Thermodynamic models for metal-salt-oxide liquid solutions

金属盐氧化物液体溶液的热力学模型

• 批准号: RGPIN-2018-06655
• 负责人: Chartrand, Patrice
• 金额: $ 3.35万
• 依托单位: École Polytechnique de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=689376
• 关键词: Thermodynamic; models; metal; salt; oxide

The objective of the proposed research program is to develop a strong and systematic approach for the modeling of mixed metallic and ionic molten phases in order to obtain reliable predictions of the liquid phase thermodynamic properties and its equilibria with solid and gas phases in multicomponent systems of industrial and scientific interests. Primary metals production tions, diffusion of species under different conditions. The CALPHAD Method has very strongly established itself as a mandatory tool in the calculation of phase equilibria and thermodynamic properties of metallurgical and chemical inorganic systems. It consists in developing Gibbs energy functions, calibrated on experimental data and First-Principles calculations, for every given phase in a chemical system. Chemical and phase equilibria can be computed by the use of minimization techniques applied to find the combination and composition of phases that give a minimum in the energy. This approach is now applied worldwide for multicomponent chemical systems. ***Unfortunately, the proper modeling of the miscibility and immiscibility between liquid metals and molten oxides/salts is not well established, especially relative to the known chemical species that are affecting their electrical conductivity. Molten metal-salt equilibria show cases of full liquid miscibility (Fe-FeS, Cs-CsCl), partial miscibility (Cu-Cu2O), strong immiscibility (Cu-Cu2S, Li-LiF), or virtually complete immiscibility (Mg-MgCl2).***The scientific approach in this project consist in systematic tests and implementation of a liquid thermodynamic model which will use ion species derived from the electrical conductivity measurements to cover, with a single Gibbs energy function, the complete composition range between the liquid metal and the ionic composition range. This model will be tested for alkali metal-alkali halide salts, for Mg-Cd-Bi-chlorides and for metal alloys that exhibits a partial ionic character, such as the alkali-heavy metals, and finally for the Cu-Fe-S-O-Si system used for Cu-smelting and converting. For the first time, the proposed research permit to evaluate correctly both the metal dissolution in ionic melts and non-metal dissolution in alloys. Benefits for Canada will be in the field of metal production (Cu smelting, specialty metals and alloys) and in the energy efficiency by increasing current efficiency in electrolysis.

拟议研究计划的目标是开发一种强大而系统的方法来模拟混合金属和离子熔融相，以获得工业多组分系统中液相热力学性质及其与固相和气相的平衡的可靠预测。和科学兴趣。初级金属生产和不同条件下物种的扩散。 CALPHAD 方法已成为计算冶金和化学无机系统的相平衡和热力学性质的强制性工具。它包括为化学系统中的每个给定相开发吉布斯能量函数，并根据实验数据和第一性原理计算进行校准。化学和相平衡可以通过使用最小化技术来计算，该技术用于找到给出能量最小值的相的组合和组成。这种方法现已在全球范围内应用于多组分化学系统。 ***不幸的是，液态金属和熔融氧化物/盐之间的混溶性和不混溶性的正确建模尚未建立，特别是相对于影响其电导率的已知化学物质而言。熔融金属盐平衡显示完全液体混溶（Fe-FeS、Cs-CsCl）、部分混溶（Cu-Cu2O）、强不混溶（Cu-Cu2S、Li-LiF）或几乎完全不混溶（Mg-MgCl2） .***该项目的科学方法包括系统测试和液体热力学模型的实施，该模型将使用从电导率测量得出的离子种类来覆盖，并用单个吉布斯能量函数，液态金属和离子成分范围之间的完整成分范围。该模型将针对碱金属-碱金属卤化物盐、Mg-Cd-Bi-氯化物和表现出部分离子特性的金属合金（例如碱重金属）进行测试，最后针对 Cu-Fe-S-O- 进行测试。用于铜冶炼和转炉的硅系。拟议的研究首次允许正确评估离子熔体中的金属溶解和合金中的非金属溶解。 加拿大将受益于金属生产领域（铜冶炼、特种金属和合金）以及通过提高电解电流效率来提高能源效率。