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Thermophysical measurements on liquid iron and nickel

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Thermophysica! measurements on liquid iron and nickel

Gernot Pottlacher, Helmut Jager, Theo Neger

Reprinted from a Pion publication

high temperatures-high pressures

High Temperatures-High Pressures, 1987, volume 19, pages 19-27

10 ETPC Proceedings page 249

Thermophysical measurements on liquid iron and nickel

Gernot Pottlacher, Helmut Jager, Theo Neger

Institut fur Experimentalphysik, Technische Universitat Graz, Petersgasse 16, A-8010 Graz, Austria
Presented at the Tenth European Conference on Thermophysical Properties, Rome, 22-25 September
1986

Abstract. Wire-shaped samples of nickel and iron, 40 mm long and 0.25 or 0.125 mm in diameter,
were pulse heated in a fast RCL discharge circuit with typical heating rates of10 9 K s~! (exploding
wire technique). From time resolved voltage and current measurements the electric resistivity and the
enthalpy were derived, with the relative volume change of the sample detected by the shadowgraph
method. The temperature was determined by a fast pyrometer. Investigations made in the range
of 2000 to 4000 K yielded molar heat capacities of 44.7 J mol~ l K~* for liquid nickel and
51.9 J mol"1 K~ l for liquid iron. The results are compared with those found by other authors.

1 Introduction
Pulse heating techniques for measuring thermophysical properties of metals at high
temperatures have been successfully applied by a number of authors (see for example
Cezairliyan 1984; Gathers 1986; Lebedev et al 1973; Seydel et al 1980). The
exploding wire technique shows several advantages over other methods:
(i) fast RCL discharge circuits ensure that no disturbances are caused by MHD
instabilities during the relevant diagnostic time interval (the first 4 /as);
(ii) chemical reactions of the liquid specimen with the surrounding medium are more
easily suppressed when the heating rates are fast;
(iii) many metallic elements can be made into wire-shaped specimens of high purity;
(iv) superheated liquid metal states can be easily achieved and temperatures reached
which are higher than those attained by other methods; and
(v) the wire sample is arranged and pulse heated in a relatively simple way.
However, the required time resolution of the diagnostic system places certain
demands with respect to the measuring equipment as well as the design of the
electric discharge circuit and especially the discharge vessel. The experimental setup
used for the investigations described here is based in principle on that described by
Seydel and Fucke (1977), somewhat modified by Gallob et al (1985) in order to
allow the measurement of the surface temperature by a fast pyrometer in addition to
the measurements of the current through the wire and the voltage drop across it.
The technically important metals iron and nickel were investigated up to
temperatures far above their normal boiling points. Seydel and Fucke (1977) had
already obtained data for these two elements, but they derived their temperature
values from the electric parameters of the discharge with the help of the so-called
'integral of action'. Therefore an independent temperature determination by
pyrometry seemed to be desirable.

2 Experimental
Figure 1 shows the block diagram of the coaxially arranged RCL discharge circuit
and the diagnostic system. Wire-shaped samples, 40 mm in length and either
0.25 mm or 0.125 mm in diameter, were pulse heated. To suppress peripheral
discharges, water at a pressure of 1 bar was used as the surrounding medium in a
discharge vessel described earlier by Gallob et al (1985).
20 G Pottlacher, H Jager, T Neger

10 ETPC Proceedings page 250

The energy was stored in a capacitor bank (C = 5.4 pF) which could be charged
up to 8 kV. From the short-circuit ringing period T = 6.2 jus an inductivity
L — 180 nH can be derived; the circuit resistance was found to be 26.3 mi}. Under
these conditions typical heating rates of about 109 K s*"1 can be achieved.
Current measurements were performed by RC integration of the d//df signal of an
induction coil. A coaxially constructed ohmic voltage divider served for the
determination of the voltage drop across the wire. The volume change of the sample
caused by ohmic pulse heating was measured by the shadowgraph method, which
has been described in detail by Gallob et al (1986), together with the fast pyrometer
(operating at 801.7 /jm; photodiode BPX 65, Siemens) used for the determination
of the surface temperature of the heated wire. The time resolution of the whole
measuring system was about 8 ns.
The determination of the various thermophysical properties starts by considering
the measured time-dependent quantities: current, J(t), and ohmic voltage drop, U(T)
[the inductive part is substracted from the U(t) signal]. The quotient yields the
'corrected' resistivity if the volume expansion of the sample is taken into account.
A flow chart of this data reduction procedure is given by Pottlacher et al (1986).
We shall now consider the problem of temperature measurement. For nickel
Seydel and Fucke (1977) carried out complex calculations and considered a number
of material parameters in order to evaluate the temperature by the so-called 'integral
of action' from the voltage and current measurement data. So it seemed desirable
to use an independent method, that of measuring surface radiation. According to

Figure 1. Block diagram of the discharge circuit: 1 capacitor bank, 2 wire sample, 3 charging unit,
4 start pulse, 5 delay, 6 trigger, 7 flashlight, 8 thyratron stage, 9 three-electrode spark gap,
10 photodetector, 11 trigger, 12 time-mark generator, 13 induction coil, 14 voltage divider,
15 pyrometer, 16 Kerr-cell camera, 17 200 MHz oscilloscopes, 18 shielded measuring room.
Thermophysicat measurements on liquid iron and nickel 21

10 ETPC Proceedings page 251

Kirchhoff-Planck law we have

T= 7[exp(t' 2 /Xr m )- 1] (1)

where T is the temperature, X is the wavelength, e is the emissivity, c2 is the second

radiation constant, / is the radiation intensity, and the subscript m indicates the
values at the melting transition.
To calibrate the sensitivity of the pyrometer it is essential to know one reproducible
temperature value with the corresponding radiation intensity recorded on the
oscilloscope. Our fast pyrometer cannot be used for temperatures lower than 2000 K
(see Gallob et al 1986). As a radiation standard we chose the melting transition of
tantalum because of its good reproducibility and its high temperature (nearly 3000 K).
To test this method we proceeded in the following way: From time-resolved
intensity measurements of the surface radiation of pulse-heated tantalum, niobium,
molybdenum, rhenium, and tungsten wire samples we obtained relative intensities at
the corresponding melting transitions, which were all showing a clear intensity
plateau with respect to time. From literature we took the emissivity values for these
metals, assumed only the value for the melting temperature of tantalum as given, and
calculated the melting temperatures of the other metals with the use of equation (1).
We found that the temperature values thus obtained did not differ by more than 5%
from the literature values.
This encouraged us to perform temperature measurements on nickel and iron—-
they both show melting temperatures lower than those directly measurable with our
pyrometer - via the melting transition of tantalum, which served as the temperature
standard. The ratio e(!T m )/e(r m>Ta ) was found from literature to be 0.74 for both
nickel and iron. Because of the lack of emissivity data for superheated liquids this
value was assumed to be constant for the liquid state throughout, an assumption
made by other authors too.

3 Results and discussion

3.1 Nickel
3.1.1 Dependence of the electric resistivity on temperature. It is usual to plot also
the electric resistivity, p c , which has not been corrected for volume change in order
to be able to compare with uncorrected data of other authors should this be necessary.

200

100

2000 3000 4000

Figure 2. Temperature dependence of electric resistivity for nickel, with volume expansion
ignored (p0, curve 1), and taken into account (p, curve 2); circles represent the values of Seydel
and Fucke (1977).
22 G Pottlacher, H Jager, T Neger

10 ETPC Proceedings page 252

Figure 2 shows that pQ is nearly constant from 2000 to 4000 K, whereas the
corrected value p (curve 2) first increases slightly and linearly up to about 3200 K,
and afterwards increases very strongly. It should be noted that the values of Seydel
et al (1977) based on the 'integral of action' are in good agreement with those of
this work.
The polynomial least squares fits are:

cm = 70+3.36 x 10-3(7YK), 2000 K < T < 4000 K,

3
p/jufi cm = 57.6+ 10.8 x 10~ (7/K), 2000 K < T < 3000 K;
and
cm = -238.6+0.215(7YK)+0.269 x 10~ 4 (r/K) 2
-0.426 x 10- ? (r/K) 3 +0.725 x lQ~n(T/K)4, T > 3000 K.
3.1.2 Dependence of electric resistivity on energy input. In figure 3 the end of
melting of nickel can be clearly seen. The slopes for p and p0 are nearly the
same for enthalpy values up to the end of the melting transition. At the
beginning of the pure liquid phase p and p0 are both showing linear behaviour
again, whereas above H = 2.5 MJ kg~'p(#) undergoes a very sharp increase. The
values of Seydel et al (1979) are in good agreement with ours. We found the
following least squares fits:
Po/p.12 cm = 72.7 + 3.2(#/MJ kg'1), 1 MJ kg'1 < H < 3 MJ kg'
and
cm = 170- 126(///MJ kg" 1 ) + 43.2(///MJ kg' 1 ) 2 ,
1 MJ kg'1 < H < 2.5 MJ kg

200

100

0 1 2 3
///MJ kg' 1
Figure 3. Electric resistivity as a function of enthalpy for nickel, with volume expansion ignored
(Po, curve /) and taken into account (p, curve 2); circles represent the values of Seydel and
Fucke (1977).

3.1.3 Dependence of enthalpy on temperature; specific heat. Curve 1 in figure 4

corresponds to a wire diameter of 0.25 mm, curve 2 to a diameter of 0.125 mm.
The normal boiling temperature of nickel is close to 3000 K. As a consequence of
the fast energy input overheating takes place. Wire 2 is more strongly superheated
because of the higher heating rate used (dT/dt = 2.2 x 109 K s~! in comparison to
9 x 108 K s"1 for wire 1). Because of the smaller wire diameter and the higher
Thermophysical measurements on liquid iron and nickel 23

10 ETPC Proceedings page 253

heating rate the temperature measurement seems to be less accurate than for the
0.25 mm wire which leads to lower enthalpy values. Within the temperature interval
investigated a linear dependence on temperature was found. The values calculated
by Bauhof (1978) match our curves satisfactorily.
The polynomial fits for the enthalpy H are:
curve
= -0.182 + 0.762 x l(T3(r/K), 2000 K < r < 4 0 0 0 K ;
curve 2:
=-0.113 + 0.667 x 10'3(r/K), 2000 K < T < 6000 K.
Using curve 1 we derived for the molar heat capacity the value Cp = 44.7 J mol""11 K"1
Cezairliyan and Miiller (1983) report for 1700 K the value Cp = 38.43 J mol'1 K'1 ;
they also give a review of Cp data reported in the literature. The melting temperature
of nickel found by them was 1729 K (Cezairliyan and Miiller 1984). Margrave (1970)
reports for Cp at melting point 43.05 J mol"1 K"1. Bauhof (1978) used for his
calculations the value Cp — 43.1 J mol"1 K"1 (curve 3). From curve 2 for the
0.125 mm wire we get Cp = 39.2 J mol"1 K~'.
As reported earlier (Gallob et al 1985) the error in heat capacities obtained by
our method is around 25%.

I 2

2000 3000 4000 5000 5000 7000

r/K
Figure 4. Temperature dependence of enthalpy for nickel: 1, 0.25 mm diameter wire, heating
rate 9 x 10s K s"1; 2, 0.125 mm diameter wire, heating rate 2.2 x 109 K s~ l . The dashed line 3
and circles represent the values calculated by Bauhof (1978).

3.1.4 The melting transition. Table 1 gives some enthalpy and resistivity values at
the beginning and the end of the melting transition. For nickel and iron we
determined these values by examining the characteristic bends in the voltage
oscillogram. Also listed are the values reported by Barin and Knacke (1973),
Cezairliyan and Miiller (1983), Guntherodt et al (1975), Hultgren et al (1973),
and Seydel et al (1979). The latent heat of fusion, A//, obtained by us is compared
with the results of Kelley (1960), Lebedev et al (1971), Margrave (1970), and
Vollmeret al (1966).
3.2 Iron
Data for iron are presented in the same way as for nickel. The agreement with the
values of Seydel et al (1977, 1979) is again good.
24 G Pottlacher, H Jager, T Neger

10 ETPC Proceedings page 254

Table 1 . The enthalpy and electric resistivity of nickel at the melting transition (s solid, 1 liquid).

ff(s) H(\) A// p(s) p(l) p(l)

MJ kg"' MJ kg'1 MJ kg"1 n$l cm /j£2 cm p(s)

This work 0.802 1.094 0.292 56.1 76.0 1.35

Seydel e t a ! (1979) 0.800 1.106 0.306
Barin and Knacke 0.805 1.106 0.301
(1973)
Hultgren et al 0.810 1.108 0.298
(1973)
Cezairliyan and 59.6
Miiller(1983)
Giintherodt et al 52.0 80.0 1.54
(1975)
Kelley(1960) 0.300
Lebedev et al 0.318
(1971)
Margrave (1970) 0.291
Vollmer et al 0.287
(1966)

3.2.1 Dependence of electric resistivity on temperature. The relations p0(T) and

p(T} obtained by us are plotted in figure 5. For the least squares fits we obtained

cm = 0.113 x 10 3 + 0.546 x 10~ 2 (r/K), 2000 K < T < 4000 K (curve 1);
and

c m = - 0 . ! 2 9 x 10 3 -f0.208(7 1 /K)-0.233 x \0~4(T/K)2- 0.156 x 10"7(r/K)3

+ 0.348 x 10""(r/K) 4 , 2000 K < J < 3 7 5 0 K (curve 2).

100

2000 3000 4000

r/K
Figure 5. Temperature dependence of electric resistivity for iron, with volume expansion ignored
(/Jo, c u r v e /) a n d taken into account (p, curve 2); circles represent the values of Seydcl and Fuckc
(1977).

3.2.2 Dependence of electric resistivity on energy input. The plots in figure 6 can
be described by the following polynomials:

cm = -1.6+266.9(#/MJ kg" 1 )+ 360.4(#/MJ kg" 1 ) 2 - 1265.7(///MJ kg" 1 ) 3 .

0 < H < 0.85 MJ kg"1;
Thermophysical measurements on liquid iron and nickel 25

10 ETPC Proceedings page 255

and
Po//ifl cm = 120 + 4.45(tf/MJ kg"1), 0.85 MJ kg"1 <H < 3 MJ kg'1 (curve 1).
Taking into account the volume change we obtained (curve 2):
p/Mfl cm = 0.4 + 240.2(tf/MJ kg- 1 )+ 435.3(ff/MJ kg"1)2- 1272.2(#/MJ kg'1)3
+ 746.6(#/MJkg- J ) 4 , 0<#<0.85MJkg- 1 ,
and
pln&cm= 152.6-36.8(tf/MJkg- I )+15.4(///MJkg- 1 ) 2 ,
0.85 MJ kg'1 <H< 3 MJ kg'1.
200

100

Figure 6. Electric resistivity as a function of enthalpy for iron, with volume expansion ignored
(po, curve 1} and taken into account (p, curve 2); circles represent the values of Seydel and
Fucke (1977)

3.2.3 Dependence of enthalpy on temperature; specific heat. For the same two
different diameters as for nickel (see section 3.1.3) the increase of enthalpy with
temperature was found to be linear. For the 0.25 mm wire we found (figure 7,

3000 4000
r/K
Figure 7. Temperature dependence of enthalpy for iron: I, 0.25 mm diameter wire; 2, 0.125 mm
diameter wire. Circles represent the values of Treverton and Margrave (1971).
26 G Pottlacher, H Jager, T Neger

10 ETPC Proceedings page 256

curve 7):

ff/MJ kg"1 =-0.486 + 0.929 x 10'3(r/K), 2250 K < T < 4250 K;

and for the 0.125 mm wire (curve 2):
///MJkg- 1 =-0.133 + 0.732 x 10"3(r/K), 2100 K < T < 4500 K.
When the values of Treverton and Margrave (1971) up to 2142 K are extrapolated to
higher temperatures, they fit our curve quite well for the 0.25 mm wire.
From curve 1 we derived a molar heat capacity of 51.9 J mol"1 K'1 (wire diameter
0.25 mm); an uncertainty of at least 25% must be assumed. For the thinner wire
(curve 2) the uncertainty would be even larger. A value of 44.62 J mol"1 K~' at
1800 K is given by Cezairliyan and McClure (1974), 42.0 J mol'1 K"1 by Vollmer
et al (1966), and 43 J mol'1 K~ l at 2142 K by Treverton and Margrave (1971).
3.2.4 The melting transition
In table 2 our enthalpy and resistivity values at the beginning and the end of the
melting transition are compared with the results of Cezairliyan and McClure (1974),
Guntherodt et al (1975), Hultgren et al (1973), and Seydel et al (1979). Our latent
heat of fusion is also compared with the results obtained by Kelley (1960), Lebedev
et al (1971), Margrave (1970), and Vollmer et al (1966).

Table 2. The enthalpy and electric resistivity of iron at the melting transition (s solid, 1 liquid).

//(s) //(I) A// p(s) Pd) P(l)

Source
MJkg ' MJkg ' MJkg' 1 /i£2cm /jQ crn p(s)

This work 1.061 1.330 0.269 129.0 136.0 1.05

Seydel et al ( 1979) 1.051 1.328 0.277
Hultgren et al 1.050 1.297 0.247
(1973)
Cezairliyan and 126.9
McClure (1974)
Guntherodt et al 126.4 135.1 1.07
(1975)
Kelley (I960) 0.275
Lebedev et al 0.244
(1971)
Margrave (1970) 0.242
Vollmer et al 0.258
(1966)

3.3 Estimate of errors

A discussion of the errors involved in the technique used by us was presented in
earlier papers (Gallob et al 1985; Pottlacher et al 1986). The results of each
individual experiment lie within the error-bars shown in the figures which give the
experimental uncertainty. An error of 5% has to be assumed for the enthalpy and
electric resistivity values. The uncertainties for the temperature measurements are
estimated to be about 20%.
Acknowledgements.
The authors wish to thank Professor U Seydel, who has greatly enhanced this work.
Thermophysical measurements on liquid iron and nickel 27

10 ETPC Proceedings page 257

References
Darin I, Knacke O, 1973 Thermochemical Properties of Inorganic Substances (Berlin: Springer)
Bauhof H, 1978 Diploma thesis, Universitat Kiel, Kiel, FRG
Cezairliyan A, 1984 in Compendium of Thermophysical Property Measurement Methods volume 1,
eds K D Maglic, A Cezairliyan, V E Peletsky (New York: Plenum) pp 643-668
CezairSiyan A, McClure J L, 1974 /. Res. Nat. Bur. Stand. Sect. A 78 1
Cezairliyan A, Miiller A P, 1983 Int. J. Thermophys. 4 389
Cezairliyan A. Miiller A P, 1984 Int. J. Thermophys. 5 315
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of Thermodynamic Properties of the Elements (Metals Park, OH: American Society for Metals)
KeSley K K, I960 US Bur. Mines Bull. 584
Lebedev S V, Sawatimskii A I, Smirnov Yu B, 1971 High Temp. USSR 9 578
Lebedev S V, Savvatimskii A I, Smirnov Yu B, 1973 Sov. Phys. Tech. Phys. 17 1400
Margrave J L, 1970 High Temp.-High Pressures 2 583
Pottlacher G, Neger T. Jager H, 1986 Int. J. Thermophys. 1 149
Seydel U, Bauhof H, Fucke W, Wadle H, 1979 High Temp. -High Pressures 11 35
Seydel U, Fucke W, 1977 Z. Naturforsch. Teil A 32 994
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Hochschmelzender Metalle mil Schnellen Pulsaufheizexperimenten (Diisseldorf: Peter Mannhold)
Treverton J A, Margrave J L, 1971 /. Chem. Thermodyn. 3 473
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 1987 a Pion publication printed in Great Britain

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