界面探针法测量液滴与固体壁面间相互作用力

液滴与固体壁面间相互作用力的测量与研究是深入理解润湿机理、调控受限空间内多相流动行为的基础。以液滴轮廓形变为原位微作用力探针,通过拍摄并分析液滴与固体壁面作用过程中轮廓形态变化实现了液滴与固体壁面间相互作用力的测量,测量结果与商用精密微作用力测量仪结果符合良好。相较近年来文献报道的原子力显微镜(AFM)与表面力仪(SFA)测定方法,本方法无须借助外部精密机械探针,具有操作简单、过程可视、成本低廉、不受研究对象透光性限制等优势。最后利用本方法测定了水相环境中十四烷液滴靠近与远离固体壁面时所受的作用力,考察了水相组成对作用力的影响,并发现液滴与壁面间的总斥力仅取决于液滴的形变能力。     

多相分散体系中微油滴与改性二氧化硅表面间作用力的AFM研究

多相分散体系广泛存在于石油、化工、新能源等众多领域，研究其微观力学作用机理具有重要意义，但对微米级液滴与表面间作用力的直接测量仍存在挑战。利用原子力显微镜液滴探针方法测量了水溶液中微米级油滴与羟基化和氨基化改性二氧化硅表面间的微观作用力。结果表明，在高盐浓度、酸性环境下由于双电层斥力被削弱，油滴更容易在范德华引力下与表面聚结；相较于羟基化二氧化硅表面，油滴与氨基化二氧化硅表面更容易聚结；阴离子表面活性剂十二烷基硫酸钠对油滴与表面的阻聚效果优于阳离子型表面活性剂十六烷基三甲基溴化铵；聚合物Pluronic F68产生的空间位阻效应有助于油滴与表面间的稳定。研究成果有助于进一步揭示油滴与表面间的相互作用机理。     

纳米乳液的研究进展

综述了纳米乳液的性能特征及其制备方法,包括高能乳化法和低能乳化法;阐明了纳米乳液的不稳定机制主要是液滴聚合与奥斯特瓦尔德熟化;介绍了纳米乳液技术在化妆品中的应用优势,并对纳米乳液用于化妆品的未来发展趋势进行了展望。     

碳纤维结构的常用表征技术

本文结合近几年的研究报道,归纳了决定碳纤维性能及应用的两个方面内部体结构和表面结构的一些常用表征技术。碳纤维聚集态的表征主要通过X-射线衍射（广角、小角）、电子衍射;碳纤维形态结构特征常用透射电子显微镜;碳纤维表面结构的表征方法有扫描电子显微镜（SEM）,原子力显微镜（ArM）,扫描隧道显微镜（STM）以及扫描力显微镜（SFM）。其中,SEM能够看到整个纤维的表面形貌,而AFM、STM、SFM用于表面几个纳米到几百个纳米范围的形貌分析。此外,表面化学状态（表面成分、表面官能团）表征主要依靠X光电子能谱。     

微通道内纳米颗粒对液滴聚并的影响规律

Pickering 乳液是纳米颗粒稳定的液液两相体系,微流控技术是制备单分散Pickering 乳液的有效方法,而含有纳米颗粒体系在微通道内的液滴聚并规律是该实施方法的关键科学问题之一。以正辛醇为连续相,水为分散相,研究了六边形扩大微通道内液滴碰撞过程,发现了液滴聚并、碰撞不聚并和不相互接触3 种流动状态,研究了流量、颗粒浓度和颗粒亲疏水性对于液滴聚并率的影响规律,分析了颗粒在液膜排空过程中的作用机理。     

SiO2纳米粒子自组装膜的制备与表征

通过静电自组装技术在玻璃基底上组装了具备纳米尺度形貌的Al2O3 和SiO2 纳米粒子薄膜,采用液滴法测量其接触角,利用紫外-可见分光光度计测量其光学吸收特性,并利用原子力显微镜(atom force microscope, AFM)对两种纳米粒子薄膜及空白对比试片的表面结构进行了表征.结果表明,利用静电自组装原理在玻璃基片上组装的表面材料确实具备纳米形貌,且粗糙程度不同,具体为nano-Al2O3＞nano-SiO2＞CTAB＞control.这将为微生物细胞及动物细胞在纳米材料表面上的粘附考评实验做好准备.     

纳米流体液滴在水平加热面上的变形行为特性

采用格子Boltzmann力矩模型模拟了纳米流体液滴在水平加热面上的变形过程,结果表明纳米流体液滴的变形经历了销联、解销阶段,并且由于纳米颗粒的强销联作用,在蒸发的后期可以明显看出环形沉积,这是在考虑布朗运动、粒子间相互作用等作用力后由于纳米颗粒的强销栓作用而表现出的纳米流体的独有性质。模拟结果与文献中的实验结果作了对比,表现出良好的一致性,表明格子Boltzmann方法可以成功模拟纳米流体液滴在水平加热表面蒸发过程中的变形特点。     

海藻酸辛酰胺协同纳米二氧化硅稳定Pickering乳液

采用辛胺疏水改性海藻酸钠合成了具有两亲性的高分子表面活性剂海藻酸辛酰胺(OAAD),并将其与SiO2纳米颗粒协同制备了稳定的Pickering乳液。通过FTIR、1HNMR、表面张力、荧光光谱、动态光散射、接触角测量、光学显微镜分别对OAAD、OAAD/SiO2纳米颗粒水分散体系和Pickering乳状液的性能进行了表征。结果表明,辛胺氨基成功接枝到海藻酸钠(SA)分子链上,OAAD界面张力较SA降低、临界聚集质量浓度为0.60 g/L,表现出良好的两亲性。将OAAD吸附在SiO2纳米颗粒表面形成的水分散体系用于稳定Pickering乳液时,发现随着OAAD质量浓度增加,SiO2纳米颗粒润湿性增加,Zeta电位减少,粒径增加;而乳液的粒径则逐渐减少,稳定性增强,其机理经初步分析为,当一定浓度的OAAD吸附在SiO2纳米颗粒表面,可导致颗粒间絮凝,从而在油水界面形成网络结构式界面膜,有利于提高Pickering乳液的稳定性。     

离子液体表面活性剂的合成与应用(XII)——微乳液

离子液体表面活性剂替代传统表面活性剂构建微乳液具有明显的优势,且结构可设计;所制备的微乳液分为单相微乳液和多相微乳液,其相图主要包括拟三元相图和“鱼状”相图;微乳液的微观结构,如液滴尺寸、相互作用或极性等,可通过电化学技术、动态激光散射、小角X射线散射等技术来确定。此类微乳液可广泛应用于纳米粒子制备、聚合反应、金属离子萃取等领域。     

离子液体表面活性剂的合成与应用(Ⅻ)——微乳液

离子液体表面活性剂替代传统表面活性剂构建微乳液具有明显的优势,且结构可设计;所制备的微乳液分为单相微乳液和多相微乳液,其相图主要包括拟三元相图和"鱼状"相图;微乳液的微观结构,如液滴尺寸、相互作用或极性等,可通过电化学技术、动态激光散射、小角X射线散射等技术来确定。此类微乳液可广泛应用于纳米粒子制备、聚合反应、金属离子萃取等领域。     

A novel approach to study the interactions between polymeric stabilized micron-sized oil droplets by optical tweezers

The well understanding of interaction forces between single dispersed droplets is crucial to the understanding of emulsion stabilization mechanism. Recently, many studies have reported the direct quantitative measurements of interaction forces between 20-200 μm single droplet coated polymers by atomic force microscope(AFM).These studies have revealed many important results about the relationship of the interaction forces and the droplet deformation. However, these studies of the quantitative relationship between the measured interaction forces and the separation distance of the front end of the droplet have rarely been reported. Optical tweezer instrument can make it possible to establish the quantitative relationship between the measured force and the separation distance of the front end of the droplet, which will make better understanding of the interaction mechanisms between droplets. Due to the differences of the measuring mechanism between atomic force microscopy(AFM) and optical tweezers, the theory model of AFM measurements cannot be fitted with the force measurement by optical tweezers. We have made an exhaustive comparison of the measuring differences between AFM and optical tweezer instrument in this work. Moreover, we built a numerical model to derive the repulsive pressure through the measured force curve in order to quantify the measured force of two micron-sized oil droplet coated polymers by optical tweezers. Furthermore, the novel method can be extended to other micron-sized emulsion systems, and these findings will be a vital progress on quantitative force measurements between micron-sized droplets.     

天然气水合物颗粒微观受力及聚集特性研究进展

水合物颗粒微观受力和聚集是影响水合物浆稳定流动的关键,本文调研了国内外研究水合物颗粒受力和聚集常用的测量装置,主要有聚焦光束反射测量仪、颗粒图像显微镜、高压差示扫描量热仪、微机械测力装置;受力测量和理论研究证明了毛细液桥力是导致水合物颗粒聚集的主要黏附力;介绍了常用于水合物聚集特性研究的受力平衡模型,通过该模型可以计算得到水合物颗粒最大临界聚集粒径;总结了众学者提出的水合物颗粒聚集机理,并阐述了基于群体平衡模型建立的接触诱导-剪切限制聚集机理的物理模型,该模型能够很好地描述水合物颗粒的动态聚集过程;水合物颗粒微观受力和聚集机理的深入研究和明确将对石油天然气的输送具有非常重大的意义,确定防聚集对水合物聚集的影响是未来研究的重点。     

固体表面温度对冻结液滴的相变过程与表面润湿特性的影响

通过液滴可视化实验,发现并归纳了冻结液滴在不同基底温度下于铝板表面融化过程的动态表面润湿特性,结合力学分析,总结了液滴润湿面积、体积、接触角等润湿参数与相变时间之间的变化规律。实验结果表明：液滴的润湿性主要受重力、表面张力、热毛细力的影响,重力对液滴的横向扩散促进作用、表面张力与热毛细力受底板温度影响具有抑制液滴润湿过程的作用;两种不同条件下,冻结液滴高度变化规律相同,随着融化的进行,液滴高度骤降,然后缓慢降低;不同冻结条件下,冻结液滴的润湿过程主要发生在融化初始阶段,重力促进液滴的润湿过程,液滴接触角处于65°~85°之间,而在润湿后阶段,接触角减小,重力的作用减弱,表面张力的作用增强,液滴的扩散进程受阻,体积下降的趋势也变缓;不同升温条件下,冻结液滴的润湿过程几乎没有发生,热毛细力与表面张力在润湿过程中占据主导性,随着基底温度的升高,液滴内部与三相线温差逐渐增大,Ma数呈增加的趋势,数值由1802增至22876,热毛细力始终抑制液滴的运动。     

Interactions between fine combustion droplets

Interactions between fine combustion droplets were directly observed using microscopic flow visualization and high speed photography. The observations revealed “attracting-revolving-repulsing” interactions between the droplets. Force analyses showed that the traditionally considered interparticle forces, including drag, gravitation, the Coulomb force and the van der Waals force, cannot explain these interactions. However, the induced dipoles on the droplets due to the non-uniform distribution of surface charges on the fine droplets have important influence on such interactions. Therefore, the inter-dipole forces must be taken into account in the interaction force analysis as well as the Coulomb force between the net charges. The inter-dipole force includes components in the radial and azimuthal directions and is inversely proportional to r⁴. This force causes the particles to revolve and repel each other at small distance. The combined effects of the inter-dipole force and the traditionally considered forces give a complete explanation for the particle interactions.     

选择性紫外曝光法修饰微流控芯片用于制备高度均一的单乳液和复乳液

利用选择性紫外曝光法对聚二甲基硅氧烷(PDMS)微流控芯片通道内壁进行了部分亲/疏水改性,通过接触角和原子力显微镜对改性表面进行表征,并利用改性后的芯片制备出了高度均一的单乳液和复乳液. 结果表明,在芯片的非曝光区域,光引发剂二苯甲酮使PDMS表面粗糙且保持疏水性,接触角为101o;而在曝光区域,由于聚合形成的聚丙烯酸交联到PDMS上使其表面光滑且具有亲水性,接触角为62o,形成的亲/疏水特性可维持30 d以上. 利用改性后芯片制备的大豆油、三羟甲基丙烷丙烯酸酯和氟碳油3种单乳液的粒径变异系数均低于3%,而复乳液外径和内径的变异系数分别为3.5%和2.9%.     

Surface roughness and its influence on particle adhesion using atomic force techniques

The surface force interactions between individual 8 μm diameter spheres and atomically flat substrates have been investigated using atomic force techniques. The lift-off force of glass, polystyrene, and tin particles from atomically smooth mica and highly oriented pyrolitic graphite substrates was determined as a function of the applied loading force in an inert nitrogen environment. While the relative magnitudes of the measured lift-off force were found to scale as expected between the various systems studied, the absolute values were a factor of ～50 smaller than expected from the Johnson, Kendall, and Roberts theory. The surface topography of representative spheres was characterized with atomic force microscopy, allowing a quantitative assessment of the role that surface roughness plays in the adhesion of micrometer-size particles to substrates. Taking into account the radius of curvature of the asperities measured from the atomic force scans, agreement between the measured and theoretical estimates for the lift-off forces was improved, with the corrected experimental forces about a factor of 3 smaller than theoretical expectations.     

Synthesis of a novel reverse demulsifier with the characteristics of polyacrylate and polycation and its demulsification performance

As the development of oilfield exploitation, more and more oil in water (O/W) emulsion was produced, thus efficient reverse demulsifier becomes increasingly important. In this paper, a series of novel reverse demulsifiers (R-PED1 ~ 4) with the characteristics of polyacrylate and polycation were prepared. The structure of the product was verified by IR specter and ¹H NMR. The thermal stability was studied with TGA and the molecular weight was obtained by GPC. Field evaluation results showed that the oil content in produced liquid after R-PED4 treatment can be reduced from 1550 to 81 mg/L at R-PED4 dosage was 50 mg/L. Furthermore, the demulsification mechanism of R-PED was discussed. The R-PED has good surface/interfacial activity. It can effectively reduce the oil–water interfacial film strength and reduce the zeta potential of oil droplets, which is beneficial for the coalescence of oil droplets. Especially, the interaction force between oil droplets was measured by the optical tweezers. R-PED4 can increase the attraction force between oil droplets. Consequently, the contact time of oil droplets during the demulsification process can be prolonged and the coalescence of oil droplets also can be effectively promoted. The novel reverse demulsifier offers a new option for the oilfield produced liquid treatment.     

Quantifying dielectric permittivity based on the electrowetting effects on the adhesion force behavior using scanning probe microscopy

An scanning probe microscopy-based approach to quantify the dielectric constant of insulating films under environmental conditions is proposed. The method is based on the electrowetting effects on the adhesion force behavior between a conductive atomic force microscopy probe and the dielectric surface under study. By carrying out a parabolic fitting of the experimental data, parameters containing interfacial and dielectric properties of the sample are obtained. This provides a simple approach to estimate the value of the dielectric permittivity if the film thickness and the surface water contact angle are known. This method does not require any geometrical calibration of the probe as proposed in previous procedures. However, measurements have to be conducted under adequate values of relative humidity (in the range from 40 to 70% approximately) in order to guarantee the stability of the adhesion force measurement. The validity of the approach was verified in a poly(methyl methacrylate) layer and two SiO₂ films, obtaining excellent agreement between the reported values in the literature and the experimental results obtained.     

Reconsideration of Dynamic Force Spectroscopy Analysis of Streptavidin-Biotin Interactions

To understand and design molecular functions on the basis of molecular recognition processes, the microscopic probing of the energy landscapes of individual interactions in a molecular complex and their dependence on the surrounding conditions is of great importance. Dynamic force spectroscopy (DFS) is a technique that enables us to study the interaction between molecules at the single-molecule level. However, the obtained results differ among previous studies, which is considered to be caused by the differences in the measurement conditions. We have developed an atomic force microscopy technique that enables the precise analysis of molecular interactions on the basis of DFS. After verifying the performance of this technique, we carried out measurements to determine the landscapes of streptavidin-biotin interactions. The obtained results showed good agreement with theoretical predictions. Lifetimes were also well analyzed. Using a combination of cross-linkers and the atomic force microscope that we developed, site-selective measurement was carried out, and the steps involved in bonding due to microscopic interactions are discussed using the results obtained by site-selective analysis.