真空下低价二氯化铝生成及其分解热力学简化研究

对不同压力下三氧化二铝与碳、氯化铝在低价氯化物法炼铝过程中生成低价二氯化铝及低价二氯化铝分解的热力学条件进行简化计算.研究得出:在100 kPa时,三氧化二铝与还原剂碳反应在1896 K以上才能生成低价二氯化铝;而当系统压力在100～10 Pa内时,温度在1294～1396 K以上就可以生成低价二氯化铝;在压力为105～10 Pa范围,1195～829 K以下都可以进行二氯化铝的岐化分解,而且温度降低,温度越低,歧化分解越容易进行,且简化计算与实验事实更接近.     

三氧化二铝在低价化合物法制备铝过程中的歧化行为研究

利用"物质吉布斯自由焓函数法",讨论了不同压力下三氧化二铝生成低价一氧化铝及低价一氧化铝分解的热力学条件.研究得出:在100 kPa时,三氧化二铝与还原剂碳反应在3097.86 K以上才能生成低价一氧化铝;而当系统压力在100～10 Pa内时,温度在2372.07～2194.31 K以上就可以生成低价一氧化铝;在压力为105～10 Pa范围,温度在2544.02 K以下低价一氧化铝都可以进行歧化分解.     

二氧化硅在真空低价法制备铝过程中的歧化行为研究

本文引入"物质吉布斯自由能函数法"讨论在低价氟化法制备铝过程中,二氧化硅在不同压力和温度下生成低价氧化硅及其分解的热力学条件并进行了实验验证.研究得出:在100kPa时,二氧化硅与还原剂碳反应在1937K以上才能生成低价氧化硅;而当系统残余压力在100Pa～10Pa内时,在1463K～1352K以上即可以生成低价氧化硅;体系压力在100Pa～10Pa范围内,即低价氧化硅歧化分解温度在1535K～1415K间进行.实验结论:采用真空碳热还原铝土矿实验,在系统压力为150Pa,反应温度为1450℃时,得到含硅为4.87%的金属铝,铝纯度达到95.13%.实验验证了理论研究的正确性,为生产工艺的研究提供了热力学理论依据和实验基础.     

二氧化钛在低价化合物法制备铝过程中的歧化行为研究

利用"物质吉布斯自由焓函数法",讨论了不同压力下低价化合物法介取铝过程中二氧化钛生成低价氧化钛及低价氧化钛分解的热力学条件.研究得出:在100 kPa时,二氧化钛与还原剂碳反应在2373.96 K以上才能生成低价氧化钛;而当系统残余压力在100～10 Pa时,在1743.41～1613.46 K即司以生成低价氧化钛;在残余压力为105～10 Pa范围,温度在1890 K以下都可以进行低价氧化钛的歧化分解.     

真空下生成AlF2的热力学研究

利用铝的低价氟化物（AlF2）在高温下存在，低温下不稳定且容易分解而得到金属铝的特性，从热力学角度引入：“物质吉布斯自由能函数法”讨论在不同压力下，氧化铝、三氟化铝与还原剂碳的反应生成低价氟化物（AlF2）的条件。研究表明在常压下反应在1820K以上发生。而在真空度（即残压）为20000～20Pa时，反应在1683～1345K时就能进行，比常压下降低了137～475℃，为真空下铝的低价卤化物歧化分解炼铝提供热力学理论依据。     

真空下生成低价氟化铝的热力学分析

本文从热力学角度引入“物质吉布斯自由函数行列式法”讨论在不同压力下氧化铝、氟化铝与还原剂碳的反应生成低价氟化物（AIF）的条件。研究表明在常压下反应在2100K以上发生；而在真空度为350～28Pa时，反应在1800～1500K时能进行，比常压下降低了300-600K，为生产工艺的研究提供了热力学理论依据和试验基础。     

对氧化铝碳热还原-氯化法炼铝过程中碳化铝的氯化反应研究

采用热力学分析及X射线衍射、扫描电子显微镜及能谱仪等方法与手段,系统研究了中真空条件下碳化铝与氯化铝的反应。通过热力学研究,在10～100 Pa,温度低于1773 K时,Al与C生成Al4C3的反应及Al4C3与AlCl3的反应满足反应发生的热力学条件。实验研究表明,Al4C3可以通过Al与C反应制得;在1773 K、10～100 Pa下,Al4C3与AlCl3可以发生反应,并在冷凝区得到金属铝,热力学研究与实验研究完全一致。在真空碳热-氯化法炼铝过程中存在着Al4C3与AlCl3发生的反应,其是氯化过程中的重要反应之一。     

SiO2在真空低价氟化法炼铝过程的分布

热力学研究得出:当系统残余压力为100~10 Pa时,SiO2与碳反应在1465~1353 K以上即可生成Si和CO;在1329~1225 K以上即可生成SiC和CO;SiO2和还原剂碳及氟化铝在1464~1353 K以上反应生成SiF4和CO及铝。实验考察了真空低价氟化法炼铝过程中SiO2的分布。XRD表明:SiO2在低价氟化法炼铝过程中有五种走向:(1)被还原成SiC,存在于残渣相;(2)被还原为单质硅,再与还原出的铁生成硅铁,存在于残渣相;(3)SiO2与冰晶石生成铝硅酸盐进入气相中;(4)SiO2与冰晶石生成气态SiF4,再与冰晶石分解的氟化钠形成Na2SiF6进入冷凝相;(5)形成气态低价氧化硅,再在合适温度下分解为单质硅进入冷凝相。     

低价硫化物法直接提取铝的热力学研究

本文利用铝的低价硫化物（AlS）在高温下存在，低温下不稳定容易分解得到金属铝的特性，从热力学角度引入“物质吉布斯自由能函数法”讨论在不同压力下，氧化铝、硫化亚铁与还原剂碳的反应生成低价硫化物（AlS）的条件。研究表明在常压下反应在2480K以上发生；而在真空度（即残压）为300Pa-15Pa时，反应在1800K-1610K时就能进行，比常压下降低了680K-870K，同时用氧化铝、硫化亚铁与还原剂碳在真空炉内试验，验证了理论研究的正确性。为生产工艺的研究提供了热力学理论依据和试验基础。     

用磷矿石真空制备黄磷的热力学研究

引入“物质吉布斯自由能函数法”讨论在不同压力下，磷酸钙、二氧化硅与还原剂碳的反应生成黄磷的热力学条件。研究表明在常压下反应在1460K以上发生；真空条件下，压力降到60～6Pa时，反应在1066～984K时就能进行，比常压下降低了446～476K。真空下磷矿石制备黄磷的热力学研究为工艺实验研究提供理论依据。     

High-temperature electrical conductivity of aluminium nitride

The electrical conductivity of hot-pressed polycrystalline aluminium nitride doped with oxygen and beryllium was measured as a function of temperature from 800 to 1200° C and over a range of nitrogen partial pressure from 10² to 10⁵ Pa. The effect of beryllium dopant, the independence of conductivity from nitrogen partial pressure, and the observed activation energy suggested extrinsic electronic species or aluminium vacancies as charge carriers. Polarization measurements made with one electrode blocking to ionic species indicated that the aluminium nitride with oxygen impurity was an extrinsic electronic conductor.     

高岭土在真空下的热分解行为

以含高岭石、一水硬铝石、黄铁矿的高岭土为原料,经过压块烘干后,在真空(15~50 Pa)、不同加热温度下,采用同步热分析仪(DSC-TGA)、X射线衍射(XRD)等分析手段对高岭土在真空下的热分解进行研究。DSC-TGA的结果与高岭石、一水硬铝石、黄铁矿三种矿物常压下的热力学计算出的分解温度相符。实验产物的XRD结果表明:在真空条件(15~50 Pa)下,一水硬铝石AlO(OH)在100~200℃之间脱水,300℃时脱水完全;黄铁矿FeS2在500~600℃分解,分解产物为FeS和S2,在700℃时,黄铁矿FeS2分解完全;高岭石Al2Si2O5(OH)4在实验煅烧过程中,在200~300℃之间脱水,生成非晶态的偏高岭石,比该矿在常压的脱水温度提前200℃左右。继而转变成A-lSi尖晶石,最后形成莫来石与方石英。实验结果与热力学计算符合,充分说明真空条件对高岭土中各种矿物分解产生气体的反应有较大的促进作用。在本实验三种矿物分解产生气体的过程中,先进行的反应对后一反应的发生影响不明显。     

Effect of residual stress on the strength of alumina-steel joint with Al-Si interlayer

The effect of residual stress on the strength of an alumina-steel joint with the Al-Si interlayer was studied. Alumina rods, 32 mm in diameter and 9 mm in length and steel pipes were diffusion bonded at 873 K and at a contact pressure of about 5 M Pa for 30 min in a vacuum of 24×10^–2Pa. The interlayer of aluminium sheet clad with Al-10% Si alloy on both sides was used. The tensile strength of the joints is influenced by the thickness of the interlayer or the intermetallic compound formed between the interlayer and the steel. The strength increases with increasing interlayer thickness and with decreasing intermetallic compound thickness. It is found that the residual stress measured by Sachs method is much lower than that by the elastic calculation. The stress decreases with increasing interlayer thickness. Increase in thickness of the aluminium core of the interlayer is effective in improving the joint strength. This improvement can be explained by considering the stress of the joint.     

CaC_2还原MgO热力学分析与实验研究

本文对常压及真空条件下以碳化钙为还原剂制取金属镁的热力学分析,计算出平衡状态下镁蒸汽的露点,并进行真空热还原实验研究.结果表明:常压下临界反应温度为2095K;当系统压力降至10~3Pa和10Pa,临界反应温度依次降为1376K和1030K;达到平衡时,还原温度1316K时,镁蒸汽的露点为熔点,还原温度为1273K、1373K时,露点分别为901K、958K.升高还原温度或延长还原时间可提高镁收率和CaC_2利用率;理论配比的反应物料在1423K条件下还原2h的镁收率为83.1%.而当还原时间达到2.5h,镁还原率和CaC_2利用率均超过80%.     

Adhesion, microstructure and composition of thermally evaporated aluminium thin layers on polyethylene terephthalate films

Industrial polyethylene terephthalate (PET) films have been metallized by aluminium evaporation in two different sets of experimental conditions. In the first set, aluminium layers of 100 nm thickness were deposited at a constant deposition rate (10 Å s⁻¹) for different residual pressures varying from 1 Pa to 10⁻⁴ Pa and, in the second set, the residual pressure was kept constant (2.6 × 10⁻³ Pa), while the deposition rate was varied from 5 Å s⁻¹ to 40 Å s⁻¹.

The adherence between the aluminium layers and the PET film was measured by means of scratch and peel tests. The critical load and the peel strength exhibit a maximum at about 10⁻² Pa when the deposition rate is kept constant.

The microstructure of the aluminium layers, mainly the mean grain size, was studied by transmission electron microscopy (TEM), while secondary ion mass spectrometry (SIMS) depth profiles through the aluminium layers were performed in order to provide the chemical information, mainly aluminium layer oxidation. Concerning the TEM results, the grain size increases when the residual pressure is decreased and also when the deposition rate is increased. The SIMS depth profiles show different levels for aluminium oxidation at the surface, in the bulk of the layers and at the interface, all increasing for high residual gas pressure and for low deposition rates.

From these results, it appears that the oxygen content at the Al---PET interface plays a critical role in the microstructure owing to its influence on the nucleation and on the growth of the aluminium layers. It also influences the adhesion between aluminium and PET for which an optimum oxygen amount seems to be required.     

On the Way to Determination of the Vapor-Pressure Curve of Pure Water

The determination of the physical properties of pure water, especially the vapor-pressure curve of water, is one of the major issues identified by the Consultative Committee for Thermometry of the International Committee for Weights and Measures (CIPM) to improve the accuracy of the national references in humidity. At the present time the saturation-pressure data, corresponding to ice or liquid?Cvapor equilibrium, at low temperature are scarce and unreliable. This study presents new measurements of vapor and sublimation pressures of, respectively, water and ice, using a static apparatus. Prior to saturation-pressure measurements, the temperature and pressure sensors of the static apparatus were calibrated against reference gauges in use at the LNE- CETIAT laboratories. The effect of thermal transpiration has been studied. The explored temperature range lies between 250 K and 374 K, and the pressure range between 70?Pa and 10⁵ Pa. An automatic data acquisition program was developed to monitor the pressure and temperature. The obtained results have been compared with available literature data. The preliminary uncertainty budget took into account several components: pressure measurements, temperature measurements, and environmental error sources such as thermal transpiration and hydrostatic correction.     

真空度对MBE GaAs光阴极激活结果的影响

采用分子束外延(MBE)技术生长的GaAs光阴极材料,按照常规方法进行高-低温两步激活时,总是出现低温灵敏度比高温低的反常现象.研究中,当激活时的系统真空度从1×10~(-7)Pa提升到1×10~(-8)Pa时,发现结果能够重新出现低温灵敏度比高温灵敏度高30%的预期规律.此外,在系统真空度为10~(-7)Pa条件下,由于变掺杂材料的表面掺杂浓度较低,其出现光电流时的首次进Cs时间也较均匀掺杂材料长,而在真空度为约10~(-9)Pa条件下,这一情况也不再明显.初步分析造成该现象的原因,是与MBE材料的掺杂元素及其低温处理特性对真空度比较敏感有关.MBE阴极激活结果受系统真空度条件影响较大,因此对MBE变掺杂光阴极的制备工艺应随系统真空度条件不同而调整.     

Oxidation of iron, aluminium and titanium films in the temperature range 50–200 °C

The oxidation kinetics of iron, aluminium and titanium films have been studied in the temperature range 50–200 °C at a pressure of 0.7 Pa with a piezoelectric quartz microbalance. For titanium, additional measurements in the pressure range 7 × 10⁻³ – 70 Pa have been carried out. All three metals under investigation showed qualitatively common features in their oxidation behaviour: a very fast initial oxygen absorption step, completed in less than 1 min, followed by a slow, temperature-independent oxide growth with logarithmic time law at lower temperatures, and an enhancement of the oxidation rate at higher temperatures. The oxidation curves are compared with the results of model calculations based on the Cabrera-Mott theory.     

Use of metastable, dissociated and charged gas species in synthesis: a low pressure analogue of the high pressure technique

Oxidation of silver using microwave-induced oxygen plasma and oxygen-ozone gas mixture was studied as a function of temperature and partial pressure. The oxide Ag₂O was formed at temperatures well above its normal decomposition temperature in oxygen plasma at a pressure of 5 Pa. The higher oxide AgO_1–x was formed in O₂₊O₃ gas mixtures at lower temperatures. The oxygen chemical potentials for the oxidation of Ag to Ag₂O, Ag₂O to AgO_1–x and AgO to Ag₂O₃ were evaluated from thermodynamic data and compared with the experimental results to obtain information on the chemical potential of oxygen in microwave plasma and gases containing ozone. The oxygen potential of the gas phase in microwave plasma operating at a pressure of 5 Pa was found to be in excess of 36 kJ/mol at 750 K. This is equivalent to a pressure of diatomic oxygen gas greater than 3 × 10⁷ Pa. In the O₂₊O₃ mixture at ambient pressure containing 5 mole percent O₃, the oxygen potential is 112 kJ/mol at 465 K. The equivalent pressure of diatomic oxygen is 4 × 10¹⁷ Pa. Thus, metastable species such as O₃ or charged species such as O^– present in plasma can be used as a powerful reagent for the syntheses of metastable oxides. Similar techniques can be used for other metastable inorganic solids such as nitrides for functional applications.     

Tensile properties and thermal expansion of discontinuously reinforced aluminium composites at subambient temperatures

The effects of temperature on the mechanical properties and thermal expansion of two discontinuously reinforced aluminium composites have been determined over the range 300–100 K. Silicon carbide particulate-reinforced 2009 and 6092 aluminium alloys were studied by tensile testing, in which both longitudinal and transverse strains were recorded, and by thermal expansion measurements. The test results clearly show that cooling to 100 K induces plastic flow in the aluminium alloy matrices due to the thermal expansion difference between aluminium and silicon carbide. At very low temperatures, the linear region of the stress-strain curve is greatly reduced or eliminated and the Poisson’s ratio, ν, increases. For the higher yield strength 2009 matrix composite, ν increases from a room-temperature value of 0.28 to 0.35 at 100 K. For the lower-strength 6029 matrix composite, ν increases from a room-temperature value of 0.33 to a value of 0.5 at 100 K. A Poisson’s ratio of 0.5 is the value characteristic of plastic flow in an incompressable material. Changes in yield strength, Young’s modulus and thermal expansion with decreasing temperature are also consistent with thermally induced plastic flow in the composite matrix. This revised version was published online in November 2006 with corrections to the Cover Date.