Comparison of Five Isotope-Corrected Water-Triple-Point Cells with the NMIA-2002 WTP Ensemble

A comparison of NMIA’s new water-triple-point (WTP) ensemble with a previously established ensemble is reported. Until 2007, the kelvin in Australia was defined as the average of an ensemble of WTP cells that were selected for stability and purity and collected over a period of several years from a variety of sources. As a result of the recent CCT-K7 comparison, a clarification of the SI definition for the kelvin was adopted, explicitly specifying the isotopic composition of the water in WTP cells. Although NMIA’s results were within the estimated uncertainties, NMIA initiated a project to acquire cells with isotope information from several manufacturers and batches to establish a new ensemble. We find that the standard deviation of the isotope-shift-corrected temperatures of five cells from three manufacturers to be 6 μK, which is significantly lower than that of the cells in the previous ensemble, which was 24 μK. The average temperature of the new ensemble is found to be approximately 107 μK higher than that of the previous ensemble. This difference is consistent with the findings of CCT-K7, which identified a group of laboratories controlling isotope effects, and is displaced 73 μK from the mean of the other laboratories.     

Isotopic Composition of Water Used in Triple-Point Cells

Isotopic analysis of the water used in KRISS triple point of water (TPW) cells was performed by three separate laboratories. The δD and δ ¹⁸O isotopic composition of six ampoules, made from two TPW cells, were analyzed by isotope ratio mass spectrometers. The analysis data showed that δD and δ ¹⁸O were − 62.17‰ and − 9.41‰ for the KRISS-2002-Jan cell, and − 36.42‰ and − 4.08‰ for the KRISS-2005-Jun cell. The temperature deviation of the triple point of water for these cells calculated from Kiyosawa’s data and the definition of the TPW were + 45.07μK for the KRISS-2002-Jan cell, and + 25.49μK for the KRISS-2005-Jun cell. The KRISS TPW temperature was + 92μK higher than the CCT-K7 KCRV after correcting for the deviation of the isotopic composition from Vienna Standard Mean Ocean Water.     

Implementing a New Group of TPW Cells as National Standard: Impact on Calibration Services

The definition of the kelvin is based on the triple-point temperature of highly pure water having the isotopic composition of ocean water (more specifically, the isotopic composition is equivalent to that of VSMOW). Belgian national metrology realizes the triple point of water (TPW) as the mean of temperatures measured in three sealed cells. In order to take into account the isotopic composition effect on TPW temperature, the ensemble of cells was replaced in 2006. Three new cells, with isotopic analysis of the contained water, were bought from different manufacturers. The new group of cells was compared to the old TPW national realization in order to quantify the effect of moving towards a new reference. Two different standard thermometers were used in all the cells to take 10 daily measurements on two different ice mantles. The measured resistances were corrected for hydrostatic head, self-heating, and isotopic composition (when available) before calculating the difference. A difference of about 87 μK was found between the old and the new national references. This difference is transferred to customers’ thermometers and cells through calibrations, and the change has to be documented in each new calibration certificate. An additional consequence of the new ensemble cell implementation is the significant reduction in the spread of deviations of individual cells from the mean temperature. The maximum difference between two cells of the ensemble is 96 μK for the old reference cells and 46 μK for the new reference cells corrected for isotopic composition effects.     

CCT-K7水三相点容器国际关键比对

在国际互认框架内,国家计量标准的国际等效性是通过国际计量委员会（CIPM）的咨询委员会组织的一系列国际关键比对来确定的。温度咨询委员会（CCT）委托国际计量局（BIPM）作为主导实验室组织了由20个国家实验室参加的CCT-K7水三相点容器国际关键比对。比对结果表明：这些国家基准水三相点值在0．171mK范围内一致。此外,为了减小国家实验室复现水三相点的系统差,需要进一步研究同位素组成对水三相点温度的影响以及同位素修正。     

VSMOW Triple Point of Water Cells: Borosilicate versus Fused-Quartz

To investigate an ideal container material for the triple point of water (TPW) cell and to reduce the influence to the triple-point temperature, due to the deviation of the isotopic composition of the water, both borosilicate and fused-quartz glass shelled TPW cells with isotopic composition substantially matching that of Vienna Standard Mean Ocean Water (VSMOW) were developed and tested. Through a specially designed manufacturing system, the isotopic composition, δD and δ¹⁸ O, of the water in the TPW cell could be controlled within ±10‰ (per mil) and ±1.5‰, respectively, resulting in control of the isotopic temperature correction to better than ± 8 μK. Through an ampoule attached to the cell, the isotopic composition of the water in the cell could be individually analyzed . After manufacture, the initial triple-point temperatures of the two types of cell were measured and compared to assess the quality of the cells and manufacturing process. Cells fabricated with the new system agree within 50 μK. Two innovatively designed borosilicate and fused-quartz TPW cells were made, each with six attached ampoules. One ampoule was removed every 6 months to track any changes in purity of the water over time.     

The Impact of Isotopic Concentration,Impurities, and Cell Aging on the Water Triple-Point Temperature

In 2005, the National Institutes of Standards and Technology (NIST) and Fluke’s Hart Scientific Division initiated a study to validate the isotopic correction algorithm applied to the realization temperature of triple point of water (TPW) cells. Additionally, the study quantified the impact of water sample impurities on the TPW cell realization temperature. For this study, eight TPW cells containing water of the same nominal isotopic concentration as Vienna Standard Mean Ocean Water (VSMOW) were used. Five of the cells were manufactured with fused-quartz envelopes and the remaining three with borosilicate envelopes. One TPW cell of each type was uniquely designed so that water samples could be periodically removed to analyze the isotopic composition and to monitor any changes in water purity with time and thereby correlate changes in composition with changes in realization temperature. The borosilicate TPW cells gave an average drift of −13 μK · yr⁻¹ and the more stable fused-quartz TPW cells gave an average drift of −2 μK · yr⁻¹.     

Realization of Low-Temperature Fixed Points of the ITS-90 at NMIJ/AIST

A new model of sealed cells with three thermometer wells for calibration of capsule-type thermometers at low-temperature fixed points of the International Temperature Scale of 1990 has been developed at the National Metrology Institute of Japan (NMIJ). The melting curves of Ar and O₂ obtained using the new cells show very flat plateaux and a linear temperature dependence as a function of the inverse liquid fraction (1/F) over the range 1/F = 1 to 1/F = 20 with a narrow melting curve width of 0.1 mK. The melting curves of Ne obtained with the new cell also show very flat plateaux and approximately linear temperature dependence versus 1/F and a narrow melting curve width of 0.1 mK, though with a slight concave structure at high 1/F. The melting temperatures with the new cells agree with previous NMIJ sealed cells within 10 μK, which is similar to the reproducibility of the realization of the triple points at NMIJ. The source dependence of the triple-point temperature of Ne was investigated by filling two of the new cells from different sources of Ne. The difference in the realized triple point temperatures between the two sources is 0.031 mK, consistent with that estimated from isotope analysis. The uncertainties in the calibration of standard platinum resistance thermometers at the low-temperature fixed points are summarized. The uncertainty of the calibration at the triple point of e-H₂ has been reduced to about one-third of its value without the correction by making the isotopic correction on the basis of the technical annex for the ITS-90 in the mise en pratique for the definition of the kelvin.     

Realization of the Triple Point of Water in Metallic Sealed Cells at the LNE-INM/CNAM: A Progress Report

A miniature metallic cell for the water triple point (TPW, temperature 273.16 K) was developed for capsule-type thermometer calibrations for realizations with adiabatic calorimetry techniques. The LNE-INM/Cnam previously developed a copper cell for the water triple point and the techniques for cleaning, filling, and sealing. On the basis of previous work, a new copper cell prototype for the TPW was developed and filled at the LNE-INM/Cnam. Measurements were performed using an appropriate calorimeter and a comparison block containing several thermometers. Preliminary results show a scatter of the temperatures measured at the phase transition of the order of 0.2 mK when measurements are repeated over a short-term period (1 month). A positive drift in the phase transition temperature of about 30μK·month⁻¹ was observed over several months. Studies are in progress to improve the cell, to reduce the reproducibility uncertainty to less than 0.1 mK and to have a phase transition with better temporal stability.     

Intercomparison of the Realizations of the ITS-90 from 83.8058 K to 692.677 K among European NMIs

The EUROMET.T-K3 comparison is the regional extension of CCT-K3. The comparison involved the six European national metrology institutes (NMIs) previously involved in CCT-K3 (LNE-INM/CNAM, SMU, INRiM, NMi-VSL, NPL, PTB) and 18 additional European national laboratories. The comparison was divided into five different loops, each coordinated by a co-pilot chosen from the laboratories having participated in the CCT-K3 comparison. LNE-INM/CNAM played the role of pilot in linking the five loops. In each loop, an artifact in the form of a standard platinum resistance thermometer (SPRT, 25 Ω) was circulated among the participating laboratories. To have sufficient information about the possible drift of the SPRTs, the co-pilots performed a calibration over the full temperature range at the beginning and at the end of the loop. A EUROMET reference value (ERV), taking into account the whole comparison, was defined, and the differences (T _Lab − T _ERV) were calculated with the associated uncertainties. The method for establishing the link between the participants in CCT-K3 and in EUROMET.T-K3 is described. Institut National de Métrologie (BNM-INM/CNAM at the time of the comparison, LNE-INM/CNAM since 1 January 2005), Paris, France.     

Method for Compensating Heat Flux Errors in Mini-TPW Cell Measurements

Small triple-point-of-water cells (mini-TPW) are used in laboratories to monitor the stability of PRTs. Compared with a standard TPW cell, heat flow in the thermometer well usually disturbs the apparent equilibrium temperature to a larger extent in a mini-TPW cell due to its smaller dimensions. In this paper, the heat flow effect is studied on the basis of experimental data. Special attention is paid to the thermal conduction along a thin thermometer probe and to the self-heating of the probe. A new method for compensating the error due to the heat flow is presented. It is shown that the compensated results are in good agreement with results obtained with standard TPW cells. The determined differences were well within the estimated expanded uncertainty of 2 mK (k = 2). The heat flow effect was studied experimentally by controlling the temperature of the upper part of a PRT inserted in a mini-TPW cell. Also, the effect of different fillings of the measurement well of the cell was studied. Without the compensation, thin metal-sheathed PRTs (1.6 and 2.2 mm) indicated 3 to 9 mK differences between mini-TPW and standard TPW cells.     

高准确度水三相点容器

水三相点的高精度复现及准确测量是保证国际温标ITS-90实施的关键。水三相点容器内高纯水的同位素组成会影响复现的水三相点温度值。为了提高水三相点复现水平,减小氢氧同位素的影响,研制了带有氢氧同位素分析的石英及硼硅玻璃高准确度水三相点容器。为了评价容器的性能,开展了硼硅玻璃和石英水三相点容器的比对。实验结果表明:同位素修正前,石英玻璃和硼硅玻璃水三相点容器复现的水三相点在0.058mK范围内一致;同位素修正之后,容器之间的差异在0.017mK范围内一致。采用高准确度水三相点容器复现水三相点的扩展不确定度为0.066mK(k=2)。     

Adiabatic Calorimetry as Support to the Certification of High-Purity Liquid Reference Materials

The certification of high-purity liquid reference materials is supported by several analytical techniques (e.g., gas chromatography, liquid chromatography, Karl Fischer coulometry, inductively coupled plasma mass spectrometry, differential scanning calorimetry, adiabatic calorimetry). Most of them provide information on a limited set of specific impurities present in the sample (indirect methods). Adiabatic calorimetry [1] complementarily provides the overall molar fraction of impurities with sensitivity down to few μmol · mol⁻¹ without giving any information about the nature of the impurities present in the sample (direct method). As the combination of adiabatic calorimetry with one (or more than one) indirect chemical techniques was regarded as an optimal methodology, NMi VSL developed an adiabatic calorimetry facility for the purity determination of high-purity liquid reference materials [2]. Within the framework of collaboration with NMIJ, a benzene-certified reference material (NMIJ CRM 4002) from NMIJ was analyzed by adiabatic calorimetry at NMi VSL. The results of this measurement are reported in this paper. Good agreement with the NMIJ-certified purity value (99.992 ± 0.003) cmol · mol⁻¹ was found. The influence of different data analysis approaches (e.g., extrapolation functions, melting ranges) on the measurement results is reported. The uncertainty of the measured purity was estimated.     

Middle Temperature Scale for Infrared Radiation Thermometer Calibrated Against Multiple Fixed Points

The NMIJ has established a temperature scale for infrared radiation thermometry from 100 to 420°C consisting of three fixed-point blackbodies at the In, Sn, and Zn points and an InSb detector thermometer at a wavelength of 4.7 μm. The blackbody cavities have large openings of 15 mm diameter. The expanded uncertainties (k = 2) of the In, Sn, and Zn fixed-point radiance temperatures are estimated to be 0.03, 0.03, and 0.05 K, respectively. The expanded uncertainties (k =  2) for the calibration of the infrared radiation thermometer are estimated to be 0.04 K at 157°C (In point), 0.04 K at 232°C (Sn point), and 0.07 K at 420°C (Zn point).     

Long-Term Stability of 0.65-μm Radiation Thermometers at NMIJ

Narrow-band radiation thermometers with center wavelengths near 0.65 μm are frequently used as standard thermometers at high temperatures. The long-term stability of ten Topcon 0.65-μm radiation thermometers was assessed at NMIJ by using fixed-point blackbodies and spectral responsivity measurements. Most of the changes are due to shifts in the center wavelength of the interference filters to longer wavelengths. Even when the center wavelengths shifted, the filter widths and transmittances remained quite stable for some radiation thermometers, but one was found for which the bandwidth increased from 15.7 to 17.2 nm and the transmittance decreased by 6%. Three Barr filters were found to be very stable in wavelength. The output signals of 0.65-μm Topcon radiation thermometers were within 2% · year⁻¹ without correcting for the wavelength change and within 0.2% · year⁻¹ after the correction. Keeping the objective lens clean is very important for radiation thermometers. Large output decreases were observed in early 2000 for many radiation thermometers at NMIJ. The output changes were as large as 1% and were recovered by cleaning the objective lens.     

Analysis of the Comparison of TPW Realizations in Europe in Light of CCT Recommendation 2 (CI-2005)

Three comparisons of different triple-point-of-water (TPW) realizations in Europe have been organized under the auspices of EUROMET (EUROMET Projects 278, 549, and 714). Thirty European national metrology institutes were involved in these three comparisons that took place from 1994 to 2005. The aim of these successive projects was to assess the uncertainties associated with the practical realization of the triple point of water in Europe. Fifty-four TPW local cells were compared to a traveling standard cell (ref 679) circulated with an isothermal enclosure. The same equipment was used for the three projects, and LNE-INM regularly checked the stability of the TPW standard cell. Recently, LNE-INM has devoted efforts to bring the French standard at the triple point of water into close agreement with CIPM Recommendation 2 (CI-2005). The isotopic fractionation between water and ice when the cell is in use was experimentally studied. Several new TPW cells delivered by the manufacturer with water samples were added to our batch of reference cells. A French laboratory analyzed the isotopic compositions of these samples. These actions allow the French national definition of temperature at the triple point of water to be changed. A new temperature was associated with TPW cell 679 in agreement with the CIPM recommendation. In this presentation, the latest TPW cell measurements carried out by LNE-INM are presented. The results from EUROMET Projects 278, 549, and 714 are investigated in light of these changes.     

Intercomparison of the Realization of the ITS-90 at the Freezing Points of Al and Ag among European NMIs

The EUROMET.T-K4 comparison is the regional extension of CCT-K4, an intercomparison of the realizations of the freezing points of Al (660.323°C) and Ag (961.78°C). The intercomparison was organized in four loops. Long-stem standard platinum resistance thermometers (SPRTs) were used as traveling standards: 25 Ω thermometers to be used only at the Al freezing point and two high-temperature standard platinum resistance thermometers (HTSPRTs) to be used only at the Ag freezing point in each loop. Parallel to the measurements with thermometers, the pilots and sub-pilots organized an internal intercomparison using an Ag fixed-point cell. Most HTSPRTs showed a strong drift which is mainly due to mechanical stress and poisoning of the sensor by impurities. This drift can be partially compensated by a correction based on Matthiessen’s rule. An evaluation of the data taking into account both HTSPRTs in each loop, the linkage of the sub-pilots by measurements at the Ag freezing point, and a possible compensation according to Matthiessens’s rule, allows calculation of the results of the participants’ measurements at the Ag freezing point. The results of the participating laboratories are summarized, and proposals for key comparison reference values and linking of the results to CCT-K3 and CCT-K4 are presented.     

Evaluation of laboratory performance through interlaboratory comparison

This paper reports the performance of the calibration results obtained by 21 laboratories using digital pressure calibrator as an artifact in the pressure range 7–70 MPa. National Physical Laboratory (NPLI), New Delhi has coordinated this programme and also acted as a reference laboratory. The program started in May, 2006 and completed during May, 2008. The comparison was carried out at 10 equally spaced pressure points i.e. 7,14,21,28, 35,42,49,56, 63 and 70 MPa throughout the entire pressure range of 7–70 MPa. The calibration results thus obtained were analyzed as per ISO / IEC GUM document. The 92.7 % measurement results are found in agreement with the results of NPLI. The relative deviations between laboratories values and reference values are well within the 0.05 %for 123 measurement points, 0.1% for 162 measurement points and 0.25% for 177 measurement points. The difference of the laboratories values with reference values are found almost well within the uncertainty band of the reference values at 68.0 % measurement results, within their reported expanded uncertainty band at 81.5% measurement results and within the combined expanded measurement uncertainty band at 92.7 % measurement results. Overall, the results are considered to be reasonably good being the first proficiency testing for most of the participating laboratories.     

EURAMET.T-K7 Key Comparison of Water Triple-Point Cells

The results of a EURAMET key comparison of water triple-point cells (EURAMET.T-K7) are reported. The equipment used, the measuring conditions applied, and the procedures adopted for the water triple-point measurement at the participating laboratories are synthetically presented. The definitions of the national reference for the water triple-point temperature adopted by each laboratory are disclosed. The multiplicity of degrees of equivalence arising for the linking laboratories with respect to the ??mother?? comparison CCT-K7 is discussed in detail.     

Isotopic Effects on the Temperature of the Triple Point of Water

An investigation into the effects of isotopic composition on the triple point temperature of water has been carried out at the National Institute of Metrology (NIM), China, since redefinition of the kelvin with respect to Vienna Standard Mean Ocean Water (V-SMOW) was officially proposed by the Consultative Committee for Thermometry (CCT) in 2005. In this paper, a comparison of four cells with isotopic analyses and relevant results corrected for isotopic composition, employing the isotope correction algorithm recommended by the CCT, is described. The results indicate that, after application of the corrections, the maximum temperature difference between the cells drops from 0.10 mK to 0.02 mK and that these cells are in good agreement within 0.02 mK. Also, temperature deviations arising from isotopic variations fall in the range from −55.9 μK to + 40.7 μK. We consider that the distillation temperature and degassing time of the production procedure lead to isotopic variations.     

Comparison System for the Calibration of Capsule-Type Standard Platinum Resistance Thermometers at NMIJ/AIST

A new comparison system has been constructed using a Gifford- McMahon type cryogenic refrigerator for the calibration of capsule-type standard platinum resistance thermometers (CSPRTs) below 273.16 K at the National Metrology Institute of Japan (NMIJ). The system can compare six CSPRTs at once. A gold-plated comparison block, in which CSPRTs are mounted for calibration, is made from oxygen-free high-conductivity copper. The standard uncertainties related to the temperature control of the system are estimated to be 0.04 mK. The calibrated values for CSPRTs and a rhodium–iron resistance thermometer obtained using the comparison system are in good agreement with those obtained by the direct realization of the low-temperature fixed points of the ITS-90 within the combined standard uncertainty for the calibration using the comparison system.