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.     

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.     

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.     

Assembly and Study of Different Mercury Cells with Known Impurity Content and Isotopic Composition

The “Centro Español de Metrología” is carrying out a project to improve the knowledge of the influence of impurities and isotopic composition on the temperature of the mercury triple point. High-purity mercury from the Almaden mine (stated purity of 99.9998%) was further purified by vacuum distillation. Three mercury fractions, the original mercury from Almaden and two distilled fractions, were characterized in terms of both impurities and isotopic composition and used to measure the mercury triple point. The original mercury sample contained silver at 560 ng · g^?1 as the main impurity while the impurity levels were much lower (silver < 1 ng · g^?1) in the two distilled fractions. The isotopic composition of the distilled fractions showed delta values, expressed as $1,000\times(^{198/202}{\rm Hg}_{\rm sample}-^{198/202}\,{\rm Hg}_{\rm reference})/^{198/202}{\rm Hg}_{\rm reference}The “Centro Espa?ol de Metrología” is carrying out a project to improve the knowledge of the influence of impurities and isotopic composition on the temperature of the mercury triple point. High-purity mercury from the Almaden mine (stated purity of 99.9998%) was further purified by vacuum distillation. Three mercury fractions, the original mercury from Almaden and two distilled fractions, were characterized in terms of both impurities and isotopic composition and used to measure the mercury triple point. The original mercury sample contained silver at 560 ng · g⁻¹ as the main impurity while the impurity levels were much lower (silver < 1 ng · g⁻¹) in the two distilled fractions. The isotopic composition of the distilled fractions showed delta values, expressed as , of 1.37±0.07 (1σ) for the first distilled sample and −1.55±0.03 (1σ) for the second distilled sample with reference to the original Almaden mercury. For the measurement of the mercury triple point, an alcohol stirred bath was used that allowed two cells to be compared nearly simultaneously. It was observed that the presence of the silver impurities in the high-purity mercury modified slightly the mercury triple point while the effect of variations in the isotopic composition can be considered negligible.     

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.     

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.     

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。     

The Long-Term Drift of Triple-Point-of-Water Cells

As the triple point of water is of great importance for the International Temperature Scale of 1990 (ITS-90) and for the definition of the unit of thermodynamic temperature, its long-term stability has attracted a great deal of attention. In a study of long-term stability, a mystery has been uncovered. Some triple-point-of-water cells remain stable for many decades, while others decrease with increasing age of the cells, which is called long-term drift. To investigate this mystery, we used cells with different manufacture dates ranging from 1974 to 2002 and compared their analyses, which were done in 1984 and 2003. Using the same model of long-term drift as that used by Hill, the long-term drift rates of the two data sets are –4.7 μK·year⁻¹ and –9.2 μK·year⁻¹, respectively. One is consistent with the observed depression of about –4 μK·year⁻¹ measured by Hill, whereas the other differs greatly from Hill’s result. In addition, corresponding factors influencing long-term drift are discussed in this paper.     

水三相点复现的不确定度评定

水三相点是开尔文热力学温度的唯一基准点，也是ITS-90国际温标重要的定义固定点。因此，水三相点不确定度分析对整个温标的建立、温度量值传递起着至关重要的作用。近3年来，中国计量科学研究院研制出一系列高质量的水三相点容器，加强了水三相点的研究，为不确定度的分析提供了更为可靠的实验依据。同时，不确定度的分析也是客观评价新研制容器性能的一个重要指标。因此，根据实验结果对新研制容器所复现的水三相点进行了不确定度评定。评定结果表明，其扩展不确定度为0．16mK(k=2．69，P=0．99)。     

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.     

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.     

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.     

Development of the Sealed-Type Triple-Point-of-Argon Cell for Long-Stem SPRT Calibration at KRISS

A system was fabricated to realize the triple point of argon for the calibration of long-stem standard platinum resistance thermometers. A cryostat was constructed so that the temperature could be controlled quasi-adiabatically, and the melting was realized using the continuous-heating method. The combined uncertainty of the realization of the triple point of argon for a confidence level of 95% was 0.6 mK.     

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.     

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。     

The effect of natural variations in the isotopic composition on the reproducibility of the temperature of the triple point of water

The effect of long-term natural variations in the isotopic composition on the temperature of the reproduction of the triple point of water – the main reference point of the ITS-90 International Temperature Scale – is investigated. Translated from Izmeritel’naya Tekhnika, No. 12, pp. 31–33, December, 2008.     

不同系统锡凝固点装置的比对

本文介绍MM与美国HART公司的两种不同系统的锡凝固点装置比对的方法,以供使用与参考.     

不同系统锡凝固点装置的比对

本文介绍NIM与美国HART公司的两种不同系统的锡凝固点装置比对的方法,以供使用与参考。     

提高曲面近似展开精度的方法与实现

通过对不可展曲面近似展开精度的研究，提出了根据曲面曲率的大小对曲面自动进行网格划分，通过对综合展开误差数据场进行数据拟合来选取最优展开基点，基于空间曲面与其展开图间近似的等距变换关系进行展开样形的误差矫正等3种方法，这几种方法的实现在不同程度上有效地减小了曲面的近似展开误差，提高了曲面的近似展开精度。     

模拟W/O法测乳化炸药水相析晶点的研究

为准确测出乳化炸药水相析晶点,分析比较了析晶点测试主要方法的优缺点,设计一种模拟W/O法乳化炸药水相析晶点测试装置,对乳化炸药的水相析晶点进行了测试,并与烧杯自然降温法和橡胶塞密闭试管法测得的析晶点进行对比。结果表明,模拟W/O法测得的析晶点误差小于1℃,测试结果准确,测试方法简单,值得推广应用。