复杂流体-固体界面相互作用热力学机制

具有复杂结构的纳微界面往往是界面复杂作用和宏观实验现象的主导因素。要准确描述界面处复杂流体的行为,需要引入能描述复杂流体-固体界面相互作用的分子热力学模型。本综述围绕分子热力学模型化方法拓展至纳微界面传递问题,提出"分子热力学建模+分子模拟+纳微实验"三者有机配合新思路。并针对复杂流体-固体界面相互作用的定量研究,着重综述了作者在热力学建模,分子模拟以及采用原子力显微镜(atomic force microscopy,AFM)实验方面的研究进展,创新性地提出将AFM定量化分析作为桥梁,用于构建分子模拟模型,描述复杂界面作用,揭示分子热力学机制,为构建纳微界面传递模型以及分子热力学模型由体相拓展至界面提供了可能。     

限域传递机制初探：以限域状态为切入点描述传递阻力

纳米限域空间中分子的传递是新一代化工过程的共性问题。限域空间引入界面润湿性与限域自由度，导致固体-流体受到的非对称相互作用显著，使得流体状态大幅度偏离均一主体相，经典传递理论不再适用。面向限域的传递理论的缺失，已不能满足现代化工发展的需求。本文综述本团队及前沿的限域传递研究工作，并基于统计力学与非平衡热力学方法进行分析，发现前沿研究分别涵盖三个角度：新自由度下分子间相互作用力决定流体反常状态，反常状态描述流体限域传递物性，反常传递物性描述限域传递阻力实现通量描述。针对三个角度，总结出限域传递阻力雏形，并从三个角度对限域热点工作初探分析，以限域状态为起点，将三个角度贯通是发展限域传递模型的方向，进而为现代化工发展基础数据和模型。     

受限界面处流体分子行为的调控及相关分子热力学模型初探：基于高比表面氧化钛的研究进展

纳米受限界面处的流体由于受到界面性质的影响显著,且存在复杂的传递和反应机制耦合问题,其流体分子行为难以调控,成为了现代化工新技术（如膜过程、多相催化）突破的瓶颈。结合了近几年本课题组的相关工作进展,以化学性质稳定的高比表面氧化钛作为研究平台,对界面处流体分子受限行为进行分析,研究了传递和反应机制分别对界面处流体行为的影响,并探索其调控机制;同时对建立的相应分子热力学模型进行了初步探索,通过原子力显微镜技术将界面摩擦性质和分子间相互作用关联,为分子热力学模型提供分子参数。     

受限界面处流体分子行为的调控及相关分子热力学模型初探:基于高比表面氧化钛的研究进展

纳米受限界面处的流体由于受到界面性质的影响显著,且存在复杂的传递和反应机制耦合问题,其流体分子行为难以调控,成为了现代化工新技术(如膜过程、多相催化)突破的瓶颈。结合了近几年本课题组的相关工作进展,以化学性质稳定的高比表面氧化钛作为研究平台,对界面处流体分子受限行为进行分析,研究了传递和反应机制分别对界面处流体行为的影响,并探索其调控机制;同时对建立的相应分子热力学模型进行了初步探索,通过原子力显微镜技术将界面摩擦性质和分子间相互作用关联,为分子热力学模型提供分子参数。     

利用二维变阱宽方阱链流体分子热力学模型计算吸附等温线

以二维硬碟流体为参考,借助现代分子热力学研究方法建立了一个二维变阱宽方阱链流体的分子热力学模型(SWCF-VR-2D),并将建立的模型用于气体在固体界面吸附的关联计算中,获得了相应吸附质和吸附剂的模型参数。发现模型能满意再现氮气、甲烷、乙烷、乙烯等气体在硅胶、活性炭、沸石、金属有机骨架(MOF)等不同固体界面上的吸附等温线,总的平均绝对偏差为3.42%,其中能量参数εw反映了吸附剂与吸附质之间的相互作用大小。     

利用二维变阱宽方阱链流体分子热力学模型计算吸附等温线

以二维硬碟流体为参考,借助现代分子热力学研究方法建立了一个二维变阱宽方阱链流体的分子热力学模型(SWCF-VR-2D),并将建立的模型用于气体在固体界面吸附的关联计算中,获得了相应吸附质和吸附剂的模型参数。发现模型能满意再现氮气、甲烷、乙烷、乙烯等气体在硅胶、活性炭、沸石、金属有机骨架(MOF)等不同固体界面上的吸附等温线,总的平均绝对偏差为3.42%,其中能量参数ε _w反映了吸附剂与吸附质之间的相互作用大小。     

纳微界面增强CO2吸收及机理分析

CO₂捕集与分离是解决当前全球温室效应和发展可再生能源的关键步骤，传统CO₂分离及过程强化方法存在速率与效率的博弈。纳微界面强化广泛用于多相传递的化工过程，其对CO₂传递过程的影响也比较显著。本综述从纳微界面处CO₂传递模型的建立及阻力调控、纳微界面处CO₂平衡态化学位的获取(推动力调控)以及界面强化机制的分子模拟分析等三个方面进行阐述。基于上述结果进一步分析真实吸收塔分离CO₂过程的阻力调控并提出“三段式强化方案”，以优化CO₂分离过程的投资与运行成本。     

利用二维流体分子热力学模型计算气体混合物在固体界面的吸附等温线

结合流体混合规则,将之前建立的二维变阱宽方阱链流体分子热力学模型（SWCF-VR-2D）扩展至混合流体,并利用模型计算了甲烷/二氧化碳、甲烷/氮气和甲烷/乙烷等气体混合物在不同吸附剂上的吸附等温线。由于混合气体间的相互作用会使得混合气体的吸附不同于单一气体的吸附,通过调节气体与固体壁面间的相互作用参数ε_w以描述这种变化。调节能量参数后模型能满意计算混合气体的吸附等温线,总的平均偏差为5.06%。     

流体-固体两相流的数值模拟

鉴于流体 -固体两相流及其数值模拟在化学工程中愈来愈广泛的应用 ,本文综述了Euler坐标系下流体相湍流模型、颗粒轨道模型以及流体 -颗粒双流体模型的基本原理和数值模拟方法 ;对相间耦合和颗粒间的相互作用也进行了介绍 ,特别是对能详细描述多颗粒间相互作用的颗粒离散单元法在流体 -固体两相流中的应用进行了详细描述 ;在评述各模型的优缺点和分析目前存在的问题的基础上 ,提出了今后的发展方向     

超临界二氧化碳微乳反胶束体系的分子动力学模拟进展

超临界CO2微乳液/反胶束体系,是在表面活性剂作用下形成的CO2包水（W/C）或者水包CO2（C/W）型且热力学性质稳定的透明液体。通过改善超临界CO2的性质,可以极大地拓展超临界流体技术的应用领域。其热力学性质、传递性质以及相行为是应用的基础。对此复杂体系由实验量测所获得的信息远不能满足实际需要,但分子动力学模拟则可以达此目的。总结了有关分子动力学模拟在超临界CO2微乳液/反胶束体系研究中的进展,重点分析了模拟实施过程中应该注意的关键问题,对于分子力场构建、单元体设计、平衡控制等热点问题给予分析和阐述,并就应该致力于研究的核心方向进行了初步探讨。     

基于微量热法对多孔碳与双氧水相互作用过程的传质阻力分析

多孔材料作为催化剂对现代化学工业起到重要推动作用,但其纳米受限孔道造成的界面传递问题不容忽视。直接法合成双氧水（H₂O₂）过程中,揭示H₂O₂脱附过程传递与反应竞争博弈的介尺度机制是提高产率的关键。线性非平衡热力学为解耦界面扩散及反应提供了统一框架,但缺少合适通量测定方法。因此,本文设计多孔碳与H₂O₂相互作用的微量热实验,结合分子模拟及孔结构表征实验揭示多孔碳材料的界面传递结构,实现了非平衡热力学的定量传质阻力分析,进一步获取了表界面浓度场的动态变化。研究结果表明：微量热法是定量解耦并揭示扩散-反应机制的有效线性非平衡热力学阻力分析方法;介孔结构、生物骨架结构及担载1%（质量） Pd元素均能增强H₂O₂在多孔碳中的传质通量,但实现超高通量需要扩散与反应阻力的匹配;非平衡热力学阻力解耦方法是揭示多相反应过程介尺度机制的重要定量描述方法,有望为过程的调控及优化提供理论依据。     

材料化学工程科学内涵及方法初探:从介观尺度界面流体行为出发认知材料

作为一门新兴的交叉学科,材料化学工程科学内涵的进一步凝练和方法论的建立显得十分重要和迫切。介观尺度下界面流体的研究对于材料化学工程具有重要意义,材料化学工程的科学内涵在于通过认识介观尺度下界面处流体行为来"认知"材料,以期建立材料结构、性能(应用)与制备(生产)三者之间的关系。其中,弄清介观尺度下复杂作用和复杂结构对界面流体行为的影响,是"认知"材料的关键。分子模拟技术作为单因素遴选介观尺度各影响因素的有效手段,在实际应用中存在两大难点:如何同时获得界面流体反应和传递两个方面的信息;如何实现分子层面认识在材料应用层面的转化。基于此,初步讨论了材料化学工程研究方法的发展趋势。     

Atomistic Investigation on the Effects of Thermal Loading on Interfacial Adhesion of Dissimilar Materials

Heat transfer has a large effect on the adhesion and the corresponding failure at material interfaces. When a system becomes extremely small, the conventional finite element method is not capable of accurately capturing all the information, and precise modeling of interfacial properties is essential. In this paper, molecular dynamics (MD) simulations are used to investigate the effects of heat transfer on the adhesion properties of material interfaces. For Al–W and Cr–W interfaces, the interfacial strengths are calculated by MD simulations and are compared with the critical loads obtained from scratch tests. Both the results of MD simulations and experiments show that the interfacial strength of an Al–W interface is larger than that for a Cr–W interface; and furthermore, the Cr–W interface is more sensitive to thermal loading than the Al–W interface. In this work we concluded that the proposed MD model can be used to estimate interfacial adhesion under the effects of heat transfer.     

界面性质对气液传质的影响

界面性质对气液传质有重要影响。分子通过界面时需克服界面自由能，界面两侧的浓度不一致。本文导出了两者之间的关系     

醇/烃系统的分子热力学(Ⅱ)1-2-4模型应用于汽液平衡

建立了1个醇/烃系统的分子热力学模型,用红外光谱法获得的醇的标准缔合常数应用于汽液平衡,能够很好地区分醇类缔合物质的化学作用和物理作用,所得化学参数和物理参数具有明确的物理意义.计算表明:本文提出的1-2-4缔合模型在应用1个二元可调参数的情况下能较好地描述含醇系统的汽液平衡性质.即使对于不同链长的正构醇采用统一的缔合常数,同样可获得较好的结果.     

Volume of fluid method for interfacial reactive mass transfer: Application to stable liquid film

A volume of fluid method is developed in order to simulate reactive mass transfer in two-phase flows and is applied to study reactive laminar liquid film. The thermodynamic equilibrium of chemical species at the interface is considered using Henry's law. The chemical species concentration equation is solved using primitive variables and local fluxes are locally directly calculated at the interface. The present treatment of jump discontinuity of chemical concentration is consistent with a volume of fluid approach and the difficulty to calculate accurate local mass flux across interface is overcome. For plane interface, the precision of the numerical simulation is found to be very satisfactory while for curved interface a special procedure has been developed to reduce the development of spurious fluxes at the interface. The algorithm is validated for different cases by comparison with available solutions. The method is then applied to study non-reactive and reactive mass transfer in a falling liquid film. The results show that the liquid side mass transfer is well predicted by the Higbie (1935) theory when the transfer is controlled by the film advection provided that adequate parameters are considered, i.e. the actual velocity at interface and not the average liquid film velocity. For situations controlled by diffusion, the Sherwood number tends to a constant value characteristic of purely diffusive situations. For the reactive mass transfer, first and second order irreversible chemical reactions in the liquid phase are considered. The numerical results are compared respectively, with Danckwerts (1970) and Brian et al. (1961) solutions and good agreement is observed. The proposed Volume of Fluid method is shown to be well adapted to deal with interfacial reactive mass transfer problems.     

Wetting and Interfacial Bonding of Metals with Ionocovalent Oxides

The adhesion and interfacial bonding between nonreactive liquid metals and solid inocovalent oxides are studied on the basis of the experimental work of adhesion W data. An analysis of the experimental W values of different liquid metals on various solid oxides is first performed to put into evidence the dependences of the work of adhesion of a metal/oxide system on the electron density of the metal and on the thermodynamic stability of the oxide. An electronic model is then proposed to describe the microscopic mechanism of metal–oxide interactions. Based on the model, the work of adhesion and the contact angle of different liquid metals on various solid oxides can be interpreted and estimated, and their correlations to the various physical properties of the oxides can be easily deduced. The basic consideration of the model is that the adhesion between a metal and an oxide is assured by the electron transfer from the metal into the oxide valence band which is not completely filled with electrons at high temperatures, and is enhanced when this electron transfer at the metal/oxide interface is increased. The extension and application of the model to solid metal/solid oxide systems is also presented.     

The mechanism model of gas–liquid mass transfer enhancement by fine catalyst particles

In order to present the enhancement of gas–liquid mass transfer by heterogeneous chemical reaction near interface, the mechanism model has been proposed to describe the mass transfer rate for a gas–liquid–solid system containing fine catalyst particles. The composite grid technique has been used to solve the model equations. With this model the effect of particle size, first-order reaction rate constant, distance of particle to gas–liquid interface and residence time of particle near gas–liquid interface on the mass transfer enhancement have been discussed. The particle–particle interaction and slurry apparent viscosity can be considered in the model. The experimental data have been used to verify the model, and the agreement has been found to be satisfied.     

Methods of nonequilibrium thermodynamics for studying and simulating mass transfer processes in liquid-liquid systems

A mass transfer model in which the generalized thermodynamic force accounting for colloidal and chemical phenomena in the interfacial zone, such as the formation of disperse interfacial layers and films, is taken to be the driving force is considered. A method for calculating the difference between the pressures in the film and in the phase, the interfacial-film thicknesses, and mass transfer coefficients is proposed. It is found that the resistance to mass transfer in porous films varies with time, passing through a maximum.