In the range between 0 °C and 961 °C, the International Temperature Scale of 1990 (ITS-90) depends to a great extent on the freezing points of the pure metals gallium, indium, tin, zinc, aluminium and silver. An up-to-date realization of these fixed points is based on cells containing metals of ultra-high purity (6N or better) and should include a correction for the influence of relevant impurities. Still, chemical analyses of the fixed-point material can show large amounts of oxygen, which had to be neglected so far, because of the lack of detailed knowledge about it, presuming it could be removed from the cell by applying a vacuum (less than 1 Pa) for a few hours.In this paper we discuss an equilibrium of several forms of oxygen in a fixed-point cell, gaseous in the cell's atmosphere, dissolved in the fixed-point metal and as oxide in a separate (solid) phase. We will conclude that in many fixed points most of the oxygen is not dissolved in the metal, but bound in oxides of the fixed-point metal as well as oxides of some impurities. To demonstrate the impact that the precipitation of impurity oxides has on thermometry, two indium fixed-point cells were doped with magnesium and chromium, which leave the fixed-point temperature unchanged. Further evidence is drawn from earlier work. All these results support the presumed existence of (at least one) persistent separate oxide phase in the fixed points of indium, tin, zinc and aluminium, which renders them eutectic or peritectic points and is a more likely reason why the oxygen content of a cell does not influence the fixed-point temperature.To complement these studies, thermodynamic calculations show how to treat the equilibrium in the cell quantitatively. Using available chemical data, a list is provided that indicates for each fixed-point metal (including the other metal fixed points of the ITS-90: mercury, gold, copper) the impurities that probably build oxides. Due to the agreement of the calculated values with the presented experimental results, we suggest excluding those impurities from the correction of a fixed-point temperature (e.g. the SIE method), unless there is strong evidence of their dissolution.
An adiabatic calorimeter was used to measure the enthalpy of fusion of a very pure sample of indium. The new value of the enthalpy of fusion was determined to be Δfus H = (28.6624 ± 0.0076) J·g-1, where the uncertainty corresponded to a 95% confidence interval. The temperature of fusion of this sample was found to not differ from the ITS-90 assigned value within the accuracies of the thermometry used in the present study. A comparison with previous determinations is made.
The CCT has completed the guide summarizing the uncertainties in the realization of the SPRT subranges of ITS-90 between the triple point of neon (24.5561 K) and the freezing point of silver (961.78 • C). This article identifies aspects of standard platinum resistance thermometry where either data or models are lacking and further research is required. In the calibration of SPRTs, the two main concerns are the need for data on liquidus slopes for the different impurities in the fixed points and improved understanding of the impact of the thermal environment of the fixed point on the realized temperature. In the use of SPRTs, the two largest sources of uncertainty are Types 1 and 3 non-uniqueness and oxidation. The causes of Type 3 non-uniqueness are not yet understood, especially at low temperatures, and there is a paucity of data for the high-temperature subranges. In respect of oxidation, there is a need for validation of the models developed in the 1980s, especially in light of the reduced partial pressure of oxygen used in modern SPRTs. A range of other effects including vacancy effects in SPRTs, isotopic effects in fixed points, and improved statistical methods are discussed.
Results of an intercomparison of measurements of thermal conductivity, thermal diffusivity, specific heat capacity, and density of polymethyl methacrylate (PMMA) in the temperature range between −70 • C and +80 • C are presented. The purpose of this comparison is to investigate the variability of the results among guarded hot-plate (GHP) and guarded heat-flow meter (GHF) techniques on the one hand and among GHP/GHF and other measuring instruments on the other. The primary objectives are to characterize the material properties mentioned and to quantify the effects of thermal contact resistances and temperature measurements. With regard to future use of PMMA as a reference material, reference data for the thermal conductivity are derived.
The temperature and flatness (shape) of a fixed-point plateau depend on both the amount and nature of specific impurities and on thermal effects that are influenced by the fixed-point cell design and furnace properties. A better understanding and experimental proof of the influence of specific impurities on fixed-point realizations require the separation of impurity influences from thermal effects. In this paper the influence of heat exchange between the thermometer and furnace is quantified via a method based on changing the furnace temperature during the fixed-point measurement. It will be shown that the corresponding correction of this thermal effect has a dominant influence on the plateau shape compared to the influence of impurities. This leads to an explanation for why the maximum of an induced freeze is the most reproducible temperature. A secondary outcome is an explanation of why natural freezes have less flat plateaux compared to induced freezes, resulting in fixed-point temperatures that are too low. Furthermore, the suggested procedure is the basis of the direct and quantitative comparison of fixed-point cells and the detection of weak points within a specific design. It allows optimization of fixed-point cells and furnaces, and helps to deepen the common understanding of the phase transition in fixed-point cells.
The International Temperature Scale of 1990 assigns temperatures to the solid-liquid phase transitions (triple points, melting points, freezing points) of various substances. Since the ideally pure substances of the definition are unattainable in practice, the influence of impurities must be accounted for. Frequently, this is the dominant uncertainty component in realizing these most important reference temperatures. While a number of methods have been employed to estimate the uncertainty arising from the impurity effect, current thinking appears to have converged on methods that depend on chemical analyses of the materials employed. For the majority of cases, the demands of the thermometry community exceed the capabilities of routine analytical chemistry. It may, therefore, be necessary to consider a concerted action to rigorously characterize homogeneous batches of material using as many techniques as can reasonably be brought to bear on the problem in an effort to develop certified reference materials to serve both the thermometry and chemical metrology communities.
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 (24.5561 K) 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 nonuniqueness of the SPRT interpolations. The article gives a graphical summary of the total uncertainties in ITS-90 over the SPRT temperature range.
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