Behavior of Triple-Point-of-Water Cells for Different Sizes of the Ice Mantle

The effect of differences in the amount of ice mantle on the realization temperature of the triple point of water (TPW) was investigated. Three TPW cells were used in the experiment as the TPW cell under test. These TPW cells were manufactured at different times. An ice mantle was prepared for each cell, and the amount of these ice mantles was changed when the ice mantle was re-prepared. Comparison measurements were carried out between a standard TPW cell and the three cells under test, and the temperature difference was measured. As a result, although an identical TPW cell was used, a change in the temperature difference was observed when the amount of ice mantle was different. In the case of the TPW cell that was manufactured 30 years ago, the observed temperature change was larger than 0.1 mK. It is considered that the principal cause is the dissolution of glass elements from the TPW cell.     

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.     

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.     

Doping Experiments with Water Triple-Point Cells

Water triple-point cells were manufactured with the ad hoc addition of known amounts ((1 to 10) ??mol · mol^?1) of Si and Na impurities to cell high-purity water. The depressions of the triple-point temperatures realized by the doped cells with respect to 273.16 K were measured and found substantially different from what is expected by Raoult??s law for ideal diluted solutions.     

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)。     

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.     

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.     

Effect of Impurities on Water Triple-Point Cells

Water triple-point cells are the basis for the definition of the kelvin and for the realization of the International Temperature Scale of 1990. The temperature differences between the cells are mainly caused by impurities arising in the cell water from the dissolution of the cell envelope (borosilicate glass or quartz). In order to investigate the effects of such impurities on the realized triple-point temperature, water triple-point cells doped with known amounts of Si and Na impurities ( \(0.1\,{\upmu }\hbox {mol}{\cdot }\hbox {mol}^{{-1}}\) to \(1\,{\upmu }\hbox {mol}{\cdot }\hbox {mol}^{{-1}}\) of Si and \(0.2\,{\upmu }\hbox {mol}{\cdot }\hbox {mol}^{{-1}}\) to \(2\,{\upmu }\hbox {mol}{\cdot }\hbox {mol}^{{-1}}\) of Na) were manufactured at VSL by adding gravimetric mixtures of a Si standard reference material and ultra high-purity water to the cell high-purity water. Water samples were taken from the manufactured cells, partitioned into three samples, and distributed to different laboratories for isotope and impurity analysis (inductively coupled plasma mass spectrometry, ICPMS). The results of two independent ICPMS analyses were compared with impurity calculations based on the gravimetric data of the prepared mixtures and manufactured cells. One undoped cell manufactured by UME and one undoped cell manufactured by VSL were intercompared at both VSL and SMD to demonstrate the equivalence of the manufacturing processes of UME and VSL. The triple-point temperatures realized by the doped cells and the undoped cell manufactured by VSL were measured at SMD. The results showed that, in doped cells, the equilibration time after the last freezing is directly dependent on the impurity concentration, and the temperature depression of doped triple-point-of-water cells is significantly greater than the values predicted by Raoult’s law for an ideal dilute solution.     

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.     

4种不同水源的水三相点容器的比对

为了研究水源对水三相点温度的影响,采用4种不同的水源并按照相同的制作工艺研制高质量的水三相点容器.同时,将这些容器进行了比对实验.比对结果表明:这些不同水源的水三相点容器复现的水三相点值在±0.02 mK范围内一致.故推断出水源对水三相点温度的影响很小.     

An Experimental Investigation of the Long-Term Stability of Triple-Point-of-Water Cells

Contamination of triple-point-of-water (TPW) cells by the chemical components of the borosilicate glass that contains the water is now widely recognized as the principal contributor to long-term drift of the cell temperature. To add to the available experimental data, a comparison of 24 TPW cells of various ages (from 10 years to 59 years), manufacturers (NRC, Jarrett, Isotech), and materials (borosilicate glass and fused quartz) was undertaken in 2013. Twelve cells from this group were compared to one another in 1997. By comparing the current inter-cell temperature differences to those determined 16 years earlier, it was found that some cells have remained stable, others have become colder (as might be expected from ongoing dissolution of the glass), and one or two show an apparent increase in temperature that seems anomalous. Also included among the 24 cells are five cells of borosilicate glass and five of fused quartz that were purchased 10 years ago. By comparing the relative temperature differences among this group of borosilcate and fused-quartz-encapsulated cells to the values obtained when they were last compared 6 years ago, it was found that the average temperature of the borosilcate group of cells decreases by \(-6\,\upmu \mathrm{K}\,{\cdot }\,\mathrm{year}^{-1}\,({\pm }2\,\upmu \mathrm{K}\,{\cdot }\,\mathrm{year}^{-1})\) , in reasonable agreement with an average drift of \(-4\,\upmu \mathrm{K}\,{\cdot }\,\mathrm{year}^{-1}\) suggested 12 years ago. It was concluded that fused quartz is the superior container for TPW cells.     

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.     

金属外壳水三相点容器

水三相点是ITS-90国际温标中最重要的定义固定点,其复现不确定度是传递到整个温标的.目前,通常采用不同的冻制方法在硼硅玻璃或石英水三相点容器内冻制均匀的冰套来复现水三相点.冻制过程中,由于在水三相点容器内生成冰桥,会造成容器的破裂.为了解决此难题,研制了金属外壳水三相点容器,利用高纯水自发相变原理,在液体槽内自动冻制...     

液氮冻制冰套法对水三相点温度的影响

介绍了液氮作为冷却剂在水三相点容器内冻制冰套的方法。利用该方法同时在两个不同真空度的水三相点容器内分别冻制冰套。通过实验，研究了此方法对所复现的水三相点温度的影响。实验结果表明：冻制过程中产生的应力以及开始生成的小冰晶引起水三相点温度偏低；并且，其对水三相点温度的影响随着水三相点容器内真空度的降低而增大。随着应力慢慢消除，小冰晶逐渐长大为大冰晶，所复现的水三相点值逐渐回升并趋于稳定。因此，为了高精度复现和准确测量水三相点，采用该冻制方法时，必须将冰套老化至少5天以后，才可以消除其对水三相点温度的影响。     

Further Estimates of $$(T-T_{90})$$ Close to the Triple Point of Water

Recent advances in primary acoustic gas thermometry (AGT) have revealed significant differences between temperature measurements using the International Temperature Scale of 1990, \(T_{90}\), and thermodynamic temperature, T. In 2015, we published estimates of the differences \((T-T_{90})\) from 118 K to 303 K, which showed interesting behavior in the region around the triple point of water, \(T_\mathrm{TPW}=273.16\) K. In that work, the \(T_{90}\) measurements below \(T_\mathrm{TPW}\) used a different ensemble of capsule standard platinum resistance thermometers (SPRTs) than the \(T_{90}\) measurements above \(T_\mathrm{TPW}\). In this work, we extend our earlier measurements using the same ensemble of SPRTs above and below \(T_\mathrm{TPW}\), enabling a deeper analysis of the slope \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) around \(T_\mathrm{TPW}\). In this article, we present the results of seven AGT isotherms in the temperature range 258 K to 323 K. The derived values of \((T-T_{90})\) have exceptionally low uncertainties and are in good agreement with our previous data and other AGT results. We present the values \((T-T_{90})\) alongside our previous estimates, with the resistance ratios W(T) from two SPRTs which have been used across the full range 118 K to 323 K. Additionally, our measurements show discontinuities in \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) at \(T_\mathrm{TPW}\) which are consistent with the slope discontinuity in the SPRT deviation functions. Since this discontinuity is by definition non-unique, and can take a range of values including zero, we suggest that mathematical representations of \((T-T_{90})\), such as those in the mise en pratique for the kelvin (Fellmuth et al. in Philos Trans R Soc A 374:20150037, 2016. doi: 10.1098/rsta.2015.0037), should have continuity of \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) at \(T_\mathrm{TPW}\).     

Uncertainties in the Realization of the SPRT Sub-ranges of the ITS-90

Working Group 3 of the Consultative Committee for Thermometry is responsible for recommending methods to assess uncertainties in contact thermometry. Accordingly, it has now completed a guide summarizing the uncertainties in the realization of the standard platinum resistance thermometer subranges of ITS-90 between the triple point of neon (24.5561K) and the freezing point of silver (961.78 °C). The document provides guidance to assess the uncertainties of both SPRT calibrations and temperature measurements. The document describes all known sources of uncertainty and influence variables, identifies key references in the literature that discuss, model or evaluate each effect, gives an indication of the typical magnitudes of the uncertainties, and provides propagation laws. This article is an overview of the guide emphasizing aspects that may be different from common practice, which includes: associating all uncertainty terms with a physical cause to ensure they can be propagated and to prevent double counting; uncertainty due to the oxidation state of the SPRT; uncertainty due to the isotopic composition of fixed-point substances; uncertainty due to impurities in fixed-point substances; and uncertainty due to non-uniqueness of the SPRT interpolations. The article gives a graphical summary of the total uncertainties in ITS-90 over the SPRT temperature range.     

套管对水三相点的影响研究

为了研究套管对水三相点的影响,研制了计阱内径分别为16 mm和18 mm的水三相点容器以及直径为15.5 mm的套管。通过在计阱内加套管和不加套管,并利用准确度为0.02×10^-6的交流比较仪电桥测量标准铂电阻温度计在计阱内的电阻值,比较不同直径水三相点容器内套管对水三相点的影响。实验结果表明:实验中套管对水三相点值的影响小于30 μK,且在相同的测量条件下,套管的直径与水三相点容器温度计阱的内径越接近,套管对水三相点值的影响越小。     

Automated Realization of the Triple Point of Water Using the Mush Method

In order to investigate mechanisms of phase transitions of supercooled water in a triple-point-of-water (TPW) cell when a mush method was used to create an ice mantle, an automated apparatus using small TPW cells was developed to obtain the TPW. In this article, the design principle, the apparatus, and the procedure for an automated formation of ice mantles in small TPW cells are described. Supercooled water in small TPW cells spontaneously transformed into uniform metastable dendritic crystals throughout the cells at supercoolings ranging from 5.85 °C to 8.77 °C and then changed into stable hexagonal closed-packed cellular crystals, forming an outer ice mantle from the outside inward. Some pertinent explanations based on thermodynamic solidification theory were used to describe the phase transition process in the mush method. In addition, the experimental results indicated that the realized temperatures of water in the small TPW cells were in good agreement within 0.1 mK approximately 6 h after the initial spontaneous crystallization had occurred. Finally, the small TPW cells (s/n 008 and s/n 001) were directly compared with a conventional TPW cell (s/n NIM-1-211); the temperature differences between the small TPW cells and the regular TPW cell were less than 0.21 mK.     

Isotopic Correction of Water-Triple-Point Cells at NMIJ

The twenty-one participating laboratories in the international key comparison of water-triple-point cells (CCT-K7) can be classified into three groups: two laboratories that corrected the effect of the isotopic composition of water, four laboratories that had information on the isotopic composition but did not correct the effect, and the remaining laboratories that had no information. There were significant differences in the realized national standard for the triple point of water (TPW) between those laboratories that applied the isotopic correction and those that did not. The isotopic correction is now considered essential for the triple point of water. Since the National Metrology Institute of Japan (NMIJ) did not apply the isotopic correction and estimated large uncertainties at the time of the CCT-K7 comparison, we subsequently developed new cells for the TPW to improve the reliability and to reduce the uncertainty of the realization as a national reference. The isotopic compositions of seven cells were analyzed, and a chemical impurity analysis of one cell was performed. The good consistency among seven cells was shown in the results obtained when the isotopic correction was applied to the realized temperatures measured experimentally. The expanded uncertainty of the new national reference of NMIJ is estimated to be 49 μK (k = 2), and as a result of this improvement, the expanded uncertainty for calibrating a water-triple-point cell is 80 μK. The previous reference of NMIJ, reported in CCT-K7 to have an expanded uncertainty of 302 μK, is 42 μK lower than the new one. The new reference value is within the uncertainty of the previous national reference, and the new uncertainty is completely covered by the previous uncertainty. Furthermore, the new reference of NMIJ shows good agreement with the national references of the six laboratories able to apply isotopic corrects to their results for CCT-K7. These facts confirm the validity and the linkage to the CCT-K7 of both the previous and the new national references of NMIJ.     

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。