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D i f f u s i o n Processes in t h e F e - N i S y s t e m
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.
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 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
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
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
,~.~ 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
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
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.
~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
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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