阳离子表面活性剂三甲基溴化铵与硝酸铵相互作用的表面和热力学研究

本文系统研究了阳离子表面活性剂三甲基溴化铵和硝酸铵盐的表面现象和自聚集行为. 采用电导法和表面张力法研究在不同温度下阳离子表面活性剂三甲基溴化铵的表面性质和热力学性质. 通过表面张力测定得到临界胶束浓度、吸附自由能、胶束化的自由能、最小分子面积和表面过量浓度. 该研究表明,胶束化过程是自发放热反应. 电导测定结果确定了临界胶束浓度、电离程度和反离子结合度. 加入硝酸铵盐至表面活性剂溶液后,临界胶束浓度降低,电离程度和反离子结合度增加,更加有利于胶束化过程的自发. 该研究对进一步理解电解质和表面活性剂之间相互作用具有重要意义.     

阳离子表面活性剂三甲基溴化铵与硝酸铵相互作用的表面和热力学研究（英文）

本文系统研究了阳离子表面活性剂三甲基溴化铵和硝酸铵盐的表面现象和自聚集行为.采用电导法和表面张力法研究在不同温度下阳离子表面活性剂三甲基溴化铵的表面性质和热力学性质.通过表面张力测定得到临界胶束浓度、吸附自由能、胶束化的自由能、最小分子面积和表面过量浓度.该研究表明,胶束化过程是自发放热反应.电导测定结果确定了临界胶束浓度、电离程度和反离子结合度.加入硝酸铵盐至表面活性剂溶液后,临界胶束浓度降低,电离程度和反离子结合度增加,更加有利于胶束化过程的自发.该研究对进一步理解电解质和表面活性剂之间相互作用具有重要意义.     

丁二酸-水纳米气溶胶液滴表面张力的分子动力学研究

表面张力在纳米气溶胶颗粒的吸湿生长研究中具有重要意义,然而现有实验方法不能对其准确测量.本文基于分子动力学方法模拟了丁二酸气溶胶颗粒吸湿生长形成稳定液滴的动力学过程,在此基础上,建立模型计算了液滴的表面张力,进而探究了温度、粒径和丁二酸浓度对纳米液滴表面张力的影响机制.结果表明,随着温度从260 K升高到320 K,液滴内分子间作用力的减弱导致了液滴表面张力的减小,且表面张力的减小程度随丁二酸浓度的增大而增大,究其主要原因在于液滴中丁二酸分子的径向分布随温度和丁二酸浓度变化的差异;随着粒径的增大,液滴表面张力先增大后趋于定值,且粒径对表面张力的显著影响区间随着丁二酸浓度的增大而缩短;研究还发现,丁二酸分子的表面活性导致液滴表面张力随着丁二酸浓度的增大而减小,且减小趋势符合对数函数形式,尤其是在粒径小于6.12 nm时,同时,基于Szyszkowski公式对液滴的表面张力进行了拟合.本文研究成果能为气溶胶颗粒的吸湿生长和相关动力学过程预测理论及模型的改进提供参数依据.     

纳米颗粒水基分散液在岩心微通道中的双重减阻机制及其实验验证

提出了纳米颗粒水基分散液的力学-化学双重减阻机制,并通过对比岩心切片吸附纳米颗粒前后以及冲刷前后的表面微结构、润湿性的变化,进行了实验验证. 研究结果表明,经纳米颗粒水基分散液处理之后的岩心切片表面表现为强亲水性, 并且存在一层致密的纳米颗粒吸附层;冲刷之后岩心切片表面的纳米颗粒吸附层依然存在, 但其表面已逐渐转变为强/超疏水性,反映了纳米颗粒吸附层表面的表面活性剂被逐渐清洗干净. 注水初期,主要表现为表面活性剂的化学减阻作用.随着注水过程的进行, 主要体现为以疏水表面的滑移效应为主的力学减阻机制.岩心驱替实验结果表明, 纳米颗粒水基分散液驱替后的岩心的水相渗透率平均提高幅度达84.3%, 减阻效果显著,证实了纳米颗粒水基分散液的力学-化学双重减阻机制.     

底板属性对液滴蒸发过程的影响

液滴蒸发机制目前引起人们广泛重视。通过研究纳米颗粒质量溶度为0.05%的Al_2O_3液滴在铁表面和玻璃表面的蒸发过程,发现液滴在铁表面蒸发时呈现4种蒸发形态;定接触线形态、定接触角形态、黏滑形态和不稳定形态;而在玻璃表面的蒸发只有不稳定形态。主要原因是液滴在铁表面蒸发时,固-液表面张力更大,形成定接触线蒸发形态;随着蒸发进行,液滴温度下降,气-液表面张力变大,因而产生黏滑形态。     

表面单分子膜的垂悬液滴方法研究

提出一种扩展或收缩气/液界面单分子层的分子密度，用荧光成像技术检测单分子层的扩展或收缩效果的新方法——垂悬液滴分析方法-此方法通过改变液滴体积，对液滴界面上的表面活性剂分子实施扩展和收缩，具有Langmuir-Blodgett(LB槽)的功能-对表面活性剂荧光分子，用液滴的激光感生荧光图像，可以实时测量液滴界面的相对分子密度变化；用偏振荧光分析技术，可获取荧光偶极矩在液滴界面的相对取向-对罗丹明(B)表面活性剂分子ODRB的实验结果表明：1) 表面单分子层分子密度在压缩过程中遵循σ/σ_{0关键词：}     

季铵盐表面活性剂溶液中阴离子偶氮染料的光谱研究

通过紫外-可见光谱法研究了阴离子偶氮染料甲基橙(MO)与3种季铵盐表面活性剂之间的相互作用.当表面活性剂浓度远低于临界胶束浓度(CMC)时,表面活性剂与染料形成聚集体,反映为吸收带蓝移并伴随着吸收强度下降.继续加入表面活性剂,引起染料在阳离子胶束中的特征吸收.当表面活性剂浓度达到CMC及以上时,混合溶液的λ<,max>...     

表面活性剂对纳米制冷剂颗粒团聚的影响

为通过表面活性剂抑制纳米制冷剂中的颗粒团聚,需要了解不同种类和浓度的表面活性剂对纳米制冷剂颗粒团聚的影响。本文采用动态光散射技术测量纳米制冷剂中的颗粒尺度,来定量分析纳米制冷剂的颗粒团聚特性;实验所用纳米制冷剂为TiO_2-R141b;表面活性剂种类包括SDBS(阳离子型)、CTAB(阴离子型)和NP-10(非离子型)。实验结果表明,SDBS、CTAB和NP-10均可降低纳米制冷剂的颗粒尺度,即抑制纳米制冷剂中的颗粒团聚。对SBDS、CTAB和NP-10,当其浓度分别为400 mg·L~(-1)、200 mg·L~(-1)和300mg·L~(-1)时纳米制冷剂的颗粒尺度最小,最小值分别是未加表面活性剂时的58.4%、56.9%和38.0%。     

表面弹性对含可溶性活性剂垂直液膜排液的影响

针对含可溶性活性剂的垂直液膜排液过程,在考虑表面弹性作用的基础上,采用润滑理论建立了液膜厚度、表面速度、表面和内部活性剂浓度的演化方程组,通过数值计算分析了表面弹性和活性剂溶解度耦合作用下的液膜演化特征.结果表明：表面弹性是影响可溶性活性剂垂直液膜排液过程中必不可少的因素.排液初期,随表面弹性增加,液膜初始厚度增大,表面更趋于刚性化.随排液进行,弹性不同的液膜呈现不同的典型排液特征：当弹性较小时,液膜上部表面张力高,下部表面张力低,产生正向的马兰戈尼效应,与重力作用相抗衡.当弹性较大时,膜上部表面张力低,下部表面张力高,产生逆向的马兰戈尼效应,促使液膜排液加速,更易发生失稳.活性剂溶解度通过控制液膜表面的活性剂分子吸附量,进而影响表面弹性：当活性剂溶解度较大时,液膜厚度较小,很快发生破断;随溶解度降低,液膜稳定性增加,初始表面弹性也随之增大,并随液膜变薄逐渐接近极限膨胀弹性值.     

凝结初期固体表面纳米液滴尺寸分布特征

研究凝结初期纳米液滴在固体表面纳米液滴的尺寸分布特征,不仅有助于揭示纳米结构表面凝结换热的微观机理,同时还可为纳米结构表面的设计提供参考依据。借助分子动力学模拟,考察了体系温度、固体表面亲水性对光滑和纳米方柱结构表面纳米液滴尺寸分布特征的影响。结果表明:系统温度升高,表面大液滴比例降低,表面液滴覆盖率下降;表面亲水性增强,表面大液滴比例增加,表面液滴覆盖率增加;纳米结构表面相对光滑表面更易出现小尺寸液滴。     

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.     

Novel surface tension isotherm for surfactants based on local density functional theory

In this Letter we report a new general method for calculating of surface tension isotherms in the presence of surfactants, based on a local density functional. We illustrate this method by deriving the interfacial tension isotherm for nonionic surfactants at an air-water or oil-water interface by using the self-consistent field theory of polymer brushes. We consider a particular case of local density functional to calculate explicitly how the interfacial tension and the surfactant adsorption depend on the surfactant bulk concentration. Experimental data for the surface tension and the surfactant adsorption isotherm for nonionic surfactants were interpreted with the help of the new isotherm. Very good agreement between the adsorption of n-dodecyl pentaoxyethylene glycol ether (C12E5) at an air-water interface, calculated from the surface tension isotherm and small-angle neutron-scattering is obtained.     

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75?nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from ?79.8 to 15.3?mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.     

THE ADSORPTION OF ANIONIC AND CATIONIC SURFACTANTS BY THE DIFFERENT CLAY MINERALS: FTIR SPECTROSCOPIC STUDY

The adsorption of an anionic surfactant LABS (Linear alkyl benzene-sulphonate) and a cationic surfactant DDAC (Distearly dimethyl ammonium chloride) by kaolinite, bentonite and sepiolite clays was investigated by vibrational spectroscopy. The samples prepared at different concentrations, and clay-surfactant spectra in the natural state, were recorded. The spectroscopic results indicate that the LABS and DDAC adsorbed on sepiolite and kaolinite. Bentonites are coordinated to either surface hydroxyls by H-bonding interacti on (sepiolite) or to exchangeable catoins (kaolinite, bentonite) through both sulphur and nitrogen atoms as ligands. Interactions of both surfactants showed similarities, in that LABS was coordinated on clay surfaces with broken ends, and the DDAC molecule was adsorbed on the clay surface.     

Surface tension calculations of the cationic (CTAB) and the zwitterionic (SB3-12) surfactants using new force field models: a computational study

Actual CTAB and SB3-12 surfactant force field models fail to reproduce one of the most important thermodynamic property of those molecules, the surface tension. Molecular dynamics simulations were conducted to construct new force fields of the cationic surfactant, Cetyl Trimethyl Ammonium Bromide (CTAB), and the non-ionic, cocoamidopropyl betaine, surfactants using united atom models. By scaling the Lennard Jones parameters, the well depth potential (ε) and the intermolecular distance (σ), we constructed an united atom model of the cationic and the betaine surfactants. The new models were tested with actual experiments reported in the literature. With the correct parameters, surface tensions of both surfactants were calculated at different temperatures and different areas per molecule. Electrostatic properties and micelle structures were also calculated with the new set of parameters and radius of gyrations, i.e. micelle radius, were evaluated showing good affinity with experimental data. The new force fields were proved with two different water models, TIP4P/ε and SPC/E, having good agreement with actual experiments     

Wettability alteration of sandstones by silica nanoparticle dispersions in light and heavy crude oil

Unlike conventional oil production methods, enhanced oil recovery (EOR) processes can recover most oil products from the reservoir. One method, known as wettability alteration, changes the hydrophilicity of the reservoir rock via decreased surface interactions with crude oils. The mitigation of these attractive forces enhances petroleum extraction and increases the accessibility of previously inaccessible rock deposits. In this work, silica nanoparticles (NPs) have been used to alter the wettability of two sandstone surfaces, Berea and Boise. Changes in wettability were assessed by measuring the contact angle and interfacial tension of different systems. The silica NPs were suspended in brine and a combined solution of brine and the Tween®20 nonionic surfactant at concentrations of 0, 0.001, and 0.01 wt% NP with both light and heavy crude oil. The stability of the different nanofluids was characterized by the size, zeta potential, and sedimentation of the particles in suspension. Unlike the NPs, the surfactant had a greater effect on the interfacial tension by influencing the liquid-liquid interactions. The introduction of the surfactant decreased the interfacial tension by 57 and 43% for light and heavy crude oil samples, respectively. Imaging and measurements of the contact angle were used to assess the surface-liquid interactions and to characterize the wettability of the different systems. The images reflect that the contact angle increased with the addition of NPs for both sandstone and oil types. The contact angle in the light crude oil sample was most affected by the addition of 0.001 wt% NP, which altered both sandstones’ wettability. Increases in contact angle approached 101.6% between 0 and 0.001 wt% NPs with light oil on the Berea sandstone. The contact angle however remained relatively unaffected by addition of higher NP concentrations, thus indicating that low NP concentrations can effectively be used for enhancing crude oil recovery. While the contact angle of the light crude oil plateaued, the heavy crude oil continued to increase with an increase in NP concentration; therefore indicating that a maximum contact angle in heavy crude oil was not yet achieved. The introduction of NPs in light and heavy crude oil samples altered both the Berea and Boise sandstone systems’ wettability, which in turn indicated the efficacy of the silica NPs and surfactants in generating a more water-wet reservoir. Consequently, silica NPs and surfactants are most promising for EOR across the range of oil types.     

Adsorption of dissymmetric cationic gemini surfactants at silica/water interface

Adsorption of a series of cationic gemini surfactants 12-2-m (m = 8, 12, 16) on the surface of silica was investigated. The critical micelle concentrations, cmcs, of cationic gemini surfactants in the initial solutions and in the supernatants were measured by conductometry and tensiometer. The changes in cmc values indicate that the ion exchanges take place between polar groups of gemini surfactants adsorbed and ions bound on the surface of silica. The adsorption isotherms of cationic gemini surfactants were obtained by a solution depletion method. Based on the driving force, the adsorption includes two steps, one of which is ion exchange, and the other is hydrophobic interaction. In each step, the tendency of surfactant molecules in the solution to form aggregates or to be adsorbed on the silica varies with their structures. The maximum adsorption amount of gemini surfactants on the silica, τ_max, decreases as increasing in the length of one alkyl chain, m, from 8, 12 to 16. So the results show that the adsorption behaviors of gemini surfactants are closely related to the dissymmetry of gemini molecules.     

Enhancement in Magnetorheological Effect of Magnetorheological Elastomers by Surface Modification of Iron Particles

为了研制具有高磁流变效应的磁流变弹性体,从新的化学修饰的角度制备了各向异性的橡胶基磁流变弹性体. 阴离子表面活性剂、非离子表面活性剂和复合表面活性剂等三种不同类型的表面活性剂分别用于修饰铁颗粒. 使用力磁耦合动态测试仪测量磁流变弹性体的动态剪切模量,并计算材料的磁流变效应. 测试结果表明,当Span 80的含量为15%时,材料的相对磁流变效应可达到188%,除了表面活性外,Span 80的增塑效应也有利于相对磁流变效应的增加. 当使用具有强表面活性的复合表面活性剂修饰铁颗粒时,用量只需0.4%,便可使相对     

季铵盐型双子表面活性剂在空气-水界面的单分子膜

利用Langmuir膜天平测定不对称双子表面活性剂12-2-16和对称双子表面活性剂12-2-12在空气-水界面上形成单分子膜的表面压,通过单分子膜的π-A等温线、微分等温线和静态弹性,分析其相转变和成膜特性.结果表明,与传统阳离子表面活性剂DTAB比较,12-2-16、12-2-12比DTAB单分子膜的分子极限面积大,崩溃压高,并有较高的静态弹性,因而具有较高的凝聚性和稳定性,其中12-2-16单分子膜的凝聚性和稳定性最高.     

Physicochemical properties of nanoparticles affect translocation across pulmonary surfactant monolayer

Interaction between nanoparticles (NPs) and pulmonary surfactant monolayer is one of the most important parts in NP-based pulmonary drug delivery system, which can affect the result of the inhaled nano-drugs and their potential efficacy. Here, we show how surface charge of NPs affects translocation across pulmonary surfactant monolayer with coarse-grained molecular dynamics simulations. The results reveal that the surface charge position of NPs can determine the fate of the inhaled NPs about whether they can have the ability of translocation across the pulmonary surfactant monolayer, which is that NPs with face surface charge can penetrate the pulmonary surfactant monolayer and NPs with edge surface charge cannot. Besides, dynamic process, phase state and the potential of mean force profiles further confirm this result. Moreover, compared to anionic NPs, there is a greater chance for cationic NPs to be adsorbed on the surface of the pulmonary surfactant monolayer, which can further decrease the thickness of the pulmonary surfactant monolayer and reduce the distance between charged NPs and the pulmonary surfactant monolayer. Our researches provide a novel simulation model of NPs on translocation across pulmonary surfactant monolayer and the study of NP-based pulmonary drug delivery system should consider the surface charge of NPs.