Isotope and Impurity Content in Water Triple-Point Cells Manufactured at NMi VSL

The isotopic and impurity content of 15 water triple-point cells, manufactured at NMi VSL in the past three years, were investigated. The isotopic analyses were performed on water specimens sampled at three different stages of the manufacturing process. This allowed us to separate and quantify the influence of the source water and of the manufacturing process (distillation, degassing) on the final isotopic composition of the water in the cells. Inductively coupled plasma mass spectrometry (ICPMS) was conducted on selected water samples to investigate the potential contamination of the source water during the manufacturing process, and to evaluate the impact of impurities on the water triple-point temperature. The temperature differences among the manufactured cells were measured, and correlations between the observed differences and the results of isotope and chemical analysis were studied.     

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.     

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.     

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.     

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.     

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.     

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.     

密封式氩和氖三相点容器的国际比对

介绍了中国计量科学研究院（ＮＩＭ）、联邦德国物理技术研究院（ＰＴＢ）和意大利计量研究所（ＩＭＧＣ）制作的密封式氩三相点和氖三相点容器的结构，在ＰＴＢ进行比对的实验设备、实验方法，并给出了比对结果，最大差值小于０．６ｍＫ。     

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.     

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.     

Thermodynamic Temperatures of the Triple Points of Mercury and Gallium and in the Interval 217 K to 303 K

We measured the acoustic resonance frequencies of an argon-filled spherical cavity and the microwave resonance frequencies of the same cavity when evacuated. The microwave data were used to deduce the thermal expansion of the cavity and the acoustic data were fitted to a temperature-pressure surface to deduce zero-pressure speed-of-sound ratios. The ratios determine (T–T₉₀), the difference between the Kelvin thermodynamic temperature T and the temperature on the International Temperature Scale of 1990 (ITS-90). The acoustic data fall on six isotherms: 217.0950 K, 234.3156 K, 253.1500 K, 273.1600 K, 293.1300 K, and 302.9166 K and the standard uncertainties of (T−T₉₀) average 0.6 mK, depending mostly upon the model fitted to the acoustic data. Without reference to ITS-90, the data redetermine the triple point of gallium T_g and the mercury point T_m with the results: T_g/T_w = (1.108 951 6 ± 0.000 002 6) and T_m/T_w= (0.857 785 5 ± 0.000 002 0), where T_w = 273.16 K exactly. (All uncertainties are expressed as standard uncertainties.) The resonator was the same one that had been used to redetermine both the universal gas constant R, and T_g. However, the present value of T_g is (4.3 ± 0.8) mK larger than that reported earlier. We suggest that the earlier redetermination of T_g was erroneous because a virtual leak within the resonator contaminated the argon used at T_g in that work. This suggestion is supported by new acoustic data taken when the resonator was filled with xenon. Fortunately, the virtual leak did not affect the redetermination of R. The present work results in many suggestions for improving primary acoustic thermometry to achieve sub-millikelvin uncertainties over a wide temperature range.     

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。     

不同配比及其后处理方式对纳米TiO_2粒径的影响

利用超声溶胶-凝胶法制备纳米TiO2粉体,讨论了反应过程中不同配比、醇洗次数、干燥方式、煅烧方式对颗粒粒径的影响,用DSC-TG、XRD等仪器对其热性质、晶型结构进行表征,用谢乐公式计算粒子的平均粒径。结果表明,钛酸丁酯∶水∶无水乙醇∶冰醋酸的摩尔比为1∶3∶10∶1,pH值为2,超声醇洗3次,红外干燥,先升温至250℃保温1 h再加热至600℃恒温2 h得到的纳米TiO2的粒径最小。     

延期药中Sb2S3含量和贮存条件对雷管的影响

文章分析了延期药中Sb2S3含量与吸湿性能的关系,研究了贮存条件对雷管的影响,并提出了改进工艺的办法.     

不同Ti含量的W-Ti-N复合膜的微结构及性能研究

采用多靶反应磁控溅射技术制备一系列不同Ti含量的W-Ti-N复合膜。采用X射线衍射仪、扫描电镜、纳米压痕仪等检测方法对薄膜的微结构和力学性能进行表征。采用UMT-2功能摩擦试验机,在室温、大气环境、无润滑的条件下对W-Ti-N复合膜的摩擦性能进行评价,同时,探讨薄膜的致硬机理和摩擦机制。结果表明:Ti含量(原子分数,下同)为5%~23.48%时,薄膜硬度处于峰值区,硬度值最高可达39GPa,摩擦因数在0.4左右。当Ti含量高于23.48%时,硬度随着Ti含量增加而下降,摩擦因数随Ti含量的增加而升高。     

含Fe2O3组分钨系延期药的研究及应用

文章介绍了一种含Ｆｅ２Ｏ３组分钨系延期药，对影响该延期药燃速的因素进行了实验研究，并应用于导爆管雷管中，取得了良好的效果。     

Influence of Variations of the Composition of Natural Gas from Different Fields on the Results of Mass and Volumetric Flowrate Measurement under Standard Conditions in Gas Distribution Organizations

Formulas are given for the conditionally-constant values of density under standard conditions as well as for the dynamic viscosity and the adiabatic exponent. The dynamic viscosity and adiabatic exponent depend only on the natural gas temperature and pressure that we recommend be used for mass and volumetric flowrate measurements under standard conditions in gas distribution organizations.The paper considers the feasibility of correcting meter readings not by entering the daily conditionally-constant composition of natural gas into a calculator, but by correcting the readings of all the instruments participating in commercial operations during the accounting period. This would be done by using correction factors that depend on the density under standard conditions and fixed consumption patterns (absolute pressure and temperature of the gas).     

杭州市大气悬浮颗粒PM_(2.5)污染状况及化学组成特征分析

为了解杭州市大气悬浮颗粒物PM2.5污染状况及化学组成特征,2006年在杭州市内布设2个监测点位,按季节进行采样,并对悬浮颗粒物PM2.5中20种元素进行定量研究。结果表明:杭州市区大气中悬浮颗粒物PM2.5的年均质量浓度值为77.5μg/m3,其中S、Si、Ca、K等元素年平均质量浓度大于1.0μg/m3。元素Si、Al、Fe、Mg、V、K、Na、Ti、Mn、Ca、P、Cr、Ni主要来源于地壳,而元素Cl、Cu、Zn、Pb、As、Br、S、Se等主要来源于人为排放源。