反应物的相间分配对吸附相技术制备纳米CuO过程的影响

以SiO2表面的富水吸附层为纳米反应器制备CuO纳米粒子. 不同水量下的吸附量测定、溶剂置换和反应后吸附对比实验结果表明, SiO2表面存在吸附水层, 并且该吸附水层是反应的主要场所. 根据吸附数据, 认为Cu2+在体系中具有三区域浓度分布特点, 体系中水浓度和氢氧化钠浓度的增加均会使得Cu2+向吸附层区域迁移. XRD分析结果表明, 反应温度的升高和NaOH浓度的增大有利于生成更小的CuO晶粒, 其中温度的升高使吸附层厚度减小, 限制了晶粒生长; NaOH浓度的增大则会增大层内溶质过饱和度, 导致晶核形成速率加快.     

Implications of interfacial characteristics of food foaming agents in foam formulations

The manufacture of food dispersions (emulsions and foams) with specific quality attributes depends on the selection of the most appropriate raw materials and processing conditions. These dispersions being thermodynamically unstable require the use of emulsifiers (proteins, lipids, phospholipids, surfactants etc.). Emulsifiers typically coexist in the interfacial layer with specific functions in the processing and properties of the final product. The optimum use of emulsifiers depends on our knowledge of their interfacial physico-chemical characteristics - such as surface activity, amount adsorbed, structure, thickness, topography, ability to desorb (stability), lateral mobility, interactions between adsorbed molecules, ability to change conformation, interfacial rheological properties, etc. -, the kinetics of film formation and other associated physico-chemical properties at fluid interfaces. These monolayers constitute well defined systems for the analysis of food colloids at the micro- and nano-scale level, with several advantages for fundamental studies. In the present review we are concerned with the analysis of physico-chemical properties of emulsifier films at fluid interfaces in relation to foaming. Information about the above properties would be very helpful in the prediction of optimised formulations for food foams. We concluded that at surface pressures lower than that of monolayer saturation the foaming capacity is low, or even zero. A close relationship was observed between foaming capacity and the rate of diffusion of the foaming agent to the air-water interface. However, the foam stability correlates with the properties of the film at long-term adsorption.     

三元无规芳—脂族聚酯酰胺的热致液晶行为

采用低湿溶液缩聚的方法合成了对苯二甲酰氯，二甲基联苯胺和己二醇为单体的芳酯族液晶聚酯酰胺。用ＤＳＣ，Ｘ光衍射分析和偏光显微镜等手段研究了该系列聚酯酰胺的热致液晶行为，确认了二甲基联苯胺单体用量在２０％（ｍｏｌ）的情况下，所得聚酯酰胺仍为向列型液晶聚合物。由于聚酯酰胺分子间聚酰胺链段之间的氢键作用，随着二甲基联苯胺用量增加至６０ｍｏｌ％时，所得的聚酯酰胺己无液晶转变温度，其液晶区间即从熔融温度直至分     

H-shaped liquid crystals inducing nematic order in the isotropic liquid

ABSTRACT

We prepared a homologous series of H-shaped liquid crystals I-n and investigated their phase transition properties using optical microscopy and differential scanning calorimetry. All the compounds exhibited a nematic phase at room temperature. The phase transition behaviour is explained in terms of molecular shape anisotropy. Furthermore, those compounds were found to exhibit electro-optical switching in the isotropic liquid in the vicinity of the nematic–isotropic liquid transition, indicating that the microscopic nematic order with a certain coherence length of the molecules exists in the optically isotropic temperature range.     

Foam films stabilized with alpha olefin sulfonate (AOS)

Alpha olefin sulfonate (AOS) surfactants have shown outstanding detergency, lower adsorption on porous rocks, high compatibility with hard water and good wetting and foaming properties. These properties make AOS an excellent candidate for foam applications in enhanced oil recovery. This paper summarizes the basic properties of foam films stabilized by an AOS surfactant. The foam film thickness and contact angle between the film and its meniscus were measured as a function of NaCl and AOS concentrations. The critical AOS concentration for formation of stable films was obtained. The critical NaCl concentration for formation of stable Newton black films was found. The dependence of the film thickness on the NaCl concentration was compared to the same dependence of the contact angle experiments. With increasing NaCl concentration the film thickness decreases gradually while the contact angle (and, respectively the free energy of film formation) increases, in accordance with the classical DLVO theory.The surface tension isotherms of the AOS solutions were measured at different NaCl concentrations. They coincide on a single curve when plotted as a function of mean ionic activity product. Our data imply that the adsorption of AOS is independent of NaCl concentration at a given mean ionic activity.     

Dynamic adsorption and characterization of phospholipid and mixed phospholipid/protein layers at liquid/liquid interfaces

Drop profile analysis tensiometry is applied to study the adsorption dynamics of phospholipids, proteins and phospholipid/protein mixtures at liquid/liquid interfaces. Measurements of the dynamic interfacial tension of phospholipid layers give information on the adsorption mechanism and the structure of the adsorption layer. The equilibrium and dynamic adsorption of pure protein solutions, i.e. human serum album (HSA), beta-lactoglobulin (beta-LG), beta-casein (beta-CA), can be explained well by the thermodynamic model of Frumkin and the diffusion-controlled adsorption theory. The adsorption behavior from mixed phospholipid/protein solutions was also investigated in terms of dynamic interfacial tensions. Interestingly, a "skin-like" folded film of pure protein or phospholipid/protein complex layers can be observed at curved surfaces at the water/oil interfaces. The addition of phospholipids accelerates the formation of the folded structure at the drop surface through co-adsorption of proteins.     

Thermodynamics, adsorption kinetics and rheology of mixed protein-surfactant interfacial layers

Depending on the bulk composition, adsorption layers formed from mixed protein/surfactant solutions contain different amounts of protein. Clearly, increasing amounts of surfactant should decrease the amount of adsorbed proteins successively. However, due to the much larger adsorption energy, proteins are rather strongly bound to the interface and via competitive adsorption surfactants cannot easily displace proteins. A thermodynamic theory was developed recently which describes the composition of mixed protein/surfactant adsorption layers. This theory is based on models for the single compounds and allows a prognosis of the resulting mixed layers by using the characteristic parameters of the involved components. This thermodynamic theory serves also as the respective boundary condition for the dynamics of adsorption layers formed from mixed solutions and their dilational rheological behaviour. Based on experimental studies with milk proteins (β-casein and β-lactoglobulin) mixed with non-ionic (decyl and dodecyl dimethyl phosphine oxide) and ionic (sodium dodecyl sulphate and dodecyl trimethyl ammonium bromide) surfactants at the water/air and water/hexane interfaces, the potential of the theoretical tools is demonstrated.The displacement of pre-adsorbed proteins by subsequently added surfactant can be successfully studied by a special experimental technique based on a drop volume exchange. In this way the drop profile analysis can provide tensiometry and dilational rheology data (via drop oscillation experiments) for two adsorption routes — sequential adsorption of the single compounds in addition to the traditional simultaneous adsorption from a mixed solution. Complementary measurements of the surface shear rheology and the adsorption layer thickness via ellipsometry are added in order to support the proposed mechanisms drawn from tensiometry and dilational rheology, i.e. to show that the formation of mixed adsorption layer is based on a modification of the protein molecules via electrostatic (ionic) and/or hydrophobic interactions by the surfactant molecules and a competitive adsorption of the resulting complexes with the free, unbound surfactant. Under certain conditions, the properties of the sequentially formed layers differ from those formed simultaneously, which can be explained by the different locations of complex formation.     

刚柔相嵌液晶高分子的赝二级相变温度

讨论了刚柔相嵌液晶高分子的向列相一各向同性相转变与其分子结构的关系．给出了该一级相变的赝二级相变温度Ｔ＊与这类液晶高分子的液晶基元和间隔基的长度、柔顺性（相关长度）以及它们之间的相互作用的关系的解析表示式．分析了液晶基元与间隔基连接处的表观弯曲（接口效应）对Ｔ＊的影响．文中的结论与实验相符．     

氟化钾团簇的相变、成核和重结晶的分子动力学模拟

我们利用Born-Mayer-Huggins相互作用势函数对(KF)_N(N=108,256,500和864)团簇进行了分子动力学(MD)模拟。为了避免周期性边界条件对相变、成核和重结晶的干扰作用,对体系采用了自由边界。基于MD模拟结果,对团簇的熔化温度、熔化焓、扩散系数、成核速率、固液界面自由能、临界核大小等进行了计算和讨论。在对(KF)₈₆₄双晶团簇的热退火模拟中,观察到了固态的重结晶和晶粒的生长。经典的成核理论成功地解释了(KF)₈₆₄双晶团簇的重结晶MD模拟结果。     

Surface charging behaviors of electrocatalytic interfaces with partially charged chemisorbates

The surface charge is a key concept in electrochemistry. Mathematically, the surface charge is obtained from a spatial integration of the volume charge along a particular direction. Ambiguities thus arise in choosing the starting and ending points of the integration. As for electrocatalytic interfaces, the presence of chemisorbates further complicates the situation. In this minireview, I adopt a definition of the surface charge within a continuum picture of the electric double layer. I will introduce surface charging behaviors of firstly ordinary electrochemical interfaces and then electrocatalytic interfaces featuring partially charged chemisorbates. Particularly, the origin of nonmonotonic surface charging behaviors of electrocatalytic interfaces is explained using a primitive model. Finally, a brief account of previous studies on the nonmonotonic surface charging behavior is presented, as a subline of the spectacular history of electric double layer.     

Texture of zirconia obtained by forced hydrolysis of ZrOCl2 solutions

The structure and surface properties of ZrO₂ strongly depend on its preparation. In the present work the impact of prolonged aging at basic conditions (pH = 9, T = 100°C, t = 48 h), on the phase composition and textural properties, obtained by calcination of the precipitate, was investigated using several techniques conjointly (DTA/TG, DSC, XRD, porosimetry). The thermal effects accompanying the ZrO₂·xH₂O gel formation, the coalescence of the particles and crystallization were evaluated and discussed in terms of the structural differences between the aged and non-aged samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

Wetting, adsorption and surface critical phenomena

Our understanding of interfacial phenomena at the surfaces of critical systems, and in particular at the surfaces of critical binary liquid mixtures, has improved significantly in the past decade. There is now substantial agreement between theory and experiment. In this paper we review recent experimental progress, provide a conceptual framework within which the majority of these experiments can now be understood, and discuss critically any remaining unresolved discrepancies between experiments or with theory.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Light scattering near and from interfaces using evanescent wave and ellipsometric light scattering

The broad range of interface light scattering investigations in recent years shows the power and the versatility of these techniques to address new and open questions in colloid and interface science and the soft condensed matter field. Structural information for polymers, liquid crystals, or colloids close to planar or spherical colloidal interfaces are either captured with long range light scattering resolution, or in a complementary approach by high resolution ellipsometric techniques. Of special interest is the dynamic behavior close to or in interfaces, since it determines material properties and responses to external fields. Due to the broad dynamical range and the high scattering contrast for visible light, interface light scattering is a key to elucidate soft matter interfacial dynamics. This contribution reviews experimental and related theoretical approaches for interface light scattering and further gives an overview of achievements based on such techniques.