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A transient hot-wire cell for thermal conductivity measurements over a wide temperature range

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1982 J. Phys. E: Sci. Instrum. 15 839 (http://iopscience.iop.org/0022-3735/15/8/010) View the table of contents for this issue, or go to the journal homepage for more

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J . Phys. E: Sci. Instrum.. Vol. 15, 1982. Printed in Great Britain

A transient hot-wire cell for thermal conductivity measurements over a wide temperature range
E N Haran+ and W A Wakeham$$ -k Ministry of Defence. Armament Development Authority, Haifa, Israel # Department of Chemical Engineering and Chemical Technology, Imperial College, Prince Consort Road, London S W 7 ,UK Received 21 January 1982,in final form 15 March 1982

Abstract. The paper describes the design, construction and use of a new set of cells for the measurement of the thermal conductivity of gases over a wide temperature range from 77 K to 520 K by the transient hot-wire method. The design eliminates deficiencies in earlier versions which have limited the application of the experimental technique, for measurements of the highest precision. to near ambient conditions. Trial measurements with the cells are reported at 308 and 340 K which confirm that they operate in accordance with the theoretical description of them, and that the accuracy of the experimental data is one of i.o.3?;0.

(Kestin et a1 1980, Assael et a1 1981). In these circumstances the wire is subject to a changing stress during the course of the measurement which modifies its resistance-temperature characteristics from those under the calibration conditions of constant, zero stress. Clifford et a / (1980) have modified the working equations for the instrument to account for this effect and have shown that provided the stress in the wire is known at equilibrium, prior to the transient heating, the accuracy of the measurements is unimpaired. In all thermal conductivity cells of this type employed so far, the setting of the initial tension in the wire. under ambient conditions. has been achieved by means of a screw mechanism (Kestin et a1 1980. Assael et a / 1981,Castro et a1 1976). At best. such a mechanism permits a crude estimate of the stress in the wire under ambient conditions; at temperatures progressively removed from room temperature the stress is known with decreasing certainty which can lead to wire breakage. For this reason. hot-wire cells for thermal conductivity measurements in the gas phase have been almost exclusively employed near room temperature (Kestin et a / 1980. Assael et a1 1981. Assael and Wakeham 1981). In this paper the design of a new transient hot-wire thermal conductivity cell is described. which is suitable for operation in the gas phase over the temperature range 77 K to 520 K. The design permits the initial stress in the wire to be determined accurately under ambient conditions and to be chosen such that the wire is taut under all conditions. At the same time. the opportunity has been taken to simplify the procedure for mounting the 7 um diameter platinum wires employed and thereby to preserve the high quality of the original wire.

1. Introduction The transient hot-wire technique has become established as the most precise and accurate method of carrying out measurements of the thermal conductivity of fluids (Haarman 1971, Healy et a1 1976. de Groot et a / 1974, Kestin et a1 1980, Menashe and Wakeham 1981). The technique involves the determination of the temporal evolution of the temperature of a thin. vertical platinum wire immersed in the fluid following the stepwise initiation of a heat flux within it (Healy et a/ 1976).One of the constraints imposed on the design of thermal conductivity cells of this type is that the platinum wire should remain taut and vertical under all conditions and. in particular. during its transient heating (Kestin et a1 1980. Clifford et a1 1980, Castro and Wakeham 1977). Because it is not generally feasible to construct the cell body which supports the wire from platinum, a change in the equilibrium temperature of the cell leads to differential thermal expansion which may cause the wire to slacken and move or tighten and eventually break. Furthermore, the expansion of the platinum wire during the transient heatihg can also cause the wire to slacken and move. thereby invalidating the measurements (Kestin et a1 1980). In instruments designed for operation with liquids these problems may be readily overcome by suspending a weight from the lower end of the wire to provide a small, constant stress under all conditions (Menashe and Wakeham 198 1). However. in the gas phase, the same scheme cannot be employed, since the relatively small viscous damping is insufficient to prevent small, but significant, pendulum-like oscillations of the wire induced by the vibrations usually present in a laboratory environment. For this reason, in gas-phase instruments. it has been common practice to tension th? wire by means of a spring which absorbs the thermal expansion of the wire during transient heating

2. The cell design The essential features of the cell comprise a rigid cylindrical vessel made of stainless steel. together with a platinum wire stretched along its axis between two. fixed and insulated electrical terminals. A helical spring is placed between one of the terminals and one end of the wire in order to maintain the wire taut at any equilibrium temperature, To, as well as throughout the transient heating of a measurement. The discussion in the introduction makes it clear that the design of the spring is crucial to the successful operation of the instrument. T o carry out the design we first specify the temperature range of operation of the instrument to be such that To,,, To Tom,,. assuming that the cell is assembled at Then, room temperature, TR.it is possible to evaluate the differential thermal expansion, 6, of the platinum wire and its supports at the extremes of the operating range: 6 is taken to be positive when the length of the support increases by more than that of the wire. In addition to the differential thermal expansion it is also necessary to consider the time-dependent plastic extension of the wire (creep) induced by a stress within it (Van Bueren 1960). For design purposes we confine ourselves to an estimate of an upper limit to the strain induced and, because the rate of strain in creep increases with temperature, we base our estimate on operation at TO,,,. Carreker (1950) has carried out measurements of the stress-strain relationship for platinum over a period of several days and over a wide range of temperature. At a temperature of T= 550 K his results have been represented by a semi-empirical equation of the form suggested by Polakowski (1966)

< <

E=

j.7 x 10-87t010.2*

(1)

Author to whom correspondence should be addressed.

where E is the strain, o the stress, measured in pascals, and t the time measured in seconds. The time dependence of the creep implies that a design must be made for a prescribed period of operation. For the present application it is considered that operation for 100 days at the highest temperature is appropriate:

0022-3735/82/080839 + 04 $02.00 8 1982 The Institute of Physics

839

E N Haran and W A Wakeham

the extension of the wire owing to creep in this period is denoted by 6,. Because the creep is not measurable in situ it is necessary to restrict its value by design so that the accuracy of the thermal conductivity measurements, which depends upon the wire length, is unimpaired. Thus we require that

6, < 1 x 10-~1,

(2)

where 1, is the wire length, which is typically 0.15 m (Assael et a1 1981). In order that the platinum wire remains taut at all temperatures throughout the period specified it is necessary to satisfy the condition

Section AA'

at all times during the lifetime of the cell, and the condition

when the cell is first assembled (6, =O). Here, G~ denotes the stress in the wire. a the wire radius and s the spring constant of the helical spring. The maximum allowable stress G~~~ is determined by condition (2) through equation (1) for the operating period of 100 days, whereas the minimum allowable stress has been taken from our earlier work (Assael et a1 1981. Menashe and Wakeham 1981), to be ~ , i , = 1 3 M P a . The establishment of and ~~i~ then allows the limiting equalities of equations (3) and (4) to be solved to yield the required spring constant s and the wire stress to be set at room temperature during assembly o W ( T ~ ) . The present cells have been designed for the temperature range 77 To 520 K. with 6, = 0.1 mm: corresponding to omax 22 MPa. For the materials specified. the differential 'v thermal expansion amounts to 6(TOmi,)-0.1 mm and = 6(Tonax) + 0.1 mm. For a wire radius, a = 3.5 gm, these values = lead to a spring constant s = 1 + lo-' N mm-', and to a roomtemperature stress of 18.2 MPa. which corresponds to a loading of 70 mg. The design of a spring with the required elastic constant has been carried out by standard procedures subject to three additional constraints. First, the electrical resistance of the spring should be as low as possible because a correction must be applied for it in the analysis of the experimental data (Kestin and Wakeham 1978). Secondly, the diameter of the helical coil should be smaller than the outer diameter of the cylindrical cell. Finally, the spring material should be readily attached to the platinum wire and the electrical terminal of the cell. It has been found by calculation and trial that a two-turn coil made of 0.15 mm diameter drawn beryllium-copper wire with a coil diameter of 8 mm fulfils all the necessary conditions for the present cells.

Cover

Detail o f terminal

< <

Figure 1. The transient hot-wire cells.

3. The thermal conductivity cells Figure 1 contains a diagram of the present thermal conducti? ity cells. The two cells employed for the compensation of end effects (Kestin and Wakeham 1978) are both machined in a single stainless steel cylinder (EN57B) (1) by drilling two longitudinal holes of 13 mm diameter, centred on a diameter of the cylinder. The cylinder is divided into two halves along a diametral plane. as indicated in the horizontal section in figure 1; one half carries the supports for the platinum wires and the other acts as a cover. The supports for the platinum wires (2) in each cell are formed by brass terminal posts (3) and (4). The upper post (3) is a solid cylinder fixed by means of the stainless steel cylinder ( 5 ) and the set screw (6) in a ceramic bush (7) and a stainless steel sleeve (8) so that it is electrically insulated from the cell body. The upper assembly is held in position by a retaining plate (9) fixed to a mounting flange (10) by means of the bolt (1 1). A similar arrangement is employed for the hollow cylinder (4) which forms the bottom terminal post, except that the sleeve
840

(12) is screwed directly to the side wall of the cell. The entire cell assembly is mounted in a pressure vessel, described elsewhere (Assael et a1 1981), from the flange (IO). The electrical leads from the bottom terminal posts are led through glass insulated leads in the channels (13) to binding posts on the flange (10) from which they are led outside of the pressure vessel. The platinum wire itself (2) is connected to a short stub of 0.5 mm platinum wire (14) at either end by means of a small gold sphere (15), formed on the end of the platinum with a microtorch. It has been found that the gold-platinum alloy produced in this process enables the 7 ,um platinum wire to be secured in a sound mechanical joint with low electrical resistance. A t the lower end the platinum stub is spot welded to a copper rod (16) (mass 75 mg) which passes through the lower terminal post (4). This copper rod is employed to apply the initial tension to the wire during assembly in a manner to be described below. A t the upper end the platinum stub (14) is spot welded to a short length of 0.5 mm diameter gold wire (17) which is in turn spot welded to the beryllium-copper spring (18). The intermediate gold section is necessary because it proved impossible to achieve a satisfactory mechanical joint by direct spot welding of the platinum. Finally, the upper end of the spring is spot welded to the upper terminal post (3). Unlike earlier versions of gas-phase hot-wire cells (Assael et a1 1981. Kestin et a1 1980) the spring in the present arrangement is placed above the wire. This ensures that the weight of the spring makes no contribution to the stress on the wire during assembly. Any such

A transient hot-wire cellf o r thermal condtictiuity measurements

contribution is difficult to estimate and would invalidate the analysis of the preceding section. The assembly of the wire and its supports is performed in a specially constructed horizontal jig outside of the cells. All operations are carried out under a stereomicroscope with micromanipulators to avoid unnecessary handling of the wire. The entire wire assembly is then transferred to the cell and fixed in position before the jig is removed. Subsequently the active half of the cell is placed in a vertical position so that the weight (16) passes freely through the hole in the terminal post (4) and loads the wire by its mass of 75 mg. The weight is then held captive by the screw (19) while the wires are annealed. Vines and Wise (1941) indicate that a short period at 700 K is sufficient to recrystallise pure platinum, so that a procedure was employed in which the wire was heated electrically to a yellow-red glow for 15 minutes and then cooled slowly. The wires for both cells were treated in an identical fashion to ensure the similar metallurgical properties necessary for a satisfactory compensation of end effects (Kestin and Wakeham 1978). Following the annealing process the wires are retensioned at room temperature by releasing the set screw (19) so that the copper weight (16) hangs freely. The set screw is then retightened without disturbing the weight so that the wire is loaded at room temperature by exactly 75 mg. To complete the assembly the copper weight is soldered to the base of the terminal post (4) with a high-temperature soft solder to provide good electrical contact. It was found that the combination of a mechanical fixture plus soldering was essential because the solder tended to yield under the imposed stress at a temperature considerably below its melting point of 570 K. The principles of the cell design described here can obviously be carried over to a different set of operating conditions. for example at much higher temperatures, by a suitable choice of materials. gas, qo. according to the equation (Maitland et a1 1981) 2aOiw

3RgoF(T)

= 2.500

4. Trial measurements The cells described in the previous section have been employed for a preliminary series of measurements in order to ensure their correct operation. The characteristics of the cells are collected in table 1. The lengths of the wires were measured by means of a cathetometer, and their diameters with the aid of electron micrographs and a number of samples. The essential components of the remainder of the instrumentation employed have been described elsewhere (Assael et a1 1980. Pittman 1968). There are two necessary conditions which must be satisfied by any transient hot-wire instrument for the measurement of thermal conductivity. First, the measured temperature rise of a central section of the longer wire ATw,suitably corrected for the influence of the wire heat capacity and the outer boundary of the cell, should be a linear function of the logarithm of the time. t. which has elapsed since initiation of the heating. Secondly. for a monatomic gas such as argon. the measured thermal conductivity in the limit of zero density, l o , must be thermodynamically consistent with the viscosity of the same

where R is the universal gas constant and M the molecular weight of the gas. The factor F(T)? which is near unity. introduces small corrections to the first-order kinetic theory relationship and may be obtained with an uncertainty of no more than &O. 10h from a suitable intermolecular pair potential (Maitland et a1 198 1). W e have carried out measurements of the thermal conductivity of argon at two temperatures 308 K and 337 K. Following our earlier practice (Assael et a1 1981) the measurements along each isotherm have been performed as a function of density and the zero-density values deduced by extrapolation. Figure 2 contains the results of the temperature rise measurements for one run at a temperature of 337 K at a pressure of 2 MPa. The results are plotted in the form of deviations of the experimental points from a straight line fitted to the data. It can be seen that the deviations are essentially random and that they d o not exceed &0.05%, which corresponds to the precision of the temperature rise measurements (Assael et a1 198 I). It is concluded on the basis of this. and many other similar plots. that the present cells operate in accord with the mathematical model of them. Figure 3 contains a plot of the experimental thermal conductivity data for argon for the two isotherms. Owing to the possible degradation of the cells over a period of time due to creep, the measurements at a temperature of 308 K have been repeated after the cells had been maintained at the higher temperature for 150 days. The repeated measurements depart from those of the original set by less than 0.4% which is commensurate with the estimated precision of the individual measurements of &0.2%. It can be seen that the experimental data for each isotherm are in a smooth curve. The data have been represented by a polynomial in density for the purposes of extrapolation (Assael et a1 1981) and do not deviate from it by more than & 0.2%. Table 2 lists the derived values of the zero-density thermal conductivity together with the values of the zero-density viscosity obtained from the work of Kestin et a1 (1972), and the kinetic theory correction factor F(T). The thermal conductivity

0.10 r

I
...

!?
3 -005 c
O W

Table 1. The characteristics of the hot-wire cells.

Long wire Wire length Wire radius Wire resistance at 304 K Cell diameter 0.16058 k 0.00005 m 4.26 f 0.1 ,um 377.5 R 13.0 f 0.1 mm Short wire 0.061 12 h 0.00005 m 4.26 0.1 ,um

I * i : ; 8i
. *
' *

-0.10

,
I

145.0 R 13.0 0.1 mm

841

E N Haran and W'A Wakeham Castro C A N, Calado J C G , Dix M and Wakeham W A 1976 An apparatus to measure the thermal conductivity of liquids J . Phys. E: Sci. Instrum. 9 1073-80 Castro C A N and Wakeham W A 1977 Experimental aspects of the transient hot-wire technique for thermal conductivity measurements Thermal Conductivity 15 235-43 Clifford A A, Kestin J and Wakeham W A 1980 A further contribution to the theory of the transient hot-wire technique for thermal conductivity measurements Physica lOOA 310-5 de Groot J J, Kestin J and Sookiazian H 1974 Instrument to measure the thermal conductivity of gases Phjssica 15 454-82 Haarman J W 1971 A contribution to the theory of the transient hot-wire method Physica 52 605-19 Healy J J, de Groot J J and Kestin J 1976 The theory of the transient hot-wire method for measuring thermal conductivity Physica 82C 392-408 Kestin J: Paul R, Clifford A A and Wakeham W A 1980 Absolute determination of the thermal conductivity of the noble gases at room temperature and up to 35 MPa Physica lOOA 349-69 Kestin J, R o S T and Wakeham W A 1972 The viscosity of the noble gases in the temperature rpnge 25-700 "C J . Chem. Phys. 56 4 1 19-24 Kestin J and Lt7akeham W A 1978 A contribution to the theory of the transient hot-wire technique for thermal conductivity measurements Physica 92A 102-16 Maitland G C , Rigby M, Smith E G and Wakeham W A 198 1 Intermolecular Forces: Their Origin and Determinatior? (Oxford: Clarendon) Chap. 5 Menashe J and Wakeham W A 1981 Absolute measurements of the thermal conductivity of liquids at pressures up to 500 MPa Ber. Bunsenges Phys. Chem. 85 340-7 Pittman J F T 1969 PhD Thesis Imperial College. London Polakowski N H 1966 Strength and Structure ofEngineering Materials (New York: Prentice-Hall) Van Bueren I3 G 1960 Imperfections in Crj'stals (Amsterdam: North-Holland) p 229 Vines R F and Wise E M 1941 Platinum Metals and Their A I ~ o J(London: International Nickel Company) ~s

" I

D e n s i t y p ( kg

Figure 3. The thermal conductivity of argon as a function of density along two isotherms: 0. T= 308.15 K, original measurements; 0, T= 308.15 K. repeated measurements after holding for 150 days at 337.15 K: . 337 K. , T=

Table 2. The thermodynamic consistency of the experimental data for the thermal conductivity and viscosity of argon.

308.15 18.05 f 0.05 308.15 18.07 0.05 337.15 19.48 rt 0.05

23.24 i 0.04 1.0007 2.486 rt 0.010 23.24 f 0.04 1.0007 2.489 + 0.010 25.03 rt 0.05 1.0010 2.490 rt 0.01 1

data have an estimated accuracy of &0.3%, and the viscosity data one of +0.20/0 (Kestin et a1 1972). It can be seen that. within these uncertainty limits. the experimental values of the group 2&M/3RqoF( T ) are essentially consistent with the theoretical expectation. These results are taken as evidence for the correct operation of the present thermal conductivity cells. No significance is attached to the small discrepancies between the present measurements of the thermal conductivity of argon and those of our earlier work (Assael et a1 1981, Kestin et a1 1980) since they lie within the mutual uncertainty band. Acknowledgments The authors would like to express their gratitude to Mr A Lucas for his help in manufacturing the thermal conductivity cells and to Mr M Mustafa for his assistance with the preparation of the drawings. The work described in the paper was carried out with financial support from the Science and Engineering Research Council. References Assael M J, Dix M, Lucas A and Wakeham W A 198 1 An absolute determination of the thermal conductivity of the noble gases and two of their binary mixtures as a function of density J. Chem. Soc. Faraday Trans. I I 1 439-64 Assael M J and Wakeham W A 198 1 Thermal conductivity of four polyatomic gases J. Chem. Soc. Faraday Trans. I I7 697-707 Carreker R P 1950 Plastic flow o f platinum wires J. Appl. Phys. 21 1289-96 842