Materials Science and Engineering, 50 (1981) 43 - 52
D i f f u s i o n Processes in t h e F e - N i S y s t e m
B. MILLION, J. RI~I(~KOV.~, J. VELiSEK and J. VI~E~/i,L
Institute of Physical Metallurgy, Czechoslovak Academy of Sciences, 616 62 Brno, Zi]~kova 22 (Czechoslovakia)
(Received September 2, 1980)
SUMMARY
In this paper we present the experimental
results o f a study on the self-diffusion coeffi-
cients o f both components in the f.c.c, phase
o f the F e - N i binary system; these results were
obtained using the radioisotopes 59Fe and
63Ni together with the measurements o f the
interdiffusion coefficient in this system
obtained with the aid o f an electron micro-
analyser. Diffusion measurements were sup-
plemented by thermodynamic mixing data for
the same phase measured by the vapour pres-
sure technique; the two sets o f data enabled
us to verify Darken's theory o f interdiffusion.
Experimental results o f lSSw impurity diffu-
sion in the f.c.c, phase o f the F e - N i system
are also presented.
1. INTRODUCTION
To discover the basic laws governing the
changes in diffusion parameters with concen-
tration, it is important to discuss selected dif-
fusion data of the phases with a nearly ideal
thermodynamic behaviour. In binary systems
with complete solubility of components in
the solid phase, short- or long-range ordering
(of the types A3B, AB or ABa) often takes
place, as shown by structural analysis
methods. Therefore diffusion measurements
should be performed at sufficiently high tem-
peratures or ordering effects should be consid-
ered in a diffusion measurement analysis.
The f.c.c, phase of the Fe-Ni system was
selected for measurement of the concentra-
tion dependence of the diffusion parameters
since it has been shown that both components
behave as in a nearly ideal solution in the high
temperature region [1] and that both com-
0025-5416/81/0000-0000/$02.50
43
ponents are completely miscible at temper-
atures higher than 910 °C [2].
For this region, diffusion processes have
been studied by many researchers and their
results are discussed in ref. 3. No measure-
ments of the diffusion and thermodynamic
data have been performed on a sufficient
number of alloys with various component
ratios (which ensures reliable consistent
results) in any laboratory, with the exception
of Fraden's study [4] in which the diffusion
coefficients of both components were deter-
mined for specimens with 31, 52, 76 and 90
at.% Ni (however, measurements of the self-
diffusion and impurity diffusion coefficients
in pure iron and nickel were not performed
and thus a full analysis of diffusion could not
be obtained). For the f.c.c, phase of the F e -
Ni system the diffusion parameters of iron
have been measured [4 - 7] and the diffusion
parameters of nickel have also been deter-
mined [3, 4, 8 - 11].
In this study, self-diffusion data were sup-
plemented by measurements of interdiffusion
coefficients and by thermodynamic mixing
data. The self-diffusion coefficients in pure
iron and nickel have been determined
repeatedly (three sets of measurements have
been performed in the last 10 years) to obtain
reliable diffusion data; all the available
published diffusion and thermodynamic data
for the f.c.c, phase of the F e - N i system were
assembled, selected and critically discussed.
The impurity diffusion data of lSSw for the
f.c.c, phase of Fe-Ni alloys are also presented
in this paper. Such results are important and
interesting from both the theoretical and the
practical aspect since the complex effects of
concentration on the impurity diffusion are
not often studied by the majority of
researchers.
© Elsevier Sequoia/Printed in The Netherlands
44
2. EXPERIMENTAL PROCEDURE
Specimens of F e - N i alloys were melted
in v a c u o from Arema iron (containing 0.009%
C, 0.23% Mn, 0.11% Ni, 0.01% CO and 0.07%
Cu as impurities) and from nickel (with
0.006% C, 0.018% Fe and 0.005% Co as main
impurities). Specimens 12 mm in diameter
and 3 mm long were machined from cast
ingots for the diffusion measurements. They
were annealed at 1100 °C for 41 h and then at
1200 °C for 7 h with subsequent cooling in
the furnace. It was shown metaUographically
that the average grain size is larger than 0.2
mm in all specimens.
A thin (less than 1 ~m) layer of the 59Fe,
6SNi or lSSw radioisotope was electro-
deposited onto the polished surface of the
specimens and the diffusion coefficients were
determined by the modified Gruzin m e t h o d
[12] after successive anneals for 0.83 - 239 h
at 985 - 1305 °C. The influence of grain
boundaries on the measured diffusion coeffi-
cient values was particularly marked at low
annealing temperatures in specimens with
14.9 - 45.3 at.% Ni; this effect was eliminated
by the procedure described in ref. 13.
Measurements of the interdiffusion coeffi-
cients were performed in Ni/Fe/Ni specimens
which had been prepared by welding from
pure iron and nickel plates in an argon atmo-
sphere. After successive anneals at seven dif-
ferent temperatures in the range 920 -
1300 °C, the specimens were cut perpendic-
ularly to the diffusion surface with a spark
cutter and were prepared for electron micro-
analysis by the metallographic technique. The
electron probe microanalysis was carried out
on a JXA-3A instrument using the Fe K~ t
and Ni K~z radiation lines (their intensities
were corrected for absorption, fluorescence
and atomic number effects as in ref. 14). The
interdiffusion coefficients were determined
by the Boltzmann-Matano method; concen-
tration profiles were approximated by cubic
spline interpolation using a c o m p u t e r
program.
F e - N i specimens for thermodynamic
mixing data measurements (f.c.c. phase) were
melted in a vacuum induction furnace from
the same pure iron and nickel; they were then
homogenized by repeated rolling and remelt-
ing. Foils 40 - 50 p m thick were prepared
from ingots for determining the activity coef-
ficient by the Knudsen effusion method. The
saturated vapour effused through an orifice
500 p m in diameter from a chamber contain-
ing a crucible (5 mm in diameter and 11 mm
long) filled with pieces of the foil. Effusion
was carried o u t on each specimen at (1236 +
5) °C for 4 h and the effused vapour condensed
on a copper grid (of the same t y p e as used in
electron microscopy) at a distance of 51 mm
from the effusion orifice. The mass ratio
m 2 / m l of the components in the condensed
layer and the mole fraction ratio x2/x_~ of the
Components in the foil were determined b y
electron microanalysis with a JXA-3A instru-
ment. The activity coefficients 7 of the com-
ponents were determined from the above
measurements by the modified Belton-
Fruehan m e t h o d [ 1 5 ] , e.g. for c o m p o n e n t 1
using
ln71=--/" xzd In --ln (1)
Jxl = 1 \Xl ]
The experimental results of the c o m p o n e n t
activity coefficients for the f.c.c, phase of the
F e - N i system were critically compared and
processed with similar and other thermo-
dynamic mixing data for this phase (the data
used are given in refs. 16 - 18 and were deter-
mined b y the methods described in ref. 19 to
obtain reliable consistent results which are
well correlated with the phase data of the
F e - N i system [20] ). The resulting mixing
data were typified by the excess free enthalpy
values G ~ using the modified quasi-subregular
model [ 2 0 - 22] :
GE =gEx(1--X)
gE = h E __ T s E (2)
where gE, h E and s E represent the reduced
excess free enthalpy, enthalpy and entropy
respectively for the f.c.c, phase and x and T
are the mole fraction and the (absolute) tem-
perature. It is assumed that the reduced
excess enthalpy and entropy no longer change
with temperature and that they depend on
concentration in the following manner [18] :
hE(f.c.c.) = --(9.17 + 1.92) -- (11.54 + 3.10)XNi
kJ mo1-1 (3)
sE(f.c.c.) = --(2.72 -+ 0.61) --" (1.83 + 1.08)XNI
J mol -z K - t (4)
 45

The values of the thermodynamic factor are 10-g ,.~, i I ; i

determined in Section 3.3 from the above E

,_.%o
data.
~10-10

3. EXPERIMENTAL RESULTS AND DISCUSSION %%%

10-11
3.1. Self-diffusion in pure f.c.c, iron and nickel
The values of the diffusion parameters in
%%%
the F e - N i system cannot be analysed without 10-12
reliable values of the self-diffusion parameters
for pure f.c.c, iron and pure nickel. The self-
diffusion parameter for f.c.c, iron has been 10-13 q I I I
reported in refs. 23 - 38 and those for nickel 7 8
101"/T[K-I]
in refs. 8 and 39 - 54; as can be seen, many Fig. 1. Temperature dependence of the 59Fe self-
experimental data are available for compar- diffusion coefficient in ~f-Fe: ~, ref. 37 ; e, ref. 38;
ison. ---o--, this w o r k ; - - - , mean value (Table 2).
We have measured the self-diffusion coeffi-
cients for f.c.c, iron [37, 38] and nickel [38,
53] some years ago and one aim of this study 1• •
was to repeat these measurements y e t again to
estimate their reliability. Therefore measure-
ments were made on the same materials using ~I0-I0
the same technique as for our earlier investiga-
tion, and the results obtained were processed
by the same computer procedures developed
previously.
We have measured the self<iiffusion coeffi- ,%
cients for f.c.c, iron during a study o f the F e -
10q2 i i , ="%'~,,
Pt [ 3 7 ] , F e - C r [38] and F e - N i (this work) 8 7 8
binary systems and we have determined the 10L/T[K"I]
self-diffusion parameters for pure nickel Fig. 2. Temperature dependence of the 63Ni self-
together with the diffusion parameters for the diffusion coefficient in nickel: A, ref. 53;&, ref. 38;
components in the C o - N i [ 5 3 ] , Ni-Cr [38] --A--, this w o r k ; - - - , mean value (Table 2).
and F e - N i (this work) systems. All our
results are summarized in Figs. 1 and 2 and it TABLE 1
is evident that no systematic deviation can be Self-diffusion parameters for iron and nickel
detected in the various sets of measurements.
Therefore, average values of all the measured K K* (cm 2 s-1)
D0K AH K*
K (kJ mo1-1}
parameters were established. The dependence
of the self-diffusion coefficient of each com- Fe 0.721 278.7
ponent on temperature can be expressed b y Ni 3.44 290.0
the Arrhenius equation

D K* =
Do K* exp RT
(where R is the gas constant and T is the
absolute temperature). The self-diffusion
parameters Do and AH for iron and nickel are
given in Table 1.
Similar values of the parameters have been
published for f.c.c, iron in refs. 23 - 38; the
results have a small scatter when the values
from refs. 23 and 32 are omitted. The values
(5) of the self-diffusion parameters for nickel
have been published in refs. 8 and 38 - 54 and
they are all very close to each other. The
average values of the self-diffusion parameters
for both components (from published data
and from this study) are presented in Table 2;
they are close to the mean values established
by measurements performed in this laborato-
ry (see Figs. 1 and 2). The self-diffusion
parameters for pure f.c.c, iron and pure nickel
46
TABLE 2
Average values of the self-diffusion parameters for
iron and nickel
-- K* -K*
K D0K (cm2s-1) AHK (kJmol-I)
+ 0.52
Fe 0.584 281.3 +- 7 . 6
-- 0.27
+ 0.76
Ni 1.85 284.2 -+ 3.9
- - 0.53
which were determined in this study are used
in the discussion o f the diffusion data in Sec-
tion 3.2, because these data were obtained in
the same specimens and under identical con-
ditions as the self-diffusion measurements.
3.2. Diffusion of the components in the f.c.c.
phase of the Fe-Ni system
Specimens with 14.9, 29.7, 45.3, 60.5,
70.0, 75.3, 79.8 and 90.0 at.% Ni were
annealed in the temperature range 985 -
1305 °C and the diffusion coefficients were
determined for both components. The mean
values (from two independent measurements)
of the diffusion coefficients are presented in
Table 3. The values for all alloys fit the
Arrhenius equation well and the diffusion
parameters are presented in Table 4.
The impurity diffusion coefficients for iron
in pure nickel have been reported in refs. 55 -
60; the results from refs. 59 and 60 are close
to those obtained in this study and together
with our results (see Table 4) they provide the
following average values for the diffusion
parameters:/)0F~ * = (4.14 _+4:0) cm 2 s-1 ;
A/~F] * = (287.7 + 8.4) kJ mo1-1.
The results of nickel impurity diffusion
measurements for f.c.c, iron have been
presented in refs. 8, 9, 55 and 59 - 62; the
results from refs. 9, 60 and 62 are very close
to those from this study and they all provide
t h e following average values of the impurity
diffusion parameters: /~ Ni* = (1.54_+ 1.0)
~0Fe 2.6
cm2
S -1 ; ~..~AA~Ni*Fe = (288.4 -+ 11.4) kJ mo1-1 . The
results from other sources are much more
scattered and were omitted from the estima-
tion of mean values. This scatter is caused
mainly by the effects of grain boundaries and
lattice defects on the impurity diffusion
which were not taken into account in the data
analysis (because they had not been excluded
by appropriate experimental procedure).
The diffusion of components in the f.c.e.
phase of the F e - N i system has been reported
in refs. 3 - 11 and the results are critically dis-
cussed in ref. 3. The nickel self-diffusion coef-
ficients for (eight) specimens of F e - N i alloys
(with 5 - 90 at.% Ni) are presented in ref. 11
but measurements of the diffusion coefficient
for iron and nickel in both pure metals and in
a sufficient number of alloys are not available
yet; the measurements made on four alloys
and reported in ref. 4 have been the only
exception until our present results.
There is much disagreement in the
published results. For example in ref. 3 the
values of In D O and A H are presented as linear
functions of concentration for both compo-
nents, whereas in ref. 11 a deep minimum was
found near 50 at.% Ni in the curves of the
concentration against the nickel diffusion
parameters. These measurements were made
in the temperature range 810 - 1110 °C, thus
excluding a representative determination of
the bulk diffusion parameters. The selected
values of the diffusion parameters presented in
ref. 3 cannot be accepted with confidence since
they are based on measurements performed on
various materials using different experimental
techniques.
In Fig. 3 the diffusion coefficients for 59Fe
and 6SNi obtained in both this and other
studies are plotted against concentration at
950, 1100 and 1250 °C. The average values of
the self-diffusion and impurity diffusion coef-
ficients are also plotted. From this figure it is
evident that the results of this study are
situated in the middle of the range in which
the results of other studies are scattered.
Therefore any fundamental disagreement be-
tween the results from this study and the
results of other researchers cannot be estab-
lished. It is n o t e w o r t h y that the scatter for
the iron data is considerably less than that for
the nickel data.
For an analytical expression of the depen-
dence of the diffusion coefficients on the
concentration, the following set of equations
is suggested:
In . rUi FF ee *- - N i = X F e ,L n urife*
Fe ÷ XNi in D~T* (6)
In nSi*
~'Fe-Ni = X N i 1,~ nNi* Jc X F e
~ll~L'Ni in/~Fi* (7)
According to the atomic diffusion theory,
 47

TABLE 3
D i f f u s i o n c o e f f i c i e n t s f o r 59Fe, 63Ni a n d 185W in F e - N i alloys

N/ X /~e*-Ni X 1012 ( c m 2 s - 1 )
(at.%)
985 °C 1035 °C 1105 °C 11 75 °C 1245 °C 1305 °C

0 Ni 2.00 4.65 22.5 56.0 263 391

14.9 Fe 4.76 7.24 30.3 117 226 792
14.9 Ni 1.85 4.96 20.4 78.5 269 a 372
14.9 W 1.51 3.40 -- 58.8 160 328
29.7 Fe 1.15 5.42 29.3 89.8 268 854
29.7 Ni 1.68 5.49 20.1 64.3 291 411
29.7 W 0.687 1.72 -- 37.1 131 320
45.3 Fe 2.08 8.98 33.1 109 351 938
45.3 Ni 1.84 6.08 25.5 a 90.1 420 515
45.3 W 0.596 2.17 -- 51.0 122 307
60.5 Fe 3.13 13.4 38.3 149 497 1780
60.5 Ni 2.21 9.40 29.6 106 452 720
60.5 W 0.696 2.83 -- 56.6 152 432
70.0 Fe 2.59 11.5 42.2 136 419 1320
70.0 Ni 3.07 9.08 32.9 137 387 1220
70.0 W 0.480 3.49 -- 40.4 157 313
75.3 Fe 2.64 9.69 33.0 119 431 1280
75.3 Ni 1.93 6.58 40.4 119 382 687
75.3 W 0.525 3.27 38.4 121 375
79.8 Fe 2.97 8.45 34.1 141 367 1125
79.8 Ni 2.45 7.98 39.3 95.8 401 869
79.8 W 0.664 1.79 -- 39.8 118 273
90.0 Fe 2.39 7.91 75.0 116 462 1530 a
90.0 Ni 2.73 7.91 35.8 170 449 542
90.0 W 0.602 2.59 -- 48.2 82.7 224
100 Fe 3.42 12.9 52.4 146 561 1410

a T h e d i f f u s i o n c o e f f i c i e n t was m e a s u r e d o n l y o n c e .

TABLE 4
F r e q u e n c y f a c t o r s a n d a c t i v a t i o n e n t h a l p i e s for 59Fe, 63Ni a n d lSSW d i f f u s i o n in F e - N i alloys

n Fe* Fe* r~ Ni* ALrNi* W* W*

Ni log U 0 F e _ N i AHFe_Ni log U0Fe_Ni ~.a~Fe_Ni log DOFe_Ni AHFe_Ni
(at.%) ( c m 2 s- 1 ) (kJ mo1-1) ( c m 2 s- 1 ) (kJ mo1-1) ( c m 2 s- 1 ) (kJ mo1-1)

0 --0.142 ± 0.23 278.7 ± 6.2 0.049 ± 0.47 283.5 ± 12.6 --0.293 ± 0.87 a 272.0 ± 18.0 a
14.9 0.328 ± 0.65 286.3 ± 18.0 0.274 ± 0.42 289.4 ± 13.9 0.041 ± 0.38 286.4 ± 10.3
29.7 0.999 -* 0 . 3 8 305.7 ± 10.5 0.373 ± 0.45 291.9 ± 12.0 1.248 ± 0.44 324.1 ± 11.7
45.3 0.942 ± 0.29 301.8 ± 7.7 0.905 ± 0.57 303.4 +- 15.2 1.143 ± 0.48 320.5 ± 12.6
60.5 1.459 ± 0.46 311.3 ± 12.2 0.890 ± 0.46 300.5 ± 12.3 1.377 ± 0.53 324.3 ± 14.4
70.0 1.079 ± 0.35 302.7 ± 9.4 1.143 ± 0.23 305.3 ± 6.2 1.158 ± 0.51 320.2 ± 13.4
75.3 1.307 ± 0.27 309.9 ± 7.2 1.124 ± 0.51 307.3 ± 13.8 1.029 ± 0.47 317.0 ± 12.8
79.8 1.090 ± 0.20 304.2 ± 5.5 0.941 ± 0.33 301.5 ± 8.9 0.989 ± 0.46 317.5 ± 12.6
90.0 1.255 ± 0.62 307.1 ± 17.4 0.885 ± 0.73 299.6 ± 19.6 0.314 ± 0.71 299.5 ± 19.2
100 0.964 ± 0.27 297.7 ± 7.3 0.537 ± 0.22 290.0 ± 5.9 --0.134 ± 0.98 a 290.2 ± 22.2 a

a T h e s e d a t a were t a k e n f r o m ref. 75.

 48

,~.~ 10-8 [ , , , , ; , , , ,
-8
I'~--~I I0 f I I I I I I I I
1250"C
• "~ 10"9 I-
,u, 9[ 1250"C
ZX _ [- • o

o01......
°

10"11~- 1100"C
O [] [] []
+°111 I
10-1°L lO" 1100"C -"
10- A • -
=
~ o o '0
10_11 x •

10-11~ • • •

1042
950"C[] 10-12
10-11' [] n []
10-11"
], ll • 950'C
10-12 ----~"x
[] Ox 0
O C. 0"--'0"-0"0-'--0--
10-12

10-13
I I I I i i i i i 10 -'t3 I I I I I I I I I
o 50 100 0 50 100
(a) CNi [ at°/°Ni] (b) CNi[at.% Nil

Fig. 3. Concentration dependences of the diffusion coefficients in the F e - N i system (a) for 59Fe (¢, mean value;
o, this work; o, ref. 6; e, ref. 5; m, ref. 4; A, ref. 7) and (b) for 63Ni (¢, mean value; o, this work; D, ref. 11 ; o,
ref. 3; m ref. 4; A, ref. 10;A, ref. 8 ; ×, ref. 9).

15152
D = A exp --~--~ (8) logO m*
Fe-Ni = 0 . 5 3 7 - - - - - -
T
where A is the frequency factor and AG is the
-- XFe (0.488 -- 3--~--~
0) (12)
activation free enthalpy of diffusion. If we
assume that
(where D is in square centimetres per second
A F e - N i = (AFe)XFe(ANi)xNi (9) and T is in kelvins) for the relation between
then the diffusion coefficients and the temperature
and composition.
/~GFe_Ni = XFe AGFe + XNi A G N i (10)
Therefore the activation free enthalpy of dif- 3.3. Evaluation of the thermodynamic factor
fusion for the f.c.c, phase of the F e - N i sys- for the Fe-Ni system
tem depends linearly on the activation free According to D ~ k e n ' s theory, the interdif-
enthalpy of the diffusion of both pure com- fusion coefficient D is given by
ponents. By substitution of the self-diffusion
and impurity diffusion parameters into eqns. = ,~. nN,* + XNiDFFr_m)I1+d(lnTN') t
(6) and (7), we obtain ~"l'Fe'UFe-Ni d(lnXNl)J
14 561 (13)
log D Fe*
Fe-Ni = - - 0 . 1 4 2 + where the last term is often called the
T
"thermodynamic factor". The values of this
+ XNI(1.106 -- 9T93) (11) factor were determined from vapour pressure
measurements and from optimized thermo-
 49

dynamic mixing data (presented in Section 2). TABLE 6

The values of the nickel activity coefficient Frequency factors and activation enthalpies for
are expressed in terms of the mole fraction of interdiffusion in the Fe-Ni system
nickel by a polynomial function
Ni log D O AH
l n T N i = a + b X N i + CXNi2 + dXNi 3 (14) (at.%) (cm 2 S- 1 ) (kJ mo1-1)

and the values of the parameters a, b, c and d 10 --1.320 247.8

20 --1.085 250.3
are given in Table 5 for 1250, 1100 and
30 --0.916 251.1
950 °C from the optimized data and for. 40 --0.963 245.3
1236 °C from the results of the vapour pres- 50 --0.405 254.9
sure experiment [1]. In Fig. 4 the values of 60 0.284 270.0
the thermodynamic factor are plotted against 70 0.461 273.7
80 0.481 274.6
concentration for all the above temperatures. 90 0.493 277.1

TABLE 5
i
Values of the parameters in eqn. (14)

1250"C
T (°C) a b c d z
:t 0 0 0
If:] 10-g
[] Dr.1•
1250 --0.40 --0.59 2.36 --1.38 OD
1100 --0.48 --0.63 2.68 --1.58
950 --0.57 --0.68 3.08 --1.83
1236 0.36 --0.05 1.17 --0.76 10-1° ~ [] 0 {ooo{ 1100"C

0 [] QOD []
[]
i []
1.8
10-11 950"C
c c
÷ 950"C O t O O O
/ \
16 [] []
/' 1100"C \. DD []
0 []
/ //1250"C-\ \ 10-12 []
/ / /t "-\ \ \
1.4 ,,// ",,',,,
I I I I 0 I I I I
/ .1 / 1236"C \~',~
CNilet %Ni] 100

12
,;;',?" \ Fig. 5. Concentration dependence of the interdiffu-
sion coefficient in the F e - N i system: o, experimental
y values; a, values calculated from self-diffusion and

10 =j/ thermodynamic data.

1300 °C for the f.c.c, phase of the Fe-Ni sys-

I I I L 510
Fig. 4. Concentration dependence of the thermo-
dynamic factor 1 + don ?)/dOn x) in the F e - N i sys-
tem at various temperatures (1236 °C vapour pressure
measurements; 950, 1100 and 1250 °C optimized
values from the literature).
3.4. Interdiffusion in the f.c.c, phase of the
F e - N i system and verification of the Darken
theory
The values of the interdiffusion parameters
determined in the temperature range 920 -
tem are summarized in Table 6; the various
I ---. I __
100 interdiffusion coefficients are plotted against
%, [at %Ni]
concentration in Fig. 5 for three different
temperatures. The interdiffusion coefficients
reach a maximum near the composition
NiaFe; this typical curve shape has been
established previously in refs. 59 and 63 - 73
and it is discussed in ref. 74. The position of
the maximum corresponds to the minimum in
the liquidus curve and the minimum in the
solidus curve [2] providing evidence for the
relation between the diffusion and phase data.
The validity of the Darken equation,
eqn. (13), has been examined in ref. 65 using
50
the interdiffusion data presented there but
the self-diffusion and thermodynamic data
were taken from other sources. It was shown
that (at all the temperatures examined)
/)talc >/)e~p and that the difference between
Dealt and Dcxp is inversely proportional to the
temperature of the diffusion anneal. The
discrepancy between the values was explained
as due to the poor precision of the self-
diffusion values in ref. 65; this cannot be
conclusive since the examination is based on
inconsistent data from various sources.
The complex approach to diffusion and
thermodynamic data measurements realized
in this study enables us to verify the Darken
theory more confidently by comparison of
the interdiffusion coefficient values (calcul-
ated from eqn. (13) and the data presented in
Table 4 and Fig. 4) with the values obtained
from experiment. This is shown in Fig. 5; the
agreement is fairly good at 1250 °C and there-
fore we consider the Darken theory to be
verified at this temperature. At lower anneal-
ing temperatures the difference between/)talc
and/)e~p increases with decreasing temper-
ature (in all cases,/)exp >/)talc); the largest
difference found was 40% at 950 °C for
70 at.% Ni.
The discrepancy between these values can
be explained by the effects of grain bound-
aries and lattice defects on the diffusion pro-
cesses; these effects cannot be eliminated
completely by any experimental arrangement
or by any data processing. Moreover, it is
likely that the lattice defect concentration in
the deformed zone (near the welding area of
the Ni/Fe/Ni sandwiches) is much higher than
the concentration in the undeformed spec-
imen used for the self-diffusion study.
3.5. Impurity diffusion of lSSw in the f.c.c.
phase of the Fe-Ni system
Measurements of the impurity diffusion
parameters in metals and alloys are interesting
from the theoretical point of view. In this
kind of diffusion a simple mechanism of the
breaking of old bonds and the formation of
new bonds between neighbouring atoms (of
the type A--B in a pure metal and of the type
A--BxCy in an alloy) takes place as a result of
an extremely low concentration of the
impurity A. The impurity diffusion param-
eters provide valuable information about the
bonding energies between different atoms in
the solid phase, which is useful in the descrip-
tion of the diffusion-controlled processes in
multicomponent systems.
The tungsten impurity diffusion parameters
in the f.c.c, phase of the F e - N i system are use-
ful for studying the diffusion of the compo-
nents in the F e - N i - W system. From previous
measurements of the diffusion coefficient for
tungsten in Ni-W alloys (for 0 - 9.2 at.% W)
[48] and from the results of this study, suffi-
cient information is available about the
tungsten diffusion in iron- and nickel-rich
alloys in the f.c.c, phase of the Fe-Ni-W sys-
tem.
The impurity diffusion coefficients for
lSSW (measured using eight specimens of F e -
Ni alloys with various concentrations) are
summarized in Table 3. It was found that
such data obey the Arrhenius equation well
(within experimental error); the values of the
parameters determined from the above data
are presented in Table 4. The impurity diffu-
sion coefficients for lSSw are plotted against
concentration in Fig. 6 (together with the
impurity diffusion data for tungsten in pure
f.c.c, iron and in pure nickel taken from ref.
75). With increasing nickel content (up to
30 at.% Ni) the curves decrease rapidly, but
above 30 at.% Ni the impurity diffusion coef-
ficient remains almost constant (this effect is
very marked in the curve for 950 °C). We
compared our results with tungsten impurity
10"9 1 ' ' ' ' ' ' ' '
Fe"
10 11 ~
~z~
10
10-131 , , , i I J , , , I
0
Fig. 6. Concentration dependence of the
50
impurity diffusion coefficient in the Fe-Ni system:
o, this work; e, ref. 75; A, ref. 48; A, ref. 76.
CN~[at.% Ni]
100
S
lSv~

diffusion data in pure nickel only (taken
from refs. 48 and 76) because of lack of other
data. It is evident from Fig. 6 that the agree-
ment is fairly good. In this figure the curves
of the diffusion coefficients for iron and
nickel are also plotted; from a comparison
with curves for impurity diffusion it follows
that the difference between the impurity dif-
fusion of tungsten in pure f.c.c, iron and in
pure nickel is considerable. The impurity dif-
fusion coefficient for f.c.c, iron is near to the
self-diffusion coefficient value of iron b u t for
pure nickel the ratio is a b o u t 0.1. According
to the classical theory of impurity diffusion
[ 7 7 - 79] the values of D Fw*
e / D FFe* w*
e and D N i / D NNi*
i
should be very similar.
This discrepancy is probably caused by dif-
ferent bonding energies between tungsten
atoms on one side and iron and/or nickel
atoms on the other in comparison with the
bonding energy of iron to nickel atoms which
is not accounted for in the theory. It can be
explained by the assumption that the bonding
energy between nickel and tungsten atoms is
much higher than that between iron and
tungsten atoms. This assumption is supported
by the different solubilities of tungsten in
iron and in nickel [ 2].
4. CONCLUSION
The complex approach to diffusion and
thermodynamic data measurements for the
f.c.c, phase of the F e - N i system used in this
study was supplemented by similar data
published previously. It was shown that the
diffusion coefficients for 59Fe and 63Ni
expressed on a logarithmic scale depend
linearly on the concentration b u t that the
interdiffusion coefficients reach a maximum
near the concentration Ni3Fe. From our
study it appears that short-range ordering has
no effect on the self-diffusion parameters
near the concentration Ni3Fe , contrary to the
findings of ref. 10, although some deviation
was found in the curves in Figs. 3 and 6 be-
tween 70 and 75 at.% Ni. The influence of
short-range ordering on the thermodynamic
data is more marked (negative deviations from
ideal solution behaviour and a maximum in
the curve for the thermodynamic factor) and
this also shows up slightly in the values of the
interdiffusion parameters.
51
Consistent diffusion and thermodynamic
data for the f.c.c, phase of the F e - N i system
enable the Darken theory to be examined
very reliably. It was fully verified only for the
data at 1250 °C since, at lower temperatures,
diffusion data obtained from measurements
on monocrystals are needed to eliminate the
effects of the lattice defects on the diffusion
parameters.
The values of the impurity diffusion param-
eters for lSSW in F e - N i alloys are important
and interesting b u t they are still the only
values available and therefore any general
conclusions would be premature.
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