高分子基体表面褶皱的仿生构筑、微观调控及其应用

从小尺度血细胞到地球表面大尺度的山脉,表面褶皱现象无处不在.受自然界这些起皱模式的启发,研究人员在构筑表面褶皱方面已经取得很大进展.本文讨论了高分子基体表面褶皱的形成机理,归纳了利用表面失稳构筑表面褶皱的方法和表面褶皱的应用现状.首先讨论了高分子基体表面起皱的机理,引入了理论公式.高分子基体自身的不稳定性和外部刺激是其表面失稳的主要原因.其次着重介绍了表面褶皱的分类及其不同构筑方法,包括薄膜/基底双层体系、渐变型基体、同质型基体表面褶皱的构筑,以及可逆褶皱、多级褶皱和三维褶皱的构筑.最后介绍了表面褶皱的应用研究进展.表面褶皱由于具有形貌和尺度易于调控、构筑方法简易多样等优点,可用于微流控、微印刷、柔性电子器件、超疏水表面、薄膜力学测量、荧光信号增强、表面拉曼增强、表面黏附增强等领域.     

MgO缺陷和不规则表面的能带结构研究

用扩展休克尔紧束缚（ＥＨＴ）晶体轨道方法对ＭｇＯ表面缺陷和不规则结构进行能带计算,并对能带的结构及组成进行了讨论。计算结果表明,各种缺陷及不规则表面的表面状态与完整晶面比较,存在明显差异,前者由于其导带底部能带的变化造成导带和价带间的能隙减小。我们发现,ＭｇＯ缺陷及不规则表面吸附能力与其表面能大小及表面不同位置原子的净电荷数密切相关。缺陷模型的表面能均大于完整晶面,故缺陷有利于表面吸附     

富锂锰基正极材料的表面改性研究进展

随着电动汽车和储能电站等电力设备的快速发展,对高能量密度的锂离子电池的需求日益增加.高比容量（>250 mAh·g^-1）的富锂锰基正极材料,有望成为锂离子电池实现高比能量（>350 Wh·kg^-1）的关键正极材料.富锂锰基正极材料的Li₂MnO₃相和晶格氧参与电化学反应使其拥有了高容量,但这也导致表面结构和成分容易发生变化,进而造成富锂锰基正极材料存在着诸如首次库伦效率低、倍率性能差和循环后电压和容量衰减严重等问题.因此,本文综述了富锂锰基正极材料的表面包覆、表面掺杂和表面化学处理三种表面改性方法,并进一步讨论了三种表面改性方法对材料性能提升的机制机理和优缺点.在此基础上,介绍了近些年基于多方法的表面联合改性工作.通过对富锂锰基正极材料进行表面联合改性,不仅可以改善其结构稳定性和抑制电极/电解液界面副反应,而且可以缓解其在循环过程中不断发生的结构转变和晶格氧的析出问题.最后,对富锂锰基正极材料表面改性研究方向进行了总结和展望.     

聚苯乙烯-g-聚乙二醇的制备及其表面改性作用

通过沉淀聚合方法,利用自由基共聚制备了苯乙烯-顺丁烯二酸酐共聚物(SMA),利用SOCl2的酰氯反应,在SMA大分子链上接枝聚乙二醇侧链,制备了聚苯乙烯-g-聚乙二醇(PEG-g-PS)的大分子表面改性剂。利用大分子表面改性剂在聚苯乙烯基体中具有选择性迁移扩散的特性,实现了对聚苯乙烯薄膜表面极性的改善作用。采用衰减全反射傅立叶变换红外光谱仪和表面静态接触角法检测了聚苯乙烯的表面极性。结果发现,PEG-g-PS上的聚醚链段可以有效的富集在聚合物表面,明显改善PS的表面极性和亲水性,表面极性可提高3倍,达到11.6mN/m。同时,大分子表面改性剂和聚苯乙烯基体间有一定的相容性,有效地克服了小分子表面改性剂容易流失,改性寿命较短的重要缺陷,使表面改性的持久性充分增加,实现对聚合物表面改性效果终生化的目的。而且大分子表面改性剂在极性溶剂的诱导作用下,可以实现进一步的迁移扩散,充分提高了聚苯乙烯的表面极性。     

渗透汽化膜表面化学结构设计研究

综述了近年来渗透汽化膜表面结构设计调控的研究进展。膜表面结构的设计与优化是提高其分离性能的重要方法。然而高分子表面具有环境响应性,这往往导致高分子材料在使用环境中失去在表面设计时所期待的性能。因此,高分子膜表面的环境响应性是在对膜表面进行设计和调控过程中必须考虑的因素。本文介绍了渗透汽化膜表面结构设计的方法,重点阐述了高分子膜表面环境响应特性对膜表面性质以及渗透汽化性能的影响。指出了利用高分子膜的表面重构行为可以对其表面结构进行优化,从而有效地提高膜的分离选择性。     

用石英晶体微天平研究表面活性剂在银固态表面上的动态吸附

吸附是表面活性剂的一个重要特征.迄今用于原位监测表面活性剂在固体表面上吸附重量变化的方法尚不多见.近年来压电石英晶体作为一种高灵敏的质量传感器(石英晶体微天平)已被用于大气和溶液中多种微量成分的监测.用石英晶体微天平研究I~-、Br~-和表面活性剂在金电极上的吸附行为亦有报道.本文研究了十六烷基三甲基溴化铵(CTAB)、十二烷基磺酸钠(SDSO)、十二烷基硫酸钠(SDS)在银固态表面上的吸附平衡动力学特性及其吸附机制.     

LLDPE/SMA共混膜表面接枝PEG的研究

聚乙烯综合性能优良且价格低廉,但由于较低的表面能和惰性化学结构,其着色性、生物相容性及制品表面涂饰性能差,与各种涂饰剂的粘结强度很低,限制了其用途的拓展,须进行表面改性.聚乙烯制品的表面改性方法已有不少研究报道[1~4],相对而言,采用添加表面改性剂的方法在工艺上仍最     

分子自组装法制备具有可控浸润性的铜表面简

通过简单浸泡的方法在铜基底上制备出了具有微纳米复合结构的氧化铜,再利用混合硫醇溶液[含HS(CH2)9CH3和 HS(CH2)11OH]对浸泡后的表面进行修饰,通过控制溶液中HS(CH2)11OH的浓度,制备出一系列具有不同浸润性的铜表面,实现表面从超疏水到超亲水的有效调控. 研究发现,表面浸润的可控性源于表面复合结构与不同化学组成的协同作用,微纳米复合结构的存在为表面浸润性的调节提供了必要的条件.     

表面物种的化学捕获法

一、引言直接获取有关表面物种的信息和表征表面物种的化学性质是表面科学和多相催化化学的重要课题。尤其在研究催化剂表面上化学反应的微观机理时,检测表面物种就变得至关重要。化学捕获法就是近年来人们发展起来的一种检测表面物种的直观而有效的方法,这种方法尤其受到催化研究者的重视。     

润湿性表面强化冷凝传热的研究进展

固体表面的润湿特性对冷凝传热具有重要的影响。本文分析了冷凝传热的机理,介绍了现阶段对不同冷凝方式的判定方法,总结了不同润湿性表面的制备方法,概述了蒸汽在亲水表面、疏水表面和组合表面上的冷凝传热性能,总结了该领域目前存在的问题。本文为利用表面润湿性强化传热提供了较为系统的综述,为强化冷凝传热提供思路。     

The role of electrolyte and polyelectrolyte on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, at the air-water interface

The role of the polyelectrolyte, poly(ethyleneimine), PEI, and the electrolytes NaCl and CaCl(2), on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, LAS, at the air-water interface have been investigated by neutron reflectivity and surface tension. The surface tension data for the PEI/LAS mixtures are substantially affected by pH and the addition of electrolyte, and are consistent with a strong adsorption of surface polymer/surfactant complexes down to relatively low surfactant concentrations. The effects are most pronounced at high pH, and this is confirmed by the adsorption data obtained directly from neutron reflectivity. However, the effects of the addition of PEI and electrolyte on the LAS adsorption are not as pronounced as previously reported for PEI/SDS mixtures. This is attributed primarily to the steric hindrance of the LAS phenyl group resulting in a reduction in the ion-dipole attraction between the LAS sulfonate and amine groups that dominates the interaction at high pH.     

Synthesis and properties of nonylphenol-substituted dodecyl sulfonate

Nonylphenol-substituted dodecyl sulfonate (C₁₂-NPAS) was synthesized via sulfonation-alkylation-neutralization using 1-dodecene, SO₃, and nonylphenol as raw materials. The properties such as surface tension, interfacial tension (IFT), wettability, foam properties, and salinity tolerance of C₁₂-NPAS were systematically investigated. The results show that the critical micelle concentration (CMC) of C₁₂-NPAS was 0.22?mmol?·?L^?1 and the surface tension at the CMC (γ_CMC) of C₁₂-NPAS was 29.4 mN/m. When compared with the traditional surfactants sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), and linear alkylbenzene sulfonate (LAS), the surface properties of C₁₂-NPAS were found to be superior. The IFT between Daqing crude oil and a weak-base alkaline/surfactant/polymer (ASP) oil flooding system containing 0.1?wt% of C₁₂-NPAS can reach an ultralow level of 2.79?×?10^?3 mN/m, which was lower than that found for the traditional surfactant heavy alkylbenzene sulfonate (HABS). The salinity and hardness tolerance of C₁₂-NPAS were much stronger than those found for conventional surfactants, petroleum sulfonate, and LAS. C₁₂-NPAS also shows improved wetting performance, foamability, and foam stability.     

Micellization of sodium dodecyl sulfonate and Triton X-100 in polyacrylamide water solution studied by 1H NMR relaxation and two-dimensional nuclear overhauser enhancement spectroscopy

Micellization of Triton X-100 (TX-100) and sodium dodecyl sulfonate (SDSN) in the presence of partially hydrolyzed polyacrylamide (PAAM) was studied by ¹H NMR spin–spin and spin–lattice relaxation. Relaxation experiment results show that TX-100 behaves differently from SDSN in micellization in the presence of PAAM. PAAM causes a decrease in the critical micellar concentration of SDSN, while it has no influence on the critical micellar concentration of TX-100. The lack of cross peaks between protons of PAAM and those of TX-100 and SDSN in the 2D nuclear Overhauser enhancement spectroscopy (NOESY) spectra confirms self-aggregation of TX-100 and SDSN in the presence of PAAM. The identity of each of the corresponding interproton distances of TX-100 with and without the addition of PAAM further confirms the formation of normal TX-100 micelles in the presence of PAAM. Besides, the distances between protons on the hydrophilic and hydrophobic chains in TX-100 micelles, calculated from the 2D NOESY spectra, are remarkably shorter than those for an extended hydrophilic poly(oxyethylene) chain. This implies that the hydrophilic chain is curled upon micellization. Received: 2 February 1999 Accepted in revised form: 2 June 1999     

Adsorption of sophorolipid biosurfactants on their own and mixed with sodium dodecyl benzene sulfonate, at the air/water interface

The adsorption of the lactonic (LS) and acidic (AS) forms of sophorolipid and their mixtures with the anionic surfactant sodium dodecyl benzene sulfonate (LAS) has been measured at the air/water interface by neutron reflectivity, NR. The AS and LS sophorolipids adsorb with Langmuir-like adsorption isotherms. The more hydrophobic LS is more surface active than the AS, with a lower critical micellar concentration, CMC, and stronger surface adsorption, with an area/molecule ～70 ?(2) compared with 85 ?(2) for the AS. The acidic sophorolipid shows a maximum in its adsorption at the CMC which appears to be associated with a mixture of different isomeric forms. The binary LS/AS and LS/LAS mixtures show a strong surface partitioning in favor of the more surface active and hydrophobic LS component but are nevertheless consistent with ideal mixing at the interface. In contrast, the surface composition of the AS/LAS mixture is much closer to the solution composition, but the surface mixing is nonideal and can be accounted for by regular solution theory, RST. In the AS/LS/LAS ternary mixtures, the surface adsorption is dominated by the sophorolipid, and especially the LS component, in a way that is not consistent with the observations for the binary mixtures. The extreme partitioning in favor of the sophorolipid for the LAS/LS/AS (1:2) mixtures is attributed to a reduction in the packing constraints at the surface due to the AS component. Measurements of the surface structure reveal a compact monolayer for LS and a narrow solvent region for LS, LS/AS, and LS/LAS mixtures, consistent with the more hydrophobic nature of the LS component. The results highlight the importance of the relative packing constraints on the adsorption of multicomponent mixtures, and the impact of the lactonic form of the sophorolipid on the adsorption of the sophorolipid/LAS mixtures.     

Fluorescence Spectroscopic Studies on Comicellization of Anionic Surfactants

The intrinsic fluorescence of linear alkylbenzene sulphonate (LAS) has been exploited to show that sodium oleate (Na Ol) and sodium laurate (Na L) comicellize with LAS. It is also shown that comicellization occurs only at concentrations close to the critical micelle concentration (CMC) of Na Ol and Na L. ¹³C NMR results indicated that in LAS/Na Ol mixed micelles, the oleate molecule loops back and adopts a bent conformation.     

Mixing behavior of the biosurfactant, rhamnolipid, with a conventional anionic surfactant, sodium dodecyl benzene sulfonate

The use of small angle neutron scattering, SANS, neutron reflectivity, NR, and surface tension to study the mixing properties of the biosurfactant rhamnolipid with a conventional anionic surfactant, sodium dodecyl 6-benzene sulfonate, LAS, is reported. The monorhamnose rhamnolipid, R1, mixes close to ideally with LAS at the air-water interface, whereas for mixtures of LAS with the dirhamnose rhamnolipid, R2, the LAS strongly partitions to the air-water interface relative to R2, probably because of the steric hindrance of the larger R2 headgroup. These trends in the binary mixtures are also reflected in the ternary R1/R2/LAS mixtures. However, for these ternary mixtures, there is also a pronounced synergy in the total adsorption, which reaches a maximum for a LAS/rhamnolipid mole ratio of about 0.6 and a R1/R2 mol ratio of about 0.5, an effect which is not observed in the binary mixtures. In solution, the R1/LAS mixtures form relatively small globular micelles, L(1), at low surfactant concentrations (<20 mM), more planar structures (lamellar, L(α), unilamellar/multilamellar vesicles, ulv/mlv) are formed at higher surfactant concentrations for R1 and LAS rich compositions, and a large mixed phase (L(α)/L(1) and L(1)/L(α)) region forms at intermediate surfactant compositions. In contrast, for the R2/LAS mixtures, the higher preferred curvature of R2 dominates the phase behavior. The predominant microstructure is in the form of small globular micelles, except for solution compositions rich in LAS (>80 mol % LAS) where more planar structures are formed. For the ternary mixtures, there is an evolution in the resulting phase behavior from one dominated by L(1) (R2 rich) to one dominated by planar structures, L(α), (R1, LAS rich), and which strongly depends upon the LAS/rhamnolipid and R1/R2 mole ratio.     

Synthesis and properties of N-hexadecyl ethylenediamine triacetic acid

A new kind of surfactant named N-hexadecyl ethylenediamine triacetic acid (HED3A) was synthesized from anhydrous ethylenediamine, 1-bromohexadecane, and chloroacetic acid. Testing showed stability of HED3A in hard water, wetting power, dispersing power, and surface tension increased along with pH value. Stability in hard water of trisodium N-hexadecyl ethylenediamine triacetate (3NaHED3A) was at level 4, which was better than that of sodium dodecylsulfate (SDS) and sodium dodecylbenzene sulfonate (LAS). Other properties of 3NaHED3A including wetting power, dispersing power, emulsifying power, and surface tension had intermediate value between SDS, LAS, AES, peregal-O, and cetyltrimethylammonium chloride (CTAC). The ethylenediamine triacetic acid (ED3A) group in 3NaHED3A can chelate many kinds of metal ions, which indicates a promising application prospect in many fields including metal anticorrosion, corrosion control agent, additives in electroplating solution, and ore selection and solid surface treatment.     

pH-effects in the complex formation of polymers I. Interaction of poly(acrylic acid) with poly(acrylamide)

The effects of polymer concentration, molecular weight of poly(acrylic acid) (PAA), addition of sodium, potassium, ammonium and copper (II) chlorides on the complex formation ability of the system PAA-poly(acrylamide) (PAAM) have been studied in aqueous solutions. The critical pH values of the complexation were determined in different conditions. The complex formation ability of PAAM is compared with other non-ionic polymers. It was shown that an increase in polymers concentration, molecular weight of PAA and ionic strength favours the complexation and shifts the critical pH values to the higher pH region. An addition of CuCl₂ to the mixture of two polymers enhances the complexation drastically due to the formation of triple complexes.     

CaCO3粉末表面光聚合处理的研究

采用表面光聚合技术处理CaCO₃粉末,研究了反应温度、时间、单体浓度等对丙烯酰胺(AAM)在CaCO₃粉末表面光聚合的影响,并采用X光电子能谱(ESCA)、粒度分析、扫描电子显微镜(SEM)和模型模拟分析等研究了表面光聚合处理碳酸钙(CaCO₃)的结构.结果表明:紫外光能有效地引发AAM在CaCO₃粒子表面聚合.经光聚合处理后,CaCO₃粒子表面形成了聚丙烯酰胺(PAAM)包覆层,该包覆层与CaCO₃粒子结合紧密,不能被溶剂洗涤清除.光聚合处理后CaCO₃粒子表面较光滑,分散性可得到提高,CaCO₃粒子粒径增大.     

可聚硼酸酯表面活性剂的表面化学性质及与LAS相互作用

用表面张力法研究了可聚合硼酸酯表面活性剂(BES)水溶液不同温度下(288-313 K)的表面活性和热力学函数变化；考察了BES与十二烷基苯磺酸钠(LAS)在0.5 mol·L-1 NaCl溶液中的相互作用. 结果表明, 298 K时, BES临界胶束浓度cmc达到0.066 mmol·L-1, γcmc为29.2 mN·m-1；在所考察的温度范围内BES胶束形成自由能(ΔG0m)在-22.4 - -25.8 kJ·mol-1之间, 胶束形成是熵驱动过程. BES/LAS混合体系为具有较大负偏差的非理想体系, BES/LAS分子间平均相互作用参数βm=-3.48；当溶液体相中BES摩尔分数αBES＝0.5时, 混合胶束中BES摩尔分数X1m为0.46, |βm|达到最大, 而且此时混合溶液cmc为0.017 mmol·L-1, 达到最低, γcmc为27.8 mN·m-1.