| Popis: |
The International Temperature Scale of 1990 (ITS-90) defines the present S.I.(“System International”) means of measuring temperature. The ITS-90 uses the freezing points of metals to define temperature fixed points. It also uses long-stemplatinum resistance thermometers to interpolate between the fixed points from 660 °Cdown to 84 K (if one includes the Argon triple point). Impurities are a major source of uncertainty in the fixed point temperature (of the order of 1 mK). And a better understanding of the impurity effect is required to improve top-level metrologicalthermometry. Most historical experiments with impurities have worked at a muchhigher levels of impurities – say of the order of 100ppm - and in arrangements that are not used on a day-to-day basis in a metrology laboratory. This thesis describes the deliberate doping of tin and aluminium, each with three different impurities and the effects of these on the temperature of the tin and aluminium liquid-solid phase transitions. The impurities, of the order of 1-30 ppm,were Co, Pb and Sb in the tin and Cu, Si and Ti in the aluminium. The tin and aluminium samples were in the form of ~0.3 kg ingots that would normally be used to realise an ITS-90 fixed point. Measurements were made using equipment normally available in a metrological thermometry laboratory, rather than using specially prepared samples. The samples were chemically analysed (by Glow Discharge Mass Spectrometry(GD-MS)) before and after the doping. Using the amount of dopants introduced,and/or the chemical analysis data, the measured temperature changes were compared with those interpolated from the standard text. The experimental undoped liquid-solid transition curves were also compared against theoretical curves (calculated from atheoretical model MTDATA). The results obtained did not disagree with the Hansen interpolated values (though there was considerable uncertainty in some of the measurements (e.g. a factor of 2 ormore) due to the measurement of small changes. Within these uncertainties it indicatesthat the Sum of Individual Estimates (SIE) method of correcting for, at least, metal impurities in otherwise high purity metals remain valid. However the results also showed considerable discrepancies between the initial measured and calculated temperature shifts (based on the pre-existing impurities prior to doping) suggesting that there may be impurities that are not (separately) detected by the GD-MS method. There was evidence that the thermal history of the metal phase transitions can cause considerable segregation of some impurities, particularly those likely to increase the phase transition temperature through a peritectic (“positive” impurities), and that the effects of this segregation can be clearly seen on the shape of the melting curves of thetin doped with Sb. Some of the aluminium doped with Ti freezing curves may also show evidence of a“concave up” shape at the start of the freezing curve, as previously calculated by MTDATA, though the effect is not as pronounced. All individual phase transition measurements - made over tens of hours – were repeated at least three times and found to be reproducible, hence providing a real dataset that can be used for comparison with theoretical models still under development. |
