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Materials Science and Engineering, 50 (1981) 43 - 52 43

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
ponents are completely miscible at temper-
In this paper we present the experimental atures higher than 910 °C [2].
results o f a study on the self-diffusion coeffi- For this region, diffusion processes have
cients o f both components in the f.c.c, phase been studied by many researchers and their
o f the F e - N i binary system; these results were results are discussed in ref. 3. No measure-
obtained using the radioisotopes 59Fe and ments of the diffusion and thermodynamic
63Ni together with the measurements o f the data have been performed on a sufficient
interdiffusion coefficient in this system number of alloys with various component
obtained with the aid o f an electron micro- ratios (which ensures reliable consistent
analyser. Diffusion measurements were sup- results) in any laboratory, with the exception
plemented by thermodynamic mixing data for of Fraden's study [4] in which the diffusion
the same phase measured by the vapour pres- coefficients of both components were deter-
sure technique; the two sets o f data enabled mined for specimens with 31, 52, 76 and 90
us to verify Darken's theory o f interdiffusion. at.% Ni (however, measurements of the self-
Experimental results o f lSSw impurity diffu- diffusion and impurity diffusion coefficients
sion in the f.c.c, phase o f the F e - N i system in pure iron and nickel were not performed
are also presented. 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
1. INTRODUCTION
parameters of nickel have also been deter-
mined [3, 4, 8 - 11].
To discover the basic laws governing the In this study, self-diffusion data were sup-
changes in diffusion parameters with concen- plemented by measurements of interdiffusion
tration, it is important to discuss selected dif- coefficients and by thermodynamic mixing
fusion data of the phases with a nearly ideal data. The self-diffusion coefficients in pure
thermodynamic behaviour. In binary systems iron and nickel have been determined
with complete solubility of components in repeatedly (three sets of measurements have
the solid phase, short- or long-range ordering been performed in the last 10 years) to obtain
(of the types A3B, AB or ABa) often takes reliable diffusion data; all the available
place, as shown by structural analysis published diffusion and thermodynamic data
methods. Therefore diffusion measurements for the f.c.c, phase of the F e - N i system were
should be performed at sufficiently high tem- assembled, selected and critically discussed.
peratures or ordering effects should be consid- The impurity diffusion data of lSSw for the
ered in a diffusion measurement analysis. f.c.c, phase of Fe-Ni alloys are also presented
The f.c.c, phase of the Fe-Ni system was in this paper. Such results are important and
selected for measurement of the concentra- interesting from both the theoretical and the
tion dependence of the diffusion parameters practical aspect since the complex effects of
since it has been shown that both components concentration on the impurity diffusion are
behave as in a nearly ideal solution in the high not often studied by the majority of
temperature region [1] and that both com- researchers.

0025-5416/81/0000-0000/$02.50 © Elsevier Sequoia/Printed in The Netherlands


44

2. EXPERIMENTAL PROCEDURE ficient by the Knudsen effusion method. The


saturated vapour effused through an orifice
Specimens of F e - N i alloys were melted 500 p m in diameter from a chamber contain-
in v a c u o from Arema iron (containing 0.009% ing a crucible (5 mm in diameter and 11 mm
C, 0.23% Mn, 0.11% Ni, 0.01% CO and 0.07% long) filled with pieces of the foil. Effusion
Cu as impurities) and from nickel (with was carried o u t on each specimen at (1236 +
0.006% C, 0.018% Fe and 0.005% Co as main 5) °C for 4 h and the effused vapour condensed
impurities). Specimens 12 mm in diameter on a copper grid (of the same t y p e as used in
and 3 mm long were machined from cast electron microscopy) at a distance of 51 mm
ingots for the diffusion measurements. They from the effusion orifice. The mass ratio
were annealed at 1100 °C for 41 h and then at m 2 / m l of the components in the condensed
1200 °C for 7 h with subsequent cooling in layer and the mole fraction ratio x2/x_~ of the
the furnace. It was shown metaUographically Components in the foil were determined b y
that the average grain size is larger than 0.2 electron microanalysis with a JXA-3A instru-
mm in all specimens. ment. The activity coefficients 7 of the com-
A thin (less than 1 ~m) layer of the 59Fe, ponents were determined from the above
6SNi or lSSw radioisotope was electro- measurements by the modified Belton-
deposited onto the polished surface of the Fruehan m e t h o d [ 1 5 ] , e.g. for c o m p o n e n t 1
specimens and the diffusion coefficients were using
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 ln71=--/" xzd In --ln (1)
Jxl = 1 \Xl ]
boundaries on the measured diffusion coeffi-
cient values was particularly marked at low The experimental results of the c o m p o n e n t
annealing temperatures in specimens with activity coefficients for the f.c.c, phase of the
14.9 - 45.3 at.% Ni; this effect was eliminated F e - N i system were critically compared and
by the procedure described in ref. 13. processed with similar and other thermo-
Measurements of the interdiffusion coeffi- dynamic mixing data for this phase (the data
cients were performed in Ni/Fe/Ni specimens used are given in refs. 16 - 18 and were deter-
which had been prepared by welding from mined b y the methods described in ref. 19 to
pure iron and nickel plates in an argon atmo- obtain reliable consistent results which are
sphere. After successive anneals at seven dif- well correlated with the phase data of the
ferent temperatures in the range 920 - F e - N i system [20] ). The resulting mixing
1300 °C, the specimens were cut perpendic- data were typified by the excess free enthalpy
ularly to the diffusion surface with a spark values G ~ using the modified quasi-subregular
cutter and were prepared for electron micro- model [ 2 0 - 22] :
analysis by the metallographic technique. The GE =gEx(1--X)
electron probe microanalysis was carried out
gE = h E __ T s E (2)
on a JXA-3A instrument using the Fe K~ t
and Ni K~z radiation lines (their intensities where gE, h E and s E represent the reduced
were corrected for absorption, fluorescence excess free enthalpy, enthalpy and entropy
and atomic number effects as in ref. 14). The respectively for the f.c.c, phase and x and T
interdiffusion coefficients were determined are the mole fraction and the (absolute) tem-
by the Boltzmann-Matano method; concen- perature. It is assumed that the reduced
tration profiles were approximated by cubic excess enthalpy and entropy no longer change
spline interpolation using a c o m p u t e r with temperature and that they depend on
program. concentration in the following manner [18] :
F e - N i specimens for thermodynamic
hE(f.c.c.) = --(9.17 + 1.92) -- (11.54 + 3.10)XNi
mixing data measurements (f.c.c. phase) were
melted in a vacuum induction furnace from kJ mo1-1 (3)
the same pure iron and nickel; they were then
homogenized by repeated rolling and remelt-
ing. Foils 40 - 50 p m thick were prepared sE(f.c.c.) = --(2.72 -+ 0.61) --" (1.83 + 1.08)XNI
from ingots for determining the activity coef- 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 (5) of the self-diffusion parameters for nickel
have been published in refs. 8 and 38 - 54 and
(where R is the gas constant and T is the they are all very close to each other. The
absolute temperature). The self-diffusion average values of the self-diffusion parameters
parameters Do and AH for iron and nickel are for both components (from published data
given in Table 1. and from this study) are presented in Table 2;
Similar values of the parameters have been they are close to the mean values established
published for f.c.c, iron in refs. 23 - 38; the by measurements performed in this laborato-
results have a small scatter when the values ry (see Figs. 1 and 2). The self-diffusion
from refs. 23 and 32 are omitted. The values parameters for pure f.c.c, iron and pure nickel
46

TABLE 2 The diffusion of components in the f.c.e.


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


tem are summarized in Table 6; the various
I I I L 510 I ---. I __
100 interdiffusion coefficients are plotted against
%, [at %Ni]
concentration in Fig. 5 for three different
Fig. 4. Concentration dependence of the thermo- temperatures. The interdiffusion coefficients
dynamic factor 1 + don ?)/dOn x) in the F e - N i sys- reach a maximum near the composition
tem at various temperatures (1236 °C vapour pressure
measurements; 950, 1100 and 1250 °C optimized NiaFe; this typical curve shape has been
values from the literature). 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
3.4. Interdiffusion in the f.c.c, phase of the the liquidus curve and the minimum in the
F e - N i system and verification of the Darken solidus curve [2] providing evidence for the
theory relation between the diffusion and phase data.
The values of the interdiffusion parameters The validity of the Darken equation,
determined in the temperature range 920 - eqn. (13), has been examined in ref. 65 using
50

the interdiffusion data presented there but the solid phase, which is useful in the descrip-
the self-diffusion and thermodynamic data tion of the diffusion-controlled processes in
were taken from other sources. It was shown multicomponent systems.
that (at all the temperatures examined) The tungsten impurity diffusion parameters
/)talc >/)e~p and that the difference between in the f.c.c, phase of the F e - N i system are use-
Dealt and Dcxp is inversely proportional to the ful for studying the diffusion of the compo-
temperature of the diffusion anneal. The nents in the F e - N i - W system. From previous
discrepancy between the values was explained measurements of the diffusion coefficient for
as due to the poor precision of the self- tungsten in Ni-W alloys (for 0 - 9.2 at.% W)
diffusion values in ref. 65; this cannot be [48] and from the results of this study, suffi-
conclusive since the examination is based on cient information is available about the
inconsistent data from various sources. tungsten diffusion in iron- and nickel-rich
The complex approach to diffusion and alloys in the f.c.c, phase of the Fe-Ni-W sys-
thermodynamic data measurements realized tem.
in this study enables us to verify the Darken The impurity diffusion coefficients for
theory more confidently by comparison of lSSW (measured using eight specimens of F e -
the interdiffusion coefficient values (calcul- Ni alloys with various concentrations) are
ated from eqn. (13) and the data presented in summarized in Table 3. It was found that
Table 4 and Fig. 4) with the values obtained such data obey the Arrhenius equation well
from experiment. This is shown in Fig. 5; the (within experimental error); the values of the
agreement is fairly good at 1250 °C and there- parameters determined from the above data
fore we consider the Darken theory to be are presented in Table 4. The impurity diffu-
verified at this temperature. At lower anneal- sion coefficients for lSSw are plotted against
ing temperatures the difference between/)talc concentration in Fig. 6 (together with the
and/)e~p increases with decreasing temper- impurity diffusion data for tungsten in pure
ature (in all cases,/)exp >/)talc); the largest f.c.c, iron and in pure nickel taken from ref.
difference found was 40% at 950 °C for 75). With increasing nickel content (up to
70 at.% Ni. 30 at.% Ni) the curves decrease rapidly, but
The discrepancy between these values can above 30 at.% Ni the impurity diffusion coef-
be explained by the effects of grain bound- ficient remains almost constant (this effect is
aries and lattice defects on the diffusion pro- very marked in the curve for 950 °C). We
cesses; these effects cannot be eliminated compared our results with tungsten impurity
completely by any experimental arrangement
or by any data processing. Moreover, it is 10"9 1 ' ' ' ' ' ' ' '
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-
Fe"
imen used for the self-diffusion study.

3.5. Impurity diffusion of lSSw in the f.c.c.


phase of the Fe-Ni system 10 11 ~
Measurements of the impurity diffusion

~z~
parameters in metals and alloys are interesting
from the theoretical point of view. In this
kind of diffusion a simple mechanism of the 10
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
10-131 , , , i I J , , , I
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
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~
51

diffusion data in pure nickel only (taken Consistent diffusion and thermodynamic
from refs. 48 and 76) because of lack of other data for the f.c.c, phase of the F e - N i system
data. It is evident from Fig. 6 that the agree- enable the Darken theory to be examined
ment is fairly good. In this figure the curves very reliably. It was fully verified only for the
of the diffusion coefficients for iron and data at 1250 °C since, at lower temperatures,
nickel are also plotted; from a comparison diffusion data obtained from measurements
with curves for impurity diffusion it follows on monocrystals are needed to eliminate the
that the difference between the impurity dif- effects of the lattice defects on the diffusion
fusion of tungsten in pure f.c.c, iron and in parameters.
pure nickel is considerable. The impurity dif- The values of the impurity diffusion param-
fusion coefficient for f.c.c, iron is near to the eters for lSSW in F e - N i alloys are important
self-diffusion coefficient value of iron b u t for and interesting b u t they are still the only
pure nickel the ratio is a b o u t 0.1. According values available and therefore any general
to the classical theory of impurity diffusion conclusions would be premature.
[ 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-
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