汞三相点的复现

利用自制的超高纯汞三相点容器,复现了1990年国际温标(ITS-90)中新设定的汞三相点。结果表明其融化范围和凝固范围均在0.1mK以内,复现性优于0.1mK,两者的符合程度也在0.1mK之内,分别用纯度为99.99999％的超高纯商品汞和实验室清洗的汞经高真空蒸馏制备的两个密封容器,测定结果在实验误差内一致,差异不大于0.1mK。文中介绍了三相点容器的制备工艺要点。     

NMIJ Constant-Volume Gas Thermometer for Realization of the ITS-90 and Thermodynamic Temperature Measurement

The constant-volume gas thermometer (CVGT) of the National Metrology Institute of Japan (NMIJ), AIST with ³He as the working gas is used as an interpolating gas thermometer to realize the International Temperature Scale of 1990 (ITS-90) from 3 K to 24.5561 K and as a relative gas thermometer for thermodynamic temperature measurement calibrated at the triple point (TP) of Ne. The standard uncertainties of the realization and measurement are estimated to be 0.58 mK and 0.86 mK at a maximum in the mentioned temperature range, respectively. The maximum difference between both temperatures is about 1 mK. In the calibration of the CVGT, the TP of equilibrium hydrogen (e-H₂) is corrected for isotopic composition as specified in the Technical Annex for the ITS-90. The ambiguity of the TP of Ne due to the variability in isotopic composition is included in the uncertainty. Although the CVGT was also used in 2004 to realize the ITS-90, it was modified for the present experiment to reduce some measurement uncertainty components and the working gas was replaced with a higher-isotopic-purity gas. The results from 2004 were recalculated by correcting for the isotopic composition of e-H₂ and differ insignificantly from the present results, except for a wider scatter.     

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.     

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.     

镓三相点容器的研制

近年来,镓三相点作为新的温度固定点的研究已经得到了广泛的重视。本介绍了镓三相点容器的制作工艺、冻制过程及复现技术。实验结果表明,镓三相点的温度值为29.7666℃     

镓三相点的复现

本文介绍了镓三相点的复现方法,并对镓三相点值进行测量,其温度值为29．7666℃。     

Construction of Gallium Point at NMIJ

Two open-type gallium point cells were fabricated using ingots whose nominal purities are 7N. Measurement systems for the realization of the melting point of gallium using these cells were built. The melting point of gallium is repeatedly realized by means of the measurement systems for evaluating the repeatability. Measurements for evaluating the effect of hydrostatic pressure coming from the molten gallium existing during the melting process and the effect of gas pressure that fills the cell were also performed. Direct cell comparisons between those cells were conducted. This comparison was aimed to evaluate the consistency of each cell, especially related to the nominal purity. Direct cell comparison between the open-type and the sealed-type gallium point cell was also conducted. Chemical analysis was conducted using samples extracted from ingots used in both the newly built open-type gallium point cells, from which the effect of impurities in the ingot was evaluated.     

镓三相点的复现

本文介绍了镓三相点的复现方法,并对镓三相点值进行测量,其温度值为29.7666℃.     

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.     

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)。     

The Realization of Fixed Points of the Temperature Scale in Small-Size Ampoules

Results of an investigation of small-size ampoules of the fixed points of gallium and indium are described. It is concluded that they can be used as an inexpensive standard means of measuring temperature.     

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.     

Double Anomalous Peak in the Heat Capacity Just Below the Triple Point of Saturated e-H<Subscript>2</Subscript> with FeO(OH)

The heat capacity of e-H ₂ with powder of FeO(OH) used as a catalyst for ortho-para equilibration has been investigated using sealed cells fabricated at the National Institute of Standards and Technology and at the National Metrology Institute of Japan. An anomalous double peak has been observed in their heat capacities at temperatures just below the triple point independent of sources of H₂ and FeO(OH) and designs of sealed cells. Supercooling behavior has been observed not only at the triple point but also at each anomalous peak resulting from a depression of the melting temperature of a portion of solid H ₂ in close physical proximity to the catalyst. The reduction of the amount of catalyst suppresses the size of the anomalies and allows one to obtain more reliable melting curves for e-H₂ at the triple point.     

The Influence of Antimony on the Tin Point

In 2005, an agreement was reached on how to estimate uncertainties and how to correct fixed-point temperatures for the influence of chemical impurities. Although the general procedure is now specified, some problems remain. The slope of the liquidus line at very low-impurity concentrations must be extracted either from binary-phase diagrams or from doping experiments. Apart from this, there is little experimental evidence to prove that the models used to characterize the freezing and the melting plateaux are adequate, especially for impurities that increase the fixed-point temperature. Therefore, a series of measurements were carried out using a tin fixed-point cell doped with antimony. By varying the freezing and the melting conditions, some useful experimental data were collected.     

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.     

New Approach in Filling of Fixed-Point Cells: Case Study of the Melting Point of Gallium

The typical way of constructing fixed-point cells is very well described in the literature. The crucible is loaded with shot, or any other shape of pure metal, inside an argon-filled glove box. Then, the crucible is carefully slid into a fused-silica tube that is closed at the top with an appropriate cap. After that, the cell is removed from the argon glove box and melted inside a furnace while under vacuum or filled with an inert gas like argon. Since the metal comes as shot, or in some other shape such as rods of various sizes, and takes more volume than the melted material, it is necessary to repeat the procedure until a sufficient amount of material is introduced into the crucible. With such a procedure, there is the possibility of introducing additional impurities into the pure metal with each cycle of melting the material and putting it back into the glove box to fill the cell. Our new approach includes the use of a special, so-called dry-box system, which is well known in chemistry. The atmosphere inside the dry box contains less than 20 ppm of water and less than 3 ppm of oxygen. Also, the size of the dry box allows it to contain a furnace for melting materials, not only for gallium but for higher-temperature materials as well. With such an approach, the cell and all its parts (pure metal, graphite, fused-silica tube, and cap) are constantly inside the controlled atmosphere, even while melting the material and filling the crucible. With such a method, the possibility of contaminating the cell during the filling process is minimized.     

Constant-Volume Gas Thermometry with Different Helium-3 Gas Densities at NMIJ/AIST

Constant-volume gas thermometer (CVGT) measurements are conducted using ³He of three different densities as the working gas to obtain the thermodynamic temperature T _CVGT and the second virial coefficient of ³He, B, at temperatures down to 3 K, using the triple point of Ne as a reference temperature. Densities of 127 mol ?? m^?3 and 278 mol ?? m^?3 are used in addition to the density of 168 mol ?? m^?3 used in the measurement reported previously, where T _CVGT was obtained using the virial coefficient adopted by the International Temperature Scale of 1990 (ITS-90), B _ITS-90. T _CVGT is obtained by two methods, by the single- and multi-isotherm fitting of B to the three densities and by the method used in the previous work using one of the three densities and B _ITS-90. B obtained from the isotherm fitting agrees with B _ITS-90 within the uncertainty of the data used to derive B _ITS-90. Moreover, B obtained from a multi-isotherm fit agrees with that of recent theoretical ab initio calculations within 0.05?cm³ ?? mol^?1 at 5 K and above, and within 0.3?cm³ ?? mol^?1 down to 3 K. The values of T _CVGT obtained from the multi-isotherm fits assuming different forms for the temperature dependence of B agree with each other within 0.1?mK. T _CVGT obtained from the multi-isotherm fitting agrees with that obtained from the method in the previous report within 0.22?mK. The tendency of the difference between T _CVGT and the ITS-90 temperature reported in the previous work is confirmed in the present work.     

Progress Report on NMIJ Acoustic Gas Thermometry at the Triple Point of Water

Herein, progress in the development of an acoustic gas thermometry (AGT) system at the National Metrology Institute of Japan is reported. This AGT system is an initial low-cost version that uses a 1-l quasi-spherical resonator (QSR) made of oxygen-free copper. The system was tested by measuring the speed of sound in argon at the temperature of triple point of water. Measurements were conducted at ten different pressures, ranging from 60 kPa to 420 kPa. The ideal gas limit of the squared speed of sound was obtained through extrapolation, and a preliminary calculation of the Boltzmann constant, which was 12 ppm below the CODATA2014 value, was made. Large inconsistencies among microwave and acoustic modes were observed, which are dominant sources of uncertainty in speed of sound measurements. The system will be improved by replacing the present QSR with another one that is more precisely fabricated.     

Approximating the ITS-90 between Zinc and Copper with an Infrared Thermometer at NIS-Egypt

This paper presents an approximation to the International Temperature Scale of 1990 (ITS-90) between the Zn (420 °C) and Cu (1085 °C) fixed points using a 900 nm narrow-band radiation thermometer. This thermometer has a 400 mm working distance and a 150 mm objective focal length. An image of the measured target is focused by the objective lens onto a 1 mm aperture (drilled mirror). The light passing through the aperture is conveyed by a condenser lens through an interference filter with a nominal central wavelength of 900 nm and a half-bandwidth of 10 nm before reaching a silicon photodiode working in the photovoltaic mode. The thermometer was calibrated at the Zn, Al, Ag, and Cu blackbody fixed points. The results of the calibration were used to determine the constants A, B, and C of the Sakuma-Hattori interpolation equation. The results showed that the ITS-90 can be approximated within ± 0.051 °C throughout the Zn-Cu interval when the thermometer is calibrated at the Zn, Al, Ag, and Cu fixed points.     

汞三相点的研究

叙述了汞三相点密封容器的设计和制作程序，并介绍了具体的复现装置和实验方法。实验结果表明，复现性为±０．１ｍＫ，平均熔化温度与平均凝固温度的差为０．１ｍＫ，不同密封容器间的差小于０．２ｍＫ。