Journal of Nuclear Materials 69 & 70 (1978) 70-96

0 North-Holland Publishing Company

SOLUTE DIFFUSION IN DILUTE ALLOYS

A.D. LE CLAIRE
Materkrls Development Division, AERE, Harwell, UK

Expressions are written for diffusion properties in terms of solute and solvent jump frequencies and solute defect lnter-
action energies. These are used in reviewing the general experimental features of dilute alloy diffusion and in showing how,
through their interrelations, one may confirm or refute proposed mechanisms of diffusion and extract information on jump
frequencies and defect properties. Impurities diffuse by the vacancy mechanism when their diffusion rates are comparable
with the host self-diffusion rate (“normal diffusion”). When the impurity diffusion rate greatly exceeds that of self-diffusion
(“anomalous diffusion”) the vacancy mechanism is untenable and diffusion is believed to be dominated by some form of in-
terstitial migration. Evidence supporting these beliefs is described. While normal diffusion is now fairly well understood in
some detail, this is not the case for anomalous diffusion because of the present lack of knowledge of the properties of the
interstitial defects responsible for it.

Des expressions sont presentees pour dbcrire les propriites de la diffusion en termes de fr6quence de saut des atomes de
solutk et de solvant et des Energies d’interaction solutid8faut. Ces expressions sont utilisdes pour revoir les caract&istiques
exp&lmentales gkn6rales de la diffusion dans les alliages dilu6s et pour montrer comment, i travers leurs interrelations on
peut confiimer ou infirmer les mdcanismes de diffusion propo&s et en deduire des informations sur les friquences de saut
et sur les prop&t& des d6fauts. Les impure& diffusent par le m&anisme lacunaire quand leur vitesse de diffusion est com-
parable i celle des atomes du solvant, (auto-diffusion ou “diffusion normale”). Quand la vitesse de diffusion de l’impureth
excsde beaucoup celle d’auto-diffusion (“diffusion anormale”), le mbcanisme lacunaire ne peut plus dtre retenu et la diffu-
sion est probablement dominee par quelque forme de migration interstitielle. Des preuves expkrimentales supportant ces
id6es sont d&rites. Tandis que la diffusion normale est maintenant relativement bien comprise en dktail, il n’en est pas de
m6me pour la diffusion anormale en raison de l’absence actuelle de connaissance des propri&s des d6fauts interstitiels
reponsables de ce type de diffusion.

Es werden Ausdriicke fir Diffusionseigenschaften in Form von Sprungfrequenzen des Fremdatoms und des Wirtsgitter-
atoms und von Wechselwirkungsenergien zwischen Fremdatom und Defekt angegeben. Diese Ausdriicke werden zur Dar-
stellung der allgemeinen experimentellen’ Merkmale der Fremddiffusion verwendet; es wird gezeigt, wie durch ihre Wechsel-
beziehungen vorgeschlagene Diffusionsmechanismen bestgtigt oder widerlegt und Informationen iiber Sprungfrequenzen
und Defekteigenschaften gewonnen werden kannen. Fremdatome diffundieren nach dem Leerstellenmechanismus, wenn
ihre Diffusionsgeschwindigkeit mit der der Wirtsgitteratome vergleichbar ist (normale Diffusion). Wenn die Geschwindigkeit
der Fremddiffusion sehr vie1 iiber der der Selbstdiffusion liegt (anomale Diffusion), ist der Leerstellenmechanismus unhalt-
bar, die Diffusion ist vermutlich durch irgendeine Art von Zwischengitterwanderung bestimmt. Wghrend die normale Diffu-
sion heute im Detail ziemlich gut verstanden wird, ist das fiir die anomale Diffusion wegen der gegenwsrtig geringen Kennt-
nis der Eigenschaften der dafir verantwortlichen Zwischengitterdefekte nicht der Fall.

1, Introduction ments at the necessarily low concentration of solute.

Because of the comparative simplicity of diffusion
in very dilute solutions their diffusion properties have
been extensively studied, both experimentally and
theoretically, ever since the advent of readily available
radioactive isotopes made possible accurate measure-
In theoretical discussions of diffusion in “dilute
solutions” this term is usually taken to mean solutions
of such low concentration that (i) it is unlikely the
solute atoms are present other than as isolated atoms,
or as similarly isolated simple groupings of atoms such
as solute pairs, triplets etc. and (ii) that these are all

70
 A.D. Le Claire /Solute
sufficiently isolated from one another that each solute
atom or atom group can be regarded as diffusing in-
dependently of the others. The total diffusion is then
particularly simple to treat theoretically. It is neces-
sary only adequately to specify the atom jump fre-
quencies and defect interaction energies for the very
few simple and well defined solute-defect configura-
tions and then to add the calculated contributions to
diffusion from each of them. Unless there are strong
attractive interactions between them, single solute
atoms will be the predominant species, for the con-
centrations of pairs, triplets, etc. are proportional to
ca, cs, etc. Solutions of solute concentration no great-
er than about l-2% can be expected to meet these
requirements and experiments on dilute solutions are
usually confined to such concentrations.
In this paper we review the general features of the
results from such experiments and the progress that
has and is being made in their theoretical understand-
ing. Some previous reviews can be found in refs. [l--S].
2. Types of experimental measurement
We begin by briefly describing the several types of
experimental results that are commonly drawn upon.
Experimental procedures are described in [ 11.
(i) The so-called impurity diffusion coefficient,
denoted by D2, describes the limiting diffusion rate
of solute at extremely low concentration in the sol-
vent and is usually measured with a radioactive tracer
of the solute as diffusant. D2 nearly always has a sim-
ple Arrhenius type temperature dependence,
DZ = A 2 exp (-QalkT) , (1)
with “activation energy” Q2 and “pre-exponential fac-
tor” A 2 .
(ii) Da is always compared with Do, the pure sol-
vent self-diffusion coefficient, which has activation
energy Qe and pre-exponential factor A,,
DO = -40 ew (320/W.
Particular interest attaches to the differences AQ be-
tween Q2 and Q,,
AQ=Qz--Qo.
(iii) Sometimes there are available measurements
of the isotope or mass effect for Da and Do. This mea-
diffision in dilute metals 11
sures the relative difference of the diffusion coeffici-
ents D” and Dp of two isotopes of the diffusing spe-
cies having unequal masses moLand mp. It is commonly
denoted E and defined as
E = (Da/D’)- 1
(4)
(mp/m”)“2 - 1 ’
(iv) For some systems measurements have been
made of the dependence of the solvent self-diffusion
Do(c) on the atomic fraction c of solute. Usually
D,(c) can be represented in the manner
Do(c) = Do(0)(l + blc +b2c2 + . ..) , (5)
and results are expressed in terms of the solvent en-
hancement factors, bl, b2, etc. D,(O) is the Do of eq.
(2).
(v) One can also measure the self-diffusion coeffi-
cient of the solute as a function of its concentration,
D2 (c). This has a similar representation
D2(c) =D2(0)(l +Brc +B2c2 + ...). (6)
with solute enhancement factors, B1, B2, etc. D2(0) is
the D2 of eq. (1).
Experimental measurements of (i)-(v) all employ
radioactive tracer methods and chemically homogene-
ous samples. The gradients of chemical concentration,
occasioned by the tracer gradient, are so minute that
samples remain effectively homogeneous during mea-
surement: there are no complications arising from
Kirkendall effects and the mathematical analysis of the
measurements is simple because the diffusion coeffici-
ent is a constant.
(vi) If conditions are appropriate, one can some-
times obtain useful information on diffusion proper-
ties by studying solute migration due to a vacancy flux
as the defects migrate to sinks in quenched alloys or
during their sintering or irradiation.
(vii) Finally, there are several other types of experi-
ment that can provide information relevant to an un-
derstanding of dilute alloy diffusion processes, such as
X-ray and dilatometric thermal expansion measure-
(2)
ments [6], quenching and recovery experiments [6,7],
internal fraction [8], and positron annihilation studies
[9], to mention the more important examples. Some
of these topics are treated in detail elsewhere in this
(3)
volume. Experimental measurements of electromigra-
tion and thermal diffusion phenomena in dilute alloys
[lo] are also in principle of value, although their use
72 A.D. Le Claire /Solute
is hampered by inadequate understanding of the effec-
tive charges and heats of transport of solute atoms
underlying these phenomena.
3. Normal and anomatous diffusion
By far the greatest amount of experimental informa-
tion 11 l] comes from measurements of Do and Dz
and the first extensive and systematic studies revealed
a pattern of behaviour that has come to be known as
“normal impurity diffusion”. The essential feature of
this is that D2 and Do do not usually differ by more
than about an order of magnitude at the melting point,
due to there being comparatively small differences be-
tween Qs and Qe and between A2 and Ao. Roughly
0.1 < AZ/A0 < 1.0 and 0.75 < Q2/Qo < 1.25, with
the smaller (larger) values of A2 tending to be asso-
ciated with the smaller (larger) values of Qz. At the
melting point D2 is usually within an order of magni-
tude of Do. The relative values of Da and Do are de-
termined for the most part by the difference AQ
= Qa - Qe [eq. (3)], for Dz is increasingly greater or
less than Do according as AQ is more negative or posi-
tive, respectively.
Then there is for many solvents, but by no means
all, a striking dependence of AQ on the difference be-
tween the valencies 2s and Zo of solute and solvent.
For fast diffusers, i.e. when AQ is negative, Zz > Zo
and for slow diffusers, with AQ positive, Za < Z,. Dz
generally increases with the difference Z = Zs - Z,.
Some illustrative examples of this behaviour are shown
in tables 67 and 8.
These properties of normal impurity diffusion are
characteristic of a widerange of dilute alloy systems,
except that the valency dependence is less likely to be
found the larger the valency of the solvent. It is well
established for noble metals as solvents and for some
divalent solvents like Cd and Zn, but it fails for solutes
dissolved in Mg, Al and Pb, in many transition metals
and also in the highly electropositive alkali metals.
Table 9 shows the data for Al.
For systems that are normal with respect to their
diffusion rates and activation energies, even though
they may not show this valency correlation between
Z and AQ, it is usually assumed, because of the small
differences in properties, that the solute diffuses by
the same vacancy mechanism that is so well establish-
~~ffus~n in dilute metals
ed for self-diffusion of the pure solvent.
Then there are some systems that are not normal
in any respect. Some impurities in some metals show
values of D2 that may be several orders of magnitude
greater than Do, with activation energies Qz only a
half or a third of Qo. These are the so-called “anoma-
lously fast diffusers” [5]. We discuss these separately
in section 5, where we shall find that solute migration
mechanisms of an interstitial type need to be invoked
in order to explain their properties.
First we discuss normal impurity diffusion.
4. Normal diffusion properties
If normal diffusion occurs by vacancies we can ex-
press all measured quantities in terms of vacancy con-
centrations and vacancy jump frequencies. We consider
here only monovacancy diffusion. Although divacan-
ties no doubt play some role in diffusion in dilute al-
loys at high temperatures, as they do in pure metal
self-diffusion, there has so far been too little experi-
mental indication of their contribution for the theory
to have been extended to include it.
4.1. Specification of jump frequencies
Fig. 1 shows the so-called “five-frequency model”
commonly employed to discuss diffusion in dilute fee
alloys. A solute atom is shown shaded. Wz is the jump
frequency for a solute atom-vacancy exchange, unique
when the solution is very dilute. Near to a solute atom
solvent atoms may have jump frequencies that are dif-
ferent from the value w. characteristic of pure solvent:
wi is defined as the frequency for solvent-vacancy
jumps between a pair of sites that are both nearest
neighbours of a solute, w3 for vacancy jumps from
first to more distant neighbour sites (second, third or
fourth) - “dissociative jumps” - and w4 for the reverse
“associative jumps” onto first neighbour sites. All
other solvent-vacancy jumps are assumed to occur
with the frequency we.
If ~&i is the interaction energy (minus the binding
energy) of a solute atom with a nearest neighbour va-
cancy, the probability is exp [-(gv + Ag)/kT] that a
vacancy occurs on a particular site next to a solute
atom, compared with the probability exp (--g&T)
of occurrence on any other site. gv is the vacancy for-
 A.D. Le Claire/Solute diffusion in dilute metals
Fig. 1. Frequencies wi for vacancy-atom jumps in fee crystals.
The arrows indicate the direction the vacancy moves. The cir-
cled numbers indicate the order of neighbours to the solute
atom 0 at the origin.
mation energy in pure solvent. To maintain dynamic
equilibrium between these vacancy concentrations
demands the relation
w&s = exp (-&r/W. (7)
Fig. 2 shows two different models that have been
used for bee crystals. In model II the same assumptions
are made as for the fee case, but there are only four
frequencies to consider because there are no w1 type
Fig. 2. Frequencies wi for vacancy-atom jumps in bee crystals, with same conventions as fig. 1. Model I, vacancy-solute
at first and second neighbour separation. Model II, vacancy-solute binding at first neighbours only.
jumps in the bee structure. Eq. (7) applies again. Mod-
el I makes allowance for vacancy-solute interaction
with energies &r and Aga at first and second nearest
neighbour sites. This may be necessary because their
distances from the solute differ by only about 15%.
Dissociation jumps from first to second and from first
to third or fifth neighbour sites must now be distin-
guished and are assigned different jump frequencies
w3 and w;, respectively. The reverse association jump
frequencies are w4 and w>,
but the simplification is
usually made that wb = wo, because yet another fre-
quency ws has to be defined for dissociation jumps
from second neighbour sites. The dynamic equilibrium
equations are now
wo = W; exp (-&r/W = ws exp (-4&W ,
~4 =~3 expH&l - &d/kTl . (8)
Jump frequencies associated with pairs of solute
atoms are mentioned in section 4.4.
Every jump frequency has an Arrhenius type tern
perature dependence with activation enthalpy Hi and
pre-exponential factor vi, i.e.
wi = vi exp (-Hj/kT) . @a)
The activation entropy is contained in vi. These mod-
els are easily elaborated to involve more jump frequen-
cies - e.g. dissociation jumps to different types of site
should really always be distinguished - but the added
complexity cannot be resolved by existing types of
diffusion meas~ement.
binding
14 AD. Le Claire /So&e
4.2. The self- and impurity diffusion coefficients
The pure solvent self-diffusion coefficient De is
readily found to be
Do = a’f~w~ exp f-gV/kT) f
for both fee and bee metals. a is the lattice parameter,
exp (-g,/kTj the fractional concentratidn of vacancies
and fO the correlation factor, in this case, a numerical
constant equal to 0.78 15 for fee and 0.7272 for bee
crystals. fO takes account of the fact that by a vacancy
mechanism atom jumps do not occur at random - i.e.
with equal probab~ity in each allowed direction. The
probability is greater than random (i.e. >l/coordina-
tion no. 2) that after one atom jump by exchange with
a vacancy the next will be in the reverse direction, giv-
ing zero net displacement, for the same vacancy is im-
mediately available to effect such a second jump. Sim-
ilarly, a second jump in the same direction, doubling
the displacement, has probability less than 1/Z+ fO is
the fraction by whichDo is reduced in this way from
the value calculated were all jumps at random.
The equation for Dz , the impurity diffusion coef-
ficient, is similar to eq. (9) with w2 and fi in place of
w. and fO and with Agl added into the vacancy con-
centration term,
DZ = a2f2w, exp [-(s, f &I I/W .
Solvent jump frequencies enter into D2 through the
correlation factor fi . In simple cases, like vacancy dif-
fusion in isotropic crystals, f2 has the form [ 12,131
f2 = u/@w, + u> 9 (11)
where u is a function of alf the solvent jump frequen-
cies. Table 1 lists some expressions for u. In these, the
F values art? known and are usually slowly increasing
functions of their arguments. When w2 >> u, f2 is
Table 1
Expressions for u in eq. (11) for the correlation factor; im-
purity diffusion by the vacancy mechanism [l&l 31
Structure u [Es. (1111 F(m) F(1)
fee u = 2Wl + wg(w&J/w()) 2 5.15
bee I u = w&wq/wo) 3 5.33
bee II u = w’$(w3/w$ 3 5.33
diffusion in dilute metals
small. This is because one solute jump is then highly
likely to be followed by a second jump in the reverse
direction. When w2 << u, f2 is near unity. This is be-
cause the vacancy in this case makes many exchanges
with solvent atoms after one solute jump and so be-
(91 comes near randomized in position with respect to
the solute before the second jump.
From eqs. (9) and (10) and the definition of the
experimental activation energy [Q = -k ?I In D/a( l/T)],
it is easily found that AQ [eq. (3)] is
AQ=Q,-Q,=AH,+AE-C, (12)
where ar-i, = H2 - Ho, AE is the vacancy-solute in-
teraction enthalpy, and C = k 3 In f21a( l/r). fO is
constant but f2 will vary with T if the component
frequencies have different activation energies. Usually
C will be numerically smaller than AH2 + Af?.
Any small variation of C itself with temperature
will contribute a small curvature to the Arrhenius plots
of In D2 vs. 1IT. Theoretical ~l~ulations suggest this
may be negative [ 141. Since this is opposite to the sim-
ilarly small but positive curvature expected from any
divacancy contribution [ 1.51 to solute diffusion, it
may make such a contribution more difficult to iden-
tify than in the case of pure metal self-diffusion.
When C varies with temperature there is a corre-
sponding variation of A 2, for this is easily seen to con-
(10) tain the factor f2 exp (-C/R 7’), which is independent
of temperature only when C is.
Eq. (12) expresses the fact that solutes that attract
vacancies (i.e. M negative) and also exchange with
them much more rapidly than do solvent atoms, so
that wz >> w. (i.e. AH2 negative), will have negative
values of AQ and are therefore most likely to be fast
diffusers. However, it does not of course follow that
all fast diffusers necessarily have both AE and M2
negative and we shall see illustrations of this later.
Similar remarks apply with regard to slow diffusers.
4.3. Isotope or mass effect
If it is assumed that a change in the mass of the
,diffusing species alters the jump frequency of that
ROf species alone - i.e. the wi and therefore the fi in eqs.
(9) and (10) but not the L(in eq. (11) for example -
7 then it turns out that in its simplest form the mass ef-
7 fect E, as defined by eq. (4), is just
m
EQ =foAbg and .I& =f2aK2g, (13)
 A.D. te Claire /Solute di~~s~~ in dilute metals
for self- and impurity diffusion, respectively, [ I2,13,
15,161. g is a factor which is unity if jumps are of one
atom at a time, as in simple vacancy-atom exchanges;
otherwise, if groups of n atoms migrate simultaneously
(e.g. n = 2 for interstitialcy jumps)
(134
where M’ = mi + (n - I> m* is the mass of the migrat-
ing group one atom of which is an isotope i and the
others host atoms of mean mass m*. A AK is the frac-
tion by which the mass effect in the migration of an
atom or group is diluted by there being some conco-
mitant movement of other nearby atoms during the
migration. It is the fraction that resides in the migrat-
ing atom (or group) itself of the total kinetic energy
associated with passage through the saddle-point of a
jump [17,18].
The value of g is always known, but there is no reli-
able way of calculating AK. However, LX0 can always
be determined from a measurement of E. because f.
is known. (It is around 0.9 for close packed metals,
rather less for bee metals [I 41.) With regard to AKa,
simple relations have been suggested for estimating it
from AK0 with the ratio of solute and solvent masses
[ 191 or of diffusion activation volumes [ 161, but so
far these have been little employed. Rather has the
somewhat questionable assumption been made that
AK2 = AKe, from whichfs is immediately obtainable
from a measurement of E, . In any event, E, always
gives a lower limit to fi because gAK is fractional. We
refer later to the use made of these measurements of
f2*
AK is not thought to vary much with temperature
[21] so measurements of E2 as a function of T give
the quantity C in eq. (12). However, E may also, of
course, vary with temperature if there are two or more
migration mechanisms, with different correlation fac-
tors, contributing to diffusion in proportions that
change with temperature. For example, a decrease of
Eat high temperatures has been attributed to a diva-
cancy contribution to D, for diffusion of Ag [22]
and of Co f23] in Au. This may be the most sensitive
means of detecting a divacancy contribution to diffu-
sion in dilute ahoys.
The simplest relation, eq. (13), between E and f is
not general. It can be shown to be valid [24] only
when the diffusion mechanism is such that fi has the
15
formfi = (1 + G(wzi, wi)]- ‘, where G, a function of
all the jump frequencies involved, is a homogeneous
function of order one with respect to those of the
tracer diffusing species, the w2i. The Wj are the non-
tracer jump frequencies. There may be more than one
Wsi, as for example in anisotropic crystals, when it is
necessary to assume that AK2 is the same for each if
the simple form, eq. (13), is to be retained. The above
condition is clearly satisfied by eq. (1 I), representing
the form of fi for monovacancy diffusion in fee and
bee crystals, as well as for several other mechanisms,
such as divacancy and direct interstitialcy diffusion in
fee crystals. In cases where it is not satisfied, such as
for a-axis diffusion in hcp crystals and for some types
of interstitial and interstitialcy diffusion, E may differ
considerably from fAKg. See, for example, ref. [25],
But, given expressions for D2 and f2 for any mech-
anism, E can always be calculated from its definition
as some function of the jump frequencies.
A comparison of predicted with experimental val-
ues of E is often of considerable diagnostic value in
identif~ng or con~rming mechanisms of diffusion.
4.4. The enhancement factors bi and Bi
Eq. (5) describes how the solvent diffusion coeffi-
cient Do(c) in a dilute alloy varies with the solute con-
centration c.
The quantity br is determined by the extent to
which solvent jump frequencies near to isolated solute
atoms differ from w. - i.e. by the frequencies wr , w3
and w4. By carefully counting all the different types
of solvent jumps one can calculate Do(c) and identify
the terms in eq. (5). For fee crystals the result for b r
is
t 14%) exp(+).
(14)
This form illustrates the effect of the altered vacancy
concentration near a sol&e through the factor exp
(-Agt/M). With eq. (7), br can be written wholly in
terms of frequencies. The solute jump frequency w2
enters into br only through the quantities x1 and x2
which are mean partial correlation factors and known
functions of the three ratios w2/wl, w l/wg and we]
wo ]261.
16 A.D. Le Claire / Solute diffusion in dilute metals
There are similar relations for bee crystals. For
model I, with eq. (8)
w3 Vl
(bcc1) bl =-20+141’t6-
fo wo fo
and for model II
P2 w3 v2
(bccI1) b1 =-20+6-+ 14-
fa WI fo
(16)
~1 9 VI @2/d 9 w3hb) and 112, ~2 (w2Iw3, w4lw0)
are mean partial correlation factors and known func-
tions of the frequency ratios in the parentheses [27].
The term b2 in eq. (5) derives from the modifica-
tion of solvent jump frequencies in the neighborhood
of pairs of solute atoms. One needs to consider, for
fee crystals, all pairs out to eighth nearest neighbour
separation, because with any of these there are always
some solvent jumps that cannot be unambiguously
identified as of the types wl, w3 or w4, and which
may therefore have different frequencies from these.
It turns out [28] that, even with some simplification,
there are as many as six new solvent jump frequencies
to be defined. The resulting expressions for b2, due to
Bocquet [28], are therefore rather lengthy and we
shall not reproduce them. Little use seems so far to
have been made of them.
In eq. (6) for the solute self-diffusion coefficient
as a function of its own concentration, the concentra-
tion independent term comes from isolated solute
atoms, while the terfn in BE is due to pairs of solute
atoms close enough together for a solute jump frequen-
cy to differ from the value w2. Similarly, B2 derives
from solute triplets, and so on.
There have been no calculations ofB2, but B1 has
been considered in a model that defines three new
frequencies to describe single solute jumps that re-
orient a nearest neighbour pair (wzl), that dissociate
a pair (Wan) or that create a new pair (w?~). Nearest
neighbour pairs will not occur at random if solute
atoms interact and one defines for such pairs an inter-
action energy Agp. There then exists the equilibrium
relation
w24 exP (-&,lkT) = w23 exP (--&l/W 9 (17)
-Agl being, as previously, the binding energy of a va-
cancy with each solute. With the assumption that f2
is inde~ndent of concentration, which Stark’s calcula-
tions [29] suggest may not be unreasonable, B, is
found to be [28] *
B1 =-6- 12exp(-2) t [4~ exp( -3)
+ 1421 exp(-3)) (18)
for fee crystals.
If we assume no solute-solute binding (Agp = 0)
and that w 21 = w23 = w2, eq. (18) becomes
B1 = 18[exp (-Ag,/kT) - l] . (19)
Similar assumptions were made by Miller [30] in an
earlier calculation of B1, but the result differs from
(19) in having 11 in place of 18. This is because Miller
assumed that all solute jumps had the common fre-
quency w2 : this is inadmissable because, from (17),
w24 = w2 exP (-~~/k~.
The two equations (14) and (18) for bl andB, are
very similar in form. This is not surprising. Both des-
cribe the interaction of tracer atoms with solute atoms
- B1 that of solute tracers and bl that of solvent tra-
cers. If these tracers were to become identical we
should have kp =O,W?~ =w1,w2 =wo,etc.andeq.
(18) would go over into eq. (14) as it then should.
Furthermore, if the frequency ratios in one equation
do not differ markedly from those in the other, as
would be the case if all perturbations were weak, we
would expect b1 and B1 to be of the same sign and of
comparable magnitudes, apart from the effects of
solute-solute interactions - the Agp terms in BI.
This is indeed just what is found experimentally for
normally diffusing solutes, with B1 usually numerical-
ly somewhat less than b, suggesting, as might be ex-
pected, a repulsive interaction between solutes (Agp
positive). Table 2 shows some results that illustrate
this.
Numerical values of b 1 and B, are best discussed
when bl is written in terms of the ratio Dz/Do. Com-
bining eqs. (7), (9), (lo), (11) and (14) gives
* Eq. (18) differs from Bocquet’s [ 281 result following a car-
rection to his expression for the concentration of single
solute-vacancy pairs and the use of eq. (17).
 A.L).Le Cl&e / Solurediffusionin dilute metals

Table 2
Values of Dz/Do, b 1 and B1 for a few fee (a) and bee (b) systems
(a)
-
T= 730°C %Fe &Pd &AU &Cd &In &Tl &Sb &Pb
(1020”) [321 1331 1341 [341 [351 [361 [371
[17,311

D2h 1.06 0.04 0.26 3.1 5.3 8.4 7.6 11

bi -5 -8.2 -1.2 +7.0 +13.0 +37 +52 +87
- -7.5 -0.56 +5.5 +8.5 +30 +11 +50
31

(b)

aF_h @Y VT1 orFeSi lfFe

(895”) (1400”) (1400”) (1x7’) (1300)
[381 [391 [391 1401 [41I

&/Do 0.74 1.26 1.66 1.64 4.06

br -1.1 -4.3 +16 +20.4 +18.7
Bl -2.5 +27 +12.4 -

The term in braces will have the order of magnitude wa/wr -+ =. That is, when vacancies are near perma-
unity. It becomes unity, leading to Lidiard’s equation nently associated with solute atoms and exchange ex
for br 1421, if we assume F= 1 and that ~rturbations tremely rapidly with them. Then
are weak so that x1 $ x2 + fo. (fee) bI = -18 + ~xI(Dz/‘Do).
Eq.(20) shows that br is more likely to be positive
the larger Da is compared with De, i.e. fast diffusing = -18 + 1.945(D2/Do), (21
solutes tend to enhance solvent diffusion rates, an ef- when the value x1 = 0.4862 [26,43] for these condi-
fect attributable in large measure to the higher vacancy tions is inserted.
concentration. Values of D2 fDo range up to about 10 Values of b,,,h, can also be calculated for bee crys-
or so and a typical value of f2 is about i. Positive val- tals. For example, for model I the equation for br can
ues of br are therefore expected to be in the range be written
O-100, say, Similarly, for slowly diffusing solutes br
will tend to be negative: their presence slows up sol- bl =-20+&+1j~ (22)
vent diffusion, but the values of b 1 cover a narrower fo w3fo’
range for they cannot exceed -18, however small D2 by substituting eq. (8) into (15). A rnin~~ allowed
may be. These properties are illustrated by the data in value of ws/w;, and therefore of b 1, can be deduced
table 2, where it is also seen that whenDa and Do do irom the relation [27]
not differ greatly the other factors in eq. (20) can be-
~2 _ foPz/Do) F{w&; 1
come important to give some fast diffusers negative (23)
values of b 1, e.g. CQ Au, BV. $ - F{w&; I - 2fo (DzlDo) ’
What few values there are of bz are very roughly obtained by combining eqs. (8)-(11). Since ws/w;
up to an order of magnitude greater than b, . There must be positive, F cannot be less than 2foDz/Do:
seem to be no values reported of Ba for normal diffu- this sets a minimum value to ws/w; consistent with
sers [4]. an experimental value of Dz/Do, because F is an in-
From eq. (20) can be derived an important expres- creasing fiction of ws/w;_ The factors pr and v1
sion for the absolute rn~~urn value of b, consistent are evaluated at (w~/w~)“i~ and for the ratio w2/w;
with an experimental value of D&&, b 1 has its mini- = 00with which it corresponds. The calculations for
mum value when wr/ws + m and fa -+ 0, which implies model II are similar.
 78 A.D. Le Claire I’Solute diffusion in dilute metals
As one might expect, measured values of br for
normal solutes are well ,above these minimum values,
as can easily be seen. Even with as high a value of LX,/
Do = 10, eq. (21) gives a bk of only about t2, well
below the experimental values for such solutes (see
table 2). This is not surprising because the limiting
conditions associated with bti represent an extreme
situation.
This compatibility between b 1, Dz and Do, when
their values are expressed theoretically and compared
in terms of a vacancy mecha~sm, provides of course
additional support for the presumption that normal
diffusion is by vacancies. However, for the anomalous-
ly fast diffusing solutes that we discuss later, this com-
patibility breaks down completely. Measured values
of bl are strikingly less than b,,,h and the vacancy
mechanism has to be rejected in their case, as we shall
see.
4.5. The determination of frequency ratios
The various vacancy equations for normal diffusion
can be exploited more quantitatively to derive infqr-
mation on the jump frequencies involved. The key to
this is the property that all the three experimental
quantities, i&/Do. b 1 and fi , derived from a mass ef-
fect measurement, can be written as functions of the
same set of frequency ratios. For fee crystals these ra-
tios are wz/wl, wI/w3 and wq/wO. Thus, from eqs.
(9) and ( 101,
D2
--..- _f2 ~2
---_-,
Do fo wo
the second relation following from the use of eq. (7).
It is easily seen that eq. (11) for f2 and eq. (14) for
bl can similarly be rewritten to contain only the same
three ratios. For bee crystals .the three experimental
quantities are determined by sets of two frequency ra-
tios, namely wJw\ and wJw\ (= w,Jws) for model
Table 3
Frequency ratios in fee systems calculated from measured values of Dz/Do, b 1 andf2
_I~
fee &/Do bl f2
-
CUZil 3.4 +8.8 0.47
qgZn 3.9 +12.1 0.57
&Fe 1.06 -5 0.79
I and wJw3 and wq/wo for model II. It follows that
if all three experimental quantities have been measur-
ed for an fee system, or any two for a bee system, the
relevant equations can be solved to yield numerical
values for the frequency ratios. Tables 3 and 4 show
the results of such calculations for most, if not all, of
the systems for which data are available. All the fre-
quency ratios are positive, as they must be, and the
calculated values of f2 in table 4 are within the allow-
ed range of 0 < f2 < 1, confirmation again of the va-
cancy model as appropriate for describing such nor-
mal systems. (This is particularly true for the high and
the low temperature regions in the YFe system, which
are in this case characterized by different activation
energies above and below about 14OO”C,aithou~
earlier measurements of the mass effect [46] have
suggested divacancy diffusion in the high temperature,
high Q2, region.) (see section 4.3.) The frequency
ratios are, for the most part, all well within an order of
magnitude of unity, indicating that the perturbing ef-
fects of solute atoms are not gross. It is unfortunate
that one cannot derive a value for we/w3 because this
would give [eq. (7)) the solute-vacancy binding en-
ergy. But wq/w3 is a ratio of frequencies for vacancy
jumps in opposite directions between a pair of sites,
whereas diffusion data only give the ratios of frequen-
cies of alternative jumps from the same site.
When w4 > wo, or >ws in the bee model I, vacan-
cies tend to move towards solute atoms rather than
further from them. This is equivalent to there being a
solute-vacancy binding and indeed the ratios wq/wo,
or wq/w5, tend to be greater than one for the fast dif-
(24)
fusers and less than one for the slower diffusers. Again,
one might expect ratios with a w2 numerator to be
larger for the faster diffusers and this tends to be the
case, although not regularly so. Finally, we turn to the
ratio w , /w3. When this is greater than unity vacancies
are more likely to jump around a solute atom than
away from it. This is sometimes said to indicate bind-
WllW3 w2h w4ho T("C) Ref.
1.1 3.6 1.5 947 v41
2.56 1.54 1.3 880 1451
10.5 0.35 0.3 1020 [311
 A.D. Le Claire /Solute diffusion in dilute metals 19

Table 4
Frequency ratios and impurity correlation factors in bee systems calculated from Dz/Do and bt

bee &ho bl Model I Model II T (“0 Ref.

wz/wj w4lw5 f2 w2fw3 w4lwo f2

=w3/w;

EC0 0.74 -1.1 0.69 0.80 0.78 0.74 0.92 0.79 895 [381

ZV 1.26 -4.3 1.73 0.34 0.53 2.64 0.67 0.52 1400

0.94 -3.7 1.01 0.43 0.67 1.42 0.72 0.67 1100 [391

fli 1.66 +16 1.49 4.6 0.81 0.64 2.4 0.78 1400 1391
VFe 4.06 +18.7 5.33 4.89 0.55 2.51 2.48 0.47 1300
- 0.59 1.9 1728 [411
3.04 +12.6/15.6 3.7 3.7 2.1 0.55

ESi 2.1 24.4 1.86 6.8 0.82 0.61 3.2 0.78 1127 1401

ing, but it does not necessarily mean that a nearest
neighbour solute-vacancy pair then has a lower energy
than a separated solute atom and vacancy, which is the
usual meaning of binding. The point is illustrated by
@Fe in table 3. wI/w3 is large but there is no sugges-
tion of strong binding in the low value of Dz/Do and
the sizeable and negative value of b 1.
It is sometimes said thatf2 >fo for slow diffusers
while f2 < f. for fast diffusers. Experimental results
may frequently conform to these relations but they
have no theoretical basis and table 4 contains some ex-
ceptions to them. &Si is fast withf2 > f. and TJV at
1100°C is slow with f2 < fo.
There are various other transport phenomena mea-
surements which can be employed, especially when
other diffusion data are available, to give information
on these jump frequency ratios. Particularly important
their own concentration gradient which, in a homoge-
neous alloy, must be in the same direction as the va-
cancy gradient. That is to say, in this case the solute
moves in the same direction as the vacancy flux and
its concentration around sinks is increased. Both such
effects have been observed experimentally. Table 5
summarizes some observations on the solute concen-
tration changes near different types of vacancy sinks
and shows that one may indeed have either enrichment
(E) or depletion (D), depending on the system.
To treat the phenomenon quantitatively one writes
down the formal equations for the fluxes of solute
(Ju) and of vacancies (Jv) and these lead to the result,
for a very dilute homogeneous alloy AB of solute con-
centration Cu = (1 - CA), [47,12]
JBIG3
-= D2

are phenomena associated with there being a net flux
of vacancies in a dilute alloy, such as occurs in a quench-
ed or an irradiated alloy as the excess vacancies flow
towards vacancy sinks [47]. Here the ratio wI/w3 is
particularly relevant. One might expect both solute
and solvent atoms to migrate in a direction opposite
to the vacancy8flux, and in amounts roughly propor-
tional to their concentrations and to their diffusion
coefficients, so that the solute concentration around
sinks becomes reduced. However, if w I >> w3 a va-
cancy can remain associated with a solute atom for
very many solute jumps, for it moves among the sites
around a solute atom, between solute jumps, rather
than moving away. Such pairs therefore diffuse inde-
pendently of the vacancy flux and therefore down
J” (C,&,/fo)+ CBDZ
where@=[6+7F+14(1-F)((w,-,/w~)- l)].The
fluxes are referred to the vacancy sinks so, if wr is suf-
ficiently greater than w3, JB and J, are in the same
direction (JB/Jv positive) and there is an enrichment
of solute near sinks. Otherwise, if wr is comparable
with or less than ws there is, unless D2/Do is too small,
a depletion of solute, J*/J, being negative.
Anthony’s measurements in table 5 (ref. [Sl]) were
used in eq. (29, with the approximation F = 1 to de-
termine the values shown for w3/wI. (The inequality
signs results from no account being taken in eq. (25)
of diffusion due to the concentration gradients built
up as solute migrates.) The integrated vacancy flux
was obtained from the size of the condensation cavities
80 A.D. Le Claire /Solute diffusion in dilute metals

Table 5
Systems showing depletion or enrichment of solute near vacancy sinks due to solute flux induced by a vacancy flux

System Temp. Deplete OI w3 Sinks

(” C) enrich
Wl

‘AJMg 480 +ve E grain boundaries in quenched samples

[481
GMn 800 +ve E _
CuZn 800 -ve D _ 1 pores in diffusion samples [49]
-
CuAg 1070 --ve D _
&CU
CsIn

4Zn
950
1070

585
-ve
-ve

+0.08
D
D

E
_
_
<0.20
1 necks in sintered samples [50]

vacancy condensation cavities in quench-

+cu 585 0 None 0.36
ed samples [5 1]
&lCe 585 -0.92 D >0.22 I

QZn 947 -1.65 D 0.90 [441

&Zn 880 -0.43 D 0.37 calculated [451
QFe 1020 +1.18 E 0.095 1 [311

and the integrated solute flux from the change in con-
centration near the cavities as measured by microprobe
analysis. The three items at the bottom of table 5 show
the effects predicted (D or E) from eq. (25) using the
frequency ratio data of table 3.
These same vacancy flow effects feature also in the
phenomena of electro- and thermomigration in dilute
alloys, where a knowledge of atom jump frequency ra-
tios, in particular wr/ws and wq/we, is necessary for
a complete interpretation of the measured effective
charges (Z) and heats of transport, Q [lo]. Such trans-
port measurements could therefore in principle be
used to provide information on frequency ratios, al-
though the present lack of understanding of the Q
and the Z values may hamper this as a general method.
However, Doan [52] has pointed out that measure-
ments of the concentration dependence of the marker
shift during electromigration in dilute alloys could be
used, when combined with data on b 1 and Dz/Do,to
determine the ratios wa/wr
, ws/w, and wq/we. This
concentration dependence is determined only by these
three ratios, in fee crystals, and the measurable effec-
tive charges of solute and solvent atoms. This method
would have the merit of avoiding the use, as described
earlier, of the quantity fi ,
the value of which may be
uncertain to the extent that the assumptions made
about aKz may not be valid.
4.6. Theoretical calculation of diffusion parameters
There seem to have been no absolute calculations
of any impurity diffusion coefficient or activation en-
ergy. Attention has been focused rather on attempts
to calculate only differences in diffusion properties of
solute and solvent, and especially those expressed by
the quantities Af? and AQ. aE is attractive because it
is comparatively easy to calculate [6,53,54], and par-
ticular attention has been given to AQ [eq. (3)] be-
cause it is readily and directly measurable and is the
quantity for which the largest body of data exists.
AQ is given by eq. (12). The quantity C is readily
shown to contain only the differences AHi = Hi - Ho
and the ratios vi/v,, , for i = 1 to 4 in fee crystals, for
example. AQ is therefore determined wholly by these
quantities, with AE.
There have been many attempts to rationalize the
data on AQ either by just seeking empirical correla-
tions between it, or Q,, and seemingly relevant pro-
perties of solute and solvent species - like atomic or
ionic radii, elastic properties or their various thermo-
dynamic properties - or, and often with the help of
such correlations,’ by calculating AQ in terms of such
properties with the aid of appropriate atomic models
(e.g. [55-591). Although many such calculations have
ignored C, and so have estimated AQ from considera-
 A.D. Le &ire /Solute diffusion in dilute metals
tion only of the sum AH2 t Al?, they are frequently
successful in revealing useful relations for AQ in rea-
sonable agreement with experiment, at least for limit-
ed range4 of solvents.
An example of a simple empirical correlation is
Moore’s result [57] that Q2 is roughly an exponential
function of the solute atomic volume V. This allows
AQ to be written as
AQ=b-alogY,
where a and b are characteristic of each solvent metal,
but different for transition and non-transition solutes
in that metal.
An example of a calculation, and one wherein C is
properly considered, is that of Neumann and Hirsch-
waid [59 J. They employ a model to calculate the AHi
that combines a Morse potential description of atomic
interactions with certain correlations between energies
and melting points, TM~ and TMo, of pure soIute and
solvent. They obtain the result
and with their calculated values of C added, values of
AQ are obtained in reasonable agreement with experi-
ment for solutes in the noble metals.
The only model from which AQ has been derived
in a direct manner, avoiding any dependence on corre-
lations or adjustable parameters, is the so-called half-
vacancy electrostatic model [ 14,601. This calculates
AQ in terms of electronic properties and gives an im-
mediate explanation of the correlation of AQ with va-
lency that is observed in many systems, and of why
the correlation by no means always obtains (see see-
tion 3).
One calculates the electrostatic interaction between
a vacancy and the screened potential V(r) due to an
impurity, both at the nearest neighbour distance a,
giving AE, and in the saddle-point con~gurations for
the various solvent and solute jumps of interest, giving
aJri - AE. The vacancy is usually approximated as a
point charge equal to -2, le 1, so that immediately
AE = -20 1eI V(a), and the ~p~ity as a point charge
Zle I=: (2, - 2,) ie 1.In a saddle-point config~ation
the vacancy is regarded as split into two h~f-vacancies
carrying effective point charges of -fZe le I at dis-
tances 1 la116 on either side of the jumping atom, this
being the distance to the centroids of each half-vacan-
81
cy, represented as hemispheres. AHa + AE is then easily
seen to be just -lelV(l k/16); the other AHf are simi-
larly calculated for estimating C. It has been usual to
assume that only the ratio v2/vo differs from unity
and this is introduced into the calculation through the
easily proved relation
VZ/VO = &fd&fd exp (C/RT).
The simplest form for V(r> is that of the Thomas-
Fermi potential [61 J
Zlel
V(r) = y---aexp(-49 ,
where a! is a known function of 2 [62J and of order
unity, and 9 is the “screening constant” given by q2
= 47r times the density of electron states at the Fermi
level of the solvent. V(r) has everywhere the same sign
as Z. For positive 2 impurities both AE and m2 are
therefore negative: they attract vacancies and there is
a reduction of the saddle-point energy of their jumps
relative to that for pure solvent atom jumps. C also
turns out to be negative in this case [ 141 but apprecia-
bly less numerically than the sum ivIa + AE, so that
AQ is negative. Similarly, for negative Z impurities
AQ is positive. These are precisely the properties of
completely normal impurity diffusion as described in
section 3.
Tables 6,7 and 8 show some values of AQ calculat-
ed from the model to iiiustrate the good agreement
with experiment for diffusion of various solutes in
monovalent Cu [64,63] and Ag [14J and in divalent
Cd 1681. They illustrate too the typical magnitudes of
AQ for such systems and how it varies with the value
and sign of Z. For Cd (table 8) it is interesting how
the calculations reproduce the anisotropy, at least
quantitatively. Table 7 also contains some similarly
calculated values of Br Jeq. (1 S>J, again in reasonable
agreement with experiment j7 1 J. Successful calcula-
tions have also been made of AQ for solutes in a few
other solvents such as Zn [72] and Ni 1731, and there
have been a few calculations of b, [14]. In all cases
agreement tends to be best for solutes in the same row
of the Periodic Table as the solvent, probably because
the ion cores are then isoelectronic so that 2 actually
is a point change. The model has also been extended
successfully to homov~ent systems (2 = 0), using
both Thomas-Fermi and Hartree (vi.) type expres-
82 A.D. Le Ckire / Solute diffusion in dilute metals

Table 6
Theoretical and experimental values of A@ (kcai moi-’ ) for impurity diffusion in Cu [63,64] (Qo = 50.50 kcaI mol-I) 1671

Zn Ga Ge AS Sn Sb
[651 1661 (631 f661 [641 f641
~._ --._-..-~ ____
z +1 +2 +3 +4 +3 +4
AQexpt -4.90 -4.60 -5.74 -8.50 -5.55 -6.86
AQtheor -3.98 -4.58 -5.82 -8.41 -5.1 -6.2
-

sions for V(r> appropriate for a “potential well” repre-
sentation of the solute atom [74].
It is well known, however, that the Thomas-Fermi
equation (26) is a rather rough approximation to V(r)
and that more accurate expressions are available. These
are based on the Hartree equation and have been de-
veloped by Kohn and Vosko, Friedel, March and
others ([54] and [75-801). They do not differ much
from the Thomas-Fermi potentials at short distances
but have the important and highly significant property
of becoming oscillatory at larger distances: the differ-
ences here are therefore profound.
Now, at least for monovalent metals, it turns out
that the distances of interest in a calculation of AQ
are comfortably within the region where the potentials
are similar, so it matters little which potential is used:
both give similar values of AQ (see e.g. 1741). However,
for polyvalent metals, on account of their higher elec-
tron density, the oscillations become effective at near-
est neighbour distances or less and so have a profound
influence on the value of AQ. In particular, with pos-
sible changes now in the sign of V(r) in the relevant
range of r, there is no reason always to expect for
solutes in polyvalent solvents the same simple depen-
dent of AQ on valence that one finds for normal mono-
valent solvents.
It is perhaps surprising, in view of these remarks,
that a normal valency dependence is found for solute
diffusion in Cd and Zn. However, this is not found in
Mg [81] nor in Al, for which the data, as shown in
table 9, are particularly extensive. All the non-transition
solutes show normal diffusion in that A2 and Qz dif-
fer little from A,-, and Qe, but AQ remains compara-
vely small and shows no obvious dependence on the
valency difference, despite this varying all the way
from -2 to t2. The other interesting feature isihat
the transition-period solutes show unusually large val-
uesofQz andAa, although Dz and Do still differ com-
paratively little near the melting point.
For a few of these solutes in Al calculations have
been made [91,92] of AQ that recognize the need to
use a more correct oscillatory type of potential for
v(r). The results are included in the table. There is
reasonable a~eement in sign and ma~itude both with
the small experimental values of AQ shown by non-
transition solutes and with the much larger values
found for transition solutes. It is interesting that for
Cu, Zn and the transition solutes the oscillations are
such that there is an attraction between vacancy and
solute at the nearest neighbour distance (AE negative)
but a stronger repulsive interaction at the saddle-point
(AHa positive), making the total AQ positive. For Ag

Table I
Theoretical and experimental values of AQ and El for impurity diffusion in Ag (Qo = 44.27 kcal mol-‘) [ 14,711

Pd Cd In Sn Sb Tl Pb Ge
[32,70a] 134,691 [34,693 1691 [36,70] [351 [371 [351
--
2 -1 +1 +2 +3 +4 +2 +3 +3
AQew +12.6 -2.57 -3.64 -4.97 -5.95 -6.37 -6.17 -1.17
AQtheor + 7.4 -2.45 - 3.40 -4.65 -5.70 -4.66 -4.84 -6.13

Blexp - 7.5 +5.5 +8.5 - +11 +30 +50 +15

B1 theor +4.7 +8.4 +11.0 +11.8 +8.4 +11.0 +11.0
 A.D. Le Ckziref Solute diffusion in dihte metals 83

Table 8 valid strictly only for large r 1771. kF is the Fermi

Theoretical and experimentabvalues of AQ (kcal mol-‘) for wave vector, ozo a constant and # a phase factor -
impurity diffusion in Cd [68] which it is important to include. The value of (x0 and
#I can be estimated from electrical resistance or NMR
In Ag AU
measurements.
i- +1 -1 -1 The simple half-vacancy electrostatic model seems
to provide a satisfactory qualitative, and in many res-
AQ ew II c -1.16 +6.03 +6.86
IC -2.65 +5.48 +6.84 pects quantitative, description of the main features of
normal impurity diffusion in spite of its obvious short-
Abeor u C -1.6 +6.0 +6.0
+5.1 comings. Treating the ~purities, vacancies and haif-
IC -2.5 +5.1
vacancies as effective point changes, ignoring differ-
ences in size and lattice relaxation, and employing
and Ge AQ is negative because of a strong attractive only the free electron (Sommerfeld) model in the de-
interaction at the saddle point with a smaller vacancy- rivation of the expressions for V(r), as has been done,
solute repulsion at the nearest neighbour distance. are ail gross approximation that better models must
These features are consistent with the vacancy flux avoid.
experiments (table 5): Zn is enriched and Ge depleted While there has been considerable effort over the
in dilute alloys of these solutes in Al. last decade or more to develop more satisfactory theo-
These calculations employed an asymptotic solu- retical descriptions of vacancy-solute interactions
tion for V(r), (A@, and this topic is reviewed in, for example [53]
and by Doyama and by March elsewhere in this Con-
(27) ference 1541, very much less attention has been given
to treating the saddle-point conflation in a more

Table 9
impurity diffusion in Al, with some theoretical [91,92] values of AQ (Qo = 29.0 kcal mol-’ [82])

Zz-Zo Solute A2 Q2 AQ ew @theor Ref.

(cm%-l) (kcal mol- ‘)

-2 cu 0.65 32.3 +3.3 +1.15 [82]

Ag 0.12 21.8 -1.2 -1.15 [821
Au 0.13 27.8 -1.2 - [821
-1 Mg 1.24 31.15 +2.15 +3.2 1831
1.1 30.9 +1.9 1841
Zn
0.26 28.9 -0.1 +2.0 I821
(
Cd 1.04 29.1 W.7 _
[W
0 0.49 29.2 +0.2 WI
{: 1.16 29.2 +0.2 [861
+1 Si 0.346 29.6 +0.6 V71
Ge 0.48 29.0 0 -0.71 1821
Sn 0.25 28.5 -0.5 _ [881
+2 Sb 0.09 29.1 +0.1 [891

Cr -5.104 -58 +29 +20 1821

Mn 104 50.4 +21.4 +24
135 46.0 +17 f”s!!
Fe +27
9.1.105 61.5 +32.5 1911
464 41.7 +12.7 1821
CO
250 41.6 +12.6 +20 1921
84 A.D. Le Claire / Solute ~~ffus~~nin dilute metals
realistic way for calculating the mi. Among the few
efforts in this direction is the work of Corless and
March [93] who, using self-consistent Hartree type po-
tentials, calculated AQ for Zn in Cu by a point ion
method that avoided reference to half-vacancies. AHa
and C were found to be appreciably smaller and AE
rather larger than derived by the crude model [ 141,
the net result for AQ being in rather less good agree-
ment with experiment. More recently, pseudopotential
methods have begun to be applied to calculating the
migration energies A.@{[94,95], but there seem so far
to be no results suf~ciently complete for direct com-
parison with experiment.
5. Anomalously fast impurity diffusion
5.1. General features
We have already mentioned in section 3 that there
exist some dilute alloy systems wherein the solute dif-
fusion rates show gross departures in ali respects from
normal solute diffusion. Perhaps the most thorou~y
studied systems are those with Pb as solvent and fig. 3
shows the Arrhenius plot of D2 for several solutes in
this metal [5], There are some impurities like Bi, Sn,
Tl and Na that are normal in that their properties are
close to those for Pb self-diffusion, but there is an-
other group Ag [96], Ni [97], Au [98], Pd [99], Zn
[ 1001 and Cu [96] with quite different properties.
The Da values are 3 to 5 orders of magnitude greater
than for Pb self-diffusion and the activation energies
Qa only half to a third of Qo. Then there are Cd [IO1 ]
and Hg [102] with D2 values smaller, but still rather
large, which we shall see form an intermediate class.
Such exceptionally large D2 and low Q, values are
not peculiar to solutes in Pb. These same solutes and
others like them diffuse very fast in certain other fair-
ly well-defined types of solvent and these are listed in
table 10. Although the diffusion of every solute in
every solvent has not yet been studied, the pattern of
behaviour that is becoming established seems to be
that Cu, Ag, Au and Zn, and maybe Be too, plus the
her transition elements, all tend to diffuse anoma-
lously fast in the high valent metals Sn, In and Tl
[ 103-1071 as well as in Pb, [96- 1001 and also in the
ear& members of each of the d-transition groups
[108-1201, the lanthanide series [121-1271 and the
10-11
-
200 0
IO‘ITFK-')
Fig. 3. Arrhenius plots for various solutes diffusing in Pb, af-
ter [S].
actinide series of elements [ 128- 1321. And at least
the noble metals diffuse very fast in the alkali metals
[133-l 361, especially Na and K for which the Q, are
particularly small. While there is within a given solvent
a tendency for Dz for the transition metal solutes to
decrease in the order shown, the D2 for the noble me-
tals seems invariably to decrease in the order Dcu >
DA,, > DAg. For solutes in allotropic solvents the ratio
D.&Do is usually much the larger in the more close
packed or, usually, the lower temperature phase. Fig.
4 shows an example. The early transition metals are
often considered to behave on alloying like elements
of high valency and the late transition metals like ele-
ments of low valency [ 1371, so there is the rough rule
that these very fast diffusing systems tend to be of
low-valent solutes in high-valent or highly electroposi-
tive solvents, although such a rule may not remain in-
violable.
It is well established that neither gram boundary
nor dislocation enhanced diffusion are responsible for
these exceptionally large values of D2 and the only
way one could explain them in terms of a vacancy
mechanism would be to assume a very strong vacancy-
solute binding. But this would entail a very large value
for b 1, the solvent enhancement factor [see eq. (14)]
 A.D. Le Claire / Solute diffusion in dilute metals 85

Table 10
Systems in which “anomalous” impurity diffusion occurs; the solutes on the left tend to diffuse anomalously fast in the solvents
on the right.

Solutes Solvents
____..
(1) Low valency groups I & II (1) High valency groups III & IV
Cu > Au > Ag Pb [96-1021, Sn [103-1051,
Be, Zn Cd, Hg Tl [106], In (1071

(2) Later transition metals (2) Early members of d-transition groups lanthanides, actinides
Ni, Co, Fe Cr, Mn Ti [108-lll],Zr [111-116],Hf (1171,
Pd Nb [118-1201,
La [121], Ce [122-1241, Pr [124-1271, Nd [122]
f U [130-1321, Pu [128-1291
02 decreasing

(3) Highly electropositive alkalis

Li [135-136],Na [133],K (1341
____ ___

and experimentally one does not find this. In the few
cases where they have been measured, experimental
values of b 1 for very fast diffusing systems are very
much less even than the minimum theoretical value
for vacancy diffusion, such as given by eq. (2 1) for
fee alloys. Table 11 shows the data that are available.
For Ag and Au in Pb, with their very high D,/Do, b,
is only a few per cent of the minimum allowed value.
A similar situation prevails for Co in y-U, fl-Zr and
/3-Ti and for Fe in Nb, whichever bee vacancy model
is employed to calculate bh. Cd in Pb is also anoma-
lous, although only just so, and maybe Hg too because
bh corresponds to an extreme situation and baxp is
rather close to it. But at least for the other systems in

Table 11
Observed values of bl for anomalously fast diffusing impurities compared with the minimum theoretical values consistent with the
measured Dz/Do ratio, if diffusion were wholly by vacancies.

T (“C) Dz/Do b, (obs) bl (min) Ref.

~_ _~
AuPb
- 199 15 x 104 5.7 x 103 3 x 105
215 89 x lo3 4.3 x 103 1.7 x 105 ]1381

Age 300 870 1.4 x 102 1.7 x 103 11381

CdP& 199 44.9 45.2 69.3
248 29.1 30.0 38.5 [loll
300 19.9 19.1 20.8

HgPb 252 17.6 21.2 16.1

295 14.3 22.1 9.8 [lo21
.
I II

UC0
_ 940 100 197 277 369 [I311
ZrCo
- 933 384 94.3 1095 1407 [I391
SC0 1205 41 5 109 153
1504 31 14 83 112 [llOl
NbFe
- 1756 116 61.4 334 446
1988 49 55.0 144 191 [ 140,141]
86 A.D. Le Claire / Solute diffusion in dilute metals
the table the incompatibilities of b 1 with the vacancy
model predictions are so gross that this mechanism
must be rejected and another sought to explain their
behaviour, and very probably also that of all systems
with similarly large diffusion rates, even though b 1
measurements may not be available to dictate unam-
biguously the need of another mechanism.
The current hypothesis is that fast diffusing solutes
are elements that dissolve at least in part interstitially
and that diffusion is dominated by some type of inter-
stitial migration. If cr and c, are the fractional concen-
trations of interstitial and of substitutional solute, and
Di and D, the corresponding diffusion coefficients,
the total Dl will be
(28)
Because Di, unlike D,, does not contain a fractional
defect concentration we expect Di >> D,, so that D,
may be dominated by interstitials even if ci is quite
small.
Equilibrium is presumed to.be maintained by a
‘~dissociative-a~ociative” mechanism whereby the
rate at which interstitials are created by substitutional
solute atoms jumping into interstitial sites, creating
vacancies from which the interstitials subsequently
separate, is balanced by the reverse, associative, recom-
bination rate of vacancies and interstitials. If there are
sufficient sinks to maintain the normal equilibrium va-
cancy concentration, the ratio cifc, is
exp (-I/kT)
CJC, = CY , (29)
where I is the energy to form a free interstitial and Q
the ratio of the numbers of interstitial to substitution-
al sites. There is now much evidence in support of this
hypothesis [5,142].
5.2. Evidence for interstitial solution and d~f~s~n
To the extent that they can diffuse independently
of the solvent, interstitial solutes are unlikely to influ-
ence very strongly the vacancy controBed solvent dif-
fusion rates. The comparatively small values of b 1 in
relation to Dz/DO are then immediately explicable.
Whereas the activation volumes AV for normally
effusing solutes are about the same as for self-diffu-
sion (eg. [143]), those for the diffusion of very fast
solutes are at most only a half of the self-diffusion
value - at least for Pb, where they range from AI’/
AI’, = 0.5 for Ag down to 20.06 for Pd [99]. This
difference is not inconsistent with an interstitial mech-
anism, for in such a case AT will not contain the va-
cancy formation volume that is its major component
in self-diffusion.
A necessary criterion for the occurrence of intersti-
tial solution is that the solute should fit with little dif-
ficulty into interstitial sites. All the fast diffusing sys-
tems satisfy such a criterion provided ionic size is
taken as the relevant parameter, for all the solutes
have ionicradii sufficiently small to be accommodat-
ed in the interstices between solvent ions with little
or no ion-core overlap [ 142,116]. The corresponding
criterion based on atomic radii, the “Hagg rules”, is
not satisfied, but this may not be surprising. Hagg’s
rules refer to interstitial compounds, or “complete”
interstitial solution with ci = 1. A rather less demand-
ing criterion should be required for the quite small
interstitial fractions that may be sufficient to provide
significant interstitial diffusion. The ionic size condi-
tion seems appropriate.
It is not however a sufficient condition: there are
many solutes small enough to be interstitial but that
diffuse normally and so are presumably not necessarily
in that state. Therefore, in addition to size effects,
electron interactions must also be important, as one
might expect, in deciding the propensity for interstitial
solution formation. These have been discussed in rela-
tion to ion polarizability, d-d core interactions and,
most simply, in terms of valency. Anthony argues
[ 1421 that the electronic contribution to the energy
of interstitial solution must increase with the valency
of the solute in a given solvent, being near zero for
zero valent solutes. For substitutional solution on the
other hand it will increase with the absolute difference
between solute and solvent vacancy, becoming zero
when the two are equal. it follows that, provided the
ionic size criterion is satisfied, interstitial solution may
be more preferred the lower the solute valency and the
higher the valency of the solvent. As we have seen, the
fast diffusing systems all conform to these expecta-
tions, being of low valent solutes in high valent sol-
vents. It follows too that Dz should decrease with in-
crease in the valency of a series of solutes in a given
solvent, and this also is observed for solutes in, for ex-
ample,Ti [109], Zr [115] and Li 11441. This is a par-
ticularly interesting correlation because it is just the
 A.D. Le Cl&e ! Salute diffusionin dilute metals
opposite of the way D2 varies with valency among
normally diffusing solutes.
While the ionic radii have to be compatible for in-
terstitial solution to occur, atomic radii seem to be
relevant in discussing fast diffusion rates for these of-
ten correlate with atomic radii more satisfactorily
than with ionic radii. In Zr [ 1151 and Ti [ 1091, for
example, Dz tends to decrease with increase in solute
atom radius. This behaviour could probably be related
in some way to the dependence on valency [145].
Size effects also explain, in terms of interstitials,
another interesting property of very fast diffusers.
When the solvent shows a phase change, the associated
changes in the diffusion properties of fast solutes are
very much less than the usually large changes in self
and normal solute diffusion properties. Fig. 4 illus-
trates this for solute diffusion in Pr [ 1251. Sometimes
D, and Q2 may even be quite continuous through
the phase change, e.g. Ag in Tl [ 1061, Co in Hf [ 11’73.
In fig. 4 the two orders of magnitude increase in DO
on going from the hcp to the bee phase one can attri-
bute to the bee phase having the more open struc-
ture. One might expect similar increases in Di and D,;
but interstitial sites are srna~ie~ in the bee phase. This
should decrease ci so that the product cpi may suffer
a relative small change in the transformation hcp +
bee. If diffusion is dominated by interstitials (DiCi >>
Dsc,), a correspondingly small change in D2 will re-
sult, as observed, and it may be an increase or a de-
crease or near zero.
Again with regard to geometry, when the solvent is
anisotropic, like Tl or Sn, there is an anisotropy in the
t BCC I Dwble HCP
l/T.16"(K-'t
Fig, 4. Arrhenius plots for various solutes diffusing in bee and
hcp Pr, [125].
81
diff~ion rates of fast solutes that can be most readily
understood if the solute is diffusing interstitially [ 106,
1031. In Sn, for example [ 1031, D2 for the diffusion
of Au is about 100 times greater parallel to the c-axis
than at right angles to it, and it is along the c-axis that
wide interstitial channels occur in this metal.
Simple consideration of valency and of size, parti-
cularly ionic size, therefore suggests an interstitial solu-
tion in, and some particular properties of, just those
systems wherein fast diffusion occurs and so supports
the interstitial explanation of their behaviour. Never-
theless, they can suggest interstitial solution in systems
that do not show fast diffusion, e.g. Na in Pb [ 1461.
Also, they do not immediately explain some of the de-
tail of fast diffusion behaviour, e.g. why always DA,, >
DAg when the valencies and atomic radii are the same
and the ionic radius of Au is the greater of the two,
namely 1.37 vs. 1.26 A. (But see section 5.3). Obvi-
ously other factors are important too in deciding
whether an interstitial solution should form, but these
have not yet been clearly identified.
There are several experimental techniques that have
been used to demonstrate, in particular cases of fast
diffusing systems, that the solute is in interstitial solu-
tion. Centrifuge experiments, for example, determine
the partial molar volume 7 of the solute from measu-
rements of its sedimentation equilibrium distribution
[147,148]. From the value T-0 found for Au in K
11491 complete interstitial solution of Au seems clear-
ly indicated. The same conclusion has been drawn
from measurements on Au in Na [ 1481, In [ 1SO] and
Pb [ 15 I], although these show rather larger values of
v, but still appreciably less than the -1 atomic vol-
ume expected for pure substitutional solution. The
larger 7 are presumed due to relaxation around the in-
terstitial Au atoms, but could indicate an appreciable
c, (see section 5.3). Electron channeling experiments
[152] have also indicated Au interstitials in Pb. There
is evidence for Ag dissolving interstitially in Pb from
the 15fold increase in the yield point of Pb on adding
-0.2 at.% of Ag, compared with the undetectable ef-
fects of adding the same amount of normally diffusing
Sn fl53j. Among results for other solvents are M&s-
bauer experiments that gave evidence of Co dissolving
interstitially in In [ 1541. On the other hand for Au in
Sn channelling experiments with Ne ions have indicat-
ed a predominantly substitutions solution [ 1551. On
this evidence the fast diffusion of Au must be attribut-
88 A.D. Le Ciaire / Sohrte d~fusio~ in dilute metals
ed to a small fraction of highly mobile interstitials.
The interstitial hypothesis seems then to be quite
well established as a general concept and basis for the
explanation of fast diffusion behaviour. The very large
range of values that D, can cover - 3 to 4 orders of
magnitude between Cd and Cu in Pb for example, com-
pared with the one, or at most two, among a set of
normal diffusers - suggests th.,: cr varies from small
values for the lowest Dz to values perhaps near unity
for the excessively fast solutes like Cu in Pb or Au in
Na. Then there are various properties that indicate the
interstitial defects cannot always be of the simplest
type and to deal with these the interstitial hypothesis
has been elaborated into the defect models we discuss
in the next section. But there is at present comparati-
vely little quantitative information firmly established
either with regard to the ct or to the detailed proper-
ties of the interstitial defects, as these apply to the
wide range and variety of anomalous systems.
5.3. I~~te~stiti~~
defect diffusion models
Most detailed theoretical considerations have been
prompted by the particularly extensive data on diffu-
sion in Pb-based systems.
At least for these systems it is evident from measure-
ments of the mass effect E, [eq. (4)] that we cannot
be dealing with the very simplest type of interstitial
diffusion. This shows values of E2 near to unity [ 131,
so that AK = 1 becauseg = fi = 1. By contrast, fast
diffusers in Pb show very much smaller values: for
both Ag [1.X] and Cu [I571 E2 = 0.25 and it is even
smaller at 0.12 for Cd in Pb [ 158 1. Unless these figures
just represent extraordinar~y small values of AK for
simple interstitial diffusion, which seems unlikely,
they must be attributed to multi-atom (g << 1) or to
highly correlated cfa << 1) types of migration proces-
ses.
An indication of one type of interstitial defect that
may be responsible is obtained from consideration of
the finite magnitudes of b, . We first note that this is
not only much too small to be accounted for wholly
by vacancy diffusion but also much too large to be at-
tributed to vacancy diffusion by a possibly small sub-
stitutional fraction of the solute. Normally diffusing
solutes in Pb have particularly small ratios of Dz/Do
(due perhaps to a near complete screening of their ex-
cess ionic charges at short distances in such a high
electron density metal) and bi is correspondingly
smail. For Tl it is about unity [159]. We can therefore
ignore such a contribution in relation to any of the
experimental values of b I in table 11, and must asso-
ciate the solvent enhancement wholly with interstitial
diffusion. This requires there to be some interaction
of the interstitials with the vacancies that are respons-
ible for the solvent diffusion, otherwise b 1 would be
zero. That this interaction is particularly strong in the
case of Cd and Hg is evident from the result that, for
these two solutes, b 1 and D, /Do differ comparatively
littie; for Cd they remain nearly equal over the whoIe
temperature range investigated. Exact equality would
mean that the number of additional effective solvent
jumps, due to the presence of solute, was the same as
the effective number of solute atom jumps. This rela-
tionship and a low value of E could both arise if solute
diffusion was by the migration of tightly bound inter-
stitial-vacancy pairs and it was from these considera-
tions that Miller [30,160] proposed such defects as
primarily responsible for diffusion in systems like Cd
in Pb.
Fig. 5 depicts Miller’s vacancy-interstitial pair de-
fect and the jump frequencies associated with it. A
pair may form either by the association of a free inter-
stitial and vacancy or by the jump of a substitutional
solute atom, with frequency ur , onto a nearest neigh-
bour site. It may be annihilated by a reverse jump of
frequency ua. If -B is the binding energy of a pair and
cp their fractional concentration, then in equilibrium
k,+B+O
(30)
kT ! ’
where z is the number of nearest nei~bour interstitial
sites around a substitutional site. From eqs. (29) and
(30) the fractions of solute atoms occurring as pairs,
p, or as free interstitials, q, are
and
q =:= pcUexp (-I,fkT) , (32)
where @= { 1 + OLexp (-~/k~ + z exp [--(gv + B t I)/
WI-‘, and ~1 when the ~terstitial fraction is very
small.
The interstitial solute can move to another inter-
 A.D. Le Claire/ Solute diffusion in dilute metals 89

Fig. 5. The Miller model for vacancy-interstitial pairs with frequencies of solute and solvent jumps. The arrows indicate the direc-
tions of atom jumps. Open circles, solvent atoms, shaded circles, impurity solute atoms, interstitially sited on left, substitutionally
sited on right. V = vacant site.

stitial site by jumps of frequency k, that dissociate
the pair or of frequency kz that reorient it. Solvent
atoms can move by exchange with the vacancy in
jumps of frequency w1 that dissociate or of frequency
w2 that reorient the pair. All other solvent and inter-
stitial jumps occur with frequencies w. and k,, res-
pectively. It follows that
(33)
If there is no contribution to D2 from substitutional
vacancy diffusion b, is readily found to be, for fee
crystals,
bl = -6 + (2w2 + 4wr)
tions that differ in the assumptions made about the
relative magnitudes of the frequencies involved. Both
assume very tight binding of the pairs so that k, and
wr are relatively very small and ~7<< p. The free inter-
stitial contribution to D2, the term 4( 12ko) in eq.
(35) is therefore ignored.
In the first approximation Miller [160] assumed
that the jumps of the interstitial members of the pairs
were much more frequent than those of the vacancy
members, i.e. a relatively mobile interstitial jumps
around, or into, a relatively immobile vacancy. Thus
k,, u2 >> wI, kl, w2, and with these assumptions f2
is calculated approximately as
‘iW2 + 8wr + 20kl
f2 = (36)
v2 + 4k2 ’

Eqs. (34)-(36) now give, with Miller’s further assump-

(34) tionfr =fo,
and D2 is D2
(fee) by =fo2 l+ <fo--_,
D2 = $,Q204~2 +4k2 +8k,) +&12ko)lfi > (35) Do

where a is the nearest neighbour distance between in- (37)

terstitial sites and fl and f2 are the correlation factors a result in near accordance with the data for Cd in Pb.
for diffusion of solvent and solute, respectively. In A similar calculation for bee crystals gives [ 1 lo]
deriving eq. (35) p + Q is assumed small and u1 does the relation
not appear because eq. (30) has been used to eliminate
(bee) by s $fo@',/Do> . (38)
it.
The model has been developed in two approxima- Experimental measurements of b 1 for Co in Ti [ 1 lo]
90 A.D. Le Claire /Solute di~~us~o~
and for Fe in Nb [140,141] are at high temperatures
quite close to, at lower temperatures somewhat less
than, this value of $fe Da/Do. Accordingly, solute
diffusion in these systems has also been attributed to
Miller-type pairs.
With Miller’s assumptions applied to eq. (36)fs
will clearly be very small, in agreement with the low
value ofB found for Cd in Pb [158] and the even
smaller values for Fe in Nb, 0.025 to 0.05 [140,141].
A similarly small value is found for Fe in Ti [ 1081, It
is to be noted, however, that eq. (36) is not of the
form to allow writing E = fAK (see section 4.3). Hunt-
ley [25] has calculated E itself for an extended Miller-
type model and shown that it can indeed be small,
provided kz/ko is sufficiently Iarge, and even without
there necessarily being the very tight interstitial-va-
cancy binding that Miller assumes.
Eq. (36) does not, however, accommodate the
data for Hg in Pb because bi cannot exceed D2fDo.
Warburton [ 1611 therefore modified the model to
provide for a rather greater degree of solvent enhance-
ment by supposing that pairs were completely stable
against dissociation, so putting kl = w, = 0, and that
the vacancy jumps rapidly around a relatively immo-
bile interstitial, i.e. w2 >> k2. To simplify the calcula-
tion, particularly offa to which f. would no longer
be a good approximation, k, was actually assumed
zero, such jumps being argued as anyway unlikely
from geometrical considerations. Solute is therefore
now mobile only through vr and v2 type jumps. With
these assumptions f2 is
f2 = ~W~/(UZ+ 4~2) , (39)
and bt becomes, from eqs. (34), (35) and (38)
(40)
Warburton evaluated f t as a function of wa/va (al-
though explicit expressions are not given) and arrived
at the result that bi must lie between about 0.85 D2/
Do and 3.8 Da/Do, these limits corresponding to wa/
v2 e 0 and w2/v2 -, ~0, respectively. The data for both
Cd and Hg in Pb are now accommodated in this ver-
sion of the model.
From eq. (40) and the experimental data, the ratio
w2/v2 can be calculated. It is roughly i for Hg and 4
for Cd. Eq. (39) then givesfa = 0.33 for Cd in Pb, to
be compared with the experimental value E2 = f2 AK
= 0.12 ] 158 J. The agreement is reasonable allowing
in dilute metals
for AK < 1 and the gross approximation in the model.
Although both the Miller and Warburton treat-
ments entail considerable approximation that a more
complete study would avoid, they seem to establish
that diffusion of Cd and Hg in Pb can be attributed to
the migration only of tightly bound vacancy-intersti-
tial pairs. But their assumptions cannot be appropriate
for the solutes that diffuse in Pb very much more
rapidly than Cd and Hg. As we go from Cd to Ag to
Au to Cu, D2/De becomes increasingly large and bl ,
though increasing too, becomes a very small fraction
of D2/Do (table 11) - and much too small for all the
diffusion to be due to pair migration, for this entails
bl being not too different from D2/Do.
The small b, values can be most simply understood
by supposing that Dz for these solutes is predominant-
ly due to the migration offree interstitials, contribut-
ing nothing to bl , with only a relatively small fraction
of interstitial-vacancy pairs to effect the small solvent
enhancements that are observed. A smaller fraction of
pairs might be expected than for Cd and Hg solutes be-
cause the vacancy interaction with the univalent noble
metal interstitials will be weaker than that with dival-
ent Cd and Hg. If we take b,/(D,/D,) as a rough mea-
sure of the fraction of solute diffusion attributable to
pair migration, this is about 16% for Ag and 4-5% for
Au in Pb.
The increase in Dz is most likely due in large part,
because of the large range covered, to an increasing
interstitial fraction [CJ(Ci + c,)] of solute as we g0
from Cd to Cu, although some variation in Di itself
[eq, (28)] may also be responsible. This is consistent
with the interstitial solution being energetically more
favoured the lower the solute valency (section 5.2).
A smaller effective valency for Au than for Ag seems
then indicated if the fact that DA” is greater than L)A~
is due to the interstitial fraction being larger for the
Au. This smaller valence could arise from the larger
ionization potential of Au causing its ions in solution
to be more effectively screened than those of Ag
[ 1421. A larger Au interstitial fraction is in fact indi-
cated from the observation that Au is three times more
effective in hardening Pb than the same concentration
of Ag [162].
The equation [eq. (28)] for D2 can now be written
in a more general way as
Dz=(l-p-q)D,+qDf+pDn, (41)
 A.D. Le Claire /Solute diffusionin dilute metals 91

D,, Df and D, being the coefficients of diffusion of The common ratio of Df/Dp was deduced as equal
substitutional, free interstitial and vacancy paired in- to -15.9 so that pairs appear to be much less mobile
terstitial solute atoms, respectively. Decker et al. [99] than free interstitials.
have used this equation, with two others derived from Although the authors do not consider b 1, it can be
it, for the activation energy Q, and activation volume estimated from p, q, Df/Dp and the measured Dz/DO,
AV, to determine, from the data on D,, Q, and AI’, if we assume b 1 = cy~D,,/Do with cr a constant. The
the values of p and ~7for the solutes Hg, Cd, Ag, Zn, results agree with experiment for Ag and Au with OL
Ni, Au and Pd in Pb, assuming that the differences in = 1.2 and 2.5, respectively, so the p and q values for
behaviour are due only to differences in p and 4. That these elements may be reasonable. However, the esti-
is to say, it was assumed that the parameters in D,, Df mates of bI for Cd and Hg agree with experiment
and D, were the same for each solute. Those of D, only if we assign (Y= 45 for Cd and (Y= 10 for Hg.
were supposed the same as for Pb self-diffusion while These seem unacceptable, being so very much larger
those of Df and D, were determined along with p and than the successful Miller or Warburton models allow.
4 in fitting the data. This rather questionable assump- The conflict arises because the relatively large values
tion limits the significance of the results, but they are of q make the contribution to D2 from free intersti-
nevertheless of some interest. tials much greater than that of pairs and this is con-
The values of p and 4 are shown in table 12. There trary to the Miller-Warburton assumptions, pDp >>
is almost wholly substitutional solution of Cd in Pb, 40,. The p and q values for these two solutes in table
as expected, with but a few tenths per cent of inter- 12 may therefore be suspect and this could arise be-
stitials. Cu is present almost entirely as free intersti- cause of the assumption of common diffusion para-
tials while the total interstitial concentration of Au is meters for all solutes. Those for divalent Cd and Hg
very much smaller, and of Ag smaller still, consistent may well be very different from those that neverthe-
with their hardening effect [ 1621. Both have an ap- less may reasonably represent the properties of all
preciable proportion of pairs, especially Ag. The low the other lower valent solutes. The diffusion proper-
value of 4 for Au may explain the rather high partial ties of Cd and Hg, particularly the values of Qa,are
molar volume of Au in Pb found by centrifuge experi- indeed rather different from the others.
ments [ 15 11. Although Pd, Ni and Zn have diffusion The values of I and Q (= g, + I + B) in table 12
properties similar to those of Au, their solution pro- were calculated from p and q via eqs. (3 1) and (32)
perties differ significantly in that the proportions of and represent the only experimentally based estimates
interstitials are much larger with about 70% or more available of these quantities. Those for Cd and Hg
as pairs. Clearly a measurement of b, for Pd, Ni or Zn may, for the above reasons, be the least reliable.
would be of interest to compare with existing data on It would seem that in most fast diffusing systems
Au or Ag. there is but one dominant mechanism of migration,
i.e. one dominant term in eq. (41), because experimen-
tal Arrhenius plots of D, rarely show any significant
Table 12 curvature. The data of table 12 lead to calculated Ar-
Fractions q and p of various solutes dissolved in Pb as free in- rhenius plots for all solutes that are “linear within a
terstitials (q), with energy I, and as vacancy-interstitial pairs few per cent” [99] for all solutes over the experimen-
@), with energy Q (= gv + B + r) (from [99])
tal temperature range, due to the dominance of free
Solute P 4 QW) I I(eV) interstitial diffusion. The diffusion of several solutes
in P-Ti [ 1081 provides rare examples of significant
CU 0.01 0.98 0.08 -0.22 curvature, suggesting two or more mechanisms in these
Pd 0.54 0.28 0.04 -0.02 systems with comparable contributions to D2. The
Au 0.05 0.18 0.21 0.07
Ni 0.65 0.11
curvatures in this case may not be unconnected with
0.04 0.04
0.45 0.10 0.09 0.08 that seen also in the self-diffusion Arrhenius plot of
E 0.06 0.024 0.23 0.19 this “anomalous bee metal”.
Cd 0.0003 0.0008 0.52 0.37 Whereas the small mass effect that has been observ-
Hg 0.002 0.0004 0.40 0.40 ed for Cd in Pb can be understood in terms of diffusion
92 AD. Le Claire /Solute difj%sion in dilute metals
dominated by vacancy-interstitial pairs, it is more dif-
ficult to understand the similarly small mass effect for
Ag and Cu diffusion in Pb where such pairs would ap-
pear to contribute very little to D2 - 15% for Ag,
nearly zero for Cu. If the diffusion of these solutes is
indeed dominated by what we have called free inter-
stitials, then it would seem that these must exist in
some form more complex than as isolated solute atoms
freely migrating by simple jumps from the centre of
one octahedral interstitial site to another, for which
we expect E = 1. There are some experimental results,
in addition to the mass effect, that support this for ail
the noble metals in Pb.
Particularly striking are Warburton’s measurements
[ 1631 showing that the diffusion coefficient of Au in
Pb decreases as the Au concentration increases (i.e. B,
is negative), and more rapidly the lower the tempera-
ture, despite the fact that Pb self-diffusion is enhanced
by the presence of-Au (i.e. bl positive). (There is a
similar but smaller effect for the even faster diffusing
Co in p-Zr [ 1391.) This behaviour is quite inexplicable
in terms of the vacancy or the vacancy-interstitial
pair mechanisms and the simplest interpretation is to
suppose there must be a second type of defect contain-
ing two Au atoms, a “doublet”, in equilibrium with a
“singlet” defect containing one Au atom. If the dou-
blets are energetically favoured their relative concentra-
tion must increase as the total concentration increases,
or as the temperature decreases. Then, if, as seems like-
ly, they are less mobile than the singlets, the measured
D, will vary in the way observed. From the data one
can derive a doublet defect formation energy of -4.5
kcal/mol per Au atom.
There is further evidence for two major types of
Au defect in Pb from measurements in P&Au alloys of
the temperature dependence of their electrical resis-
tivity and of the kinetics of the precipitation in them
of AuPbs [ 1641. In fact, comparison of these measure-
ments with the diffusion data indicates a need to in-
poke at lower temperatures even higher order defects
of 3 or more Au atoms if a consistent set of energy
parameters is to be derived [ 1631.
That there were two types of defect in all the dilute
noble metal - Pb alloys was actually first suggested
from internal friction experiments, and these also gave
~formation on their likely con~gurational nature.
Turner et al. [165] reported two doublelpeaks in the
damping spectrum of each of the alloys &Au, &Ag
and PbCu. From the way the peak heights changed on
annealing it was evident that two types of defect were
involved. The higher temperature double peak in each
alloy had an activation energy very close to the Q, for
diffusion at very low concentration of the solute in
that alloy; it is reasonable then to associate the relaxa-
tion process and the diffusion with the same defect.
The concentration of this defect must vary little with
temperature, otherwise the Q values would differ ap-
preciably, and this suggests a very low value for I [eq.
(29)]. The lower temperature double peaks correspond-
ed with a defect that became more stable as the tem-
perature decreased and might therefore be associated
with the two atom defect indicated by the dehance-
ment results on Au in Pb. This assignment is support-
ed by the fact that in &Ag alloys the defect respon-
sible for the lower temperature peaks was found to be
unstable above about room temperature, consistent
with the observation that the diffusion of Ag in Pb
does not noticeably change with increasing Ag con-
centration [ 1661. Now the anisotropy of the relaxa-
tion and the occurrence of double peaks (i.e. two
relaxation times) showed that both types of defect
must have a (100) orthorhombic type symmetry. It
was therefore proposed, as the simplest configuration
satisfying this requirement and retaining the intersti-
tial nature of the solute, that the defects might be of
the split interstitial or dumbbell type, i.e. two atoms
sharing a lattice site but each displaced from it in op-
posite directions along a (100) direction. Warburton
and Turnbull propose the term “diplon” [S] . The high
temperature diplon in &Au alloys could be a Au-Pb
pair, such as depicted in fig. 6(a), the low temperature
diplon, or doublet defect, a Au-Au pair. In &Ag al-
loys only the Ag-Pb pairs occur at diffusion tempera-
tures.
However, later work [167,168] has shown that ex-
tremely pure Pb doped with Cu, Ag or Au does not
show the internal friction peaks originally reported by
Turner et al., whose Pb samples turned out to have had
x300 ppm of Bi. The peaks might therefore have to
be associated with this impurity, but other explana-
tions for the difference in results have been proposed
[5,167]. For example, the Bi may just serve to facili-
tate the observation of the noble metal peaks through
its precipitating on dislocations. This would pin them
and in~bit their movement, so reducing the background
damping, and at the same time may deny precipitation
 A. D. Le Claire / Solute diffusion in dilute metals
b fect kinetics is clearly needed.
n n
Fig. 6. (a) (100) plane of atoms in fee crystal containing
solute-solvent split interstitial defect, or diplon. (b) Displace-
ment of solute by diplon rotation. (c) Displacement
by diplon dissociation and association. From [ 51.
sites to the noble metals, obliging enough to remain in
solution to produce the peaks observed. Again, the
much larger solute concentrations used in some of the
later experiments [ 1681 may have exceeded the criti-
cal supersaturation value, causing precipitation of sol-
ute and leaving too little in solution to provide observ-
able damping in the absence of Bi to reduce the back-
ground. None of these explanations has been proved
and it is unfortunate that this uncertainty in the sig-
nificance of the internal friction results remains un-
resolved. Nevertheless, the experiments have served
to suggest the defect models described above and these
at least provide a basis for understanding the low mass
effect values for Cu and Ag in Pb [ 1561.
The long range migration of Ag atoms can be ef-
fected by the joint action of two processes, the rota-
93
tion of Pb-Ag diplons, as shown in fig. 6(b), and their
dissociation and association, the Ag atom dissociating
from one Pb atom and entering into association with
another, as shown in fig. 6(c). Both processes entail
concomitant motion of heavy Pb atoms so that the
mass effect in Ag diffusion is diluted through the factor
g in eq. (13a). For the rotation process n = 2 and g
= 0.34 for Ag, 0.24 for Cu. If the association-dissocia-
tion process is considered as a case of n = 3, g = 0.20
and 0.14 for Ag and Cu, respectively, although the ef-
fect of the Pb motion in this case ought perhaps to be
described through the AK factor. In any event, the
coupling of the noble metal atom with the lattice im-
plicit in this dumbbell defect model is clearly capable
of reducing the mass effect into the r’ange of the ob-
served values, although a more careful study of the de-
The displaced solvent atom in a singlet defect
might exchange more rapidly than usual with a vacan-
cy and this could provide an alternative way of con-
sidering the kinetics of what would be a modified
form of, though still essentially, the interstitial-va-
cancy pair model to account for the small values of
bt.
One would also expect small mass effects in the
migration of the noble metal-noble metal diplons,
a although it is by no means clear how their slower mi-
gration might occur. It is presumed slower to account
of solute for the dehancement and the precipitation results, but
if the internal friction results are confirmed this defect
relaxes at the lower temperatures and therefore more
readily than the singlet. Some other rate determining
process must therefore govern its migration. However,
further speculation might perhaps be premature in
view of the unsettled internal friction results, if only
because without the symmetry constraints these would
seem to impose other types of two atom defects could
be candidates for consideration. A firm conclusion
on the internal friction data is clearly much needed.
In summary, the quite extensive experimental in-
formation on fast solute diffusion in Pb has led to the
conclusion that, unlike normal diffusion, at least three
defects need to be invoked to explain the facts. These
are vacancy-interstitial pairs, solute-host diplons and
solute-solute diplons, their contributions to diffusion
varying considerably from solute to solute. The thermo-
dynamic and kinetic properties of these defects are
far from well established in any quantitative sense and
94 A.D. Le Claire /Solute
even their structures have the status only of tentative
proposals. Further work to define more closely their
properties, particularly for the MS studied Zn, Ni and
Pd solutes, may also indicate the need to add to their
number and variety.
For the very many other systems showing fast dif-
fusion, information from which to draw conclusions
on the defect properties is exceedingly sparse, but the
similarities with the more fully studied Pb systems
naturally suggest a similar catalogue of defects.
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