Determination of the Fe-Rich Portion of the

Fe-Ni-C Phase Diagram

A. D. ROMIG, J r . AND J . I. GOLDSTEIN
The i r on- r i c h por t i on of the Fe - Ni - C phase di agr am has been det er mi ned in the composi -
t i on r ange f r om 0 to 20 wt pct Ni and 0 to 6.67 wt pct C for four t emper at ur es , 773, 873,
923 and 1003 K. Long t er m heat t r eat ment s wer e used to)growh the f e r r i t e plus aust eni t e
as s embl ages , whi l e slow cool i ng heat t r eat ment s (25 K/ wer e used to grow the met al
pl us car bi de a s s e mbl a ge s . Ot her t ypes of heat t r eat ment s pr oduced met al pl us gr aphi t e.
The two phase t i e- l i nes and t hr ee phase t i e - t r i a ngl e s wer e meas ur ed usi ng el ect r on mi -
cr opr obe t echni ques. In s ampl es wher e bulk equi l i br at i on had not been achi eved, t i e - l i ne s
wer e obt ai ned by usi ng ext r apol at ed i nt er f ace composi t i ons, on the assumpt i on of l ocal
equi l i br i um at the i nt er f ace. The t i e- l i nes lie at hi gher Ni cont ent s than the equi l i br i um
t i e- l i ne t hr ough the bul k composi t i on. The t i e- l i ne shi ft was r equi r ed to pr oduce mat ch-
ing growt h r at es of Ni and C f or the car bi des . The addi t i on of Ni sl i ght l y r educes the
sol ubi l i t y of car bon in aust eni t e and de c r e a s e s the st abi l i t y of the car bi de phase. In addi -
tion, the car bi de is al ways Ni - poor r el at i ve to the coexi st i ng met al phase( s) .
METALLI C par t i cl es have been obs er ved in met eor -
i r es, 1 and l unar r ocks, and s oi l s . 2 Thes e met al l i c par -
t i cl es ar e pr edomi nant l y i r on- ni ckel with s ma l l
amount s of ot her el ement s i ncl udi ng Co, P, S, and C.
In i r on met eor i t es s e ve r a l t ypes of car bi des have
been obser ved, i ncl udi ng coheni t e, (FeNi)3C and hax-
oni t e, (FeNi)z3C6J Recent l y, coheni t e has al so been
i dent i f i ed in l unar r ocks and s oi l s J A t heor et i cal
phase di agr am f or the Fe - Ni - C s ys t em has been de-
vel oped by Br et t 4 in or der to des cr i be the st abi l i t y
r ange of coheni t e. Al t hough s ome exper i ment al phase
di agr am dat a i s al so avai l abl e, ~-v the ent i r e i r on- r i c h
cor ner of the di agr am has not yet been det er mi ned in
the sol i d phase t e mpe r a t ur e r egi on. The pur pose of
t hi s wor k i s t o det er mi ne exper i ment al l y the sol i d
phase r el at i ons in t he Fe - Ni - C s ys t em. Thi s phase
di agr am i s ne c e s s a r y in or de r to under st and the de-
vel opment of me t a l - c a r bi de as s embl ages obs er ved
in e xt r a t e r r e s t r i a l s ampl es .
Two key pr obl ems have pr event ed the det er mi na-
t i on of the Fe - Ni - C di agr am: a) t her modynami cal l y
unst abl e Fe3C is r ender ed even l es s st abl e by the
gr aphi t i zi ng ef f ect of Ni, which gi ves r i s e to exper i -
ment al and i nt er pr et i ve di f f i cul t i es, and b) the t r ans -
f or mat i on y ~ ~ + y is so sl uggi sh at low t e mpe r a -
t ur es t hat es t abl i s hment of equi l i br i um in a r eas on-
abl e t i me i s ei t her di ffi cul t or i mpos s i bl e. 8 The f i r s t
pr obl em can be cont r ol l ed by s el ect i ng a heat t r eat -
ment whi ch f avor s the nucl eat i on and i ni t i al growt h
of car bi de over gr aphi t e. The second pr obl em in-
vol ves det er mi ni ng t i e- l i nes when bul k equi l i br i um
has not yet been at t ai ned. Ti e - l i ne det er mi nat i on
under such condi t i ons i s, however , possi bl e if the as-
sumpt i on of l ocal equi l i br i um is empl oyed and the two
phase i nt er f ace composi t i ons ar e meas ur ed with the
el ect r on mi cr opr obe. 9
A. D. ROMIG, Jr. is a Research Assistant and J. I. GOLDSTEIN is
Professor of Metallurgy and Materials Engineering, Lehigh University,
Bethlehem, PA 18015. *Removed in melting~
Manuscript submitted December 16, 1977.
ISSN 0360-2133/7811113-1599500.75/0
METALLURGICAL TRANSACTIONS A 9 1978 AMERICAN SOCIETY FOR METALS AND
THE METALLURGICAL SOCIETY OF AIME
EXPERI MENTAL PROCEDURE
Al l oy Pr e pa r a t i on
The t er nar y al l oys used in t hi s study wer e pr e-
par ed by i nduct i on mel t i ng of wei ghed quant i t i es of the
pur e el ement s in al umi na cr uci bl es under a pr ot ect i ve
at mos pher e of ar gon and hydr ogen (see Tabl e I). Com-
pl et e mi xi ng of feed mat er i al occur r ed dur i ng mel t i ng
al t hough most s peci mens showed some por os i t y upon
met al l ogr aphi c exami nat i on. Over 30 ma s t e r Fe - Ni - C
al l oys wer e pr oduced (see Tabl e II).
Af t er mel t i ng, the al l oys wer e homogeni zed at 1473
10 K (1200~ f or 10 to 14 days. To pr event decar -
bur i zat i on and oxi dat i on each al l oy was pl aced in an
al umi na cr uci bl e, and s eal ed under vacuum (~10 ~
Tor r ) in a f used s i l i ca tube. A pi ece of Ta foi l was
al so pl aced in the s i l i ca tube and used as an 02 get t er .
The al l oys wer e t hen quenched in wat er and pr epar ed
f or exami nat i on in the el ect r on pr obe, Homogenei t y
of the sampl e was det er mi ned by r epeat ed pr obe
Table I. Alloy Feed Material Impurity Levels (ppm)
Ni
Fe Ni 99.9 Powder, C
99.999 Rod 99.999 Rod -100 Mesh 99.999 Chips
Ni - solvent solvent -
Si 5 <1 - <1
A1 - <I -
Ca - <1 - -
Cr . . . .
Cu 2 2 50 -
Fe solvent 15 300 -
Mg 2 <1 - <1
Ag <1 <1 - -
Mn 5 - -
C 70 + 3 9 -+1 300 solvent
N 200 + 10 1.2 + 0.5 -
Co <1 - -
0 * - 1000
CO* - - 500 -
VOLUME 9A, NOVEMBER 1978-1599
me a s u r e me n t s o f n i c k e l i n t e n s i t y ( >2 0 p o i n t s ) . T h e
r a n g e o f h o mo g e n e i t y 1~ f o r a c c e p t a b l e a l l o y s wa s
- 0 . 1 wt p c t Ni a t a 9 9 p c t c o n f i d e n c e l e v e l . T h e a v e r -
a g e Ni c o u n t wa s a l s o u s e d t o d e t e r mi n e t h e b u l k
n i c k e l c o n t e n t o f e a c h a l l o y . C a r b o n wa s me a s u r e d o n
e a c h a l l o y a t s e v e r a l p o i n t s t o d e t e r mi n e t h e b u l k
c a r b o n c o n t e n t .
He a t T r e a t me n t s
He a t t r e a t me n t s we r e c a r r i e d o u t i n t u b e f u r n a c e s
c o n t r o l l e d t o wi t h i n ~=0.5 K. A c a l i b r a t e d P t - P t 1 3 R h
t h e r mo c o u p l e wa s p l a c e d n e x t t o t h e s a mp l e s i n t h e
f u r n a c e t o mo n i t o r t h e a c t u a l t e mp e r a t u r e . R e p o r t e d
t e mp e r a t u r e s a r e a c c u r a t e t o K. As i n t h e h o mo -
g e n i z a t i o n t r e a t me n t s t h e a l l o y s we r e v a c u u m e n c a p s u -
l a t e d i n f u s e d s i l i c a t u b e s .
T wo t y p e s o f h e a t t r e a t me n t s we r e u s e d t o p r o d u c e
c~ + y p h a s e a s s e mb l a g e s . 1) Al l o y s we r e a u s t e n i t i z e d
a t 1 2 7 3 K ( 1 0 0 0 ~ a n d t h e n q u e n c h e d i n wa t e r . S u b s e -
q u e n t l y t h e a l l o y s we r e r e h e a t e d t o t h e t e mp e r a t u r e of
i n t e r e s t . T h e 1 0 0 3 K ( 7 3 0 ~ a l l o y s we r e r e h e a t e d f o r
3 0 d a y s a n d t h e 9 2 3 K ( 6 5 0 ~ a l l o y s we r e r e h e a t e d f o r
4 5 d a y s . F o l l o wi n g t h e r e h e a t i n g t r e a t me n t , t h e a l l o y s
we r e q u e n c h e d i n wa t e r . T h e s e s a mp l e s we r e s u i t a b l e
f o r d e t e r mi n i n g t h e ot + y e q u i l i b r i u m t i e - l i n e s . 2) Al -
l o y s we r e a u s t e n i t i z e d a t 1 2 7 3 K ( 1 0 0 0 ~ a n d t h e n
c o o l e d , e i t h e r c o n t i n u o u s l y o r i n o n e s t e p , f r o m t h e
a u s t e n i t i z i n g t e mp e r a t u r e t o t h e t e mp e r a t u r e o f i n -
t e r e s t . T h e ot + 7 p h a s e s p r o d u c e d b y t h i s t r e a t me n t
we r e i n a c o n d i t i o n o f p a r a e q u i l i b r i u m i n wh i c h t h e
c o mp o s i t i o n o f t h e a a n d 7 p h a s e s wa s d i f f e r e n t i a t e d
wi t h r e s p e c t t o c a r b o n b u t wa s o f e q u a l Ni c o n t e n t .
A c o n t i n u o u s s l o w c o o l i n g c y c l e wa s u s e d t o g r o w
t h e me t a l + ( F e Ni ) 3 C p h a s e a s s e mb l a g e s ; ot + ( F e Ni ) 3 C ,
+ ( F e Ni ) 3 C a n d o~ + ), + ( F e Ni ) 3 C . Al l t h e a l l o y s we r e
a u s t e n i z e d f o r 2 4 h a t 1 2 7 3 K a n d c o o l e d a t a r a t e
o f 25 K/ h t o t h e f i n a l h e a t t r e a t me n t t e mp e r a t u r e . T h e
f i n a l h e a t t r e a t me n t t e mp e r a t u r e s a n d t i me s we r e
1 0 0 3 K- 36 h , 9 2 3 K- 60 h, 8 7 3 K- " 9 6 h , a n d 7 7 3 K
- 1 2 0 h . At t h e e n d o f t h e h e a t t r e a t me n t , t h e s a mp l e s
we r e g i v e n a d u p l e x ( wa t e r / l i q u i d Nz ) q u e n c h .
At h i g h e r b u l k Ni c o n t e n t s ( g r e a t e r t h a n 10 wt p c t ) ,
c a r b i d e s c o u l d n o t b e g r o wn b y t h e c o n t i n u o u s s l o w
c o o l i n g c y c l e . E v e r y a t t e mp t t o d o s o p r o d u c e d
+ g r a p h i t e . A t wo - s t e p p r o c e s s wa s t h e r e f o r e u s e d
i n wh i c h t h e a l l o y s we r e f i r s t c o o l e d a t 25 K/ h t o
1 0 0 3 K a n d h e l d a t t h a t t e mp e r a t u r e f o r 2 4 h . T h e
s a mp l e s we r e t h e n c o o l e d i n o n e s t e p t o t h e t e mp e r a -
t u r e o f i n t e r e s t . F i n a l a n n e a l i n g t i me s we r e 3 6 , 4 8 ,
a n d 6 0 h , a t 9 2 3 , 8 7 3 , a n d 7 7 3 K r e s p e c t i v e l y . T h e
s a mp l e s we r e g i v e n a d u p l e x q u e n c h a t t h e e n d o f t h e
h e a t t r e a t me n t .
Ot h e r h e a t t r e a t me n t c y c l e s , s u c h a s q u e n c h i n g a n d
r e h e a t i n g o r d i r e c t q u e n c h i n g f r o m t h e a u s t e n i z i n g
t e mp e r a t u r e t o t h e t e mp e r a t u r e o f i n t e r e s t , p r o d u c e d
me t a l p l u s g r a p h i t e . T h e mi c r o s t r u c t u r e s o f t wo s a m-
p l e s o f i d e n t i c a l c o mp o s i t i o n wh i c h r e c e i v e d d i f f e r e n t
h e a t t r e a t me n t s a r e c o mp a r e d i n F i g . 1.
Tabl e I I . Tabl e of Val ues Used t o Const ruct t he Phase Diagram
Bulk Composition, Temperature, (FeNi)3 C , c~, % 3`,
Alloy Wt Pct Ni Wt Pct C K Matrix Precipitate Wt Pct Ni Wt Pct Ni Wt Pct Ni Wt Pct C Remarks
X9A2 6.0 1.0 1003 Y (FeNi)aC 1.90 -+ 0.05 - 6.45 -+ 0,10 0.71 0.05 GBC
X10A2 7.2 0.5 3` - - - 7.20 0.50
X12A2 3.7 1.0 3` (FeNi)sC 0.55 -+ 0.05 - 4.20 -+ 0.05 0.72 0.20 GBC
X18A2 10.3 1.8 3` (FeNi)sC 4.05 -+ 0.05 - 11.20 -+ 0.10 0.71 0.10 GBC
X19A2 16.8 2.3 3` (FeNi)sC 7.90 -+ 0.10 - 18.40 -+ 0.20 0.71 -+ 0.05 GBC
X16AI* 1.l 0.5 c~ 3` 0.70-+0.05 1.25-+0.10 0. 58
X17AI* 4.4 0.15 ~ 7 2.75-+0.10 4-80-+0.20 0,22-+0-05
X1B2* 14.5 0.2 923 3` - - 14.5 0.20
X2B2* 4.1 1.0 pearlite (FeNi)sC 1.40 -+ 0.10 4.45 +- 0.10 - - GBC
X3B2* 2.0 1.5 pearlite (FeNi)sC 0.60 -+ 0.05 2.40 0.05 - - GBC
X8B2 5.4 1.1 c~ + 3` + (FeNi)3 2.20-+0.10 5.30-+0.10 7.95-+0.20 0. 48
X11B1 9.6 0.02 ct 3` - 5.30 0.10 13.20 -+ 0.20 0.03 -+ 0.03
X14B4 18.1 1.2 3` (FeNi)3C 5.15 0.20 - - 0.40 -+ 0.20 GBC
X15B4 13.7 1 . S. 7 (FeNi)3C 3.20 + 0.05 15.05 -+ 0.20 0.42 -+ 0.10 INC
X1E2* 5.4 0.5 873 a (FeNi)~C 2.85 -+ 0.10 5.55 -+ 0.05 - - pearlite
X2E2* 2.0 1.5 a (FeNi)sC 0.40 -+ 0.10 2.60 -+ 0.10 - - pearlite
X3E2* 4.1 1.0 a (FeNi)3 C 1.10 -+ 0.10 4.50 -+ 0.05 - pearlite
X7E2 6.5 1.0 ~ + 3' + (FeNi)sC N.A. 5.55 -+ 0. I0 t 1,0 -+ 0.20 0.41 -+ 0.20
X12E4 18.1 1.2 7 (FeNi)aC 6.45 -+ 0.10 - 18.85 -+ 0.10 0.35 -+ 0,10 GBC
X13FA 10.3 1.8 7 (FeNi)3 C 2.25 -+ 0.05 - 11.60 -+ 0.10 0.38 -+ 0.15 INC
X1D2 6.3 0.5 773 ~ (FeNi)3C 1.75 -+ 0,10 6.70 -+ 0. I0 - pearlite
X2D2 2.0 1.5 a (FeNi)sC 0.05 -+ 0.05 2.40 -+ 0.10 - - pearlite
X3D2 4.1 1.0 c~ (FeNi)sC 4.55 0.10 1.30 -+ 0. I0 - - pearlite
X4D2 14.2 0,2 3` - - 14.20 0.20
X7D2 6.5 1.0 c~ + 7 + (FeNi)3 C N,A. 6.70 -+ 0.10 12.20 -+ 0.20 0.25 -+ 0.15
Xl l D4 10.3 1.8 c~ + 7 + (FeNi)3C 1.80_+0.05 6. 70_+ 0. t 0 12.10_+0.20 0.25-+0.10 INC
X141M- 14.7 1.9 3` (FeNi)sC 4. I0 -+ 0.10 6.50 -+ 0.10 0.21 -+ 0.10 INC
N.A. = Not available; carbide too
GBC = Grain boundary carbide.
INC = Island Network Carbide.
* = Equilibrated sample.
small for EMP analysis.
1 6 0 0 - VOLUME 9A, NOVEMBER 1978 METALLURGI CAL TRANSACTI ONS A
El ect r on Pr obe Techni que
El ect r on pr obe anal ysi s has s e ve r a l i mpor t ant ad-
vant ages over ot her phase di agr am det er mi nat i on
t echni ques such as X- r a y and quant i t at i ve met al l og-
raphy. If the al l oy phas es ar e in equi l i br i um at t he
des i r ed t e mpe r a t ur e , t he el ect r on pr obe can me a s ur e
the composi t i on of the phases di r ect l y. Ti e - l i ne s can
be obt ai ned di r ect l y by meas ur i ng the composi t i on of
t he two coexi st i ng phases at equi l i br i um. A t hr ee
phase t i e - t r i a ngl e can be obt ai ned f r om one s ampl e
by di r ect l y meas ur i ng the composi t i on of the t hr ee
coexi st i ng phas es . Even when the var i ous phases ar e
not in equi l i br i um, it has been demons t r at ed t hat
phase equi l i br i a dat a can s t i l l be obt ai ned by me a s ur -
ing the i nt er f ace composi t i on of coexi st i ng phases. 9
Thi s pr ocedur e i s sui t abl e as long as equi l i br i um i s
mai nt ai ned at the two phase i nt er f ace.
The heat t r eat ed s ampl es wer e mount ed, pol i shed,
and et ched f or met al l ogr aphi c exami nat i on. In s am-
pl es wher e the phase s t r uct ur e could not be seen in
the as - pol i s hed condi t i on, f i duci ar y mar ks wer e used
to defi ne the a r e a s of i nt er es t f or pr obe anal ysi s. The
sampl e was t hen r epol i shed and coat ed with A1 in a
vacuum evapor at or .
The el ect r on pr obe anal ys es wer e obt ai ned with an
ARL mi cr opr obe. For quant i t at i ve i r on and ni ckel
anal ysi s the el ect r on pr obe was oper at ed at 20 kV and
0.05 ~za s peci men cur r ent . For quant i t at i ve carbon
anal ysi s, t he el ect r on probe was oper at ed at 12.5 kV
and 0.05 ~a s peci men cur r ent . An ai r j et was al so used
to mi ni mi ze car bon cont ami nat i on, zz'~2 A pur e Ni s am-
ple was used for the Ni st andar d and a pur e Fe s am-
pi e was used f or the Fe st andar d. Met eor i t i c coheni t e
(FeNi)3C, f r om the i ron met eor i t e Canyon Di abl o,
whi ch cont ai ns 6.67 wt pct C was used f or the carbon
st andar d. The backgr ound i nt ensi t y f or Ni was meas -
ur ed on pur e Fe and the backgr ound i nt ensi t y f or Fe
was meas ur ed on pure Ni . The backgr ound i nt ensi t y
f or carbon was me a s ur e d on the Fe - Ni f e r r i t e of the
Canyon Di abl o st andar d. A modi f i ed ve r s i on of Col by' s
Magi c IV ~3 ZAF mat r i x cor r ect i on pr ogr a m and the
car bon absor pt i on coef f i ci ent s of Henke and Ebi su z4
wer e used to conver t the mi cr opr obe dat a to composi -
t i on.
(a)
Ti e - Li ne and Ti e - Tr i a ngl e Det er mi nat i on
Concent r at i on pr of i l es of Ni, Fe and C wer e meas -
ur ed acr os s two phase (eL/y, ~/ ( FeNi ) 3C, 7/ (FeNi )3C)
i nt er f aces usi ng the el ect r on mi cr opr obe. The fo-
cused el ect r on beam was el ect r oni cal l y def l ect ed in 1
/zm st eps except in the vi ci ni t y of the two phase i n-
t er f ace wher e 1/ 2 ~m st eps wer e used. A mi ni mum
of t hr ee concent r at i on pr of i l es wer e me a s ur e d f or
each of two a r e a s in ever y al l oy. For the t hr ee phase
(b)
Fig. 1--Microstructure of an Fe-6.0 Ni-l. 0 C alloy (X9A)
heat treated at 1003 K (730~ Sample (a) was cooled at 25
K/h from 1273 to 1003 K and held therefore 36 h prior to
quenching. Structure is austenite (transformed to marten-
site on quenching) and grain boundary carbide. Scale bar
= 45 ~tm. Sample (b) was quenched from 1273 K and reheated
at 1003 K (730~ for 36 h pri or to final quenching. Structure
is austenite (transformed to martensite on quenching) and
spherical graphite precipitates. Scale bar = 500 ~m.
Fig. 2--Fe-10.3 Ni-l. 8 C alloy (X13E4) austenized 24 h at
1273 K then cooled at 25 K/h to 1003 K (730~ and subse-
quently held for 24 h. The alloy was then cooled directly to
873 K (600~ and held for 48 h. Island network carbides are
observed in the austenite matrix. This assemblage has
formed along a pri or austenite grain boundary. Graphite pr e-
cipitation is also present, and the austenite phase has t rans-
formed to lath martensite on quenching from 873 K. Scale
ba r - 40 ~tm. C-island network carbide; T-austenite; G-gra-
phite.
METALLURGICAL TRANSACTIONSA VOLUME 9A, NOVEMBER 1978-1601
al l oys , at l eas t t hr ee concent r at i on pr of i l es wer e ob-
t ai ned a c r os s each t ype of two phas e i nt er f ace. In
addi t i on, i ndi vi dual el ect r on mi c r opr obe anal ys es of
t he ~, 7 or (FeNi)3C phas es wer e obt ai ned in appr o-
pr i at e al l oys .
When t he al l oy was compl et el y equi l i br at ed, as in
the high t e mpe r a t ur e c~ + 7 al l oys , the me a s ur e d com-
posi t i on of each phase was used to defi ne t he two
phase t i e - l i ne . For many of t he car bi de cont ai ni ng
s a mpl e s , Ni gr adi ent s wer e me a s ur e d in t he par ent
7 or ot phas es . I nt er f ace compos i t i ons wer e obt ai ned
by ext r apol at i ng t hes e Ni gr adi ent s to the posi t i on of
t he i nt er f ace. Thes e i nt er f ace val ues wer e a s s ume d to
r e pr e s e nt l ocal equi l i br i um compos i t i ons and wer e
used to def i ne the two phas e t i e - l i ne s with (FeNi)3C.
The appl i cabi l i t y of t hi s t echni que f or t i e- l i ne det er -
mi nat i on wi l l be di s c us s e d in a l at er s ect i on of the
paper .
The t e r na r y i s ot he r ms wer e cons t r uct ed usi ng t he
t i e - l i ne s obt ai ned f r om t he me a s ur e d phase compos i -
t i ons a nd/ or i nt er f ace compos i t i ons . The cur r ent l y
accept ed Fe - Ni equi l i br i um di a gr a m 15 and Fe - C me-
t as t abl e equi l i br i um di a gr a m TM wer e used to es t abl i s h
the bi nar y s i des of t he i s ot he r ma l s ect i ons .
RESULTS
Mi c r os t r uc t ur e s and El ect r on Pr obe Anal ys i s
Aus t eni t e + (FeNi)~C. Two s t r uc t ur e s wer e obs er ved.
The f i r s t t ype oc c ur r e d as thin (2 to 5 ~tm) gr ai n
boundar y car bi des in an aus t eni t i c mat r i x, whi ch ap-
pe a r s as ma r t e ns i t e af t er the fi nal quench. An exam-
pl e of t hi s mi c r os t r uc t ur e i s shown in Fi g. l ( a) . Thi s
s t r uct ur e was obs er ved in al l sl ow cool ed 1003 K
14.
12"
I0-
6-
20 kV
~' (Fe,Ni)3C ~" (Fe, Ni)3 C ~"
rO 20 0 40 50 6
DISTANCE (~rn)
Ca)
u
S"
6'
4'
2'
12. 5 kV
( e:NLL3c r
l - 9 - - w
- ml - -
, _.
IO 20 30 40
DISTANCE (/j,m)
(b)
Fig. 3- - Mi cr opr obe dat a obt ai ned a c r os s the i sl and net work
car bi de s t r uct ur e in a Fe- 10. 3 Ni - l . 8 C alloy (X13E4) heat
t r eat ed at 873 K. The mi c r os t r uc t ur e of t he alloy i s shown
in Fig. 2. Fi gur e 3(a) gi ves the Ni profi l e and Fig. 3(b) gi ves
the C profi l e.
Fig. 4- - Fe- 6. 3 Ni -0. 5 C alloy (X1D2) aust eni zed 24 h at
1273 K then cooled at 25 K/h to 773 K (500~ and held for 120
h. Gr ai n boundary coheni t e i s obser ved in a f er r i t e zone
sur r ounded by a pear l i t i c mat r i x 9 Scale bar = 50 ~tm. a - l e t -
ri t e; C- car bi de; P- pear l i t e.
S
0
6
9 4
12.5 kV
O: ( Fe, Ni ) 3C
*~4,--JL. = . =
20 kV
k 9 .
- g -
,'o 2'0
DISTANCE (#m)
Fig. 5- - Mi cr opr obe dat a obt ai ned acr os s gr ai n boundar y co-
heni t e sur r ounded by f er r i t e in a Fe- 6. 3 Ni -0. 5 C alloy
(X1D2) heat t r eat ed at 773 K. The mi c r os t r uc t ur e of the al -
loy i s shown in Fi g. 4.
1602-VOLUME 9A, NOVEMBER 1978 METALLURGICAL TRANSACTIONS A
(730~ 7 + c ohe ni t e s a mpl e s and i n a l l 7 + c ohe ni t e
s a mpl e s wi t h bul k Ni c ont e nt s gr e a t e r t ha n 15 wt pet
at t he t hr e e l owe r t e mpe r a t ur e s , 923, 873, and 773 K.
At t he t hr e e l owe r t e mpe r a t ur e s , a l l oys wi t h a bul k
Ni c ont e nt l e s s t ha n a ppr oxi ma t e l y 15 wt pct c ont a i ne d
a s ponge - l i ke c ohe ni t e ne t wor k i n a n a us t e ni t i c ma -
t r i x c ont a i ni ng s ome gr a phi t e ( Fi g. 2). Thi s mi c r o-
s t r uc t ur e i s c a l l e d t he i s l a nd ne t wor k c a r bi de s t r uc -
t ur e . Mos t of t he 7 + ( Fe Ni hC a s s e mbl a ge s a l s o s how
gr a phi t e pr e c i pi t a t i on. Fi gur e 3(a) and (b) gi ve an
e l e c t r on pr obe t r a c e a c r os s an i s l a nd ne t wor k c a r -
bi de i n an a us t e ni t i c ma t r i x f or t he Fe - 10. 3 Ni - l . 8 C
al l oy s hown i n Fi g. 2. The c onc e nt r a t i on pr of i l e s ob-
s e r ve d f or gr a i n bounda r y c ohe ni t e i n a n a us t e ni t i c
ma t r i x ( Fi g. l ( a) ) we r e s i mi l a r .
Fe r r i t e + ( FeNi ) aC. The ba s i c mor phol ogy of a
+ ( FeNi ) 3C i n al l t he he a t t r e a t e d a l l oys was pe a r l i t i c .
I n s ome c a s e s gr a i n bounda r y c a r bi de s s ur r ounde d
by a f e r r i t e zone f or me d and we r e s ur r ounde d by
t he pe a r l i t i c ma t r i x. I n ot he r c a s e s , t he pe a r l i t i c
c ol oni e s e xt e nde d a l l t he way t o t he pr i or a us t e ni t i c
gr a i n bounda r i e s . Fi gur e 4 s hows a t ypi c a l pe a r l i t i c
a + ( FeNi ) 3C mi c r os t r uc t ur e . Fi gur e 5 s hows a n e l e c -
t r on pr obe t r a c e a c r os s a gr a i n bounda r y c a r bi de
pr e c i pi t a t e s ur r ounde d by f e r r i t e i n a Fe - 6. 3 Ni - 0. 5 C
a l l oy. The ( FeNi ) aC and a we r e e qui l i br a t e d i n t he
973 and 923 K s a mpl e s . Sma l l gr a di e nt s oc c ur r e d i n
t he pa r e nt a pha s e of t he 773 K s a mpl e s .
Fe r r i t e + Aus t e ni t e . Se ve r a l di s t i nc t mor phol ogi e s
we r e obs e r ve d f or t he f e r r i t e + a us t e ni t e pha s e a s -
s e mbl a ge s . Fi gur e 6(a) s hows a bl oc ky gr a i n bounda r y
(a)
(a)
(b)
Fig. 6--(a) Fe- 4. 0 Ni -0. 1 C alloy aust eni zed 24 h at 1273 K,
cooled di r ect l y to 1003 K (730~ and held at 1003 K for 30
days pr i or to quenchi ng. The mi cr os t r uct ur e i s bl ocky gr ai n
boundary f er r i t e in an aust eni t e mat r i x whi ch has s ubs e-
quent l y been t r ans f or med to mar t ens i t e on quenchi ng. The
(~ and 7 phases have di f f er ent C cont ent s, but i dent i cal Ni
cont ent s. Scal e bar = 320 pm. M- l at h mar t ens i t e; a - l e t -
ri t e, (b) Fe- 10. 4 Ni -0. 2 C alloy aust eni zed at 1273 K for 14
h, cool ed at 25 K/h to 873 K (600~ and held at 873 K f or 96
h pr i or to quenchi ng. The mi cr os t r uct ur e i s Wi dmanst 5t t en
f er t i l e in an aust eni t e mat r i x whi ch has subsequent l y been
t r ans f or med to mar t ens i t e on quenchi ng. The a and 7 phases
have di f f er ent C cont ent s, but i dent i cal Ni cont ent s. Scal e
bar = 40 ~tm. a - f e r r i t e ; 7- aus t eni t e.
(b)
Fig. 7--(a) Fe - l . 1 Ni-O.5 C alloy (X16A1) aust eni zed 24 h at
1273 K, quenched to 70 K and then r eheat ed to 1003 K (730~
for 30 days. The mi cr os t r uct ur e consi st s of gl obul es of aus-
t eni t e in a f er r i t e mat r i x. The a and T phases have di f f er -
ing Ni and C cont ent s. Scal e bar = 100 pm. a - f e r r i t e ; T-
aust eni t e, (b) Fe- 9. 6 Ni -0. 02 C alloy (Xl l B1) aust eni zed 24
h at 1273 K, quenched to 70 K and t hen r eheat ed to 923 K
(650~ for 45 days. The mi cr os t r uct ur e consi st s of a fine
di s per s i on of 7 in a f er r i t e mat r i x. Scal e bar = 50 /~m.
METALLURGICAL TRANSACTIONS A VOLUME 9A, NOVEMBER 1978-1603
f er r i t e s t r uct ur e i n an aust eni t i c mat r i x and Fi g. 6(b)
shows a Wi dmanst ~i t t en pat t er n of f er r i t e in an aust en-
ite mat r i x, Both s t r uct ur es shown i n Fi g. 6 were
f or med on cool i ng and the anst eni t e mat r i x of bot h
s t r uct ur es has subsequent l y been t r ans f or med to ma r -
t ensi l e on quenchi ng. Fi gur e 7(a) shows gl obul ar pr e-
0.7 84
0. 6
0. 5
0.4
0.3
02
0.1
2
0 4 @ @ @
@
12.5 kV
~ A ~ j v w
20 kV
~0 20 30
DISTANCE (/~m)
(a)
ci pi t at es of aust eni t e i n a f er r i t e mat r i x while Fi g. 7(b)
shows a fine di s per s i on of ~ i n a mat r i x of ~. Both
s t r uct ur es shown in Fi g, 7 were f or med af t er r eheat -
i ng of a pr i or mar t ens i t e mat r i x.
Mi cr opr obe anal ysi s of the bl ocky gr ai n boundar y
f er r i t e and Wi dmanst ~t t en f er r i t e (Fi g. 6) shows i den-
t i cal Ni cont ent s in the a and y phases. On the ot her
Fi g. 9- - Fe - 5. 4 Ni - l . 1 C al l oy (XSB2) a us t e ni z e d at 1273 K f or
24 h, cool ed at 24 K/ h to 923 K (650~ and hel d at 923 K f or
60 h. The ma t r i x i s l at h ma r t e ns i t e ( aus t eni t e T pr i or to
f i nal quenchi ng) . Fe r r i t e ~ has nucl eat ed and gr own at pr i or
a us t e ni t e gr a i n bounda r i e s . Coheni t e i s pr e s e nt wi t hi n t he T,
and at af t i nt e r f a c e s . Scal e ba r = 80 ~zm. C- c a r bi de ( gr ai n
boundar y) ; M- ma r t e ns i t e ; ~- f e r r i t e . ( Ar r ows i ndi cat e l oc a -
t i on of coheni t e. )
I0
9
e.
7-
6"
5'
13
II
20 kV
/
oC
I
~0 20
I
3O 40 50 60
\
DI STANCE (/~m)
(b)
Fi g. 8- - ( a) El e c t r on pr obe t r a c e a c r os s t he gl obul ar ce + Y
s t r uc t ur e obt ai ned f r om a heat t r eat ed Fe - l . 1 Ni - 0. 5 C al l oy
(X16A1) s hown i n Fi g. 7( a) , (b) El e c t r on pr obe t r a c e a c r os s
t he f i nel y di s pe r s e d T pha s e obt ai ned f r om a heat t r e a t e d
Fe - 9. 6 Ni - 0. 02 C al l oy ( Xl l B1) whos e mi c r os t r uc t ur e i s
s hown i n Fi g. 7( b) ,
z
.,2
7-
6
5
4
5
I
j
12. 5 kV
,,,, -(Fe, Ni)~
O~
20 kV
L
DISTANCE (/a,m)
Fi g. 10- - Conc e nt r a t i on pr of i l e s a c r os s a t hr e e pha s e a s s e m-
bl age i n an Fe - 5. 4 Ni - l . 1 C al l oy (X8B2) heat t r e a t e d at
923 K. The al l oy mi c r os t r uc t ur e i s s hown i n Fi g. 9.
1604- VOLUME 9A, NOVEMBER 1978 METALLURGICAL TRANSACTIONS A
hand mi c r o p r o b e a n a l y s e s of a and ~ i n t he r e h e a t e d a l -
l o y s ( Fi g. 7) show a r e d i s t r i b u t i o n of Ni b e t we e n t he c~
and ~ p h a s e s . F i g u r e 8(a) g i v e s t he Ni and C c o n c e n -
t r a t i o n p r o f i l e s a c r o s s t he g l o b u l a r a + ~ a s s e mb l a g e
s hown i n F i g . 7(a) and 8(b) g i v e s t he Ni c o n c e n t r a t i o n
p r o f i l e a c r o s s t he f i ne d i s p e r s i o n of V i n a n a ma t r i x
s hown i n F i g . 7(b). The c a r b o n cont ent of t he y p h a s e
i n t he F e - 9 . 6 Ni - 0 . 0 2 C a l l o y wa s v e r y s ma l l , c l o s e
t o t he d e t e c t a b i l i t y l i mi t . T h e r e f o r e , t he e l e c t r o n
p r o b e d a t a f or C i s not s hown i n F i g . 8(b).
F e r r i t e + Au s t e n i t e + ( FeNi ) 3C. Al l t h r e e p h a s e
a l l o y s s how s i mi l a r mo r p h o l o g i e s , s e e F i g . 9. The
ma t r i c e s a r e c o n s i s t e n t l y a u s t e n i t e whi ch ha s t r a n s -
f o r me d t o l a t h ma r t e n s i t e on f i na l que nc hi ng. The
f e r r i t e ha s a b l o c k y s t r u c t u r e and a p p a r e n t l y nu-
c l e a t e d a t p r i o r a u s t e n i t e g r a i n b o u n d a r i e s . Th e
c a r b i d e s we r e f ound t o t a l l y wi t hi n c~, t o t a l l y wi t hi n V,
a nd a t t he o~/v i n t e r f a c e s . A c o n c e n t r a t i o n p r o f i l e
f r o m y t o ~ t o ( FeNi ) ~C t o a p h a s e i n a F e - 5 . 4 Ni - l . 1
C a l l o y h e a t t r e a t e d at 923 K i s s hown i n F i g . 10. The
l o c a t i o n of t he mi c r o p r o b e a n a l y s i s i s i n d i c a t e d by t he
a r r o w on t he mi c r o s t r u c t u r e s hown i n F i g . 9. The
c a r b o n cont ent of f e r r i t e i s e s s e n t i a l l y z e r o , a nd
c ohe ni t e a l wa y s c o n t a i n s 6. 67 wt pc t C. The i n t e r f a c e
c o mp o s i t i o n v a l u e s f or e a c h of t he t h r e e p h a s e s di d
7
6
5
3
2
I
Fe-Ni-C
(Fe, Ni)I,C -
Q ~ 1 0 0 3 " K
, (730"C1
D Shormo e t o l
Z~ bulk composition
0 this study(interface composition)
9 t hi s study {OOUilibfot~6
compositio.)
N ~ C
"
= + t - ~ t
9 I I I l I . - ~
IO t2 14 16 18 20
Wt . %N i
Fe-Ni-C
7 ( Fe, Ni).,jC
9 2 3 " K
6 ~ ( sso' c)
~ L", but k composition
5 0 }nterfoce composition
9 e(luilibroted composition
U 4
(Fo, Ni)3C
', ~ i , , . , ~ ' ~ ,
2 " 4 6 8 I 0" 12 14 16 18 20
Wt . %N i
(b)
Fig. 11--Full isothermal sections at (a) 1003 K, (b) 923 K,
(c) 873 K and (d) 773 K, extending to 20 wt pet Ni and 6.67 wt
pct C.
7
!
?
6
5
4
2
I '
Fe-Ni -C
( Fe, Ni hC
(600"C)
[3 Hut f qr en, et ol.
bul k composition
0 t hi s study (interfoce composition)
9 1hi1 Sl a t y | equi l i br ot ed composition)
Fe,Ni)3C
r162 2 4 6 8 , I 0 12 14 16 18 ZO
Wt %N i
( : )
Fe-Ni-C
7 7 3 " K
Fe, Ni)3C
: ; " 4 S 8 I 0 12 14 16 l e 20
Wt.% Ni
(d)
not v a r y wi t h t he mo r p h o l o g y of t he t wo p h a s e i n t e r -
f a c e s .
S u mma r i z i n g t he e l e c t r o n p r o b e da t a , c a r b o n g r a d i -
e n t s we r e not o b s e r v e d in t he V pha s e and Ni g r a d i e n t s
we r e not o b s e r v e d i n any of t he c a r b i d e s . I n t he a + y
a s s e mb l a g e s , Ni g r a d i e n t s we r e not o b s e r v e d i n t he
f e r r i t e . When a u s t e n i t e wa s g r o wi n g i nt o f e r r i t e , F i g .
8(a), Ni p r o f i l e s i n ti~e ~ p h a s e we r e a l s o f l a t . How-
e v e r f or c a s e s when f e r r i t e wa s gr owi ng i nt o a u s t e n -
i r e, F i g . 8(b), s t e e p Ni g r a d i e n t s we r e o b s e r v e d i n t he
a u s t e n i t e p h a s e . I n t he me t a l c a r b i d e a s s e mb l a g e s ,
Ni g r a d i e n t s whi c h d e v e l o p e d i n t he s u r r o u n d i n g me t a l
p h a s e we r e s t e e p e r in t he a u s t e n i t e t ha n i n t he f e r r i t e
( c o mp a r e F i g s . 3, 5, and 10).
I s o t h e r ma l Se c t i o n s
The t i e - l i n e and t i e - t r i a n g l e v a l u e s u s e d t o pl ot t he
p h a s e d i a g r a ms we r e o b t a i n e d by e x t r a p o l a t i n g t he Ni
c o n c e n t r a t i o n g r a d i e n t s t o t he t wo p h a s e i n t e r f a c e . I n
p h a s e s wh e r e c o n c e n t r a t i o n g r a d i e n t s we r e a b s e n t t he
bul k c o mp o s i t i o n of t hat p h a s e de f i ne d an e ndpoi nt of
t he t i e - l i n e o r t i e - t r i a n g l e . F o r e x a mp l e , i n t he t h r e e
p h a s e F e - 5 . 4 Ni - l . 1 C a l l o y he a t t r e a t e d at 923 K
( F i g s . 9 a nd 10), t he f e r r i t e c o r n e r of t he t i e - t r i a n g l e
h a s a c o mp o s i t i o n of ~0 wt pc t C and 5. 25 wt p c t Ni .
The c ohe ni t e a nd a u s t e n i t e c o r n e r s have a c o mp o s i -
t i on of 6. 67 wt pc t C, 2. 20 wt pc t Ni a nd 0. 50 wt p c t
METALLURGICAL TRANSACTIONS A VOLUME 9A, NOVEMBER 1978-1605
C and 7.95 wt pct Ni r espect i vel y. The car bi de cam- 07
posi t i on is const ant while concent r at i on gr adi ent s
ar e pr es ent i n the adj acent aust eni t e and f er r i t e
O 6
(Fi g. 10). Hence, and a and y composi t i ons were ob-
t ai ned by ext r apol at i on of the Ni concent r at i on gradS- o.s.
ent to the a / 7 two phase i nt er f ace. The gr adi ent i n the
aust eni t e was s t eeper maki ng the ext r apol at i on some-
what l ess accur at e, o o4
Tabl e H s umma r i z e s the t i e- l i ne and t i e- t r i angl e ~ o3
endpoi nt s used to plot the i s ot her mal sect i ons, as de-
t er mi ned f r om the el ect r on probe concent r at i on pr o-
f i l es. For unequi l i br at ed sampl es each val ue l i st ed o2
r epr es ent s the aver age of at l east si x i nt er f ace com-
posi t i ons. Typi cal l y t en r andom poi nt s were anal yzed o~
i n each phase which had a fl at concent r at i on pr of i l e.
The r ange of dat a s cat t er is al so shown in Tabl e II.
Fi gur es 11 and 12 show the four i s ot her mal sect i ons
at 1003, 923, 873 and 773 K. Two i s ot her ms ar e shown
for each t emper at ur e. The f i r st ext ends to 6.67 wt pct
C ( st oi chi omet r i c coheni t e). The second i s an ex-
pansi on of the low car bon r egi on. Both the bul k com-
posi t i on of the exper i ment al al l oys and the cor r e-
spondi ng t i e- l i ne composi t i ons ar e pl ot t ed on the
phase di agr am. Ti e- l i ne dat a obt ai ned f r om equi l i b-
r at ed s ampl es and f r om ext r apol at ed i nt er f ace cam-
9 o.8t
Fe-Ni-C
L8-
1003. K
I # " ' - ~ ~. ( . o - ~ )
04 ~ ] / t ~ ' ~ - - 0 this Study (interface composition)
] / / , / . . . / ~ ----/ ~ Shui~176
I I t /r162 / / " ~ 9 this study{equilibrated
~ _ ~ composition)
; 2 3 4 5 6 7 8 9 I0 I I IZ
Wt . % Ni
F e - N i - C
/ l
I (650"C)
0.6 | OL+~" ZI bul k composition -~.+(Fe, Ni)3C
+ D interface composition
(Fe Ni)3C
0.5 . ' 9 equilibrated composition
0.4
~. +( F )aC
. ,o ,o ,~ ~o
Wt %N i
(b)
Fi g. 12--Expanded i sot her mal sect i ons at (a) 1003 K, (b)
923 K, (c) 873 K, and (d) 773 K, extending to 20 wt pct Ni and
0.7 wt pct C (1.8 wt pct C at 1003 K).
0.7.
0 6
05.
04.
U
9 03.
02..
01.
~ + (Fe, Ni)3C
4
F e - N i - C
(600"C1
/ I | ! D ~. . g, e. . ot o, 1
~l ~ ~ bulk composition
I I I ~ o this study (interface compoeition)
/ ~ e this study (equilibrated
~' T ~ composition)
I I | I ~r+(Fe a,)3C I
6 8 I0
Wt . % Ni
(c)
F e - N i - C
+ (Fe,Ni)3C
12 14 16 18 20
7 7 3 " K
( 500* C)
A bulk coral ,osition
o intarfoc composition
~r+ (Fe, Ni)3C
8 I0 12 14 16 IB 20
Wt %Ni
(d)
posi t i ons ar e di f f er ent i at ed on the phase di agr ams .
Where avai l abl e the exper i ment al dat a of ot her i nves-
t i gat or s were i ncl uded. Si nce a + y al l oys were not
pr epar ed at the l ower t emper at ur es (873, 773 K), the
(at + y) / 7 sol vus l i ne shown i s onl y est i mat ed.
DISCUSSION
Assumpt i on of Local I nt er f ace Equi l i br i um
When two phases ar e separ at ed by a movi ng i nt er -
face, t r ue equi l i br i um cannot exi st at t hat i nt er f ace. 17'18
In the equi l i br i um condi t i on the chemi cal pot ent i al for
a gi ven el ement i n each phase must be equal . How-
ever if the chemi cal pot ent i al s at the two phase i n-
t er f ace ar e equal , t her e wi l l be no dr i vi ng f or ce to
move the i nt er f ace. Hence, a s mal l amount of l ocal
i nt er f ace di s equi l i br i um is r equi r ed to pr omot e phase
growt h or to al l ow i nt er f ace mot i on. The key con-
si der at i on t hen i s how far r emoved f r om equi l i br i um
ar e the i nt er f ace composi t i ons. If the devi at i on f r om
equi l i br i um i s s ma l l e r t han the e r r or as s oci at ea with
the t echni que used to meas ur e the i nt er f ace composi -
t i on, one can t r eat the i nt er f ace as if it were at equi -
l i br i umY Exper i ment al evi dence obt ai ned in t hi s i n-
vest i gat i on as wel l as in a maj or i t y of the cases r e-
por t ed i n the l i t er at ur e i ndi cat e t hat the amount of
i nt er f ace di s equi l i br i um when compar ed to r es ul t s
1606-VOLUME 9A, NOVEMBER 1978 METALLURGICAL TRANSACTIONS A
Table I I I . Some Binary Systems Where Interface Equilibrium Has Been
Investigated wi th the Electron Microprobe
Time to
Sys t e m Temperature, K Equilibration, h Reference
Ag-Zn 873 <12 19
A1-Ni 1273-1573; 873 <340; <24 20, 21
Au-Co 1223, 1173 >4 22
Fe-C 1023-1061 <0.2 23
Nb-Cr ~1373 <167 24
Nb-Fe ~1373 <48 24
Nb-Mo ~1373 <48 24
Nb-Ni ~1373 <24 24
Nb-Ti 823-1213 <96 at 1213 K 25
Re-W 2497-2700 <1.6 23
Cu-AI 1073, 1178, 1273 Not attained in 85 26
at 1073 K
f r om equi l i br at ed al l oys i s wi t hi n the anal yt i cal
s ens i t i vi t y of the el ect r on mi cr opr obe, often 0.01 wt
pet . 19-e6 A s umma r y of the exper i ment al evi dence is
gi ven in Tabl e HI.
The condi t i on of near or l ocal i nt er f ace equi l i br i um
is not achi eved i nst ant aneousl y. Whet her the second
phase i s pr oduced in a di ffusi on coupl e, or pr eci pi -
t at ed in a homogeni zed par ent phase, a fi ni t e l engt h
of t i me wi l l be r equi r ed f or near or l ocal equi l i br i um
t o be est abl i shed at the i nt er f ace. For the ease of di f-
fusi on coupl es, i nves t i gat or s r epor t t i mes of up to
s e ve r a l hour s f or the i nt er f ace composi t i on to ap-
pr oach the equi l i br i um val ue (Tabl e Il l ). For gr owi ng
pr eci pi t at es , near equi l i br i um at the i nt er f ace cannot
exi st unt i l the i nt er f ace becomes ful l y i ncoher ent . At
ver y low t e mpe r a t ur e s phase growt h may be con-
t r ol l ed by i nt er f aei al di ffusi on (grai n boundary, and
so fort h) r a t he r t han vol ume di ffusi on. 27'28 What ef f ect
t hi s change in growt h mechani s m has on i nt er f ace
equi l i br i um is cur r ent l y unknown and war r ant s f ur -
t her exper i ment al i nvest i gat i on.
In t hi s st udy the assumpt i on of l ocal i nt er f ace equi -
l i br i um appear s val i d f or the case of ot + (FeNi)3C t i e-
l i nes. Onl y at the l owest exper i ment al t e mpe r a t ur e
(773 K) was any ext r apol at i on ne c e s s a r y (see Fi gs .
11 and 12). The ext r apol at i on at t hi s t e mpe r a t ur e was
no l a r ge r t han 0.2 wt pct Ni, i ndi cat i ng t hat equi l i -
br i um had near l y been obt ai ned (see Fi g. 5). As seen
in the 973 and 923 K i s ot her ms ( Fi gs. 11 and 12), the
sl opes of t he o~ + (FeNi)3C t i e- l i nes ar e es s ent i al l y
const ant with t e mpe r a t ur e . The sl opes of the
+ (FeNi)3C t i e- l i nes at 773 K ar e vi r t ual l y i dent i cal
to the hi gher t e mpe r a t ur e sl opes. Thi s consi st ency
of t i e- l i ne sl opes obt ai ned f r om both equi l i br at ed al -
loys and f r om al l oys wher e i nt er f ace composi t i ons
wer e me a s ur e d suppor t s the assumpt i on of l ocal i n-
t er f ace equi l i br i um.
Fi gur e 13(a) and (b) shows exper i ment al conf i r ma-
t i on of the concept of l ocal i nt er f ace equi l i br i um for
ol + y a s s e mbl a ge s . Fi gur e 13(a) shows a Ni pr of i l e
f or equi l i br at ed ~ + y phases in an Fe- 4. 4 Ni - 0. 15 C
al l oy t e mpe r e d at 1003 K (730~ The Ni sol ubi l i t y is
1.7 wt pct in f e r r i t e and 4.8 wt pct Ni in aust eni t e.
Fi gur e 13(b) shows a Ni pr of i l e for the case of f er r i t e
gr owi ng in an aust eni t e mat r i x in anot her a r e a of the
s ame al l oy wher e the ~- y phases ar e not equi l i b-
r at ed. The ~ phase has a const ant composi t i on of 1.7
wt pct Ni . However , Ni gr adi ent s exi st in the par ent
aust eni t e. The ext r apol at ed i nt er f ace composi t i on of
t he aust eni t e i s 4.8 wt pct Ni . Bot h the equi l i br at ed
and unequi l i br at ed ~ - y as s embl ages yi el d the s ame
t i e- l i ne. Equi l i br i um was pr obabl y obt ai ned e a r l i e r
in some a r e a s of t hi s al l oy because of l ocal i mpi nge-
ment ef f ect s. Thi s t i e- l i ne agr eement i ndi cat es that
the assumpt i on of l ocal i nt er f ace equi l i br i um is al so
val i d for ~ + ~ phase a s s e mbl a ge s .
No di r ect evi dence is avai l abl e to subst ant i at e l ocal
equi l i br i um f or the case of car bi de growt h in y. How-
ever the Ni concent r at i on pr of i l es f or (FeNi)sC growt h
in 7 ar e ver y s i mi l a r to t hose f or ~ growt h in y (Fi g.
3(a) v s Fi g. 8(b) and 13(b)) and to s ome ext ent s i mi -
l ar to t hose f or car bi de growt h in ~ (Fi g. 3(a) v s Fi g.
5). The Ni gr adi ent s devel oped dur i ng car bi de growt h
in the par ent ~ phase ar e s t eeper t han the Ni gr adi ent s
in the par ent ~ phase. In bot h cases Ni is r ej ect ed
f r om the gr owi ng car bi de and must di ffuse wi t hi n the
6
Fig. 13--Ni profiles across 5
ce- y assemblages in an Fe-
4.4 Ni-0.15 C alloy quenched
and tempered at 1003 K for " - - 4
30 days. In this heat t reat - Z
ment c~ grows in a y matrix.
Figure 13(a) shows equili-
brated (~-' y phases with a 9 :3
Ni solubility of 4.8 wt pct in
5'. Figure 13(b) shows an-
other area of the same alloy 2
where the c~ - y phases are
not equilibrated.
a
b
m ,
(4.8 wt.%Ni)
u
B u l k N i C o n t e n t
E q u i l i b r a t e d ~ - r
/ ( 4 . 8 wt.%Ni)
I"
G r o w t h o f ~ , P h a s e
I ~ I
I 0 2 O 3 0 4 0
I 0 2 0 3 0 4 0
D I S T A N C E ( ~ m )
METALLURGICAL TRANSACTIONS A VOLUME 9A,NOVEMBER 1978-1607
ma t r i x a wa y f r o m t he gr owt h i n t e r f a c e . At t he s a me
t e mp e r a t u r e Ni d i f f u s e s mo r e s l o wl y t h r o u g h f c c r
t ha n t h r o u g h b c c o~ r e s u l t i n g i n s t e e p e r g r a d i e n t s .
Si nc e t he n i c k e l d i s t r i b u t e s i t s e l f s i mi l a r l y i n bot h o~
a nd r p a r e n t p h a s e s , l o c a l i n t e r f a c e e q u i l i b r i u m i s
a l s o a s s u me d t o be v a l i d f or c a r b i d e g r o wt h i n 7.
E l e c t r o n P r o b e Me t h o d - P r e c i s i o n and Ac c u r a c y
The mo s t s i g n i f i c a n t s o u r c e of e r r o r i n t he d e t e r -
r ui na t i on of t h i s pha s e d i a g r a m i s due t o t he e l e c t r o n
p r o b e a n a l y s i s t e c h n i q u e . Th i s e r r o r s o u r c e can be
d i v i d e d i nt o t wo p a r t s . The f i r s t s o u r c e of e r r o r i s
due t o t he s t a t i s t i c a l n a t u r e of t he d a t a whi c h i n t u r n
l e a d s t o t he a n a l y t i c a l s e n s i t i v i t y a nd d e t e c t a b i l i t y
l i mi t of t he t e c h n i q u e . The mi n i mu m e r r o r t ha t c a n
be a s s o c i a t e d wi t h a ny c o mp o s i t i o n d e t e r mi n a t i o n i s
t he a n a l y t i c a l s e n s i t i v i t y . Us i n g t he o p e r a t i n g p a r -
a me t e r s p r e v i o u s l y d e s c r i b e d , t he d e t e c t a b i l i t y l i mi t
of c a r b o n a t t he 95 pc t c onf i de nc e l i mi t , i s 0. 02 wt
p c t C, a s c a l c u l a t e d by t he me t h o d of Zi e b o l d . 1~ The
a n a l y t i c a l s e n s i t i v i t y 1~ wa s c a l c u l a t e d a s 0. 01 wt pc t
f o r n i c k e l and 0. 02 wt pc t f or c a r b o n .
The s e c o n d s o u r c e of e r r o r i s due t o t he me a s u r e -
me nt of i n t e r f a c e c o mp o s i t i o n . The X- r a y s whi ch a r e
g e n e r a t e d i n t he s a mp l e do not n e c e s s a r i l y e me r g e
t h r o u g h ma t e r i a l of t he s a me c o mp o s i t i o n p a r t i c u l a r l y
i n t he v i c i n i t y of an i n t e r f a c e . The ZAF ma t r i x c o r -
r e c t i o n mo d e l , h o we v e r , a s s u me s t ha t t he X- r a y s a r e
g e n e r a t e d and p a s s t h r o u g h ma t e r i a l of t he s a me c o m-
p o s i t i o n . Whe n t h i s a s s u mp t i o n i s v i o l a t e d t he con-
v e r s i o n of X- r a y i n t e n s i t y to we i ght p e r c e n t i s not un-
a mb i g u o u s . Th i s i n a c c u r a c y wa s mi n i mi z e d by t he hi gh
t a k e - o f f a ngl e of t he ARL e l e c t r o n p r o b e (52. 5 de g) . A
c e r t a i n a mo u n t of e r r o r was due t o t he e x t r a p o l a t i o n
of t he me a s u r e d c o n c e n t r a t i o n g r a d i e n t t o t he i n t e r -
f a c e . Th e o b s e r v e d c o n c e n t r a t i o n g r a d i e n t s we r e no
l a r g e r t han 0. 1 wt p c t Ni p e r ~ m, s o t hat t he e x t r a p -
o l a t i o n s we r e a t mo s t 0. 1 wt pc t Ni .
The e r r o r s r e p o r t e d i n Ta b l e I I r e p r e s e n t t he
s p r e a d i n e x t r a p o l a t e d i n t e r f a c e c o mp o s i t i o n s . To
o b t a i n t he t i e - l i n e v a l u e s gi ven i n Ta b l e I I , t he a v e r -
a ge i n t e r f a c e va l ue f or a l l t he p r o b e t r a c e s i n e a c h
s a mp l e was c a l c u l a t e d . E r r o r r a n g e s we r e t he n e s -
t a b l i s h e d s o t hat a l l i n t e r f a c e c o mp o s i t i o n s woul d l i e
wi t hi n t he r e p o r t e d e r r o r s . Ca r b o n p r o f i l e s we r e a l -
wa y s f l a t , s o t hat no e x t r a p o l a t i o n wa s r e q u i r e d . How-
e v e r , t h e r e wa s c o n s i d e r a b l e s c a t t e r a bout t he a v e r a g e
C va l ue f o r e a c h p r o b e t r a c e . The e r r o r r a n g e wa s e s -
t a b l i s h e d s o t ha t t he s c a t t e r of a l l C d a t a wa s i n-
c l ude d wi t hi n t he r a n g e . I n a l l c a s e s t he e r r o r r a n g e s
a r e muc h l a r g e r t han t he r a n g e s p r e d i c t e d f r o m a
c o n s i d e r a t i o n of a n a l y t i c a l s e n s i t i v i t y a l o n e .
P r e v i o u s Wo r k
The me a s u r e d F e - Ni - C i s o t h e r ma l s e c t i o n s a r e
qui t e s i mi l a r t o t h o s e p r e d i c t e d by Br e t t . 4 T h e r e a r e ,
h o we v e r , s e v e r a l ke y d i f f e r e n c e s . The me a s u r e d
t h r e e p h a s e f i e l d s , a + 7 + ( Fe Ni ) s C e x t e n d o v e r a
muc h s ma l l e r Ni r a n g e t ha n p r e d i c t e d by Br e t t . I n
a d d i t i o n t he me a s u r e d ma x i mu m s o l u b i l i t y of c a r b o n
i n a u s t e n i t e i s s i g n i f i c a n t l y l e s s t ha n t he p r e d i c t e d
v a l u e . The d i f f e r e n c e s b e t we e n t he p r e d i c t i o n of Br e t t
and t he me a s u r e d d i a g r a m c a n bd a t t r i b u t e d t o t he
1608-VOLUME 9A, NOVEMBER 1978
f a c t t hat t he p r e d i c t i o n i s a s i mp l e e x t r a p o l a t i o n f r o m
t he b i n a r y d i a g r a ms .
The a mount of p r e v i o u s d a t a a v a i l a b l e f or c o mp a r i -
s on i s v e r y l i mi t e d . Al t hough a few t i e - l i n e s have
be e n me a s u r e d , no c o mp l e t e i s o t h e r ms have b e e n d e -
t e r mi n e d . The a + 7 t i e - l i n e s (1103 K) p r e d i c t e d by
S h a r ma and Ki r k a l d y 7 we r e c o n s i s t e n t wi t h t hos e
me a s u r e d i n t h e s e e x p e r i me n t s (not e F i g s . 11 and 12).
One ~ + ( FeNi ) 3C t i e - l i n e (873 K) was d e t e r mi n e d by
Hul t gr e n. 5 Th i s t i e - l i n e pl ot s c o h e r e n t l y wi t h t h o s e
d e t e r mi n e d i n t hi s s t u d y . The a g r e e me n t b e t we e n t hi s
wo r k and 1 wt pc t C v e r t i c a l s e c t i o n of Sa mu e l , et al 6
i s , h o we v e r , p o o r . Th i s d i s c r e p a n c y i s mo s t p r o b a b l y
due t o t he f a c t t hat Ni - b e a r i n g s t e e l s c ont a i ni ng 0. 3
wt pc t Mn, 0. 2 wt p c t Si , and o t h e r t r a c e i mp u r i t i e s
we r e u s e d . 6
Ca r b i d e Nu c l e a t i o n
The c a r b i d e p h a s e s n u c l e a t e a l ong t he p r i o r a u s t e n -
i t e g r a i n b o u n d a r i e s of t he F e - Ni - C a l l o y s . Re g a r d -
l e s s of t he f i na l mi c r o s t r u c t u r e , n u c l e a t i o n a l wa y s
o c c u r r e d i n t he a u s t e n i t e . F o r t he 7 + ( Fe Ni ) s C a l l o y s
g r a i n b o u n d a r y n u c l e a t i o n can be c l e a r l y o b s e r v e d .
The c o r e s of t he i s l a n d n e t wo r k c a r b i d e s a l s o c oi n-
c i de d wi t h a u s t e n i t e g r a i n b o u n d a r i e s ( s e e F i g s . l ( a )
and 2).
F o r t he o~ + ( FeNi ) 3C a l l o y s n u c l e a t i o n of t he c a r -
b i d e s a l s o o c c u r r e d at t he a u s t e n i t e g r a i n b o u n d a r i e s
on c ool i ng. As t he c a r b i d e s gr e w t he y d e p l e t e d t he
s u r r o u n d i n g me t a l of c a r b o n p r o d u c i n g a r i m of f e r -
r i t e . When t he t e mp e r a t u r e f e l l be l ow t he e u t e c t o i d
t e mp e r a t u r e t he a u s t e n i t e i n t he g r a i n i n t e r i o r t r a n s -
f o r me d t o p e a r l i t e ( s e e F i g . 4).
Ca r b i d e n u c l e a t i o n i n t he t h r e e - p h a s e a l i o y s a l s o
o c c u r r e d a t t he p r i o r a u s t e n i t e g r a i n b o u n d a r i e s . The
c a r b i d e n u c l e a t e d a l o n g t he g r a i n b o u n d a r y and b e g a n
t o gr ow. One of t he t h r e e gr owt h s e q u e n c e s t hen o c -
c u r r e d . Ei t h e r t he c a r b i d e c ont i nue d t o gr ow i n 7 o r
t he c a r b i d e e x h a u s t e d t he l o c a l s u p p l y of c a r b o n
t h e r e b y s u r r o u n d i n g i t s e l f wi t h ~ p h a s e o r a c o mb i n a -
t i on of a a nd 7 p h a s e r e g i o n s e v e n t u a l l y d e v e l o p e d .
T i e - L i n e Mot i on Du r i n g Ca r b i d e Gr owt h
F o r t e r n a r y t wo p h a s e a l l o y s t he me a s u r e d t i e -
l i n e s do not go t h r o u g h t he bul k a l l o y c o mp o s i t i o n un-
l e s s t he s a mp l e i s c o mp l e t e l y e q u i l i b r a t e d d u r i n g he a t
t r e a t me n t . The r e q u i r e me n t s of ma s s c o n s e r v a t i o n
and l o c a l i n t e r f a c e e q u i l i b r i u m i n t e r n a r y s y s t e ms
p e r mi t p h a s e g r o wt h t o o c c u r by c ont i nuous a d j u s t -
me nt i n t he t i e - l i n e s e l e c t e d d u r i n g t he g r o wt h of t he
p r e c i p i t a t e . 2 9 ' ~
F o r p h a s e g r o wt h i n a t e r n a r y s y s t e m, t he g r o wt h
r a t e , d~/ dt , of t he p r e c i p i t a t e i s gi ve n by e a c h c o m-
ponent of t he a l l o y . To s a t i s f y t hi s r e q u i r e me n t :
d~Ni d ~ c d~ [1]
dt dt dt
, . . d ~ N i . d ~ c
i n wmc n ~ ar i a ~ } - a r e t he g r o wt h r a t e s gi ve n by
t he f l ux of Ni a nd C a t o ms r e s p e c t i v e l y . Si nc e t he
di f f us i on r a t e of C i s muc h g r e a t e r t ha n t ha t of Ni i n
d~ C d~Ni
a u s t e n i t e , - ~ wi l l i n g e n e r a l be g r e a t e r t ha n - - ~ - - .
METALLURGICAL TRANSACTIONS A
T o s a t i s f y E q . [ 1] , a t i e - l i n e s h i f t i s r e q u i r e d . T h i s
s h i f t wi l l b e o n e wh i c h wi l l i n c r e a s e t h e Ni g r a d i e n t
i n a u s t e n i t e a n d , t h e r e f o r e , t h e Ni f l u x b y i n c r e a s i n g
t h e Ni c o n t e n t a t t h e ~ , / c a r b i d e i n t e r f a c e .
T o a c h i e v e t h i s h i g h e r g r o wt h r a t e wi t h r e s p e c t t o
Ni t h e t i e - l i n e wh i c h o c c u r s f o r i n i t i a l c a r b i d e g r o wt h
wi l l b e d i s p l a c e d t o h i g h e r Ni c o n t e n t s . As t h e c a r -
b i d e g r o ws , t h e t i e - l i n e wi l l s l i d e b a c k t o wa r d t h e
b u l k c o mp o s i t i o n . I f e q u i l i b r i u m we r e a c h i e v e d t h e
t i e - l i n e wi l l p a s s d i r e c t l y t h r o u g h t h e b u l k c o mp o s i -
t i o n . As s h o wn i n F i g s . 11 a n d 1 2 , t h e T + ( F e , Ni ) 3 C
t i e - l i n e s d o n o t p a s s t h r o u g h t h e b u l k c o mp o s i t i o n .
Mo s t o f t h e t i e - l i n e s l i e t o t h e r i g h t o f t h e b u l k c o m-
p o s i t i o n ( h i g h e r Ni c o n t e n t s ) , wh i c h i s c o n s i s t e n t wi t h
t h e p r e d i c t e d d i r e c t i o n o f d i s p l a c e me n t . Ho we v e r , a
f e w a l l o y s h a v e t i e - l i n e s wh i c h l i e t o t h e l e f t o f t h e
b u l k c o mp o s i t i o n . T h i s e f f e c t c a n b e e x p l a i n e d b e -
c a u s e d u r i n g t h e e a r l y s t a g e s o f t h e h e a t t r e a t me n t
c y c l e g r a p h i t e p r e c i p i t a t e d i n t h e s e a l l o y s . T h e r e f o r e ,
t h e me t a l wa s d e p l e t e d i n c a r b o n b e f o r e t h e c a r b i d e
n u c l e a t e d . He n c e , c a r b i d e g r o wt h a c t u a l l y o c c u r r e d
i n a l l o y s wi t h l o we r e f f e c t i v e c a r b o n c o n t e n t s t h a n
t h e b u l k a l l o y c o n t e n t s .
AC KNOWL E DGME NT S
T h e a u t h o r s wi s h t o t h a n k Do u g B u s h o f L e h i g h f o r
a s s i s t a n c e wi t h t h e mi c r o p r o b e wo r k . T h e r e s e a r c h
h a s b e e n s u p p o r t e d b y NAS A Gr a n t NGR 3 9 - 0 0 7 - 5 0 6 .
R E F E R E NC E S
1. E. R. D. Scott: Nature, 1971, vol. 229, pp. 61-62.
2. J. I. Goldstein, H. J. Axon, and C. F. Yen: Proc. 3rdLunarSci. Conf. Geochim.
Cosmochim. Acta, 1972, vol. 1, pp. 1037-64.
3. J. I. Goldstein, R. H. Hewins, and A. D. Romig, Jr.: Proc. 7th LunarScL Conf.,
Geochim. Cosmochim. Acta, 1976, vol. 1, pp. 807-18.
4. R. Brett: Geochim. Cosmochim. Acta, 1967, vol. 31, pp. 143-59.
5. A. Hultgren: Trans. Roy. Swedish Science Academy, 1953, vol. 4, no. 3, pp.
20-23.
6. P. Samuel, L. G. Finch, and J. R. Rait: Nature, 1955, vol. 175, pp. 37-38.
7. R. Sharma and J. Kirkaldy: Can. Met. Quart., 1973, vol. 12, pp. 391-401.
8. R. P. Elliot: Metals Handbook, 8th ed., T. Lyman, ed., vol. 8, pp. 412-13,
American Society for Metals, Metals Park, Ohio, 1973.
9. J. I. Goldstein and R. E. Ogilvie: Optique desRayons etMicroanalysis, R.
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