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Int J Thermophys (2011) 32:361–371 DOI 10.1007/s10765-011-0944-8

Calibration of Radiation Thermometry Fixed Points Using Au/Pt Thermocouples

F. Jahan · M. J. Ballico

Received: 6 April 2010 / Accepted: 3 February 2011 / Published online: 2 March 2011 © Springer Science+Business Media, LLC 2011

Abstract At NMIA, radiation thermometers are calibrated by comparison with a number of reference radiation thermometers which are themselves calibrated using fixed-point cells on the ITS-90 temperature scale (In, Sn, Zn, Al, Ag, and Au). The suitability of NMIA fixed-point cells used for standard platinum resistance thermom- eters (SPRTs) is evaluated by the comparison of ensembles of cells at each fixed point, and by participation in the international BIPM Key-Comparisons K3 and K4. How- ever, the NMIA fixed-point cells used for radiation thermometry are typically much smaller (only 110 mm in length) and the thermowell length immersed in the metal much shorter (85 mm) than those used for SPRTs. Further, the insulation at the front of the crucible needs to accommodate the F/10 viewing cone of the radiation thermometers, so significant temperature gradients exist near the top of the crucible. As a conse- quence, the conduction errors obtained using SPRTs are too large to be of practical use. A convenient methodology based on the use of a Au/Pt thermocouple, together with a protective tube assembly to reduce conduction errors, has been developed. This allows the convenient measurement of the phase transition temperature traceable, at the 30 mK level, to the fixed-point cells used at NMIA to realize and maintain the ITS-90 scale. As the measurements are made in situ, the temperature environment, and hence the geometry and formation of the liquid–solid interface during melting and freezing, are similar to that occurring when used with radiation thermometers. Results are presented for ITS-90 fixed points up to Ag, establishing formal traceability of radiation thermometry fixed-point cells to NMIA’s primary ITS-90 cells.

Keywords

Au/Pt thermocouples · Conduction error · Fixed point · Melt–freeze

F. Jahan ( B) · M. J. Ballico National Measurement Institute of Australia, Lindfield, Australia e-mail: Ferdouse.Jahan@measurement.gov.au

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1 Introduction

Traditionally, the fixed-point cells used to define the ITS-90 temperature scale were regarded as primary reference standards, as long as material of sufficient purity was used in their construction and the quality of the phase-transition plateaus was suffi- ciently good. The typical calibration uncertainty for NMIA’s primary radiation ther- mometers is at the 0 .1 C level, so uncertainties in the primary fixed points at the 50 mK level are adequate. As metal at the 1 ppm impurity level is readily available for constructing fixed points, and this corresponds to uncertainties at the <1 mK level, issues of source material purity may be neglected. However, fixed points for radiation thermometry differ from those used to realize the ITS-90 using SPRTs in several ways, giving rise to a number of “furnace-effects” as follows.

(i)

The graphite well is usually much shorter than those used for SPRTs. In the latter, the well must typically be immersed 170 mm to 220 mm into the metal, to reduce conduction errors in the SPRT to a sufficiently small level. However, for pyrometry fixed points, a depth of less than 100 mm can achieve a suitably high cavity emissivity, and longer cavities lead to viewing an increasing proportion of the cavity wall (due to the finite F-number of the pyrometer). A consequence is that during melting/freezing, when the outer surface of the crucible is a few degrees hotter/colder than the liquid–solid interface, a larger fraction of this temperature difference may be conducted to the cavity base.

(ii)

The crucible is usually mounted horizontally in a furnace rather than vertically, and as a consequence, the heat transfer to the melting or freezing metal is far from cylindrically symmetric. For example, the crucible has much better ther- mal contact with the furnace on its underside. Consequently, the liquid–solid interface may not properly surround the blackbody cavity.

(iii)

The low F-number of the radiation thermometers used to view the blackbody cavity does not allow the crucible to be placed deeply inside a long furnace. Consequently, the axial temperature gradients are generally much larger, and the liquid–solid interface often advances axially rather than radially as for SPRT fixed points.

(iv)

Unlike fixed points for SPRT use, no additional “inner nucleation” is performed to provide a second solid–liquid interface, over the inner well. Consequently, any breaks in the solid–liquid interface surrounding the thermowell will provide a heat leakage from the well to the furnace.

At present, any systematic errors arising from furnace-effect factors are assessed in two ways: (a) first, the use of redundant fixed points (e.g., fitting the Sakuma–Hattori interpolation equation [1] using Zn, Al, and Au points and checking the measured temperature at the Ag point) and (b) secondly, examination of the melt–freeze dif- ferences and the flatness of the freeze plateau. Our experience is that the uncertainty we assign to the radiation thermometry fixed points is dominated by the measured melt–freeze differences and plateau flatness. However, as part of ongoing work to improve the quality assurance of NMIA’s calibration services, we wish to develop a formal traceability of radiation thermometry fixed points to NMIA primary standards validated by participation in a CIPM key comparison. This would confirm that the

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uncertainty estimate based on the observed melt–freeze behavior adequately covers the systematic errors arising from furnace effects. In the region above 960 C, the key-comparison K5 provides assurance for the Au points that NMIA uses to real- ize ITS-90. In the region up to 960 C, however, the key-comparisons K3 and K4 considered only the large fixed points used for SPRT calibration. We sought a meth- odology to calibrate the fixed-point cells together with furnace assemblies used in our Radiation Thermometry Laboratory. Initial experiments using SPRTs to calibrate radiation-thermometry fixed points quickly determined that although SPRTs can be used to measure the temperature at the mK level, the conduction errors when used in the short cells led to large uncertainties. We therefore attempted to use Au/Pt ther- mocouples, which, although only able to achieve 30 mK level uncertainties, offered significantly smaller conduction errors. This approach has allowed NMI to formally connect the radiation-thermometry fixed points to key comparisons, and to validate the uncertainty estimates based on the measured melt–freeze behavior.

2 Experimental Details

The NMIA radiation-thermometry fixed-point cells [2,3] are graphite crucibles 95 mm in length and 43 mm in diameter, containing about 47 cm 3 metal. Figure 1 shows a schematic diagram of a crucible. A re-entrant graphite well 85 mm in length forms the blackbody cavity. The Al and Ag cell wells have an 8 mm ID, as they are used with visible or near-IR radiation thermometers with small “size-of-source effects” (SSE), whereas the Sn and Zn cells, which are used with longer wavelength pyrometers with poorer SSE, have 14 mm ID wells. They are held in 50 mm ID Pyrex tubes (for In, Sn, and Zn) or fused quartz tubes (for Al and Ag), with a series of graphite rings with increasing internal diameter from the crucible to the end of the tube to give a clear viewing path for the viewing system of the radiation thermometers. The In and Sn cells are held in a closed-end Hg heatpipe furnace liner, the Zn cell in a closed-end Cs heatpipe, and the Al and Ag cells in a Na heatpipe liner open at both the front and the rear. All the furnaces are mounted horizontally. The front of the crucible is approx- imately 100 mm from the front of the furnace liner. During melt–freeze realization, the assembly is filled with high-purity argon (Ar) and held at a slight overpressure of Ar gas when not being viewed by the radiation thermometers. Freezes and melts generally have a duration of (1 to 2) h when the furnace temperature is held at 3 C to 5 C above or below the nominal metal freezing point. No additional inner nucleation is used, although some of the fixed points require a gentle shake to initiate nucleation. Three NMIA-design Au/Pt thermocouples were used to measure the temperature of the radiation-thermometry fixed points. They consist of 0.5 mm diameter high-purity Au and Pt wires in a 4.75 mm diameter high-purity recrystallized alumina twin-bore insulator. Further construction details are given in [4,5]. One advantage of this design is that it can be used in vertical as well as horizontal furnaces, as it does not use a fragile expansion coil. This design is also insensitive to mechanical and thermal shock [4] and can be put directly into the Ag-point furnace at 960 C, unlike an SPRT, which needs to be pre-heated gradually from 440 C to 960 C, before use at the Ag point. The Au/Pt thermocouples were calibrated [6] using NMIA ITS-90 fixed points: ice

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Schematic diagram

of a radiation-thermometry fixed-point crucible

Fig. 1

85 mm 43 mm 30 mm 95 mm
85 mm
43 mm
30 mm
95 mm

point, Ga, Sn, Zn, Al, and Ag. A 7 mm OD sealed-end quartz tube is used to sepa- rate the thermocouple from the fixed-point cells and prevent cross contamination. The reference junction was immersed 180 mm into a crushed ice slurry in a 30 cm deep Dewar. Electrical measurements were performed using an HP34420A nanovoltmeter. The series of graphite rings of increasing diameter placed at the front of the cruci- ble for radiation thermometry provide very poor thermal contact (a 10 mm to 15 mm air gap) between the furnace tube and the thermocouple, and inadequate immersion could be achieved with this arrangement. Instead, several thin carbon disks separated by 10 mm long quartz tube spacers were used in the region from the front of the crucible to the front of the furnace. This significantly increased the thermal contact

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from the furnace to the guide tube, without significant disruption to the temperature environment near the crucible. This is supported by the observation that the furnace set points are unchanged, and the melt- and freeze-plateaus have the same duration.

A 3 mm thick carbon sleeve was used in the Sn and Zn cells to improve the thermal

contact between the 7 mm quartz thermocouple tube and the 14 mm blackbody cavity.

3 Results and Discussion

For each of the NMIA’s radiation thermometry fixed-point cells, several calibrated

Au/Pt thermocouples were used to realize several melt–freeze plateaus. Typical results

in each of the fixed point cells are shown in Figs. 2, 3, 4, 5, and 6. The average results

for each thermocouple are presented in Table 1 and compared to the values obtained in NMIA’s reference cells (only freeze values are considered). There is excellent agree- ment between the cell temperature difference results obtained by the two (three for Al) thermocouples. While the measured values of the freezing plateaus of the radiation thermometry cells adequately serve the purpose of providing formal traceability of these cells to the NMIA reference cells, a more detailed examination of the curves provided some important additional information about the freezing and melting processes. When the radiation thermometry Zn cell is used to calibrate radiation thermometers, a melt–freeze difference of about 20 mK is observed, and prior to this measurement, it

4952 4945 0.12 °C 30 mK 1 cm out 4950 4944 4943 4948 4942 0
4952
4945
0.12 °C
30 mK
1 cm out
4950
4944
4943
4948
4942
0
15
30
45
60
4946
Reference Zn cell
4944
4942
0
50
100
150
200
250
300
EMF , μV

Time , min

Fig. 2 Freezing plateau of a radiation-thermometry Zn point realized by Au/Pt thermocouple. A conduction error test is shown in the inset. The EMF value obtained in the reference Zn cell is also shown

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2.569 60 mK f u ll immersion 2.568 Reference Zn cell 2.567 10 mm ou
2.569
60 mK
f
u ll immersion
2.568
Reference Zn cell
2.567
10 mm ou t
20
mm out
30 mm o ut
2.566
2.565
60
80
100
120
140
Resistance ratio

Time , min

Fig. 3

error test. The resistance ratio obtained in the reference Zn cell is also shown

Freezing plateau of a radiation thermometry Zn point realized by an SPRT, showing a conduction

was unclear how much systematic error in the actual Zn-point temperature this implied. The Au/Pt thermocouple data in Fig. 2 also show a melt–freeze difference (0 .1 C), although larger than that obtained with radiation thermometry. The conduction-error test, in which the thermocouple is withdrawn by 10 mm, shows a change of only about 15 mK, confirming that the melt–freeze difference is a real effect. The thermocou- ple data show that the actual cell temperature is within the range of the melt–freeze data, confirming that this effect arises from the conduction effects within the cell, and that the melt–freeze range provides a good estimate of the associated uncertainty. For comparison, a freezing plateau of the same Zn cell realized by an SPRT in this same assembly is shown in Fig. 3. With the SPRT withdrawn by 20 mm, the conduction errors are significant, about 0 .12 C, consistent with the measured freeze value at full immersion being apparently 60 mK lower than the reference cell; as expected, the 40 mm long SPRT sensor is more sensitive to conduction from the furnace. The thermocouple results obtained using the Sn cell (Fig. 4) show a nearly 0 .1 C difference between the melt and the freeze curves, and indicate that both the melt and the freeze are biased towards the furnace temperature outside the cell (the melt is “higher” and the freeze is “lower”). When the cell is viewed by a radiation thermom- eter a similar, but slightly smaller difference of 40 mK to 70 mK is observed. These thermocouple results support the use of the melt–freeze difference as an uncertainty estimate.

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367

2242

2240

2238

2236 2234 EMF , Vμ
2236
2234
EMF ,

2232

367 2242 2240 2238 2236 2234 EMF , Vμ 2232 1 cm o u t 150

1 cm o u t

150 mK

Reference Sn cell

2230

0

50

100

150

200

Time, min

250

300

350

Fig. 4

The EMF value obtained in the reference cell is also shown

Typical melt–freeze curve of a radiation-thermometry Sn point realized by a Au/Pt thermocouple.

Measurements using the Au/Pt thermocouple in the Al and Ag cells (Figs. 5, 6) show much smaller conduction errors (4 mK and 10 mK, respectively) than the results obtained for the Sn and Zn cells, attributable to the smaller diameter thermowells in these cells. The measured melt–freeze differences for the Al and Ag cells are also much smaller than for the Sn and Zn cells, indicating smaller furnace effects. This is also observed when the cells are used for radiation thermometry, where melt–freeze differ- ences of about 10 mK are observed. Nonetheless, the measured melt–freeze difference can be used to give a good estimate of the error in the actual plateau temperature. Table 2 gives typical values of the uncertainty components in the measurement of temperature differences between the cells. The dominant contributions to the uncer- tainty arise from the calibration uncertainty of the Au/Pt thermocouple and from the conduction errors in the use of the thermocouple to measure the radiation thermometry cells. The thermocouple calibration uncertainty [6] is mainly due to the measured inho- mogeneity of the thermocouple wires (Fig. 7). At NMIA, thermocouple inhomogeneity is measured [7] for every thermocouple and included in its calibration uncertainty. It is important that this effect be properly considered, as the immersion depths in the ITS-90 reference cell furnaces are much deeper than in the radiation thermometry furnaces. Consequently, a different region of the thermocouple wire generates the thermoelectric signal in each cell. As it is already included in the calibration uncer- tainty of the thermocouple, it is not necessary to add this component again in Table 2. The other significant uncertainty contribution, the conduction error, is experimentally

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9323 50 mK 9322 9321 9320 Reference Al cell 1 cm out 9319 9318 9317
9323
50 mK
9322
9321
9320
Reference Al cell
1 cm out
9319
9318
9317
0
50
100
150
200
280
300
320
EMF , μV

Time , min

Fig. 5 Typical melt–freeze curve of radiation thermometry Al point realized by a Au/Pt thermocouple showing a conduction error test. The EMF value obtained in the reference Al cell is shown

determined for each cell by withdrawing the thermocouple by 10 mm, and noting the change in the measured EMF. For these thermocouples we have determined [8] that the conduction error roughly doubles for each 8 mm to 10 mm of immersion in a close fitting tube, so we use this value as the uncertainty contribution for this term. The conduction error in the Sn and Zn cells is significantly higher than for the Al and Ag cells, and this is attributed to the larger well diameter for these cells, and the poorer radiative heat transfer at low temperatures. Other minor contributions to the uncertainty arise from: the choice of position on the freezing plateau, which we take as the width of the central half of the freezing plateau; the estimated 5 mK uncertainty in the crushed-ice-point reference junction; the reproducibility of the plateau between realizations; and the calibration and drift of the 34420A nanovoltmeter used to measure the thermocouple EMF. Considering the estimated measurement uncertainties, the measured temperatures of the freezing plateaus of the radiation thermometry cells can be considered to be consistent with those of the NMIA reference cells [9].

4 Conclusions

We have demonstrated that the temperatures realized by the small fixed-point cell assemblies used for radiation thermometry can be measured traceably to ITS-90 fixed

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EMF , μ V

16121.5

16121.0

16120.5

16120.0

16119.5

16119.0

16118.5

0

30

20 mK

Reference Ag cell

16119.5 16119.0 16118.5 0 30 20 m K Reference A g cell 1 cm withdrawn 60

1 cm withdrawn

60

90

Time , min

120

150

Fig. 6 Typical melt–freeze curve of radiation thermometry Ag point realized by a Au/Pt thermocouple shows conduction error test during freeze. The EMF value obtained in the reference Ag cell is also shown

Table 1 Summary of the average EMF for several Au/Pt thermocouples in the freezing plateaus of the NMIA reference ITS-90 fixed points and the radiation thermometry fixed points

Reference cell

Radiation

TC serial

Average EMF ( µ V) measured at the fixed points

T DUT T ITS90

thermometry cell

number

(mK)

 

NMI

Radiation

reference

thermometry

cell

cell

Ag2006/1

Ag/P2

PtAu-0805

16119 . 80

16120 . 02

+8 ± 31

 

PtAu-0203

16120 . 20

16119. 96

10 ± 31

Al2006/2

Al/85

PtAu-0804

9320 . 20

9320 . 04

8 ± 23

 

PtAu-0805

9319. 96

9320 . 03

+3 ± 23

PtAu-0203

9320 . 12

9319. 98

7 ± 23

Zn02/02

Zn/95

PtAu-0804

4945.

48

4944 . 99

30 ± 29

 

PtAu-0805

4945.

18

4944 . 72

31 ± 29

Sn95/1

Sn/95

PtAu-0801

2235.

64

2235.

11

41 ± 52

 

PtAu-0203

2235.

90

2235.

14

57 ± 52

The difference and its associated expanded (k = 2) uncertainty are also given

points using simple and robust Au/Pt thermocouples. The method allows the in situ measurement of the melt–freeze plateaus of the radiation thermometry fixed-point cells, using the same furnaces with which they are normally used. The uncertainty

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μV,

ΔE

Fig. 7

-0.2

-0.4

-0.6

-0.8

-1.0

-1.2

-1.4

-1.6

-1.8

16 mK TC: P tAu TC: P tAu -0805 -0203 TC: P tAu -0804 100
16 mK
TC: P tAu
TC: P tAu
-0805
-0203
TC: P tAu -0804
100
200
300
400
500
600

Immersion , mm

Thermoelectric scans of three Au/Pt thermocouples at 200 C indicating their level of homogeneity

Table 2

points using an “Au/Pt thermocouple”

Typical values of the uncertainty components for the calibration of radiation thermometry fixed

Components

Standard uncertainties, u i ( µ V)

 

Ag

Al

Zn

Sn

Uncertainty of Au–Pt TC

0.320

0.184

0.117

0.089

Plateau determination

0.10

0.10

0.10

0.15

Conduction error

0.130

0.05

0.15

0.25

Reference junction temperature

0.062

0.05

0.041

0.031

Reproducibility

0.05

0.03

0.08

0.1

Calibration of DVM

0.05

0.05

0.05

0.05

Drift/use of DVM

0.096

0.056

0.028

0.013

Combined uncertainty, u c

0.385

0.237

0.241

0.327

Expanded uncertainty, U 95 (k = 2)

0.78

0.47

0.474

0.643

U 95 in mK

31

23

29

52

achieved, typically 30 mK, is sufficiently low to allow confirmation that melt–freeze differences provide a reasonable estimate of the errors due to furnace effects for these cells; however, conduction errors remain the limiting factor for measurement of the large aperture low-temperature radiation thermometry cells.

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Acknowledgment

assembly and general assistance during measurement.

We would like to acknowledge Mr. Steve Meszaros for constructing the parts of the

References

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