降低固-液界面粘附作用的微观结构调整方向研究

固-液界面粘附作用是影响液相在固体表面动态性能的关键因素,降低固-液界面粘附力是疏液表面迈向实际应用的关键突破点。为探讨固相表面微观结构对固-液界面粘附作用的影响,采用高粘低表面张力液相端羟基聚丁二烯(HTPB)为主要指示液相,通过反应溶液和条件控制来调控固相表面的微观结构和形貌,制备疏液表面,并利用接触角仪、高精度天平和高速摄像等手段研究HTPB在疏液表面的静态接触角和动态粘附-脱附过程行为,揭示降低固-液界面粘附作用的微观结构调整方向。结果表明,固相微观结构在一定程度的变化对静态接触角影响较小,但对HTPB在脱附过程中液滴的形变产生较大影响,同时对比研究了低粘高表面张力液相水和甘油在疏液表面的动态粘附-脱附行为和粘附力值,通过力学物理模型简化,表明固-液界面的粘附力除了与液滴形状的变形量和本质特性紧密关联,还取决于固相表面微观结构。通过固相表面微观结构对界面粘附力的影响特性,认为构筑的微观结构更均匀致密,三维(X\Y\Z)方向上尺寸均实现纳米、亚微米到微米的连续性跨越时,可使固-液界面粘附力显著下降。     

液滴在固体表面流动特性的数值模拟及验证

为了研究液滴在固体表面的流动特性,采用格子Boltzmann(LBM)分子动力学和水平集(LS)界面跟踪相结合的方法(LBM-LS)对液体在固体表面流动铺展过程进行数值模拟,用LBM求解液体运动的流场,LS捕捉运动的固液气界面。结果表明,模拟结果与实验测定结果一致,铺展接触角随时间呈指数变化规律,液体表面张力越小铺展接触角越小,证明采用LBM-LS模型模拟润湿性问题是可行的。     

超疏水固体表面的制备及其量化表征

超疏水表面是指对水的接触角θ超过150°且滚落角α低于2°的固体表面,用来解释超疏水现象的两种经典理论分别是Wenzel模型和Cassie模型.在表征表面超疏水性时,除常用的θ、α外,接触角滞后△θ、斜面上液滴滞留在材料表面上的最大半径Rc、两种状态转化时的临界压力△p以及液滴落下后能反弹的临界撞击速度Vc也是非常重要的参数.依据表面微细结构和低表面自由能是构成超疏水表面的两个重要条件,阐述了通过在疏水表面构建表面微细结构和用低表面能物质修饰粗糙表面这两种方法制备超疏水表面,并提出了今后研究中应该注意的一些问题.     

微观结构对超疏水表面润湿性的影响

润湿性是衡量超疏水表面疏水强弱的最重要特征之一,而微观结构与超疏水表面的润湿性有着密切联系。本文讨论了导致超疏水现象的两种理论模型——Wenzel模型和Cassie模型,并运用模型分析了微观结构的几何参数对超疏水表面表观接触角的影响。分析表明,在制备超疏水表面过程中应使表面状态满足Cassie模型,并可以通过改变微观结构的几何参数来控制表面润湿性,获得具有较大表观接触角的超疏水表面。     

固体表面润湿性机理及模型

润湿性是固体表面的重要特征之一。人工控制和制备固体表面润湿性已成为研究的热点，而且逐渐被应用于国防、工农业生产和人们日常生活等不同领域。论述了固体表面润湿性的有关理论基础，包括表面张力、表面自由能、润湿过程及其条件。分析了固体表面接触角的Young模型、Wenzel模型和Cassie模型等几种理论模型，以及解释了接触角滞后现象。     

基于格子Boltzmann方法的疏水表面润湿性数值模拟

润湿性对固体表面上液体的各种动力学行为具有重要影响,疏水表面的特殊润湿性是其在减阻、降噪、防污等领域有着广泛应用前景的根本原因。基于Shan-Chen模型的格子Boltzmann方法对疏水表面润湿性进行数值模拟,获得了材料属性和微形貌对疏水表面润湿性的影响规律。研究表明,要使疏水表面处于Cassie-Baxter润湿状态,微形貌高度必须大于某一临界值,而当疏水表面一旦处于Cassie-Baxter润湿状态后,继续增加微形貌高度也不会提高其疏水性能;疏水表面的表观接触角随气液界面分数先增大后减小,且存在一个最佳的气液界面分数使表观接触角达到最大。     

材料表面润湿性的控制与制备技术

润湿性是材料表面的重要特征之一.影响材料表面润湿性的主要因素有:材料表面能、表面粗糙度以及表面微纳结构,其中低表面能材料是制备超疏水性的基本条件,表面粗糙度和表面微细结构是决定性因素.理论研究和实验证明,接触角随着表面能的降低而增加,随着表面粗糙度的增加而增大,而表面微/纳结构对润湿性具有重要的影响.常用的低表面能材料是有机硅和氟树脂以及其相应的改性树脂,如硅氧烷等.常用的表面粗糙化和微/纳结构的制备方法有模板法、化学气相沉积、溶胶-凝胶法、微细加工、粒子填充等方法.此外,材料表面润湿性的调控和疏水亲水性的可逆转变也取得了进展.     

中频电源对聚丙烯表面等离子体改性

为了优化等离子体改性工艺,对聚丙烯板进行了常压空气等离子体处理.等离子体的产生采用了自制中频电源和平行板电极结构组成的介质阻挡放电系统.处理前后聚丙烯表面的微观结构、表面粗糙度和润湿性通过场致发射扫描电镜、原子力显微镜和接触角分析仪进行了分析.结果表明,等离子体处理后,聚丙烯板表面结构变粗糙且粗糙度增加了近5倍;表面接触角下降(或润湿性提高),并且等离子体剂量为1.5kJ的试样具有较好的润湿性和抗老化性能.     

规则微观结构粗糙表面浸润性研究

制作了4组具有不同规则微观结构、粗糙度为1.2～2.0的粗糙表面,并测量了各个粗糙表面的表观接触角。而后将各组粗糙表面的接触角测量值与Wenzel模型预测值和Cassie模型预测值进行比较,分析了影响各个粗糙表面浸润特性的因素。发现孔状微观结构的粗糙表面与柱状微观结构的粗糙表面的浸润性有很大区别,不同的微观结构导致液体侵入微结构内部程度的不同是引起此区别的主要原因,进而针对这两种不同微观结构的粗糙表面提出了新的预测值计算公式。     

超疏水涂膜的研究进展

从固体表面的润湿性理论出发介绍了三种不同的接触角模型和理论方程,阐明了实现超疏水性的两个必要条件:低表面能表面和特定的细微粗糙度。同时综述了国内外制备超疏水涂膜时常用的疏水材料和制备粗糙表面的方法、动态疏水性及其应用前景。     

Wettability and Bonding between Ni and Ti(C, N) with Multiple Carbide Additions

The wettability and bonding in Ni/Ti(C, N) systems with multiple carbide additions were studied by sessile drop technique and vacuum brazing technique, respectively. The phase characterizations of substrates and fracture surfaces were conducted by XRD. The microstructures at metal/ceramic interfaces and fracture surfaces were observed via SEM in back scattered mode and second electron mode, respectively. Furthermore, an X-ray energy-dispersive spectrometer (EDS) attached to SEM was used to study the elements diffusion in interfacial regions. The results reveal that diffusion and dissolution mechanism controlled reactive wetting takes place in the system in high temperature wetting. Results also show that the contact angles decrease with multiple carbide additions, and the effect of multiple carbide additions is stronger than that of single additions. The contact angle reaches the lowest value in the lowest TiC content case. The enhancement of the wettability is due to alloying procedure during high tempe     

Effects of roughness pitch of surfaces on their wettability

The surface roughness factors, such as the Wenzel roughness factor and so on, are very interrelated to each other. Therefore, it makes a precise discussion difficult on how the surface roughness affects the wettability. We already reported the effect of the surface roughness on the wettability at a constant Wenzel roughness factor using two kinds of models, the hemisphere close packing model and the hemiround rod close lining model. Nevertheless, the pitch is proportional to the height in these models. Therefore, we could not independently discuss the influence of roughness height and roughness pitch on the wettability. We developed our new models which can independently describe the influence of the surface roughness height and the roughness pitch on the wettability. We simulated loose packing sphere models by periodically placing small ball bearings and the loose lining round rod models by winding fine wires. The wettability was measured by the sessile drop method for the non-wetting system using paraffin coated samples and aqueous solutions. These results show that there is a critical pitch which determines the maximum contact angle in both systems. These results can be explained by the ratio of the solid/liquid/vapor and liquid/vapor line length at the three phase line.     

Generation of isothermal spreading data and interfacial energy data for liquid reactive metals on ceramic substrates: The copper-titanium/alumina system

The sessile drop technique is frequently used to evaluate the wettability and spreadability of liquid metals on ceramic substrates. In this study, the spreading kinetics of copper-20 wt% titanium alloys on polycrystalline alumina were evaluated based on measurements of spreading radius versus time. The process of spreading was monitored by anin situ video recording system. The tests were performed using three different initial metal configurations. It was found that conventional sessile drop testing configurations cannot be used to generate isothermal spreading kinetics data because of significant spreading during the heat-up cycle from the solidus temperature to the test temperature. An improved sessile drop technique was developed which eliminated the non-isothermal experience by introducing the liquid copper to the solid titanium/alumina at the desired testing temperature. Using this technique, only a few seconds of data were lost (while the liquid copper dissolved the solid titanium). Because very limited interfacial energy data exist for the copper-titanium/alumina system, especially at higher titanium concentrations, the equilibrium contact angle, the solid-liquid interfacial energy, and the work of adhesion from 1000 to 1300 °C are also presented.     

SiC/Co-Cr体系的润湿性研究

采用座滴法研究了反应烧结SiC/ Co-Cr 体系的润湿性。与反应烧结SiC/ 纯Co 体系进行对比, 研究了Cr 含量、实验温度和保温时间对润湿角的影响及活性元素的作用。结果表明, 加入适量的活性元素Cr 能够显著提高体系的润湿性。当体系的Cr 含量分别为5 % , 7 %和42 %时, 体系的润湿角较小, 润湿性比较好。SiC/ Co-Cr体系和SiC/ 纯Co 体系的润湿过程均属于反应性润湿, 实验温度和保温时间对体系的润湿角影响较大。微观结构研究和XRD 分析表明, 对于SiC/ 纯Co 体系, 界面区域发生了化学反应, 生成了CoSi , 减小了润湿角。加入活性元素Cr 以后, 由于Cr 元素与基体发生反应, 生成Cr₂₃C₆ , 进一步降低了体系的界面能, 提高了润湿性。      

Wetting behaviors and interfacial characteristics of molten AlxCoCrCuFeNi high-entropy alloys on a WC substrate

The wettability of molten AlxCoCrCuFeNi(x is from 0 to 1.5,mol.％)high-entropy alloys(HEA)on a WC substrate was measured using a modified sessile drop method at 1823 K in an argon atmosphere.The wetting behaviors and interfacial characteristics between HEAs and WC were studied.Good wettability with final equilibrium contact angles of 0.5°-4.6° is obtained,and addition of Al deteriorates the wettabil-ity of the HEAs.The wetting of AlxCoCrCuFeNi/WC system can be roughly divided into an initially sharp spreading stage and a subsequent steady-state phase.In the first stage,the adsorption of Cr atoms at the solid-liquid interface primarily contributes to the wetting,and the contact angle drastically reduces.However,both the wetting behavior and interfacial microstructure are determined by the Al content of the HEA in the next stage.For x≤0.5,the wetting is mainly driven by the dissolution of WC,although a few reaction products of(W,Cr)2C are observed.Moreover,an obvious dissolution pit appears at the surface of the substrate.When the Al content of x≥1,the interfacial reaction is dominant in competition with the dissolution of WC,and massive reaction products precipitate at the HEA/WC interface,which leads to the formation of a continuous reaction layer.     

动态毛吸法测定纤维及粉末料的接触角研究

本文用动态毛吸法研究了表面处理对纤维浸润性的影响,结果表明碳纤维及聚酯纤维表面经冷等离子体氧处理,浸润性有很大的改善,碳纤维约提高四倍,这是因为等离子氧表面处理过程,将含氧基团羧基,羟基及羰基等引入到表面所致。同时从测得的浸润过程表面自由能改变值△γ,计算出水对纤维的接触角,它与采用接触角测定仪倾斜法所测得的结果基本上一致。从所测得的接触角值也可以看出表面经处理之后,浸润性得以改善。如碳纤维由77°降为63°,聚酯纤维由77°降为52°。此外我们还研究了煤粉和玻璃粉体系对水的浸润性,发现水对玻璃粉的浸润性优于煤粉,前者的浸润接触角为47°、后者则为90°,此接触角值也与采用接触角测定仪由静滴法测得水对片材的接触角相一致。由此可见动态毛吸法可以用于研究纤维及粉末体系的浸润性,而且操作简单易行,测试周期短。      

Construction of a high-temperature sessile drop device

The study of the wettability in a liquid metal—solid surface system is of great technological interest for industrial processes like soldering and brazing, as well as for fundamental research in the field of diffusion, chemical reaction and formation of intermetallic phases.For the characterization of these processes the so-called contact angle between the liquid droplet and the solid substrate is measured. Therefore, a high-temperature sessile drop device was planned and constructed, and first measurements in different liquid/solid systems were performed.     

Preparation and characterization of super-hydrophobic and oleophobic surface

A novel method for preparing and characterizing super-hydrophobic and oleophobic surface is presented. Aluminum (Al) substrate was roughened by sandblasting and electrolytic etching to obtain micro- and nano-sized complex morphologies. Then, its substrate was covered by a chemically adsorbed monolayer (CAM) containing a fluorocarbon group. The surface of Al substrate roughened and covered with CAM was observed by scanning electron microscope and atomic force microscope. The roughnesses of the surface were ca. 100 μm and ca. 30–60 nm, respectively. The surface of the wettability was characterized by contact angle measurements and its surface indicated super-hydrophobicity and oleophobicity: the water contact angle (WCA) and oil contact angle (OCA) of hexadecane was 158.9° and 139.6°, respectively. The wettability was also characterized by solid surface energy. The solid surface energy of each solvent was obtained from the equation by Neumann et al. These values were extremely low, ranging from 0.31 to 1.29 mN/m. The total solid surface energy was obtained from the equation by Kaelble et al. The value was 0.3 mN/m. Their values indicated that the hydrophobicity and oleophobicity of our sample reached the highest level possible. In addition, our research demonstrates that it is easy to compare many different surfaces with super-hydrophobicity and oleophobicity using the solid surface energy.     

Zum Einfluss von in Flüssigkeiten unter Druck gelösten Gasen auf Grenzflächenspannungen und Benetzungseigenschaften

Measurements of interfacial tensions of water and ethanol in dense carbon dioxide up to 10 MPa and 373 K were performed. Also, in order to predict the wettability of these liquids on teflon and glass surfaces in the presence of carbon dioxide, contact angles between these liquids and both surfaces were determined under the same conditions of pressure and temperature. The interfacial tension were measured according to the pendant drop method. A mathematical derivation for the evaluation of the interfacial tension according to the geometry of the pendant drop and the difference of the density between the phases is presented. The contact angle determinations were performed using both the static and the dynamic method. The results show that because of the solubility of carbon dioxide in the liquids, the measured interfacial tensions are much lower than the interfacial tension of the pure substances. The interfacial tension appears as a function of only the density of CO₂ above its critical temperature [1]. Even though the solubility of carbon dioxide in the liquid phase affects the interfacial tension, such a clear relation between these variables, like the one between the interfacial tension and the density of carbon dioxide, cannot be observed. The excess concentration on the interphase, as a measurement of adsorption according to Gibbs, was calculated for both systems. The contact angle of water on teflon surface increases with pressure until total non wetting is reached. On the other hand, the contact angle of ethanol decreases with the increasing pressure until spreading occurs. The same phenomena was noted for the wetting characteristic of water on glass surface. The contact angle of water increases as pressure increases. Ethanol spreads totally on the surface of glass at all evaluated pressures. With the dynamic method, contact anglesgreater than the ones obtained with the static method were measured.