The Method of Instantaneous Comparisons applied to the Calibration of SPRTs in Liquid Nitrogen and Liquid Argon

R L Rusby, G J M Sutton, L R Stanger and R I Veltcheva

National Physical Laboratory, Hampton Road, Teddington, TW11 0LW, UK Email: richard.rusby@npl.co.uk

Is temperature drift a problem in your comparison calibrations? Then the method of instantaneous comparisons is for you!
The method
Instead of measuring the SPRT resistances separately with respect to a standard resistor, a calibrated SPRT is selected as the reference, Rref . All the other resistors (standard Rs, and SPRTs R1, R2, etc.) are measured relative to it. Step 1: measure Rs / Rref to obtain the value of Rref, Step 2; measure R1 / Rref from which R1 is determined, Step 3: similarly for R2, R3, etc. The R1 / Rref etc., are essentially instantaneous comparisons with respect to Rref . For like thermometers they are substantially independent of temperature: between LN2 and LAr the SPRT ratios typically change by < ~200 parts in 106, equivalent to about 1 mK per kelvin temperature change. Therefore  they are substantially independent of (uniform) temperature changes during the comparison sequence, and the comparisons apply as if they had all been made at the initial  temperature of Rref . The ratios can be measured at an additional current to establish the self-heating corrections, with no concerns over drift except in the case of Rs / Rref. Three experiments are described in which the method is applied to comparisons of SPRTs in liquid nitrogen and liquid argon in a simple apparatus without active control. Repeatabilities of < ~0.1 mK are achieved, in spite of significant temperature drifts.

L-SPRT

Further considerations
Because the ratios are independent of temperature, the exact value of Rref is not important: the (Rref , T90) datum can be taken at any convenient near-by point, or from a value in a previous experiment or in a certificate. What matters is that the ratios are accurately measured and that Rref is accurately related to T90.

Loose foam cover

Guide tube support plate 1 of 4 SPRT guide tubes 1 of 3 steel support rods Liquid nitrogen

Conclusions
In the three experiments it has been found that C-SPRTs can be compared with standard deviations <~0.1 mK five NPL reference C-SPRTs have been stable within 0.15 mK over 37 years differences between measurements in two argon L-SPRT triple- point cells have been confirmed dynamic comparisons have been made with reasonable accuracy in a warm-up from 77 K to 293 K.

Dewar vessel (stainless steel)

2 of 4 connections to C-SPRT

Foam plugs

Foam liner C-SPRT Copper block

The method has potential for application in all comparisons of like thermometers, eg comparisons in liquid baths, metal blocks and furnaces, profiling the baths, etc, to detect non-uniformity, investigations into (eg) thermometer cycling stability and hysteresis comparisons of thermometers in conditions of rapid drift.

Polystyrene platform Vacuum

Figure 1: the comparison apparatus, consisting of a copper block, resting on a polystyrene platform, surrounded by porous foam insulation, located in a stainless steel 8-litre liquid nitrogen Dewar (vacuum) vessel 15 cm inside diameter by 48 cm deep. The hold-time is about 24 h. L-SPRTs are inserted through guide-tubes at the top plate. C-SPRTs are located in close-fitting holes, and four electrical connections lead out to the measuring system (selector switch and ASL F18 bridge).

In comparing industrial PRTs and L-SPRTs in water baths, the ratio sensitivity is still only ~ 14 mK per kelvin change in temperature.

Experiment 1. Calibration of six C-SPRTs by comparison with NPL reference C-SPRTs

Six C-SPRTs (H. Tinsley Co) were calibrated against two NPL reference C-SPRTs (Leeds and Northrup) in liquid nitrogen (77.3 K) and liquid argon (87.3 K). Bridge readings were recorded about every 2 s. The first 10 readings were discarded and the next 10 readings were averaged, to give one measurement about every 40 s. Measurements were made at currents of 1 mA, 2 mA and 1 mA. A 6 standard resistor was used so that Rs/Rref1 ~1.25 (the exact value of Rs is not important). The differences in LAr (Figure 2) were mostly within 0.2 mK over 19 h, and the standard deviations were < 0.10 mK. These data were used to derive the calibrations of the thermometers, at ~87.3 K. The standard deviations in LN2 (Figure 3) were similar but the mean differences, 0.10 mK to +0.30 mK, were larger than in LAr because of the propagation of calibration error at the triple-point of mercury and the extrapolation from ~87.3 K to ~77.3 K. This is consistent with Euramet Technical Guide No 1 for extrapolations below the argon triple point [1].

Figure 2: Comparisons of C-SPRTs versus Ref1 (1676928) in LAr

Figure 3: Comparisons of C-SPRTs versus Ref1 (1676928) in LN2

Experiment 2: Agreement of five NPL reference C-SPRTs after 37 years

Nine comparison sequences were made in LN2 over a period of 3.5 h. Then the LN2 was drained off and replaced by LAr, and the temperature rose initially to ~82 K. In comparisons between 82.4 K and 83.2 K (18 h) the average drift was <0.001 K/min. The results are shown with respect to the Ward and Compton International Intercomparison of Realisations of the IPTS-68 [2]. The average differences from 1728839 in LN2 were -0.24 mK to -0.11 mK, with standard deviations of 0.06 mK or lower. The average differences between 82.4 K and 83.2 K were -0.04 mK to -0.13 mK, with standard deviations up to ~0.13 mK as a result of the larger drift rates. 1728839 reads high with respect to the other four C-SPRTs, and 1832689 lies somewhat below the rest in LN2. Both these effects had been detected in intervening comparisons.
Figure 4: internal consistency at ~ 77.3 K after a period of 37 years. Figures 5: internal consistency at ~ 83 K after a period of 37 years.

These results are remarkable demonstrations of the stability of the C-SPRTs over 37 years, and also of the precision of the 1976 comparisons in a vacuum cryostat and the present comparisons in liquid or partially solid cryogens.

Experiment 3: Comparisons of C-SPRTs and L-SPRTs.

NPL has used LN2 as a comparison medium for the calibration of L-SPRTs since the mid 1980s (previously liquid oxygen had been used, as specified in the IPTS-68). Agreement between the reference L-SPRTs was typically < ~ 0.5 mK. Recently calibrations of L-SPRTs in the NPL Ar triple-point cell showed differences of ~-0.3 mK with respect to calibrations in a commercial cell. To resolve this discrepancy more precise comparisons with C-SPRTs in LN2 and LAr were made, using the instantaneous comparison method. The mean difference between two reference C-SPRTs and two L-SPRTs in LN2 was -0.08 mK with a standard deviation of 0.06 mK. In LAr at 87.1 K the mean difference was -0.26 mK 0.09 mK. This broadly confirms the discrepancy, though the reason for it is not yet clear.

Dynamic calibrations
After Experiment 2, above, the logging continued as the temperature ramped up to 293 K over ~ 15 h. After the final evaporation of LN2 the ramp rate rapidly increased first to 10 K/h and then to a peak of 32 K/h (~9 mK/s) at ~ 170 K. During the ramp the C-SPRTs agreed within ~ 10 mK, rising to ~ 20 mK, and then reducing as the temperature approached 293 K. At ramp rates of 9 mK/s the SPRT response times are critical. The Tinsley SPRTs have poorer thermal contact (evidenced by larger self-heating effects) and so read lower. The maximum difference of ~25 mK is equivalent to a lag of ~3 s. The two Leeds and Northrup SPRTs show differences of ~10 mK, most likely because 1832689 was connected with finer wiring, so less heat was conducted to it than to 1676928. Tinsley B409 deviates above 220 K, probably because some moisture had condensed on the capsule. A check comparison in a steady low-temperature bath is needed to confirm dynamic calibration errors. Alternatively Inseok Yang et al[3] have discussed compensation for time lag in dynamic comparisons where measurements are taken first during the cool-down and then in the warm-up.

Figure 6: comparisons between C-SPRTs during the warm-up from 77 K to 273 K.

References
1.  Euramet Technical Guide No 1, Extrapolation of SPRT Calibrations below the Argon Triple Point, 83.8058 K, and Traceability in baths of Liquid Nitrogen at ~77.3 K, www.euramet.org (2011). 2. Ward SD and Compton JP, Intercomparison of Platinum Resistance Thermometers and T68 Calibrations, Metrologia 15, 31-46, (1979) 3.  Inseok Yang, Chang Ho Song, Kee Hoon Kang and Yong-Gyoo Kim, First-order Compensation for Time Lag in the Dynamic Calibration of Industrial Thermometers, Measurement Science and Technology 20 (2009) 015109 (6pp)

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