Temperature Dependence of the Young's

Modulus and Shear Modulus of Pure Nickel,

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