G.
Kaptay: A unified equation for the viscosity of pure liquid metals
George Kaptay
Department of Chemistry, Faculty of Materials Science and Engineering, University of Miskolc, Miskolc-Egyetemvaros, Hun-
gary
A unified equation for the viscosity of pure liquid
metals
The following unified equation has been elaborated in the
present paper, to describe the viscosity of all liquid metals
as a function of temperature:
1=2

Mi 1=2 Tm;i
gi ¼ A  2=3  T  exp B 
Vi T concept and the free volume concept and to combine them
with gi, Mi, Vi, Tm,i being the dynamic viscosity, atomic
mass, molar volume and melting point of the given metal i,
and T is temperature. The above equation was tested on
101 measured points of 15 selected liquid metals, and the
average values of the generally valid parameters were found
as: A = (1.80  0.39) · 10 – 8 (J/Kmol1/3)1/2, B = 2.34  0.20.
Based on these parameters, the temperature dependence of
viscosity was estimated for 32 liquid metals. The above
equation was derived by (i) combining Andrade’s equation
with the activation energy concept, and (ii) by combining
Andrade’s equation with the free volume concept. It is
shown, that the activation energy and the free volume con-
cepts have identical roots and lead to identical results. The
above equation is shown to be valid for liquid semi-metals
(Si, Ge, Sb, Bi), if their actual melting points are replaced
by their corrected melting points, corresponding to (un-
stable) metallic solid crystals. The ratio of viscosity to sur-
face tension of pure liquid metals is discussed, as well.
Keywords: Viscosity: Liquid metals; Modelling; Actrac-
tion energy; Free Volume; Temperature depandence
1. Introduction
Viscosity of liquid metals and alloys is one of the technolo-
gically important transport properties, needed to develop
and optimize metallurgical technologies, e. g. by using
computer software packages. Such computer packages re-
quire the value of the dynamic viscosity as a function of
temperature and composition. At the present time different
equations are used to predict viscosity of pure liquid metals
at their melting points and their temperature dependence.
Although Andrade’s equation is quite successful in predict-
ing the melting point viscosities of pure liquid metals using
only one, generally valid semi-empirical parameter, there is
no similar equation known to predict the temperature de-
pendence of the viscosity of pure liquid metals through
1
This work was financed by the Hungarian Academy of Sciences
under OTKA T037626.
Z. Metallkd. 96 (2005) 1
Carl Hanser Verlag, MFnchen
MK_mk_2005_01_18080 – 2.12.04/druckhaus
B Basic
one, or several generally valid semi-empirical coefficients.
Moreover, there are two competing concepts in the litera-
ture to describe the temperature dependence of the viscosity
of liquid metals: the activation energy concept and the free
volume concept.
The aim of this paper is to unify the activation energy
with the Andrade’s equation, to develop a generally valid
unified equation, which is able to predict the melting point
viscosity values and also the temperature dependence of
pure liquid metals using only two, generally valid semi-em-
pirical coefficients.
2. Previous models for the viscosity of pure liquid
metals
There is a number of theoretical and semi-empirical equa-
tions to estimate the viscosity of pure liquid metals (see re-
views [1 – 3]).
2.1. The Andrade equation for the melting point viscosity
of liquid metals
In 1934 Andrade [4] modeled the melting point viscosity of
liquids by considering that momentum is transferred within
atoms, being in contact with neighboring layers by their vi-
brational displacement. Supposing that the characteristic
vibrational frequencies in normal liquid and solid metals at
their melting points are approximately the same, and using
Lindemann’s equation for the latter, Andrade derived the
equation [4]:
1=2 1=2
Mi  Tm;i
gi;m ¼ CA  ð1Þ
2=3
V i;m
where gi,m (Pa · s) is the dynamic viscosity of pure liquid
metal i at its melting point, Mi (kg/mol) is the atomic weight
of metal i, Tm,i is the melting point of pure liquid metal i in
(K) and Vi,m (m3/mol) is the molar volume of liquid metal i
at its melting point.
The coefficient CA was theoretically derived by Andrade
[4] as 1.655 · 10 – 7 (J/Kmol1/3)1/2. Eq. (1) is recognized to-
day as the most successful equation for predicting melting
point viscosities of pure liquid metals [1 – 3], although with
slightly different values of the coefficient CA. From
comparison with recently measured viscosity values the
‘best’ semi-empirical value of CA is around 1.8 · 10 – 7
(J/Kmol1/3)1/2 [2, 3].
1
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G. Kaptay: A unified equation for the viscosity of pure liquid metals
It should be mentioned that expressions, similar to
Eq. (1) can also be derived in different ways from that used
by Andrade (see for example [3, 5]).
2.2. The free volume concept of viscosity of liquids
The first concept of liquid viscosity is probably due to
Batchinski [6], who suggested that fluidity (which is the in-
verse of viscosity) is proportional to the molar free volume.
This concept was later developed by Hildebrand [7] and ap-
plied to different classes of liquids, including liquid metals.
The molar free volume (Vfree,i) was defined as the differ-
ence between the absolute molar volume of the liquid (Vi)
and its “ultimate” molar volume (Vio), below which the mo-
lecules (atoms) are so close to each other that their flow be-
comes impossible. From this concept the following equa-
tion was obtained:
Vio
gi ¼ C1  ð2Þ
Vi  Vio
where gi (Pa · s) is the dynamic viscosity of pure liquid i
and C1 (and further any Ci) is a semi-empirical coefficient.
Doolittle [8] showed that in contrast to Eq. (2), the ex-
perimental fluidity values of many hydrocarbons are pro-
portional to the exponential of the free volume. This rela-
tionship was theoretically supported by Cohen and
Turnbull [9] in the framework of their hard sphere model,
leading to the following equation:


Vo
gi ¼ C2  exp c  i ð3Þ
Vfree;i
where c is a measure of the overlap of free volumes (c ffi 1
for liquid metals [9]).
The free volume was described by the following equation
[9]:
Vfree;i ¼ i  Vi  ðT  To;i Þ  ji  Vi  DP ð3aÞ
where i (1/K) is the volume expansion coefficient of the
liquid, ji (1/Pa) is the compressibility of the liquid, T and
To,i are the absolute temperature (K) and the temperature at
which the free volume disappears at DP = 0 (for liquid me-
tals To ffi 0 K [9]) and DP is the pressure increment over
the standard pressure of 105 Pa.
2.3. The activation energy concept of the viscosity of
liquids
For the temperature dependence of viscosity of pure liquid
metals Andrade in the first approximation suggested to use
the Arrhenius Eq. [10]:


Ei
gi ¼ C3  exp ð4Þ
RT
where Ei is the activation energy of viscous flow for pure
liquid i (J/mol) and R is the universal gas constant
(8.314 J/molK).
For a wider temperature interval Andrade proposed a
somewhat more sophisticated equation, being a modifica-
2 Z. Metallkd. 96 (2005) 1
tion of the Arrhenius Eq. [10]:


C4 C5
gi ¼ 1=3  exp ð4aÞ
Vi Vi  T
In 1936 Eyring, based on his concept of the rate theory, de-
rived the following simplified Eq. [11]:


h  NAv Ei
gi ¼  exp ð5Þ
Vi RT
where h is the Planck constant (6.626 · 10 – 34 J s) and NAv is
the Avogadro number (6.022 · 1023 l/mol).
As one can see, Eq. (5) is identical with the empirical Ar-
rhenius equation, if the expression h · NAv/Vi is replaced by
a semi-empirical parameter C3 (see Eq. (4)). Unfortunately,
Eq. (5) is not able to reproduce the temperature dependence
of the viscosity of pure metals, at least, if the activation en-
ergy is taken as the only temperature-independent semi-em-
pirical parameter. However, if the activation energy is de-
scribed as a linear function of temperature, using two
semi-empirical parameters for each metal, the experimental
data can be well reproduced (see for example [12]).
It should be noted that Eyring himself in 1936 and later
together with different co-authors (for a review see [13])
has developed a number of different models to predict the
viscosity of liquids. One of the modifications of Eq. (5)
was derived in the same paper with Eq. (5) [11], as:


di 1=2 Ei
gi ¼  ð2  p  Mi  R  T Þ  exp ð5aÞ
Vi RT
where di (m) is the diameter of space which is occupied by
the atom.
Unfortunately Eq. (5a) has been forgotten – the later lit-
erature on viscosity of liquid metals refers only to the sim-
plest version of Eyring’s models, Eq. (5).
The activation energy of viscous flow, described by the
Arrhenius equation was found to be proportional to the
melting point by several workers. The proportionality con-
stant was found to be 1.76 · R ffi 14.6 J/molK [14]. A linear
relationship was found between the activation energy and
T1.2
m , the proportionality coefficient being different for nor-
mal metals and semi-metals [3]. Turkdogan showed a linear
relationship between the activation energy and the melting
point in logarithmic coordinates [15] and later between the
activation energy and the complex quantity Tm/V1/3 [16].
2.4. On the statistical-mechanical theory of viscosity
The statistical-mechanical theory of liquids was developed
in the 1940s and was applied to their dynamic properties
by Born and Green [17]. Although statistical mechanics
provides a solid scientific basis to calculate viscosity of li-
quids, it is difficult to convert those integral equations into
a form being useful for the use of ordinary researchers or
engineers. One of the useful approximate solutions of the
statistical mechanical approach is due to Chapman [18],
who characterized the force between the atoms in liquid
metals by a distance parameter (the Goldschmidt atomic
diameter, di) and a semi-empirical energy parameter (ei).
Chapman showed that the reduced experimental viscosity
data can be plotted as a function of the reduced temperature
using a unique curve for all liquid metals. Unfortunately,
this unique curve is given only in a graphical form [18],
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G. Kaptay: A unified equation for the viscosity of pure liquid metals

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without an analytical equation. Although not demonstrated
by Chapman, if the atomic radius di is described as a linear
function of Vi1/3, his equations reduces to the Andrade
Eq. (1) at the melting point. It should also be mentioned that
Chapman found a linear relationship between his semi-em-
pirical energy parameter ei and the melting point of the me-
tal Tm,i.
The statistical mechanical approach is also useful to pre-
dict relationships between different physical properties of
liquid metals [19 – 22], such as:
rffiffiffiffiffiffiffiffiffiffi
gi 16 Mi
¼  ð6Þ
ri 15 RT
where ri is the surface tension of the liquid metal i (J/m2).
Eq. (6) is justified by experimental data mainly at the
melting point of metals.
2.5. Evaluation and combination of the above concepts
Comparison of Eqs. (2, 4, 4a) with experimental data of 26
liquid metals, keeping two parameters in each equation as
semi-empirical fitting parameters for each metal, proved
that there is no significant difference in performance of
these equations [23]. It is somewhat disappointing that,
while Eq. (1) is very successful in predicting viscosity of
pure liquid metals at their melting points, it seems not be a
part of any of the equations successfully describing the tem-
perature dependence of viscosity of pure liquid metals [23].
However, based on the simplified statistical-mechanical ap-
proach of Chapman [18], there is a hope that the Andrade
equation can be coupled successfully with a temperature
dependent expression using several semi-empirical para-
meters, which are expected to be unique for all liquid me-
tals (see also [24, 25]).
While searching for a unique equation for the viscosity of
pure liquid metals, one should remember the following
question, which has been argued for the last 70 years:
whether the activation energy concept, or the free volume
concept, or any combination of these two, has a more solid
physical background to explain the experimentally ob-
served temperature dependence of the viscosity of liquid
metals.
3. A unified equation of the viscosity of pure liquid
metals
The goal is to create an equation, being able to reproduce
the absolute value and the temperature dependence of the
viscosity of liquid metals with two semi-empirical para-
meters, being generally valid for all liquid metals. The uni-
fied equation should also include both the activation energy
concept and the free volume concept.
This equation can be derived by taking the atomic diameter
di as proportional to Vi1/3 in one of the Eyring equations
(Eq. (5a)). Eq. (7) can also be considered as one of the pos-
sible analytical ways to express the dimensionless viscosity
as a function of the dimensionless volume and the dimen-
sionless interaction energy, instead of the graphical way of
expressing this relationship, as was done by Chapman
[18], based on statistical mechanics.
According to its physical sense, the activation energy of
viscous flow is a certain small fraction of the cohesion en-
ergy (taken with an opposite sign), what has to be supplied
during each atomic displacement of viscous flow between
the adjacent liquid layers:
DZi
Ei ¼   Dc Ui ð8Þ
Zi
where DZi is the number of broken bonds during viscous
flow, Zi is the average coordination number in liquid metals
and DcUi is the cohesion energy of the given liquid metal.
Although usually the vaporization enthalpy is used as a
measure of the cohesion energy, it has been recently shown
on the example of the surface tension that the cohesion en-
ergy correlates better with the melting point of normal me-
tals [26]:
Dc Ui ¼ q  R  Tm;i ð9Þ
where q is a semi-empirical parameter determined to be
q ffi 25.4  2 [27].
Substituting Eq. (9) into Eq. (8) and supposing that the
ratio of DZi/Zi = DZ/Z is approximately constant for all
liquid metals, we can introduce a constant B, as:
DZ
Bq ð10Þ
Z
Substituting Eqs. (8 – 10) into Eq. (7), we finally obtain the
following equation (the temperature dependent part of the
activation energy is included in parameter A):
1=2

M  T 1=2 Tm;i
gi ¼ A  i 2=3  exp B  ð11Þ
Vi T
Eq. (11) is a new equation to the best knowledge of the
author. It contains two semi-empirical parameters, A and
B, hopefully being approximately identical for all liquid
metals at all temperatures. As follows from Eq. (11), at the
melting point of the metals it reduces to the Andrade equa-
tion, Eq. (1), with the following relationship between para-
meters CA, A and B:
CA ¼ A  expðBÞ ð11aÞ
The additional value of Eq. (11) compared to Eq. (1) is that
it provides a reasonable basis for extending the Andrade
equation to other temperatures, using a single parameter,
which has a physical meaning through Eqs. (8 – 10).

3.1. Combination of the Andrade equation with the 3.2. Combination of the Andrade equation with the free
activation energy concept volume concept

Combining Eqs. (1) and (4), the following equation can be Combining Eqs. (1) and (3), the following equation is ob-
obtained: tained:
1=2


M  T 1=2 Ei 1=2
Mi  T 1=2 Vio
gi ¼ A  i 2=3  exp ð7Þ gi ¼ A   exp c  ð12aÞ
Vi RT 2=3 Vfree;i
Vi
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G. Kaptay: A unified equation for the viscosity of pure liquid metals

The molar volume at a given temperature is approximately will hold:

expressed as:
   k
i ffi ð14Þ
Vi ffi Vi;m  1 þ i  T  Tm;i  ð1  ji  pÞ Tm;i
 
ffi Vi;m  1  i  Tm;i þ Vi;m  ði  T  ji  pÞ ð13aÞ Substituting Eq. (14) into Eq. (12c), the following equation
is obtained:
By definition, the total molar volume is the sum of the ulti- 1=2

mate molar volume (Vio), and the free molar volume, Vfree,i. M  T 1=2 Tm;i
gi ¼ A  i 2=3  exp B  ð15aÞ
The total molar volume, described by Eq. (13a), is conveni- V T
i
ently divided into the ultimate and the free volumes as fol-
lows: 1k
B¼c ð15bÞ
Vio ¼ Vi;m  ð1  i  Tm;i Þ ð13bÞ k
One can see, that Eqs. (11) and (15a) are identical. Thus,
Vfree;i ¼ Vi:m  ði  T  ji  pÞ ð13cÞ the free volume concept and the activation energy concept
lead to the identical final equation, although the semi-em-
Eq. (13c) is similar to Eq. (3a), derived by Cohen and Turn- pirical coefficient B is defined in different ways, by
bull [9]. Substituting Eqs. (13b, c) into Eq. (12a), the fol- Eqs. (10) and (15b).
lowing equation is obtained: The above result might seem surprising at the first sight.

 However, it is obvious that all properties of pure liquid me-
1=2
Mi  T 1=2 1  i  Tm;i tals are determined by two independent parameters, pres-
gi ¼ A   exp c  ð12bÞ
Vi
2=3  i  T  ji  p sure and temperature. This includes dynamic viscosity, but
also volume and cohesion energy of the liquid metal. On
At relatively low pressures (p < 100 bar), the pressure term the other hand, the free volume is proportional to the total
of Eq. (12b) can be neglected, and it can be simplified to: volume, while the activation energy of viscous flow is pro-
portional to the cohesion energy of the liquid. Thus, finally
1=2
 we can conclude that temperature and pressure determine
Mi  T 1=2 1  i  Tm;i
gi ¼ A   exp c  ð12cÞ both free volume and activation energy of liquid metals.
2=3 i  T
Vi Therefore, the relationship between (p, T) and viscosity
can be modeled equally well through the free volume, or
It is known that the volume expansion coefficient of liquid through the activation energy. Thus, the ‘free volume’ con-
metals is inversely proportional to their cohesion energy tribution and the ‘activation energy’ contribution into the
[3]. As was shown above, the cohesion energy is propor- viscosity of liquids are actually identical, i. e. Eq. (11) can
tional to the melting point. Thus, the following correlation be considered as a unified viscosity equation.

Table 1. Parameters of Eqs. (11a – b) for normal metals, with reliable experimental values (data were found using Eqs. (11b, 11a) for
each metal, separately)

Me Source of data Range of Tm,i/T ln A A · 108 B CA · 107

(J/Kmol1/3)1/2 (J/Kmol1/3)1/2

Ag [28] 0.79 – 1 – 17.93 1.63 2.35 1.71

Au [28] 0.85 – 1 – 17.64 2.18 2.03 1.66
Cd [29] 0.68 – 1 – 18.03 1.48 2.54 1.87
Cs [30] 0.62 – 1 – 17.92 1.65 2.43 1.87
Cu [31] 0.80 – 1 – 18.32 1.11 2.66 1.58
Hg [32, 33] 0.27 – 1 – 17.68 2.10 2.18 1.86
In [29] 0.34 – 1 – 17.80 1.86 2.22 1.71
K [34] 0.72 – 1 – 18.05 1.45 2.54 1.84
Li [35] 0.47 – 1 – 17.47 2.59 2.08 2.07
Na [34] 0.80 – 1 – 18.00 1.52 2.60 2.05
Pb [29] 0.47 – 1 – 17.82 1.82 2.24 1.71
Rb [30] 0.63 – 1 – 17.95 1.60 2.49 1.93
Sn [36] 0.32 – 1 – 17.78 1.90 2.20 1.71
Tl [37] 0.80 – 1 – 17.92 1.65 2.33 1.70
Zn [38] 0.71 – 1 – 17.53 2.44 2.19 2.18
Average: 1.80 2.34 1.83
standard 0.39 0.20 0.17
deviation:

4 Z. Metallkd. 96 (2005) 1
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G. Kaptay: A unified equation for the viscosity of pure liquid metals
3.3. Evaluation of the values of semi-empirical parameters
A and B of Eq. (11)
For metals with most reliable experimental viscosity values
the unified equation (11) will be tested, and the best values
of parameters A and B will be determined. Eq. (11) can be
transformed into the following equation:
! and the value of parameter q ffi 25.4  2 [27], the ratio of
2=3
gi  Vi Tm;i
ln zi  ln 1=2
¼ ln A þ B  ð11bÞ
M  T 1=2 T
i
Experimental values are given in Table 1 for 15 normal me-
tals, for which reliable experimental data are available.
From the total 41 elements, given in the compilations [2,
23], 26 are disregarded from our analysis for the following
reasons:
i. Al, Ce, Co, Fe, Ni, Ti: different experimental sets con-
tradict each other,
ii. Ca, Cr, Hf, La, Mg, Mn, Pd, Pr, Pu, U, V, Yb, Zr: only
single experimental data exist, with questionable relia-
bility,
iii. Bi, Ga, Ge, Sb, Se, Si, Te – these semi-metals are ex-
cluded from consideration when the average “best”
parameters are searched for “normal” metals.
The plot in coordinates lnzi versus Tm,i/T is shown in Fig. 1
for altogether 101 data points for the selected 15 metals.
One can see that both the slope and the intercept of the mea-
sured points seem to be quite constant, proving the ade-
quacy of Eq. (11).
In the last rows of Table 1 the average values and stan-
dard deviations of parameters A and B of Eq. (11) are given.
Accordingly, the semi-empirical parameters have the fol-
lowing approximate values:
A = (1.80  0.39) · 10 – 8 (J/Kmol1/3)1/2
B = 2.34  0.20
In Fig. 2, the theoretical values, calculated by Eq. (11) and
the above average parameters are compared to the experi-
mental viscosity values for the same 15 ‘normal’ metals.
One can see that the measured points are situated around
the theoretical values within  20 %. This shows that for
‘normal’ liquid metals the absolute value and the tempera-
ture dependence of viscosity can be described by the uni-
fied equation (11), using two, generally valid semi-empiri-
cal parameters.
Fig. 1. Experimental viscosity data for 101 measured points of 15 se-
lected pure metals, given in Table 1, presented in coordinates according
to Eq. (11b).
Z. Metallkd. 96 (2005) 1
B Basic
In Table (1), the Andrade parameter as calculated from
Eq. (11.a) is shown. As follows from the last rows of Ta-
ble 1, the Andrade parameter is found as:
CA = (1.83  0.17) · 10 – 7 (J/Kmol1/3)1/2
This value is practically the same as was found in recent re-
views [2, 3]. From the value of parameter B, found above,
broken bonds during the viscous flow can be calculated,
using Eq. (10):
DZ/Z = 0.092  0.009
If the average coordination number in liquid metals is taken
as Z = 11  0.5, the value of DZ becomes 1.01  0.12.
Thus, about 1 bond is broken in the sliding plane of liquid
metals during viscous flow. Compared to the approximately
2 broken bonds, appearing at the free liquid/gas interface
(as a manifestation of surface tension of liquid metals [26,
27]), this seems to be a reasonable value.
3.4. On the correlation between the viscosity and surface
tension of liquid metals
Once we have a unified equation for the viscosity of liquid
metals, it is of interest to compare it with an equation for
the surface tension of liquid metals [26, 27]:
 
0:182  211 þ Cp;i  Tm;i  ð2 þ 0:182  Cp;i Þ  T
ri ¼ 2=3 1=3
1:06  Vi  NAv
where Cp,i is the heat capacity of the liquid metal i
(J/molK).
Dividing Eq. (11) by Eq. (16), the following equation is
obtained:
1=2
gi 1:61  Mi  T 1=2  expð2:34  Tm;i =TÞ
¼    
ri 0:182  211 þ Cp;i  Tm;i  2 þ 0:182  Cp;i  T
(17)
At the melting point T = Tm,i, Eq. (17) simplifies to:
sffiffiffiffiffiffiffiffi
gi;m Mi
¼ 0:459  ð17aÞ
ri;m Tm;i
One can see that Eq. (17.a) is identical with Eq. (6), except
that its numerical coefficient is higher by 24 %. In Fig. 3
Fig. 2. Comparison of viscosity data calculated by Eq. (11) and mea-
sured viscosity data for 101 measured points on selected 15 liquid me-
tals, given in Table 1. The dashed lines are drawn to show  20 % of
deviation.
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G. Kaptay: A unified equation for the viscosity of pure liquid metals

Fig. 4. Comparison of calculated (Eq. (11)) and measured viscosity

data for Si, Ge, Sb and Bi. The dashed lines are drawn to show 
20 % of deviation. Fig. 4a is calculated with uncorrected melting point
data, while Fig. 4b is calculated using the corrected melting points, as
shown in Table 2 (circles: Bi, squares: Sb, rhombs: Si, triangles: Ge).

Fig. 3. The temperature dependence of the dynamic viscosity, surface
tension, and ratio of both quantities for a liquid metal, calculated by
Eqs. (11, 16, 17) and Eq. (6) (Mi = 55.85 g/mol, Tm,i = 1,808 K, Cp,i =
46.0 J/molK).
the temperature dependence of the viscosity (Eq. (11)), sur-
face tension (Eq. (16)) and their ratio (Eqs. (6, 17)) are
shown for liquid iron. As one can see from Fig. 3, although
Eq. (17) provides quite a different temperature dependence
compared to Eq. (6), the two equations provide similar ab-
solute values within a limited temperature range of Tm,i
both solid and liquid metals and also, if the vibrating unit
in a liquid metal is an atom. This condition is not fulfilled
for semi-metals, mainly because they crystallize not in a
usual, metallic crystal lattice, and therefore their melting
point is not a proper measure of their cohesion energy.
Moreover, in liquid Se there is a high degree of self-associa-
tion [2], leading to unusually high viscosity values. Thus,
the Andrade equation overestimates the viscosity for the
majority of semi-metals, and underestimates the viscosity
of liquid Se.
As our unified equation is based on the Andrade equa-
tion, the above shortcomings refer also to Eq. (11). As one
can see from Fig. 4a, Eq. (11) indeed seriously overesti-
mates the measured data for liquid Si, Ge, Sb, and Bi.
To my opinion this is due to the different structure and to
the different chemical bonding in solid Si, Ge, Sb, and Bi,

as compared to normal metallic solids. Thus, the experi-

T
2.Tm,i , in accordance with [21].
3.5. The performance of the unified equation for
semi-metals
As follows from its derivation, the Andrade equation will
work if chemical bonding and coordination is similar in
mentally observed melting point for these elements is not
an adequate indicator of the cohesion in these liquid metals.
The hypothetic metallic solid forms of these elements are
obviously less stable compared to their known stable solid
forms. Thus, these hypothetic metallic solids would provide
a lower melting point, if combined with their known metal-
lic liquids. In other words, it is justified to introduce cor-

Table 2. Corrected melting points for semi-metals, based on experimental viscosity data and semi-empirical Eq. (11)

Element Tm, exp (K) Viscosity data source Temperature range, Tm/T Tm,corr (K) from Eq. (11)

Si 1683 [39] 0.91 – 1 870

Ge 1210 [40] 0.73 – 1 450
Sb 903.9 [29] 0.71 – 1 650
Bi 544.5 [31] 0.54 – 1 450

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Table 3. Physical properties [3] and calculated viscosity values (Eq. (11)) (with an uncertainty of about – 20 %) of some pure liquid me-
tals at three different temperatures (in the 6th column experimental viscosity data are given [2, 3, 23] for comparison)

Metal Tm,i Mi Vm,i i · 104 gi at Tm,i gi at gi at gi at

experiment Tm,i Tm,i + 100 K Tm,i + 200 K

K g/mol cm3/mol 1/K mPas mPas mPas mPas

Mg 923 24.31 15.3 1.6 1.25 1.44 1.19 1.02

Ca 1124 40.08 29.5 1.6 1.22 1.31 1.12 0.98
Sr 1070 87.62 37 1.1 – 1.63 1.38 1.21
Ba 1263 137.33 41.4 0.81 – 2.06 1.79 1.59
Al 933 26.98 11.3 1.5 1.2 – 4.2 1.86 1.55 1.33
Ti 1998 47.9 11.6 0.56 2.2 – 5.2 3.57 3.26 3.00
Zr* 2130 91.22 15.4 0.54 3.5 4.21 3.86 3.57
Hf* 2480 178.4 14.9 0.53 5.0 6.49 6.03 5.63
V 1973 50.94 9.5 0.6 2.4 4.18 3.81 3.51
Nb* 2740 92.91 11.9 0.51 – 5.72 5.34 5.02
Ta* 3123 180.95 12.1 0.46 – 8.43 7.94 7.51
Cr 2178 52 8.27 1.1 5.7 4.86 4.46 4.11
Mo* 2895 95.94 10.3 0.53 – 6.58 6.17 5.81
W* 3655 183.8 10.5 0.45 – 10.10 9.59 9.13
Mn 1517 54.94 9.54 1.6 5 3.79 3.35 3.01
Re* 3440 186.21 9.96 0.44 – 10.22 9.67 9.19
Fe 1808 55.84 7.94 1.3 4.7 – 6.2 4.72 4.25 3.87
Ru* 2723 101 9.27 – – 7.02
Os* 2973 190.2 9.46 – – 9.93
Co 1765 58.93 7.6 1.4 4.1 – 5.3 4.93 4.43 4.02
Rh* 2239 102.91 9.27 – – 6.43
Ir* 2727 192.2 9.61 – – 9.46
Ni 1728 58.7 7.43 1.51 4.5 – 6.2 4.94 4.43 4.02
Pd 1828 106.4 10.14 1.17 4.2 5.56 5.02 4.58
Pt 2047 195 10.31 1.52 – 7.88 7.17 6.57
La 1193 138.91 23.3 0.4 2.45 – 2.65 2.95 2.55 2.27
Ce 1068 140.12 20.9 0.34 2.88 – 3.2 3.01 2.57 2.26
Pr 1208 140.91 21.3 0.38 2.8 3.17 2.75 2.44
Nd 1297 144.2 21.6 0.79 - 3.29 2.88 2.56
Th* 2088 232.04 22.1 0.5 - 5.22 4.79 4.43
U 1405 238.03 13.78 0.596 6.5 5.95 5.25 4.71
Pu 913 244 14.65 0.847 6 4.66 3.87 3.34

* molar volume (Vm,i) and volume expansion coefficient (i) values are not measured, but estimated for these metals [3].

rected (lowered) melting points for these elements, which
can be called “metallic melting point” of Si, Ge, Sb, and
Bi. These corrected melting points are estimated by fitting
Eq. (11) to the experimental data points, keeping the same
values of parameters A and B, and treating the melting point
as a fitting parameter (see Table 2). The calculated and
measured data points, using the corrected melting point va-
lues, are compared in Fig. 4b, demonstrating good agree-
ment.
3.6. Estimation of the viscosity of some pure liquid metals
As follows from the above, Eq. (11) can be used to predict
the temperature dependence of pure liquid metals, suppos-
ing they behave as normal metals both in solid and liquid
states. The application of Eq. (11) is mainly limited by the
lack of information on the molar volume of high melting
point liquid metals and its temperature dependence (see
footnote to Table 3). In Table 3 the basic physical proper-
ties, and the calculated viscosity values are given for 32
liquid metals at three different temperatures, for which the
necessary information is available in [3]. All values, calcu-
lated in Table 3, should be considered with an uncertainty
of – 20 % (compare with the same uncertainty range in
Fig. 2). The calculated values at the melting point were
compared to available experimental data, based on compi-
lations [2, 3, 23]. From the comparison of the 6th and 7th
columns of Table 3 one can make the following conclu-
sions:
i. in 14 cases (Ba, Ir, Mo, Nb, Nd, Os, Pt, Re, Rh, Ru, Sr,
Ta, Th, W) out of the 32 cases considered in Table 3,
no experimental data are available, at all.
ii. among the 11 cases, when only a single experimental
value is available, in 6 cases (Ca, Cr, Mg, Pr, U, Zr) the
calculated values differ less, while in 5 cases (Hf, Mn,
Pd, Pu, V) the calculated values differ more than by
20 % from the experimental value,
iii. among the 7 cases, when at least two, different experi-
mental data sets are available, in 6 cases (Al, Ce, Co,
Fe, Ni, Ti) the calculated values appear in the interval
of the experimental values, while in 1 case (La) the cal-
culated value differs less, than by 20 % from the average
of the experimental values.
Based on the above we can conclude that Eq. (11) works in
28 cases out of total 33 cases (i. e. in 85 % of cases, includ-
ing also the 15 selected metals), failing only against single

Z. Metallkd. 96 (2005) 1 7
B
Basic MK_mk_2005_01_18080 – 2.12.04/druckhaus
G. Kaptay: A unified equation for the viscosity of pure liquid metals
measurements on liquid Hf, Mn, Pd, Pu, and V. Thus,
Eq. (11) provides reasonable estimates of the temperature
dependence of the viscosity of liquid metals.
Although our Eq. (11) is not identical with the graphical
method of Chapman [18], the two methods provide similar
results. As an example, let us estimate the viscosity of li-
quid titanium at 2120 K. Following Chapman, a 7-step al-
gorithm (including the step to read a value from a graph) is
elaborated in [41], with a final result of 3.33 mPas. On the
other hand, our Eq. (11) provides the value of 3.20 mPas in
one straightforward step. The difference between the two
methods is only 4 %.
Conclusions
It has been shown that the activation energy concept and the
free volume concept of the viscosity of liquid metals have
the same roots, and can be converted into the unified equa-
tion, if combined with the Andrade equation. The unified
Eq. (11) contains two semi-empirical parameters, which ap-
peared to be approximately constant for 15 liquid metals.
Therefore, Eq. (11) is suggested to be used as a predictive
tool for the viscosity of pure liquid metals. This method is
not identical with, but provides similar values to the graphi-
cal method of Chapman [18]. It is demonstrated that the
viscosity of liquid semi-metals, Si, Ge, Sb and Bi can be de-
scribed by the same unified equation, if the melting points
of these metals are corrected to the melting points of their
(unstable) metallic solids.
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(Received &; accepted &)
Correspondence address
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