Проведено термодинамическое моделирование восстановления дихлорида меди в атмосфере различных газообразных гидридов (в аммиаке, моносилане, метане) в температурном интервале 273-1000 К. Расчеты показывают, что в более узких диапазонах значений температуры, отвечающих протеканию реакций твердотельного гидридного синтеза (ТГС) металлических веществ, образование металла, как правило, подтверждается теорией. В результате термодинамического моделирования получен принципиальный результат о подавлении конкурирующих процессов нитридирования, силицирования и карбидизации металла в условиях ТГС, имеющий значение для металлургических производств. Это дополнительно обосновывает корректность предыдущих экспериментальных исследований разработчиков ТГС металлов с модифицированной поверхностью и улучшенными свойствами. Путем моделирования выявлено, что восстановление твердого дихлорида меди до металла в атмосфере аммиака или метана происходит ступенчато (последовательно, согласно правилу Байкова) через промежуточные стадии образования соединения низковалентной меди -хлорида меди (I).Ключевые слова: металлургия меди; восстановление металлов из хлоридов; твердотельный синтез; фазовая модель; термодинамическое моделирование; хемосорбция гидридов Как цитировать эту статью: Влияние температуры на твердотельный гидридный синтез металлов по данным термодинамического моделирования / А.А.

A pulsed fiber laser with a wavelength of 1.06 µm was used to treat a commercial pure titanium surface in the air at intensities below the ablation threshold to provide oxide formation. Laser oxidation results are predicted by the chemical thermodynamic method and confirmed by experimental techniques (x-ray diffraction, energy dispersive x-ray spectroscopy). For the first time, the chemical thermodynamic method was used for determining the qualitative and quantitative phase-chemical composition of the compounds formed by a pulsed laser heating of commercial titanium in the air, and its applicability is proven. The simulation shows that multilayered composite film appears on a surface, the lower layers of which consist of Ti 2 O 3 and TiO oxides with the addition of titanium nitride; and the thin upper layer consists of transparent titanium dioxide. Also, the chemical composition of films remains unchanged within a temperature range of 881-2000 K.

A computational thermodynamic approach to determining the phase-chemical composition of films formed on the surface of metals and alloys under laser oxidation in the normal atmosphere, depending on their bulk composition, laser exposure conditions, and composition of the atmosphere, is suggested. It is demonstrated for the example of a complex alloy (alloyed steel of Russian brand 12X18H10T) subjected to laser heating in air that, among the wide variety of different possible reactions of iron, nickel, or chromium with the components of air (oxygen, nitrogen, carbon, its compounds, atmospheric moisture, etc), only strictly defined reactions can occur. First of all these are metal oxidation processes with the formation of an oxide film whose phase and chemical composition is determined by temperature and heating duration. Simulated results are confirmed by the experimental data provided by energy-dispersive x-ray spectroscopy.

theoretical methods for describing, modelling and calculation of phase-chemical transformations without limitations on numbers of components and phases has been developed with the aim of predicting, evaluating and optimizing the rheological properties of substances and materials, based on extreme thermodynamic functions principle (maximum entropy, minimum free energy, etc.). these methods and databases were implemented in the software-information complex Astics for thermodynamic simulation and calculation of phase-chemical transformations in multi-component engineering systems of different nature. the high effectiveness of the approach is illustrated by results obtained for various natural and engineering systems and processesmineral, rock, geochemical, silicate, glass, etc.

Mass flux occurring when a substance evaporates from an open surface is proportional to its saturated vapor pressure at a given temperature. The proportionality coefficient that relates this flux to the vapor pressure shows how far a system is from equilibrium and is called the accommodation coefficient. Under vacuum, when a system deviates from equilibrium to the greatest extent possible, the accommodation coefficient equals unity. Under finite pressure, however, the accommodation coefficient is no longer equal to unity, and in fact, it is much less than unity. In this article, we consider the isothermal evaporation or sublimation of low-volatile individual substances under conditions of thermogravimetric analysis, when the external pressure of the purging gas is equal to the atmospheric pressure and the purging gas rate varies. When properly treated, the dependence of sample mass over time provides us with various information on the properties of the examined compound, such as saturated vapor pressure, diffusion coefficient, and density of the condensed (liquid or solid) phase at the temperature of experiment. We propose here the model describing the accommodation coefficient as a function of both substance properties and experimental conditions. This model gives the final expression for evaporation rate, and thus for mass dependence over time, with approximation parameters resulting in the properties being sought.