Development of Microcalorimetry

许多量热法的准确数据部分归功于实验中使用了大量的纯化的葡聚糖。随着新材料合成和表征方法的发展，需要对各种类型的量热计进行热力学表征。为了使各种反应和非反应量热计小型化，同时又不损失量热数据的准确性和精密度，研制了一种低温绝热微量量热计，使其能够用小于1 g的少量样品测定第三定律熵。对激光闪光量热仪进行了改进，使其能获得1200K以下固体样品的可靠热容数据。建立了一种利用光照射交流量热技术测量1升液体样品热容的微量热计。研制了一种微型弹式量热计， 关于我们 测定无机和有机化合物的燃烧速率仅需10 mg样品。对微量溶液量热计进行了改进，使其用于测定苯与全氘代苯的混合焓，误差小于1%。气相沉积样品绝热微量热仪的研制为气相沉积非晶材料的研究开辟了新的途径。它们表现出非线性的焓松弛现象，其开始温度远低于液相淬火样品。带有稀释制冷机的极低温量热计可以测定低至20 mK的凝聚态物质的热容。这些进展使量热实验的适用范围扩大到许多可少量制备的新材料，并为热科学的研究开辟了新的途径。少

Many calorimetric methods owe their accurate data partly to large amount of purified speciman used in the experiments. Recent development in synthesis of new materials and characterization methods necessitated to miniaturize various types of calorimeters for the thermodynamic characterization. It is the purpose of this research project to aim at miniaturization of various kinds of reaction and non-reaction calorimeters for further development of thermoscience without loss of accuracy and precision of the resulting calorimetric data.A low-temperature adiabatic microcalorimeter was developed which made it possible to determine the third law entropy with small amount of specimen less than 1 g. A laser-flash calorimeter was improved so as to produce reliable heat capacity data of solid sample up to 1200 K. A microcalorimeter was built for measuring the heat capacity of a 1- l liquid sample using a light-irradiation ac calorimetric technique. A micro-bomb calorimeter was developed which req … More uired only 10 mg of sample for the determination of enthalpies of combustion of inorganic and organic compounds. A micro-solution calorimeter was improved in a sophisticated way so that the enthalpy of mixing between benzene and perdeuterobenzene was determined with inaccuracy of 1 %. An adiabatic micro-calorimeter for vapor-deposited sample clarified a new aspect of vapor-deposited amorphous material. They showed non-linear enthalpy relaxation phenomennon which started at much lower temperature than those for liquidd-quenched sample. A very low-temperature calorimeter with a dilution refrigerator made it possible to determine the heat capacity of condensed matter down to 20 mK. This clarified many aspects of magnetic material possessing weak interaction among the constituents.These development widen the applicability of the calorimetric experiments to many types of new materials which are possible to prepare only in small quantity, and surely open the door to novel way of thermoscience. Less