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Electrical
andThermoelectric
Properties
of Some
Metallic
Thermoelectric
Materials’
H, CHANGS
(Received 12 June 1969)
\ Precision non-inductive
Support
framewor?
Radiation
shields -
*.
r
*. _.....*
a.c.d~fferentlal voltameter
Powerstat
it
Alumina heater
00
reference
-
position
-
Fig. 1.
netted in series with the sample to the power supply, of a 5 in. long alumina tube (Degussa Catalog No.
into the voltage drop across the standard resistor, 80-67-065, bore diameter = 0.015 in., outside dia-
V,, i.e. Equation 3. meter = 0 -685 in. and wall thickness = 0 a085 in.). The
two free ends of the tantalum wire form the power
leads to the heater. The radiation heat loss of the heater
is reduced by placing around the heater three concentric
Apparatus layers of radiation shields made from 1 mil thick titanium
Figure 1 shows the schematic diagram and the details sheets.
of the apparatus used to measure the electrical resistivity At the top and bottom ends of the sample, holes are
of Tophel Special and Cupron Special. The cylindrical drilled to receive alumina rods, & in. dia., which extend
sample rod is O-127 in. in diameter and 5 in. long. to serve as centering and electrical insulating supports.
A 10 mil diameter wire of the same material as that of In the final assembly, the lower alumina sample
the sample is welded at each end of the sample rod. support rod fits into a hole drilled into the base of the
These wires serve as the current carrying leads into the support framework for this purpose. The top alumina
sample. A one inch length, measured one half inch above centering rod passes through a hole drilled in the center
and one half inch below the longitudinal mid-point of of the top plate of the framework, and is free to move
the sample is considered the test section. Two 5 mil up and down to allow for the thermal expansion of the
diameter wires, of the same material as that of the cylindrical sample. The alumina sample heater and the
sample, are spot welded on the sample surface, one at radiation shields are supported, both on top and bottom,
each end of that section, These serve as the voltage by 40 mil dia. alumina rods, which are in turn resting
taps for the purpose of measuring the voltage drop on the framework. The entire system is operated in
across the test section precisely. Four pairs of thermo- 1 x 10-e mm of mercury vacuum. Power is supplied to
couples (5 mil dia. Pt-10 per cent Rh) were spot welded the sample heater by powerstat bridges indicated
to the surface of the sample; they are symmetrically schematically on the right side of Fig. 1. The powerstat
located with respect to the midpoint of the sample bridges are connected directly to the output of a Sorensen
(see Fig. 1). Two pairs are located between the voltage 2501 a.c. voltage regulator. The input voltage is regulated
taps, each $ in. away from the mid-point. Two pairs are and controllable to within 10 PV as measured by a
located outside of the voltage taps, each 2 in. away Fluke 931 r.m.s. differential voltmeter. A Dale type
from the mid-point. These thermocouples monitor the (NH-lo) I Sz precision resistor (tolerance 0.05 per cent)
temperature of the sample in the neighborhood of the is connected in series with the cylindrical sample. Both
test section, which is uniformly heated and is expected the voltage drop across the test section of the sample
to be at a uniform temperature. and that of the resistor are measured by Fluke 931 r.m.s.
The co-axial sample heater is made by threading a differential voltmeter.
continuous length of 10 mil diameter tantalum wire Due to the fact that the Sorensen 2501 a.c. voltage
through the 24 bores running longitudinally in the wall regulator functions more precisely with a pure resistive
Electrical and Thermoelectric Properties of Some Metallic Thermoelectric Materials 67
load, a bank of non-inductive resistors (approximately after the sample reached the desired level during heating.
220 Q) is connected in series with the precision resistor The precision of the electrical measurements them-
and the sample for the purpose of attaining the desired selves were within & O-1 per cent. The errors introduced
value of current going through the sample. This circuit in calculating the electrical resistivity were experimental
is connected directly to the output of the Sorensen errors inherent in the measurements of the length
regulator. Furthermore, since the electrical resistance of between the voltage taps and the area of the test section.
the test section is orders of magnitude smaller than The total error in calculating the electrical resistivity
that of the precision resistor, it is desirable to connect was less than 2 per cent, a very precise measurement.
the cylindrical sample next to the low voltage lead of
Results and discussion of results
the power input to the circuit for the most precise
The electrical resistivity of Cupron Special was
measurement possible. This is done in order to reduce
measured in the temperature range between 35 and
the effect due to excessive electronic noise.
Temperature. OK
The thermocouple emfs are measured by a Leeds & 273 373 473 573 673 773 873 373 1073 1173 I 73
Northrup K-5 potentiometer against a zero-degree
reference temperature bath. The distance between the
thermocouples was measured with a Nikon measuring
microscope.
couples monitoring the temperatures of the test section 0 100 200 300 400 500 600 700 800 900 I DO
The electrical resistivity of Tophel Special was the temperature gradient experienced by that portion
measured in the temperature range between 35 and of the sample. Mathematically, the temperature gradient
1000°C. Values obtained are tabulated in Table 2 and is approximated by:
plotted in Fig. 3. The Tophel Special data at room
temperature reported here agree well within 2 per cent dT Tl-Tz AT
dL -x-=AL’ (1)
Temperature, “K
273 373
I
473
1
573
I
673
I
773
/
873
/
973 ICI73
/
1173
I
1273 where AT = the difference between the two tempera-
90 tures, Tl > TZ
AL = the distance between the locations of the
thermocouples.
Judicious choice of Pt-10 per cent Rh and Pt thermo-
couples provided the essential elements in the Seebeck
Coefficient experiment. When the free ends of the
Sample dmension platinum elements from each pair of the two thermo-
Dlo.
0427in.
>&
1~9331n.
couples were attached to the voltage inputs of the
0 Measured by Chang potentiometer, a voltage was registered. This voltage
0 Reported by Wilbur B. Driver Co. is essentially the Seebeck emf generated by a newly
created thermocouple formed with the sample material
/ I I 1 ___--J under study as one element and platinum as the other.
200 loo 200 300 400 500 500 700 800 900 1000
The new thermocouple operates at a hot junction
Temperature I “C
temperature and a cold junction temperature of TI and TZ
Fig. 3.
respectively (TI > Tz).
of the value reported by the Wilbur B. Driver Company The Seebeck Coefficient of the material under test
and it follows the same trend as Tophel, which was with respect to platinum at the average temperature,
reported by the Wilbur B. Driver Company. It is interest- TA = (TI + T2)/2, is defined by Equation 2.
ing to note that Tophel Special, although an alloy,
behaves much like a pure metal in the sense that its aE AE
crpt = ar w KT (2)
electrical resistivity is approximately proportional to the
absolute temperature. where aPt = Seebeck Coefficient of the unknown
material with respect to platinum
Measurements of Seebeck Coefficients of Tophel Special aE = Partial derivative of the Seebeck emf
and Cupron Special
z generated with respect to temperature
Description of the method
In the Seebeck Coefficient experiment, the long, AE = Seebeck emf generated between the pla-
small-diameter, cylindrical sample is heated in such a tinum leads and the material under test
way that it exhibits a longitudinal temperature gradient while subjected to hot and cold junction
in the portion of the sample which is considered to be temperature of TZ and TI respectively
the test section. AT = difference between the hot and cold
Two pairs of thermocouples (Pt-IO per cent Rh junction temperature TI - Tz.
and Pt wires) were attached to the surface of the sample
test section evenly spaced along its axis. Apparatus
The difference between the two temperatures measured Figure 4 shows the schematic diagram of the apparatus
divided by the distance between their locations yields used to measure the Seebeck Coefficient of Tophel
q,Vacuum system
Pow‘erstat
Fig. 4.
Special and Cupron Special. The temperature gradient used to establish the temperature gradient along the
along the axis of the cylindrical sample can be established axis of the cylindrical sample (see Fig. 5).
by either of two methods, the details of which are shown The first method involved heating the sample at the
in Fig. 5. two extreme ends. Two identical heaters, with one
The cylindrical sample rod is 0.128 in. in diameter heater maintained at a higher temperature than the
(average value) and 6 in. long. Four pairs of thermo- other, establish the temperature gradient causing heat
couple (5 mil dia. platinum-10 per cent rhodium) were flow in the sample from the high temperature end to
spot welded to the surface of the sample. They are the low temperature end. Each of the two heaters is
symmetrically located with respect to the longitudinal made by threading a continuous length of 10 mil diameter
mid-point of the sample (see Fig. 4). Two pairs are tantalum wire through the 24 bores running longitudinally
located one half inch away from the mid-point and the in the wall of a one half inch long alumina tube (Degussa
remaining two pairs are located one and one half inches Catalog No. 80-67-065 bore dia. = 15 mils outside
away from the mid-point. These thermocouples serve diameter = O-685 in., and wall thickness = 0.085 in.).
dual functions: they monitor the temperature of the The two free ends of the tantalum wire of each heater
sample surface at the location where they are attached, form the power leads to the heater.
and they contribute their platinum elements as one leg The heaters are placed co-axially around each end
of a new thermocouple which functions with the material of the cylindrical sample, in the manner most conducive
to be tested as the other leg. Two heating methods were to radiant energy transfer between the heaters and the
-Sample Sample
-Alumma heater
Radiation shields
Bottom
alumina heater
LSupporting frame Supporting frame
_To vacuum
Method I system
Fig. 5.
70 H. CHANG
ends of the sample. The radiation heat losses of the Experimental procedure and error
heaters are reduced by placing around the heater three At the start of a Seebeck Coefficient experiment, the
concentric layers of radiation shields. Three layers of test section of the cylindrical sample is brought up to
radiation shields are placed above and below the heaters. the desired temperature gradient by means of the radiant
The shields were fabricated from 1 mil thick titanium heat transfer between the co-axial alumina sample heater
sheets. and the sample.
The second method involving heating the sample with Method I has the advantage of being capable of
a co-axial alumina tube running almost the whole length producing a small temperature gradient with high pre-
of the sample. The heater used here is manufactured in cision, however, it produces a low sample temperature
the exact same fashion as those made for use in Method to heater power ratio due to the high heat losses at the
1, except that the alumina tube employed in this case ends of the heaters. It is, therefore, an excellent method
is 5 in. in length. Inherently, a temperature gradient of heating the sample when the Seebeck Coefficient of
exists in this alumina tube. This is because the radiant the sample material is measured below 100°C. Method 2,
heat is being lost faster at the ends of the heater than on the other hand, yields a much higher temperature
at the center. Similar to Method 1, the thermal radiation gradient with lower precision. Therefore, Method 2 is
heat losses of the heater are reduced by the use of con- found to be more satisfactory in providing the tempera-
centric layers of radiation shields. ture gradient for tests conducted above 100°C.
At the top and bottom ends of the sample, holes are The power input to the sample heater is adjusted to the
drilled to receive alumina rods which extend to serve as appropriate level through the powerstats, in a manner
centering and thermal insulating supports. In the final that the thermocouples attached to the sample surface
assembly, the lower alumina sample support rod fits would indicate the desired temperature gradient. After
into a hole drilled into the base of the support frame- the temperature of the entire system is established, the
work for this purpose. The top alumina centering rod temperature of all four thermocouples is measured and
passes through a hole drilled in the centre of the top the Seebeck emf’s generated between the platinum legs
plate of the framework and is free to move up and down of any two adjacent thermocouples and the material
to allow for thermal expansion of the cylindrical sample. to be tested between the two thermocouples are measured
The alumina sample heater and the radiation shields and recorded. In this manner, each test would result in
are supported both on top and bottom by 40 mil diameter at least three independent sets of data, which may be
alumina rods, which are in turn resting on the frame- used to advantage in reducing the total number of tests.
work as shown in Fig. 5. The above test procedure is repeated at every 50°C of
The entire system is operated in 1 x 10-s mm of rise of the average temperature of the test section between
mercury vacuum. Power is supplied to the sample the temperature range of 30 and 800°C. Experimentally,
heater by powerstat bridges indicated schematically in it is found that a 10°C difference measured between any
Insert AA of Fig. 4. The powerstat bridges are con- two adjacent thermocouples yields the most accurate
nected directly to the output of a Sorensen 2501 a.c. Seebeck Coefficients for the following reasons:
voltage regulator. The input voltage to the heater is
regulated and controllable to within 10 mV as measured 1. As the temperature difference measured between
by a Fluke 931 PB r.m.s. differential voltmeter. The any two adjacent thermocouples increases the
thermocouple emf is measured by a Leeds & Northrup approximation of AEjAT representing aEjaT = apt
K-5 potentiometer against a 0” reference temperature becomes less and less accurate.
bath. The distance between the thermocouples was 2. As the temperature difference measured between
measured by a Nikon measuring microscope. any two adjacent thermocouples decreases, the
inaccuracy of the calculation of apt. 273 373 473 573 673 773 873 973
I I I I
Theoretically, therefore, the temperature measured
E I ---o-- Calculated from W.El0EMFV.S.T. data
between any two adjacent thermocoupIes should be -x- Measured by Chang
made as small as the accuracy of the calculated apt & Length
Sample dimension 0.28in. 6-O in.
permits. However, the errors introduced are usually Ni Cu Mn
from the calculation of the temperature difference when Approximate composition 39.7 59.9 0.4
-6Oi I I I I I
100 200 3210 400 500 600 700 I
Temperature, “C
Fig. 7.
absolute Seebeck Coefficient of Tophel Special (Ni; Cr resistivities and Seebeck Coefficients of Tophel Special
9 *25 per cent), each at a different temperature. Three and Cupron Special can be adapted for similar measure-
of these values fall in the temperature range of the ments on metals and alloys.
present measured data. The absolute Seebeck Coefficient
of Tophel Special can be transformed to the relative
Acknowledgement--The author would like to express his gratitude
Seebeck Coefficient of Tophel Special with respect to to the Atomic Energy Commission and the Nuclear Materials and
platinum by subtracting out the absolute Seebeck Equipment Corporation for their equipment and financial support
Coefficient of platinum given in Ref. [4]. For additional of this work. Appreciation is extended to Mr. Stanley Stein for his
assistance in the laboratory.
comparison, the relative Seebeck Coefficients, so trans-
formed, are also plotted in Fig. 6 as dark circles. The
agreement between the transformed value and the present
measured values are also excellent. References
[I] H. Chang and M. G. Blair, A longitudinal symmetrical heat
Conclusions flow apparatus for the determination of the thermal con-
ductivity of metals and their alloys, Thermal Conductivity-Proc.
The measured electrical resistivities and the Seebeck 7th Co& NBS Special PubI. 302, p. 355, September (1968).
Coefficients of Tophel Special and Cupron Special are [2] H. Chang and M. G. Blair, A longitudinal symmetrical heat
flow apparatus for the determination of the thermal con-
precise and accurate. This conclusion is substantiated ductivity of metals and their alloys: on armco iron, Proc. 8rh
by the fact that the reproducibility of the data is excellent Co& on Thermal Conductivity, Purdue Univ., October (1968).
and that a very close agreement exists between the [3] T. P. Wang, C. D. Starr and N. Brown, Thermoelectric charac-
teristics of binary alloys and nickels, Acta metall. 14 (1966).
present data and those previously available. [4] J. Nystrom, Thomson coefficients for copper at high tem-
The method used for the measurements of electrical peratures, Ark. Mat. Astr. Fys. 34A (1937).