This document summarizes research measuring the temperature dependence of elastic moduli (Young's modulus and shear modulus) in pure nickel, platinum, and molybdenum using a pulse-echo technique with a magnetostrictive waveguide. The measurements found linear behavior for all three metals over temperature ranges from 25°C to 1000°C, except for nickel below its Curie point, where the elastic moduli decreased nonlinearly with increasing temperature. The significance of the linear relationship between temperature and elastic constants in molybdenum is discussed in relation to the observed non-Arrhenius behavior of carbon diffusion in molybdenum.
This document summarizes research measuring the temperature dependence of elastic moduli (Young's modulus and shear modulus) in pure nickel, platinum, and molybdenum using a pulse-echo technique with a magnetostrictive waveguide. The measurements found linear behavior for all three metals over temperature ranges from 25°C to 1000°C, except for nickel below its Curie point, where the elastic moduli decreased nonlinearly with increasing temperature. The significance of the linear relationship between temperature and elastic constants in molybdenum is discussed in relation to the observed non-Arrhenius behavior of carbon diffusion in molybdenum.
This document summarizes research measuring the temperature dependence of elastic moduli (Young's modulus and shear modulus) in pure nickel, platinum, and molybdenum using a pulse-echo technique with a magnetostrictive waveguide. The measurements found linear behavior for all three metals over temperature ranges from 25°C to 1000°C, except for nickel below its Curie point, where the elastic moduli decreased nonlinearly with increasing temperature. The significance of the linear relationship between temperature and elastic constants in molybdenum is discussed in relation to the observed non-Arrhenius behavior of carbon diffusion in molybdenum.
Platinum, and Molybdenum R. FARRARO AND REX. B. McLELLAN A pul se- echo t echni que ut i l i zi ng a wave guide oper at i ng at high t e mpe r a t ur e s has been used to meas ur e the var i at i on i n t he Young' s modul us and shear modul us of pur e pl at i - num, ni ckel , and mol ybdenum i n the t emper at ur e r ange f r om 25 to 1000~ Wi t h the except i on of Ni i n the t emper at ur e r ange bel ow the Cur i e poi nt , l i near behavi or was found for al l t hr ee met al s . The si gni f i cance of the l i near r el at i on bet ween t emper at ur e and the el ast i c const ant s for Mo to the obser ved nonl i near i t y of the Ar r he ni us plot of t he di f f usi v- i t y of car bon i n Mo i s di s cus s ed. I ~ECENT work 1 has poi nt ed out the i mpor t ance of consi der i ng t he vol ume changes i n sol i d sol ut i on f or - mat i on i n under s t andi ng the f or m of t he i nt er act i ons bet ween the component at oms . The effect s of such vol ume changes may be par t i al l y el uci dat ed by a knowl edge of the var i at i on of the el ast i c pr oper t i es of the sol ut i on with sol ut e concent r at i on. Thi s has been the mot i vat i on for me a s ur e me nt s of the var i a- t i on of the el ast i c pr oper t i es of aust eni t e at high t em- per at ur es as a f unct i on of car bon concent r at i on. 2 How- ever , the t emper at ur e var i at i on of the el ast i c pr oper - t i es of pur e met al s, especi al l y at high t emper at ur es , i s al so of i mpor t ance i n el uci dat i ng the cause of depar t - ur es f r om Ar r heni us behavi or obser ved i n cer t ai n cases of i nt er s t i t i al di ffusi on. In the case of the de- par t ur e f r om Ar r heni us behavi or obser ved i n the di f- f usi vi t y of car bon and ni t r ogen i n bcc i r on, Bor g 3 has r el at ed the accel er at i on i n di ffusi vi t y found on appr oach- i ng the Cur i e t emper at ur e with the change found i n t he el ast i c const ant s i n t hi s t emper at ur e r ange. The non- l i near i t y i n the el ast i c modul i of i r on has been meas - ur ed by Dever 4 usi ng bcc i r on si ngl e cr ys t al s . Dever has al so di s cus s ed the anomal ous di ffusi on behavi or of N and C i n i r on i n t e r ms of t he effect of the non- l i near var i at i on i n t he el ast i c modul i on the act i vat i on ent r opy AS for i nt er s t i t i al di ffusi on. Such model s ar e cl osel y r el at ed to the pr oposal of Wut t i g 5 who con- s i der ed di r ect l y the effect on AS due to the change i n the magnet i c st at e. Si nce the el ast i c modul i ar e the second der i vat i ves of the t ot al Hel mhol t z f r ee ener gy wi t h r es pect to s t r ai n, i t i s cl ear t hat the degr ee of spi n or der wi l l be r ef l ect ed i n the el ast i c const ant s. Despi t e di f f er ences i n f or mul at i on, the model s of Borg, 3 Dever , 4 and Wut t i g 5 as cr i be the devi at i ons f r om " nor ma l " di ffusi on behavi or to t emper at ur e var i at i ons i n the t her modynami c f unct i ons char ac- t er i zi ng a s i n g l e - s t a g e di ffusi on mechani s m. Such a s i ngl e- s t age mechani s m has al so been i nvoked by Ki - mur a and Yoshi oka 6 to account for the di ffusi on anomal y i n the Mo-C s ys t em. Thei r anal ysi s is based on the nonl i near var i at i on i n the Young' s modul us of Mo obs er ved by K6st er . 7 However, t hi s model has R. FARRARO is Graduate Student and REX B. MCLELLAN is Professor of Materials Science at Rice University, Houston, Texas, 77001. Manuscript submitted January 25, 1977. been r ecent l y cr i t i ci zed by McLel l an s who has poi nt ed out t hat a sof t eni ng of the par ent met al l at t i ce wi l l l ead to var i at i ons i n the at t empt f r equency of the i nt er s t i t i al at om gi vi ng r i s e to a cur vat ur e i n the opposi t e sense to t hat ar i s i ng f r om the effect on AS. A mor e l i kel y expl anat i on for the Mo- C s ys t em i s the t wo- st age mechani s m i nvol vi ng C- j umps bet ween bot h the oct a- hedr al and t et r ahedr al si t es i n the bcc l at t i ce. Such a mechani s m has been pr oposed e a r l i e r . 9'1~ In or der to r es ol ve the quest i on posed above, i t was deci ded to meas ur e the el ast i c pr oper t i es of pur e Mo i n t he t e mpe r a t ur e r ange i n which t he di ffusi on anomal y i s obser ved. In addi t i on to the r el at i vel y sl i ght cur vat ur e found by KSst er 7 i n the t emper at ur e var i at i on of the Young' s modul us of Mo, he found a much mor e pr onounced effect for Pt and a ver y l ar ge effect i n Ni whi ch st r ongl y depends on the magnet i c st at e. Thus, i t was deci ded to r ei nves t i gat e Ni and Pt al so. E X P E R I M E N T A L M E T H O D A p u l s e - e c h o t e c h n i q u e u t i l i z i n g a m a g n e t o s t r i c t i v e w a v e g u i d e w a s e m p l o y e d t o d e t e r m i n e t h e e l a s t i c c o n s t a n t s o f t h e m a t e r i a l s . T h e s a m p l e s , i n t h e f o r m o f w i r e s c o n f o r m i n g t o t h e t h i n - l i n e l i m i t , 2 w e r e b u t t w e l d e d t o t h e e n d o f t h e w a v e g u i d e . T h e s a m p l e s w e r e h e l d a t t e m p e r a t u r e i n a h o r i z o n t a l f u r n a c e h a v - i n g a c e n t r a l c o n s t a n t t e m p e r a t u r e z o n e o f : ~ 3 ~ a t 1 0 0 0 ~ u n d e r a p r o t e c t i v e f l o w o f h i g h p u r i t y a r g o n g a s . T h e t e m p e r a t u r e w a s m e a s u r e d u s i n g c h r o m e l - a l u m e l t h e r m o c o u p l e s h e l d w i t h i n 1 m m o f t h e s a m p l e w i r e s . T h e t h e r m o c o u p l e s c o u l d b e t r a v e r s e d a l o n g t h e l e n g t h o f t h e s a m p l e . T h e d e t a i l s o f t h e e x p e r i - m e n t a l p r o c e d u r e h a v e b e e n d i s c u s s e d p r e v i o u s l y . 2 T h e Y o u n g ' s m o d u l u s E a n d t h e s h e a r m o d u l u s G a r e r e l a t e d t o t h e l o n g i t u d i n a l ( 1 ) a n d t r a n s v e r s e ( t ) s o u n d v e l o c i t i e s i n t h e m a t e r i a l b y t h e r e l a t i o n s , 2 E = V~p G = V~p where p i s the densi t y of the medi um. Cor r ect i ons wer e made for bot h l engt h and densi t y changes with t e mpe r a t ur e usi ng val ues of the t her mal expansi on coeffi ci ent s of the met al s n The Ni and Pt s ampl es wer e MARZ Grade ma t e r i a l METALLURGICAL TRANSACTIONS A VOLUME 8A, OCTOBER 1977-1563 obt ai ned f r om Mat er i al s Res ear ch Cor por at i on i n t he f or m of 0.049 cm di am wi r es . The Mo was made i nt o a wi r e of the s ame di amet er by r ot at i ng a r od of zone r ef i ned Mo i n an et chi ng sol ut i on. RESULTS The r es ul t s obt ai ned can be seen i n Fi gs. 1, 2, and 3, showi ng pl ot s of E and G as funct i ons of t e mpe r a - t ur e. The val ues of E found for Ni ar e shown i n Fi g. 1. The t r i angul ar dat a poi nt s (4) ar e due to KSst er . In t he t emper at ur e r ange bel ow the Cur i e t emper at ur e, t he me a s ur e me nt s wer e made i n a s at ur at i ng magnet i c field.l~ The dept h of pr onounced mi ni mum seen i n the f er r omagnet i c r egi on i n the demagnet i zed st at e i s de- pendent on the t her mal hi st or y and gr ai n si ze of the sample.12 Thi s effect has been as cr i bed to the effect of r es i dual s t r e s s e s on t he magnet i c or der i ng. 12 The dat a t aken i n the cur r ent i nvest i gat i on ar e i l l us t r at ed by fi l l ed ci r cl es (o t aken on heat i ng) and open ci r cl es (o t aken on cool i ng). The sampl e was anneal ed for 20 h at 1000~ pr i or to maki ng t he me a s ur e me nt s . Af t er terminating the experiment, a metallographic exami- nation showed the grains to be equiaxed and to have a mean diameter about one-third of the wire diameter. 2 6 9 He a t i n g Ni o Coohng K o s | e r z t 6 1 4 i J ] I ..... I , J I ' + ' l 0 (IDO 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 SO0 9 0 0 I 0 0 0 ~ C Fi g. 1- - Te mpe r a t ur e var i at i on of the Young' s modul us of ni ckel . ~8 16 84 14 1 2 . x t O 0 B " 0 6 " O4 0 9 Heat i nq ~ . . ~ o Cool i ng Pt A Kost er I -+--- I - - f - ' - - l I ' - - I I 00 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 ~ ! -+~-+ i 8 0 0 9 0 0 I O00 Fig. 2--Temperature variation of the Young's modulus E and shear modulus G of platinum. 3 4 3 2 ~ - ~ ~ ~ ~ 9 Heotlnq Cooling Mo z~ KOsfer ~o o + ~ " - - , ~ o so*el a do Klerk K)O 2 0 0 5 0 0 6 0 0 9 0 0 I 0 0 0 4 0 0 8 0 0 3 0 0 7 0 0 ~ C 3 0 2 8 ~ 2 6 z . l l O 9 Fi g. 3- - Temper at ur e var i at i on of t he Young' s modul us E and t he s he a r modul us G of mol ybdenum. The posi t i ons of the maxi mum and mi ni mum cor - r espond cl osel y to t hose found by KSst er 12 The dat a do not show any nonl i near i t y above the Cur i e t e mpe r a - t ur e and a l e a s t - s qua r e s r e gr e s s i on of t he dat a poi nt s gi ves the r epr es ent at i on, E = (2.42 - 9.33 10 -4 T 0.092) 1011 N/ r n 2. Fi gur e 2 shows the dat a found for Pt . The sampl e had been anneal ed i n pur e ar gon for 20 h at 1000~ pr i or to maki ng the me a s ur e me nt s . Both the E and G val ues found wer e r epr oduci bl e on heat i ng ( 9 ) and cool i ng ( o ) and the t emper at ur e was cycl ed s ever al t i mes . In con- t r as t to the E val ues det er mi ned by Kbst er , a l i near var i at i on wi t h the t emper at ur e was found. A l eas t - s quar es r e gr e s s i on to the dat a yi el ds the r e pr e s e nt a - t i ons. E = ( 1. 68- 3.38 x I0 -~ T 0.046) 1011 N / m 2 G = (0.624 - 1.15 10 -4 T 0.015) 1011 N / m L The dat a obt ai ned for Mo ar e shown i n Fi g. 3. Agai n, no depar t ur e f r om l i near i t y was det ect ed. The dat a ar e i n good accor d wi t h the low t emper at ur e me a s ur e - ment s of Bolef and de Kl er k. 13 A l east s quar es anal y- s i s yi el ds: E = ( 3. 12- 4.18 10 -4 T 0.63) 1011 N/ m 2 G = (1.27 - 2.23 10 -4 T 0.033) 1011 N / m 2. DISCUSSION With the exception of Ni below the Curie tempera- ture, none of the measured elastic properties ex- hibited a nonlinear variation with temperature. The reason for the discrepancy between the current meas- urements and those of KSster is not obvious. The present measurements on Mo do not support the model of Kimura and Yoshioka s in which the anomalous diffusion behavior in the Mo-C system is based upon a nonlinear variation of the elastic properties of the parent metal with temperature. It has been pointed out s that if the diffusion anomaly is due to a dual site occupancy mechanism, the effect may be observable in the thermodynamic properties of the Mo-C solution at high temperatures. Thermodynamic measurements 1564-VOLUME 8A, OCTOBER 1977 METALLURGICAL TRANSACTIONS A on Mo - C s o l u t i o n s at hi gh t e mp e r a t u r e s a r e c u r r e n t l y be i ng ma d e . ACKNOWLEDGMENT The a u t h o r s a r e g r a t e f ul f o r t he f i n a n c i a l s uppo r t p r o v i d e d by t he Ro be r t A. We l c h Fo unda t i o n. REFERENCES 1. C. Wagner: Acta Met., 1971, vol. 19, pp. 843--49. 2. W. J Arnoult and R. B. McLellan: Acta Met., 1975, vol. 23, pp. 51-56. 3. R. V. Borg: m "Diffusion m Body.Centered Cubtc Metals, "p. 225, Am. Soc. Metals, 1965. 4. D. J. Dever: J Appt. Phys, t972, vol. 43, pp. 3293-3305. 5 M, Wuttlg: Scr. Met., 1975. vol. 5, pp 33-36. 6. H. Kimura and K. Yoshioka. Mats. Sct Eng, 1976, vol. 24, pp. 171-177. 7. W. Koster: Z Metatlk, 1948, vol. 39, pp. 1-9 8. R. B. McLellan Mats. Sci Eng, 1977, vol 28, pp, 161-163. 9~ R. B. McLellan, M. L. Rudee, and T. Ishlbachi. Trans. TMS-AIME, 1965, vol. 233, pp. 1938-1943. 10 R H. Cond~t and D. N. Beshers: Trans. TMS-AIME, 1967, vol. 239, pp. 680- 687. 11. C J. Smithells: "'Metals Reference Book, "Third Edition, 1962, Butterworth's, Wasbangton. I2. W. Koster" Z Metallk, 1943, vol 3, pp. 57-67. 13. D. I Bolef and J. de Klerk" J. Appl. Phys, 1962, vol. 33, pp. 2311-2314. METALLURGICAL TRANSACTIONs A VOLUME 8A, OCTOBER 1977- 1565
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