A. S. T . M. Standard Cards 9-185 l /I , 100 3.88 80 2 . 4 4 8 0 5.61 30 CuAlO. C O V E R ALUMIPUTE L Cute A 1.548 Filter Nl Out 1 ' C u t 0 8 V I S U A L R a t HAHN AND L O R E N T , Z . ANORG. A L L G E U . C H E M . 2JJ9. 241 (1955) Sgrt. ftMUBOHt-DRAL* •» S . 8 M h . • 2 8 . 1 ° t L 10ID. c A C T Z 1 D i ncoff Sign mp "HflACONALI A0=2.849, c 0=16.98, C=5.95, Z=l» D , 5.104, D 4 . W 7 . ISOStRUCTURAL N ITH CUFEOJJJ NArF, T Y P E . d A I/I, hkl d A I/I, hkl HEXAGONAL 0 . 9 7 4 2 0 1 . 0 . 1 6 3 0 I N D I C E S . 9 3 9 ' 5 0 . 0 . 1 8 5 . 6 1 0 0 3 . 9 3 S 1 0 1211.211 2 . 8 2 ao 0 0 6 Tt.O.lT 2 . 4 3 7 8 0 101 . 9 1 2 10 2 1 4 2 . 3 7 6 100 102 2 . 1 3 3 5 0 104 1 . 8 7 7 20 009 1 . 7 3 2 10 107 1 . 6 1 2 5 0 108 1 . 4 2 6 4 0 110 1 . 4 0 1 3 0 1 . 0 . 1 0 1 . 2 7 4 4 0 116 1 . 2 2 5 2 0 202 1 . 1 8 8 10 204 1 . 1 4 8 2 0 1 1 9 , 0 . 0 . 1 ! 1 . 0 8 9 10 1 . 0 . 1 4 1 . 0 6 9 3 0 2 0 8 1 . 0 0 B 3 0 J l . 1 . 1 2 D 2 . 0 . 1 0 me i 2-1412 1 . 4 2 2 . 4 2 1 . 5 5 2 . 8 3 C U ( A L 0 J ) 2 ALj.O5.CuO V I . 2-1414 100 9 0 9 0 4 0 COPPER A L U U I N A T E . ALUUINUU C O P P E * OX IDE I I1 B a d . D U . V I i B t l S E E B E L O * A 0.709 Cut off Filter C a l l dcorr.sbt,? 9TS. CUBIC s> 8.060 b. • $ E s t « Y S T S.G. 0 „ A Z 8 F D 3 U C ft"* SV D 4.732 mp Bat, CC. I r Sign Color CHOCOLATE G . HOLGEPSSON, Z . ANOAG. C H E U . 2Q1, 38l(l932)l P A S S E P I N I , G A U . C H I M . U A L . SQ, 391 ( 1 9 3 0 ) ' Wrs G I V E S Ao » 8 . 0 4 4 d A 2.83 2.42 2.01 1.64 1.55 1.42 1.36 1.27 1.23 1.21 1.16 1.13 1.08 1.05 1.01 40 90 70 80 90 lCO 40N 50 70 60N 70 60N 80 90 70 hU d A 0.949 .930 .845 .823 VI. 60N TON 7 0 N I O ONI hkl A . S. T . M. Standard Cards - ^ 82 -V I I I . REFERENCES 1. B a r t e l l , . F . E . , and. W o l l e y , - A . D . , J . Am. - Ceram. Soc. 5J>, 351 (1933). 2. Comeforo, J . E . , and • Hursh, R. K . , J . Am. Ceram. Soc. 3_5_, 130 (1952). 3. Bondi , A . , . Chem. Rev. 5_2, kYJ (1953). 4. Glasstone, S . , "Textbook of P h y s i c a l Chemist ry" , N . Y . , Van Nostrand, ' 19^6. 5. A l l e n , B . C . , and K i n g e r y , W. D . , Trans . A . I . M . E . 215, 30 (1959). 6. . S h e v l i n , T . . S . J . Am. Ceram. .Soc . 37, l4o (1954). 7. C a r t e r , R. E . , J . Am. Ceram. Soc. 44, 116 (196l). 8. Adams, R. B . , and Pask, J . A . , . J . A m . Ceram.. Soc. 44, 430 ( i 9 6 i ) . .9. Campbell , J . . B . , . M a t e r i a l s and Methods 3_1 (5), 59 (May 1950) . 10. Symposium on physics of powder metal lurgy , Bayside , N . Y . , 1949., . "The Physics of Powder M e t a l l u r g y " , ed . by W. E . K i n g s t o n . 1st e d . , N.Y.- , M c G r a w - H i l l , I95I. 11. .Pask, . J . A . , and F u l r a t h , . R. M . , J . Am. Ceram. Soc. 4_5_, 592 (1962). 12. P incus , A . G . , J . - Am..Ceram.. Soc. 36, 152 (1953). 13. .Kingery , W. D . , and Humanik, M . , J r J . Phys. Chem. 5_J_, 359 (1953). 14. Economos, G . , and K i n g e r y , W. D . , J . - Am. Ceram. Soc. 36, 403 (1953). 15. Kingery , W. D . , J . Am. Ceram. • Soc. 3_J_, 42 (1954). 16. Humanik, • M . , J r . , and Kingery , W. D . , J . Am. Ceram.. Soc . 37_, 18 (1954). 17. Baes, C . F . , J r . , and K e l l o g g , • H . • H . , Trans . A . I . M . E . 197, 643 (1953). 18. Eremenko, V . N . , and N a i d i c h , . Y u . V . , • U k r a i n . . Khim. Zhur. 23, 573 (1957), 19. Eremenko, V . N. : , Ivashchenko, Yu. V . , Nizhenko, V . I . , and Fesenko, V . V . , I z v e s t . Akad. Nauk.SSSR, J u l y I 9 5 8 , p . . l 44 . 20. Young, T . , P h i l . Trans . 1805, p . 74; Young, T . , Miscel laneous works, London, J . Murray, 1855; v - 1 ( ed . .Peacock) , p . 432. 21. Dupre, A . , "Theorie m^chanique de l a c h a l e u r " , P a r i s , G a u t h i e r - V i l l a r s , 1869, P . .369. 22. Bashfor th , • F . , and Adams, J . C . , "An Attempt to T e s t ' t h e Theories of C a p i l l a r y A c t i o n " , Cambridge,. U n i v e r s i t y Press , I883. 23. E l l e f s o n , B . S , , and T a y l o r , N.W. , J . Am. Ceram. Soc. 21, 205 (1938). 24. Mack, G. L . , J . Phys. Chem. 40, I59 (1936). References Continued. 25. Grant,. N . J . „ and Preston, 0.,. Trans . A . I . M . E . . 209, 3 k 9 (1957) • 26. .Zwilsky , K. M . , and Grant, N. J . ,• Trans . . A . I . M . E . 209, H 9 7 (1957)-27. A d a c h i , M . , and Grant , N. J . , Trans, - A . I- .M.E. .218, 88l (i960). 28. S a v i t s k y , Ye. M . , and V l a s o r , A . I . , Tsvetnye M e t a l l y No. 7, 72 (i960). (Nat ional Aeronautics and Space A d m i n i s t r a t i o n T e c h n i c a l : T r a n s l a t i o n F-6k). 29. ..Smothers, W. J . , and Reynolds, H. . . J . , J . Am. Ceram. . Soc . 37, 588 (I95U). .30. Bron, V.- A . , Ogneupory 16 (7), 312 (1951). ( C e r a m . A b s . I 9 5 2 , k2g). 31. Comstock, G. E . , I l l , (Norton Company), U.S . .P . 2,618,567, Nov. 18, 1952. (Ceram. Abs . . 1953, 27f). 32. K o m a t s u , N . , and Grant,- N. J . ,• Trans . A . I . M . E . . 22k, 705 (1962). .33. .Siemens and Halske A . . - G . , German Patent 734,274, March 11, 1943. 34. • Dutch Patent 115,435. 35- Baxter, , J . R . , and Roberts , A... L . , "Symposium on Powder M e t a l l u r g y " , London,- Iron and S t e e l I n s t i t u t e , 1954, P- 315-36. Von Wartenberg, H . , and Reusch, H . J . , Z . anorg. allgem.-Chem. 207,1 • (1952). .37- Hann, H . , et a l . , . Z . anorg. a l lgem. • Chem.. 279, 2kl (1955). 38. Holgersson, S . , Z . anorg. al lgem. .Chem. 20k, 378 (1932). ,39a. .Rose, D. J . , M ; A . S c . t h e s i s , . U n i v e r s i t y of B r i t i s h Columbia, 1962. b . C l a r k e , J . F . , - M . A . S c . t h e s i s , • U n i v e r s i t y of B r i t i s h Columbia., i960. kO. . D e C l e e n e , - M . , . M.A.Sc . t h e s i s , U n i v e r s i t y of B r i t i s h Columbia, 1961. kl. Long, E . L . , J r . , and Gray, R. J . , • U . S . Atomic Energy Commission Report No. 0RNL-2494 (1958). k2. Ibrahim, M . , and B r i g h t , . N. .F . .H. , . J . Am. Ceram. Soc. 4_5_, 221 (I962); Ibrahim, M . , and B r i g h t , N . F . H . , and Rowland, J . F . , I b i d , 329. 43, , Sauerwald, F . , , Z . M e t a l l k . ,35_, 105 (1943). kk. . F o s t e r , . P . - A . , J . Am.-Ceram. Soc. 4_3, 66 (i960). 45. . Baumann, H. N . , Am. Ceram... Soc. . B u l l . . 3jJ_, 179 (1958). References Continued. Kingery , W. D . , " I n t r o d u c t i o n to Ceramics" , N . Y . , W i l e y , i960. H a r k i n s , ' W . D . , " P h y s i c a l Chemistry of S u r f a c e . F i l m s " , • N . Y . , R e i n h o l d , 1952. C o n t r i b u t i o n s t o the d a t a . o n . t h e o r e t i c a l metal lurgy , X I I , "Heats and Free Energies of Formation of Inorganic Oxides" , by James: P. C o u g h l i n . • Wash., D - . C , U . S . G o v t . . P r i n t e r , 1954. (U .S . Bureau of M i n e s . B u l l . . N o . 542). 

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