UDC 539. 219.

3
A STUDY OF DIFFUSION OF SODIUM AND POTASSIUM IN IRON

A. V. T o m i l o v and G. V. Shcherbedinskii

Fiziko-Khimicheskaya Mekhanika Materialov, Vol.~ 3, No. 3, pp. 261-263, 1967

Coefficients o f diffusion of potassium and sodium in iron were measured by a radioactive tracer method, and
their temperature dependence at 600-800 ~ C was determined, It was established that the rate of diffusion of
these elements is faster in armco iron than in electrolytic iron.

Diffusion plays an important part in reactions between liquid and solid metals; hence the present investigation
whose a i m was to study the diffusion of sodium and potassium in iron. No specific data on the rates of diffusion of these
elements have been published, but there are indications [ 1 - 3 ] that they should be slow.

A radioactive tracer technique was used in our measurements carried out at 500-800" C. Isotopes Na ~ (h/* = 15 hr)
and K ~ (h/2 = 12.4 hr) in the form of compounds NaC1 and KC1 were used for this purpose. The measurements were c a r -
ried out on iron specimens of various degrees of purity, whose c h e m i c a l analysis is given in Table 1.

Table 1

Element concentration, wt. %

Material ,
C Mn S P Cu

Armco iron
Electrolytic
iron
0.03
0,003
0.04
Traces
[ 0,009
0.004
0;005
0.001
Traces
0.035

The specimens were given a 2 hour recrystallizing annealing treatment in vacuum at 1000 ~ C to stabilize their
structure and relieve internal stresses. They were then placed in iron ampoules filled with sodium or potassium and their
radioactive chlorides. The ampoules were h e r m e t i c a l l y sealed and held for 3 0 - 8 0 hr at 500, 600, 700 and 800" C in

Table 2

D. I0~, Ig D Do, Q,
T, ~ System cmZ/se c cmZ/sec cal/mole

8OO 820 11.914

7OO 105 iT.020
K'C1 + Na --" Armco Fe 0.036 42 300
600 22.5 12.350
50O 0.38 14.580
8OO 76.9 12.866
7OO $ 11,3 12,053
KC1 + K "-~ Armco Fe 4.16.10 - 4 30 200
600 2.47 13.393
5OO 0.38 14,456
8OO 15.1 12.178
7OO KCL + K -~ Electrolytic 4.34 13.638 1.17.10 - 7 24 200
6OO Fe 1.26 I-3.102
800 7.31 13.860
7OO ik 1.50 13,176
NaCI + Na -~ Armco Fe 4,10-10-1~ la 900
6OO 1.83 13.260
5OO 0,91 14,957
8OO 1.81 13.252
$
7OO NaCI + Na --*Electrolyti( 0.318 14.502 5.75-10-11 12 500
6OO Fe 0.69 14.219

18'7
stainless steel tubes which had been previously evacuated and then filled with argon. The following systems served as the
source of diffusion atoms: Na+C1 + Na; K ' C 1 + K; K ' C 1 + Na. Exchange reactions t o o k p l a c e during the diffusion treat-
ment and the radioactive isotopes diffused into the materials studied.

Generally speaking, diffusion parameters depend on the concentration of the diffusing elements, in the present
case this dependence may be neglected in view of very small concentrations of sodium and potassium.

The solution of the diffusion equation in this case is

C -. Co eric x/2 V-fit.
Diffusion coefficients were determined by removing consecutive metal layers and measuring the integral radioac-
tivity of a given specimen. Since i = bc, i = i0erfc x / 2 4 - ~ . Since both Na a n d K are characterized by hard B-radiation

and since the depth of diffusion is small, i n = Itt--ln+]. Knowing i/J0 from experiment, we find x / 2 4 " ~ from the
ax
graph of the function erfc x/2 D4"~". After plotting the dependence of x / 2 4 - ~ on x, we determine D from the slope of
the straight line obtained.
Effective diffusion coefficients determined in this way are given in Table 2, and their temperature dependence is
reproduced in a figure. It will be seen that the experimental values of D obtained for all the test temperatures lie quite
close to straight lines representing the relation D = Do exp (-Q/Rt); this makes it possible to determine the diffusion
parameters Do and Q (Table 2).
If the diffusion coefficients are known, it is possible to compute the time dependence of the diffusion depth for any
given temperature. Strictly speaking, the meaning of the diffusion depth in solid solutions is not definable. If the dif-
fusion depth is taken to be the position of a plane at which the concentration is C0 = 0. 16, then 0.16 [C (xlt)/C0 ] =
= erfc Ix/24"fft] and x/24"DT= 1; hence the time dependence of the diffusion depth is described by x = 2 4 ~ .

d~ 700 ~ 600 100 700 600 5"DO~ ~00 700 EO0 500~
ml' +..... ' ! I ~1-'~'" ' ' '
' ' ' c

,+
7~
| '1 I,, I I ~3~ "l ItI IX
m 70 71 12 13 # ro 71 12 ~ . 1 0 * m 70 71 ~2 ~.10 ~

Temperature dependence of diffusion coefficients: a)sodium diffusing from a

system Na*C1 + Na into armco iron and electrolytic iron; b) potassium dif-
fusing from a system K ' C 1 + K into armco iron and electrolytic iron: c) potas-
sium diffusing from a system K ' C 1 + Na into arrnco-iron. 1+) Armco iron;
2) electrolytic iron.
Although, according to the constitution diagrams of the systems Fe-K and Fe-Na, neither sodium nor potassium is
soluble in iron, it appears that both these elements diffuse in iron at the temperatures studied. Their effective diffusion
coefficients are smaller for electrolytic iron than for armco iron; this is probably associated with differences in grain-
boundary diffusion whose contribution should be smaller in the case of a purer material. Characteristically, the values
of the activation energy Q are small; since, however, D0 is also small, the diffusion coefficients are not very large. The
low values of Do are evidently due to the probability of atoms passing from one equilibrium state to another being very
low. Comparison of our experimental data shows that the diffusion rate of sodium is faster and the activation energy for
diffusion of this elemeiat larger than the corresponding diffusion parameters of sodium; this is in accordance with the atom
size of these elements.

The magnitude of diffusion coefficients may vary, depending on the system which serves as a source of the diffus-
ing element. And so, the diffusion of potassium from the system K ' C 1 + Na is faster than from the system K ' C 1 + K. This
is very likely because in the former case the diffusion of both sodium and potassium takes place, while in the latter case
potassium is the only diffusing element; evidently, the diffusion of potassium in iron is accelerated in the presence of
sodium.

188
~FERENCES

1. V. S. Lyashenko, V. V. Zotov, V. E. Andreev, M. D. Abramovieh, and V. A. Ivanov, Proceedings of the

Second International Conference on Peaceful Uses of Atomic Energy Contributions of Soviet Scientists [in Russian], 8,
G42, 1959. =
2. V. I. Nikitin, Teploznirgetika, no. 2, 90, 1962.
3. E. E. Hofman and N. D. Manly, J. Amer. Chem. Soc., 82, 1957.

6 December 1966 Bardin Central Research Institute

of Ferrous Metallurgy, Moscow

189