Beruflich Dokumente
Kultur Dokumente
George Kaptay
Department of Chemistry, Faculty of Materials Science and Engineering, University of Miskolc, Miskolc-Egyetemvaros, Hun-
gary
MK_mk_2005_01_18080 – 2.12.04/druckhaus
B
Basic MK_mk_2005_01_18080 – 2.12.04/druckhaus
It should be mentioned that expressions, similar to tion of the Arrhenius Eq. [10]:
Eq. (1) can also be derived in different ways from that used
C4 C5
by Andrade (see for example [3, 5]). gi ¼ 1=3 exp ð4aÞ
Vi Vi T
2.2. The free volume concept of viscosity of liquids In 1936 Eyring, based on his concept of the rate theory, de-
rived the following simplified Eq. [11]:
The first concept of liquid viscosity is probably due to h NAv Ei
Batchinski [6], who suggested that fluidity (which is the in- gi ¼ exp ð5Þ
Vi RT
verse of viscosity) is proportional to the molar free volume.
This concept was later developed by Hildebrand [7] and ap- where h is the Planck constant (6.626 · 10 – 34 J s) and NAv is
plied to different classes of liquids, including liquid metals. the Avogadro number (6.022 · 1023 l/mol).
The molar free volume (Vfree,i) was defined as the differ- As one can see, Eq. (5) is identical with the empirical Ar-
ence between the absolute molar volume of the liquid (Vi) rhenius equation, if the expression h · NAv/Vi is replaced by
and its “ultimate” molar volume (Vio), below which the mo- a semi-empirical parameter C3 (see Eq. (4)). Unfortunately,
lecules (atoms) are so close to each other that their flow be- Eq. (5) is not able to reproduce the temperature dependence
comes impossible. From this concept the following equa- of the viscosity of pure metals, at least, if the activation en-
tion was obtained: ergy is taken as the only temperature-independent semi-em-
pirical parameter. However, if the activation energy is de-
Vio scribed as a linear function of temperature, using two
gi ¼ C1 ð2Þ semi-empirical parameters for each metal, the experimental
Vi Vio
data can be well reproduced (see for example [12]).
where gi (Pa · s) is the dynamic viscosity of pure liquid i It should be noted that Eyring himself in 1936 and later
and C1 (and further any Ci) is a semi-empirical coefficient. together with different co-authors (for a review see [13])
Doolittle [8] showed that in contrast to Eq. (2), the ex- has developed a number of different models to predict the
perimental fluidity values of many hydrocarbons are pro- viscosity of liquids. One of the modifications of Eq. (5)
portional to the exponential of the free volume. This rela- was derived in the same paper with Eq. (5) [11], as:
tionship was theoretically supported by Cohen and di 1=2 Ei
Turnbull [9] in the framework of their hard sphere model, gi ¼ ð2 p Mi R T Þ exp ð5aÞ
Vi RT
leading to the following equation:
where di (m) is the diameter of space which is occupied by
Vo the atom.
gi ¼ C2 exp c i ð3Þ Unfortunately Eq. (5a) has been forgotten – the later lit-
Vfree;i
erature on viscosity of liquid metals refers only to the sim-
where c is a measure of the overlap of free volumes (c ffi 1 plest version of Eyring’s models, Eq. (5).
for liquid metals [9]). The activation energy of viscous flow, described by the
The free volume was described by the following equation Arrhenius equation was found to be proportional to the
[9]: melting point by several workers. The proportionality con-
stant was found to be 1.76 · R ffi 14.6 J/molK [14]. A linear
Vfree;i ¼ i Vi ðT To;i Þ ji Vi DP ð3aÞ relationship was found between the activation energy and
T1.2
m , the proportionality coefficient being different for nor-
where i (1/K) is the volume expansion coefficient of the mal metals and semi-metals [3]. Turkdogan showed a linear
liquid, ji (1/Pa) is the compressibility of the liquid, T and relationship between the activation energy and the melting
To,i are the absolute temperature (K) and the temperature at point in logarithmic coordinates [15] and later between the
which the free volume disappears at DP = 0 (for liquid me- activation energy and the complex quantity Tm/V1/3 [16].
tals To ffi 0 K [9]) and DP is the pressure increment over
the standard pressure of 105 Pa.
2.4. On the statistical-mechanical theory of viscosity
2.3. The activation energy concept of the viscosity of The statistical-mechanical theory of liquids was developed
liquids in the 1940s and was applied to their dynamic properties
by Born and Green [17]. Although statistical mechanics
For the temperature dependence of viscosity of pure liquid provides a solid scientific basis to calculate viscosity of li-
metals Andrade in the first approximation suggested to use quids, it is difficult to convert those integral equations into
the Arrhenius Eq. [10]: a form being useful for the use of ordinary researchers or
engineers. One of the useful approximate solutions of the
Ei statistical mechanical approach is due to Chapman [18],
gi ¼ C3 exp ð4Þ
RT who characterized the force between the atoms in liquid
metals by a distance parameter (the Goldschmidt atomic
where Ei is the activation energy of viscous flow for pure diameter, di) and a semi-empirical energy parameter (ei).
liquid i (J/mol) and R is the universal gas constant Chapman showed that the reduced experimental viscosity
(8.314 J/molK). data can be plotted as a function of the reduced temperature
For a wider temperature interval Andrade proposed a using a unique curve for all liquid metals. Unfortunately,
somewhat more sophisticated equation, being a modifica- this unique curve is given only in a graphical form [18],
2 Z. Metallkd. 96 (2005) 1
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without an analytical equation. Although not demonstrated This equation can be derived by taking the atomic diameter
by Chapman, if the atomic radius di is described as a linear di as proportional to Vi1/3 in one of the Eyring equations
function of Vi1/3, his equations reduces to the Andrade (Eq. (5a)). Eq. (7) can also be considered as one of the pos-
Eq. (1) at the melting point. It should also be mentioned that sible analytical ways to express the dimensionless viscosity
Chapman found a linear relationship between his semi-em- as a function of the dimensionless volume and the dimen-
pirical energy parameter ei and the melting point of the me- sionless interaction energy, instead of the graphical way of
tal Tm,i. expressing this relationship, as was done by Chapman
The statistical mechanical approach is also useful to pre- [18], based on statistical mechanics.
dict relationships between different physical properties of According to its physical sense, the activation energy of
liquid metals [19 – 22], such as: viscous flow is a certain small fraction of the cohesion en-
rffiffiffiffiffiffiffiffiffiffi ergy (taken with an opposite sign), what has to be supplied
gi 16 Mi during each atomic displacement of viscous flow between
¼ ð6Þ
ri 15 RT the adjacent liquid layers:
DZi
where ri is the surface tension of the liquid metal i (J/m2). Ei ¼ Dc Ui ð8Þ
Eq. (6) is justified by experimental data mainly at the Zi
melting point of metals. where DZi is the number of broken bonds during viscous
flow, Zi is the average coordination number in liquid metals
2.5. Evaluation and combination of the above concepts and DcUi is the cohesion energy of the given liquid metal.
Although usually the vaporization enthalpy is used as a
Comparison of Eqs. (2, 4, 4a) with experimental data of 26 measure of the cohesion energy, it has been recently shown
liquid metals, keeping two parameters in each equation as on the example of the surface tension that the cohesion en-
semi-empirical fitting parameters for each metal, proved ergy correlates better with the melting point of normal me-
that there is no significant difference in performance of tals [26]:
these equations [23]. It is somewhat disappointing that,
Dc Ui ¼ q R Tm;i ð9Þ
while Eq. (1) is very successful in predicting viscosity of
pure liquid metals at their melting points, it seems not be a where q is a semi-empirical parameter determined to be
part of any of the equations successfully describing the tem- q ffi 25.4 2 [27].
perature dependence of viscosity of pure liquid metals [23]. Substituting Eq. (9) into Eq. (8) and supposing that the
However, based on the simplified statistical-mechanical ap- ratio of DZi/Zi = DZ/Z is approximately constant for all
proach of Chapman [18], there is a hope that the Andrade liquid metals, we can introduce a constant B, as:
equation can be coupled successfully with a temperature DZ
dependent expression using several semi-empirical para- Bq ð10Þ
meters, which are expected to be unique for all liquid me- Z
tals (see also [24, 25]). Substituting Eqs. (8 – 10) into Eq. (7), we finally obtain the
While searching for a unique equation for the viscosity of following equation (the temperature dependent part of the
pure liquid metals, one should remember the following activation energy is included in parameter A):
question, which has been argued for the last 70 years: 1=2
M T 1=2 Tm;i
whether the activation energy concept, or the free volume gi ¼ A i 2=3 exp B ð11Þ
concept, or any combination of these two, has a more solid Vi T
physical background to explain the experimentally ob-
Eq. (11) is a new equation to the best knowledge of the
served temperature dependence of the viscosity of liquid
author. It contains two semi-empirical parameters, A and
metals.
B, hopefully being approximately identical for all liquid
metals at all temperatures. As follows from Eq. (11), at the
3. A unified equation of the viscosity of pure liquid melting point of the metals it reduces to the Andrade equa-
metals tion, Eq. (1), with the following relationship between para-
meters CA, A and B:
The goal is to create an equation, being able to reproduce CA ¼ A expðBÞ ð11aÞ
the absolute value and the temperature dependence of the
viscosity of liquid metals with two semi-empirical para- The additional value of Eq. (11) compared to Eq. (1) is that
meters, being generally valid for all liquid metals. The uni- it provides a reasonable basis for extending the Andrade
fied equation should also include both the activation energy equation to other temperatures, using a single parameter,
concept and the free volume concept. 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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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)
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3.3. Evaluation of the values of semi-empirical parameters In Table (1), the Andrade parameter as calculated from
A and B of Eq. (11) Eq. (11.a) is shown. As follows from the last rows of Ta-
ble 1, the Andrade parameter is found as:
For metals with most reliable experimental viscosity values CA = (1.83 0.17) · 10 – 7 (J/Kmol1/3)1/2
the unified equation (11) will be tested, and the best values
of parameters A and B will be determined. Eq. (11) can be This value is practically the same as was found in recent re-
transformed into the following equation: views [2, 3]. From the value of parameter B, found above,
! and the value of parameter q ffi 25.4 2 [27], the ratio of
2=3
gi Vi Tm;i broken bonds during the viscous flow can be calculated,
ln zi ln 1=2
¼ ln A þ B ð11bÞ using Eq. (10):
M T 1=2 T
i
DZ/Z = 0.092 0.009
Experimental values are given in Table 1 for 15 normal me- If the average coordination number in liquid metals is taken
tals, for which reliable experimental data are available. as Z = 11 0.5, the value of DZ becomes 1.01 0.12.
From the total 41 elements, given in the compilations [2, Thus, about 1 bond is broken in the sliding plane of liquid
23], 26 are disregarded from our analysis for the following metals during viscous flow. Compared to the approximately
reasons: 2 broken bonds, appearing at the free liquid/gas interface
i. Al, Ce, Co, Fe, Ni, Ti: different experimental sets con- (as a manifestation of surface tension of liquid metals [26,
tradict each other, 27]), this seems to be a reasonable value.
ii. Ca, Cr, Hf, La, Mg, Mn, Pd, Pr, Pu, U, V, Yb, Zr: only
single experimental data exist, with questionable relia-
3.4. On the correlation between the viscosity and surface
bility,
tension of liquid metals
iii. Bi, Ga, Ge, Sb, Se, Si, Te – these semi-metals are ex-
cluded from consideration when the average “best”
Once we have a unified equation for the viscosity of liquid
parameters are searched for “normal” metals.
metals, it is of interest to compare it with an equation for
The plot in coordinates lnzi versus Tm,i/T is shown in Fig. 1
the surface tension of liquid metals [26, 27]:
for altogether 101 data points for the selected 15 metals.
One can see that both the slope and the intercept of the mea- 0:182 211 þ Cp;i Tm;i ð2 þ 0:182 Cp;i Þ T
sured points seem to be quite constant, proving the ade- ri ¼ 2=3 1=3
quacy of Eq. (11). 1:06 Vi NAv
In the last rows of Table 1 the average values and stan-
dard deviations of parameters A and B of Eq. (11) are given. where Cp,i is the heat capacity of the liquid metal i
Accordingly, the semi-empirical parameters have the fol- (J/molK).
lowing approximate values: Dividing Eq. (11) by Eq. (16), the following equation is
obtained:
A = (1.80 0.39) · 10 – 8 (J/Kmol1/3)1/2
1=2
B = 2.34 0.20 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
In Fig. 2, the theoretical values, calculated by Eq. (11) and
the above average parameters are compared to the experi- (17)
mental viscosity values for the same 15 ‘normal’ metals. At the melting point T = Tm,i, Eq. (17) simplifies to:
One can see that the measured points are situated around sffiffiffiffiffiffiffiffi
the theoretical values within 20 %. This shows that for gi;m Mi
‘normal’ liquid metals the absolute value and the tempera- ¼ 0:459 ð17aÞ
ri;m Tm;i
ture dependence of viscosity can be described by the uni-
fied equation (11), using two, generally valid semi-empiri-
One can see that Eq. (17.a) is identical with Eq. (6), except
cal parameters.
that its numerical coefficient is higher by 24 %. In Fig. 3
Fig. 1. Experimental viscosity data for 101 measured points of 15 se- Fig. 2. Comparison of viscosity data calculated by Eq. (11) and mea-
lected pure metals, given in Table 1, presented in coordinates according sured viscosity data for 101 measured points on selected 15 liquid me-
to Eq. (11b). tals, given in Table 1. The dashed lines are drawn to show 20 % of
deviation.
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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-
Fig. 3. The temperature dependence of the dynamic viscosity, surface tion [2], leading to unusually high viscosity values. Thus,
tension, and ratio of both quantities for a liquid metal, calculated by the Andrade equation overestimates the viscosity for the
Eqs. (11, 16, 17) and Eq. (6) (Mi = 55.85 g/mol, Tm,i = 1,808 K, Cp,i =
46.0 J/molK). majority of semi-metals, and underestimates the viscosity
of liquid Se.
As our unified equation is based on the Andrade equa-
the temperature dependence of the viscosity (Eq. (11)), sur-
tion, the above shortcomings refer also to Eq. (11). As one
face tension (Eq. (16)) and their ratio (Eqs. (6, 17)) are
can see from Fig. 4a, Eq. (11) indeed seriously overesti-
shown for liquid iron. As one can see from Fig. 3, although
mates the measured data for liquid Si, Ge, Sb, and Bi.
Eq. (17) provides quite a different temperature dependence
To my opinion this is due to the different structure and to
compared to Eq. (6), the two equations provide similar ab-
the different chemical bonding in solid Si, Ge, Sb, and Bi,
solute values within a limited temperature range of Tm,i
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)
6 Z. Metallkd. 96 (2005) 1
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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)
* 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 of – 20 % (compare with the same uncertainty range in
can be called “metallic melting point” of Si, Ge, Sb, and Fig. 2). The calculated values at the melting point were
Bi. These corrected melting points are estimated by fitting compared to available experimental data, based on compi-
Eq. (11) to the experimental data points, keeping the same lations [2, 3, 23]. From the comparison of the 6th and 7th
values of parameters A and B, and treating the melting point columns of Table 3 one can make the following conclu-
as a fitting parameter (see Table 2). The calculated and sions:
measured data points, using the corrected melting point va- i. in 14 cases (Ba, Ir, Mo, Nb, Nd, Os, Pt, Re, Rh, Ru, Sr,
lues, are compared in Fig. 4b, demonstrating good agree- Ta, Th, W) out of the 32 cases considered in Table 3,
ment. no experimental data are available, at all.
ii. among the 11 cases, when only a single experimental
3.6. Estimation of the viscosity of some pure liquid metals value is available, in 6 cases (Ca, Cr, Mg, Pr, U, Zr) the
calculated values differ less, while in 5 cases (Hf, Mn,
As follows from the above, Eq. (11) can be used to predict Pd, Pu, V) the calculated values differ more than by
the temperature dependence of pure liquid metals, suppos- 20 % from the experimental value,
ing they behave as normal metals both in solid and liquid iii. among the 7 cases, when at least two, different experi-
states. The application of Eq. (11) is mainly limited by the mental data sets are available, in 6 cases (Al, Ce, Co,
lack of information on the molar volume of high melting Fe, Ni, Ti) the calculated values appear in the interval
point liquid metals and its temperature dependence (see of the experimental values, while in 1 case (La) the cal-
footnote to Table 3). In Table 3 the basic physical proper- culated value differs less, than by 20 % from the average
ties, and the calculated viscosity values are given for 32 of the experimental values.
liquid metals at three different temperatures, for which the Based on the above we can conclude that Eq. (11) works in
necessary information is available in [3]. All values, calcu- 28 cases out of total 33 cases (i. e. in 85 % of cases, includ-
lated in Table 3, should be considered with an uncertainty ing also the 15 selected metals), failing only against single
Z. Metallkd. 96 (2005) 1 7
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measurements on liquid Hf, Mn, Pd, Pu, and V. Thus, [13] S. Glasstone, K.J. Laidler, H. Eyring: The Theory of Rate Pro-
Eq. (11) provides reasonable estimates of the temperature cesses. The Kinetics of Chemical Reactions, Viscosity, Diffusion
and Electrochemical Phenomena, McGraw-Hill Book Co., New-
dependence of the viscosity of liquid metals. York, 1941.
Although our Eq. (11) is not identical with the graphical [14] B. Ilschner: Z. Metallkd. 57 (1966) 194.
method of Chapman [18], the two methods provide similar [15] E.T. Turkdogan: Can. Met. Quart. 41 (2002) 151.
results. As an example, let us estimate the viscosity of li- [16] E.T. Turkdogan: Can. Met. Quart. 42 (2003) 433.
[17] M. Born, H.S. Green: A General Kinetic Theory of Liquids, Uni-
quid titanium at 2120 K. Following Chapman, a 7-step al- versity Press, Cambridge, 1949.
gorithm (including the step to read a value from a graph) is [18] T.W. Chapman: AIChE J. 12 (1966) 395.
elaborated in [41], with a final result of 3.33 mPas. On the [19] M. Shimoji: Adv. Phys. 16 (1967) 705.
other hand, our Eq. (11) provides the value of 3.20 mPas in [20] I. Egry: Scripta Metall. et Mater. 26 (1992) 1349.
one straightforward step. The difference between the two [21] I. Egry: Scripta Metall. et Mater. 28 (1993) 1273.
[22] N.H. March: J.Non-Crys. Sol. 250 – 252 (1999) 1.
methods is only 4 %. [23] R.P. Chhabra, D.K. Sheth: Z. Metallkd. 81 (1990) 264.
[24] M. Hirai: ISIJ Intern. 33 (1993) 251.
[25] S. Morioka, B. Xiufang, S. Minhua: Z. Metallkd. 93 (2002) 288.
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414 – 415 (2003) 235.
It has been shown that the activation energy concept and the [27] G. Kaptay: Mater. Sci. Forum, & (2004) 1.
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the same roots, and can be converted into the unified equa- [29] T. Iida, Z-I. Morita, S. Takeuchi: J. Japan Inst. Metals 39 (1975)
1169.
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335.
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not identical with, but provides similar values to the graphi- 218.
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[35] I.I. Novikov, A.N. Soloviov: Atomnaia Energiia 1 (1956) 92.
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[38] E. Gebhardt, K. KUstlin: Z.Metallkd. 50 (1959) 379.
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8 Z. Metallkd. 96 (2005) 1