阴离子表面活性剂链长对蠕虫状胶束溶液流变性能的影响

制备了三种阴离子表面活性剂--烷基羧酸钠(C<,n>ONa,n=14,16,18).利用流变学方法研究了在0.5mol·L<'-1>KCl存在下C<,n>ONa所形成的胶束溶液的流变性能.结果表明,C<,14>ONa体系表现为牛顿流体,C<,16>ONa和C<,18>ONa体系在达到一定浓度后形成了蠕虫状胶束;三个体系...     

十六烷基三甲基溴化铵/油酸钠混合体系蠕虫状胶束流变性研究

阴、阳离子表面活性剂之间强烈的相互作用利于形成自由弯曲的蠕虫状胶束。本文利用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和阴离子表面活性剂油酸钠(Na OA)制备了CTAB/Na OA蠕虫状胶束,研究了两表面活性剂的混合比和表面活性剂总浓度的变化对蠕虫状胶束体系稳态流变性及动态粘弹性的影响。结果表明,蠕虫状胶束在剪切过程中的解缠、拟网状结构的破坏以及最终沿剪切速度方向取向等是蠕虫状胶束产生剪切稀释特性的原因。两表面活性剂的混合比和表面活性剂总浓度的变化导致表面活性剂之间的静电作用、疏水作用发生较大的变化,最终引起体系内部表面活性剂聚集体形态的差异。体系内蠕虫状胶束长度、体系结构复杂程度、蠕虫状胶束形成的网络结构的致密度等都影响着体系的流变行为。在混合比R=3.6、总浓度CT=0.24mol/L时,体系中蠕虫状胶束最长,网络结构最为紧密,体系的零剪切粘度达到最大值。表面活性剂浓度一定时,混合比的提高有助于蠕虫状胶束的定向生长,弛豫时间τR和储能模量高频区平台模量G0提高,R=3.6时两者皆达到极大值,此后由于蠕虫状胶束的分枝化及(或)胶束破裂导致τR及G0下降。在表面活性剂混合比一定(R=3.6)时,表面活性剂浓度的提高利于蠕虫状胶束的增长或者分枝化,增加了胶束网络结构缠绕(融合)点的密度,导致G0逐渐增大。Cole-Cole图证实本文研究的蠕虫状胶束体系是符合Maxwell模型的线性粘弹性流体。     

由碳酸钠诱导形成的油酸钠蠕虫状胶束的流变学性质

当Na₂CO₃浓度逐渐增加时, 用流变学的方法研究了阴离子表面活性剂油酸钠(NaOA)在溶液中从胶束转变成蠕虫状胶束的过程. 首先测量体系剪切粘度(η)和剪切速率的关系得到零剪切粘度(η₀). 然后由动态振荡实验得到复合粘度(|η^*|)、动态模量(储能模量G'、损耗模量G"和结构松弛时间τ_s)等物理量. 应用Cox-Merz规则和Cole-Cole图, 证明NaOA (0.040～0.080 mol/L)/Na₂CO₃ (0.25～0.50 mol/L)体系形成蠕虫状胶束, 且蠕虫状胶束的动态粘弹性在NaOA (0.050～0.080 mol/L)/Na₂CO₃ (0.35～0.45 mol/L)范围是符合Maxwell模型的线性粘弹性流体.     

智能型蠕虫状胶束体系

智能型蠕虫状胶束体系是指宏观性能随着外界环境条件的微小变化而发生明显改变的胶束体系,是智能型胶体材料和软物质的重要组成部分。本文按照“体系组成-微观结构-宏观性能”的思路分别介绍了具有温度、光、pH和氧化还原响应的智能型蠕虫状胶束体系的组成、性能及响应机理,并展望了其发展前景。     

粘弹性蠕虫状胶束及其应用

介绍了粘弹性蠕虫状胶束的形成、类型、基本性质及其应用情况.粘弹性蠕虫状胶束具有重要的微观结构,因其特殊的流变性能而在不同领域具有重要应用.最近,蠕虫状胶束的结构和动态性质的研究已经延伸到不同类型的表面活性剂,如阴离子、两性离子和聚合物表面活性剂.目前,其应用领域已经拓展到油田、社区冷热流体的减阻、个人护理和家庭清洁产品的增稠剂等方面.     

两性/阴离子表面活性剂形成具有耐盐性能的蠕虫状胶束

利用流变学方法研究了两性表面活性剂十四烷基磺基甜菜碱(TDAPS)和阴离子表面活性剂十二烷基硫酸钠(SDS)混合体系中蠕虫状胶束的耐盐性能, 分析了二价金属离子对蠕虫状胶束微观结构的影响. 结果表明, 在加入MgCl₂和CaCl₂使Mg^2＋和Ca^2＋总浓度达到0～1900 mg/L的情况下, TDAPS/SDS体系中形成的蠕虫状胶束的粘弹性能和耐剪切能力不仅没有损失而且增强. 对静态流变和动态流变结果进一步分析表明体系中同时存在两种可区分尺寸的蠕虫状胶束. 加入二价金属离子, 体系的微观结构发生了由小尺寸蠕虫状胶束向大尺寸蠕虫状胶束转变, 同时, 大尺寸蠕虫状胶束线性增长并发生枝化. 两性表面活性剂头基上的正电荷中心减小了蠕虫状胶束的反离子结合程度, 抑制了线性生长到枝化生长的过程, 使体系表现出优异的耐盐性能.     

水杨酸钠对阳离子Gemini表面活性剂水溶液中蠕虫状胶束形成和性质的影响

用稳态和震荡剪切实验研究了水杨酸钠(NaSal)对50 mmol·L^-1阳离子Gemini表面活性剂2-羟基-(三亚甲基-α,ω-双十二烷基三甲基溴化铵和三亚甲基-α,ω-双十二烷基三甲基溴化铵, 简写为12-3(OH)-12和12-3-12)水溶液中形成蠕虫状胶束及其性质的影响. 在无盐状态下, 50 mmol·L^-1的12-3(OH)-12或12-3-12在水溶液中仅形成球状或棒状胶束. NaSal可促进上述两体系胶束的生长, 生成蠕虫状胶束. 比较而言, 12- 3(OH)-12对NaSal更敏感, 可以在低盐浓度下生成蠕虫状胶束. 而且与12-3-12体系相比, 12-3(OH)-12生成了更长的蠕虫状胶束. 这些差别在于12-3(OH)-12体系中存在羟基连接链之间的氢键作用, 这增加了12- 3(OH)-12头基的亲水性, 促进了反离子的解离, 增大的胶束表面电荷密度更强烈地结合水杨酸根反离子, 减小了头基间的静电斥力, 反过来又增强了分子间氢键, 致使 12-3(OH)-12胶束迅速生长.     

阴离子疏水缔合共聚物/阳离子蠕虫状胶束协同增粘自组装网络

将阴离子疏水缔合丙烯酰胺共聚物P(NaAMC14S-b-AM)与阳离子蠕虫状胶束十六烷基三甲基溴化铵/水杨酸钠(CTAB/NaSal)在水溶液中自组装制备了新型的缔合增粘体. 由稳态剪切和动态流变实验结果得出: 自组装体系在80 ℃下仍具有显著的协同增粘效应, 其流变行为符合Maxwell模型. 同蠕虫状胶束相比, 自组装体系的稳态模量G0、力学松弛时间τR和缠结点密度ν都有增加, 由此分析缔合体系中两组分间形成了相互缠结的网络结构, 在链缠结处共聚物主链上的疏水侧链嵌入到了蠕虫状胶束的内核.     

长链阳离子表面活性剂蠕虫状胶束的剪切带转变行为研究

报道一种含有不饱和疏水尾链的超长链阳离子表面活性剂——N-芥酸酰胺丙基-N,N,N-三甲基碘化铵(EDAI)自组装所形成的蠕虫状胶束及其剪切带行为. EDAI浓溶液表现出了明显的剪切带转变特征, 即溶液的流动曲线被介于两个临界剪切速率之间的剪切应力平台分割为粘度不同的两部分. 在剪切带转变区域, 原本均质的流体表现出机械剪切不稳定性, 沿速度梯度方向被分割为剪切速率不同的两个宏观流体层.     

疏水缔合聚丙烯酸与蠕虫状胶束的协同作用

从宏观流变性和介观尺度方面, 研究了疏水缔合聚丙烯酸(HMPA)与油酸钠(NaOA)构筑的蠕虫状胶束的协同作用. 考察HMPA对蠕虫状胶束溶液流变性和表观粘度的影响, 结果表明, 极少量HMPA的引入导致蠕虫状胶束溶液体系动态模量明显增加; 其表观粘度随HMPA浓度的增加先增强后减弱. 另一方面, 通过耗散颗粒动力学(DPD)分子模拟方法研究了混合体系中溶液组成对HMPA分子链的均方根末端距的影响. 结果表明,随着NaOA浓度增加, HMPA的均方根末端距会出现峰值; HMPA的伸展程度受其自身浓度变化制约, 相对于纯HMPA体系, NaOA胶束的存在对高浓度区的HMPA伸展程度影响更明显. 结合流变实验和分子模拟结果,初步解释了聚合物与蠕虫状胶束的协同作用机制.     

阴离子蠕虫胶束

本文从分析蠕虫胶束形成的分子几何条件和自由能驱动因素入手,总结了传统阴离子表面活性剂蠕虫胶束的形成和性质,指出制约其构筑和产生优良黏弹性的原因。在此基础上,介绍了Gemini表面活性剂构筑蠕虫胶束的分子结构优势,以及由此构筑阴离子蠕虫胶束的研究进展,尤其是长刚性联接链Gemini表面活性剂形成的蠕虫胶束。最后特别指出,基于新颖分子结构优势,Gemini表面活性剂可望成为蠕虫胶束构筑的主要分子对象。     

Rheological Properties of Wormlike Micelles Formed by Cetyltrimethylammonium Bromide and Sodium Laurate

Aqueous solutions of mixed cationic and anionic surfactants, cetyltrimethylammonium bromide (CTAB) and sodium laurate (SL), have been studied by steady-state rheology and dynamic oscillatory technique. Wormlike micelles can form due to attractive interactions between the oppositely charged headgroups of CTAB and SL. The wormlike micelles formed by CTAB/SL have been compared with that of cetylpyridinium bromide (CPB)/SL by steady-state rheology method. Effects of additional components such as NaBr, 1-propanol, 1-butanol, polyvinylpyrrolidone (PVP) on the micelles formation process have also been investigated. Cole-Cole plot has been applied to study the dynamic viscoelasticity of the wormlike micelles.     

Rheological properties of wormlike micelles formed in the sodium oleate/trisodium phosphate aqueous solution

Aqueous solution of anionic surfactant,sodium oleate（NaOA）,was studied by means of steady-state shear rheology and dynamic oscillatory technique.The system of NaOA/Na3PO4 showed high viscosity,strong viscoelasticity and good ability of countering Ca^2＋,Mg^2＋.The Maxwell model and Cole-Cole plot were applied to study the dynamic viscoelasticity of wormlike micelles.The microstructures of the wormlike micelles were characterized by FF-TEM.     

Rheological Properties of Anionic Surfactant Solutions in the Presence of Al3+ Counterion

Aqueous solutions of ionic surfactants with strongly binding counterions exhibit wormlike or network properties. The properties of anionic micelles of sodium dodecyltrioxyethylene sulfate (AES) in the presence of multivalent counterion Al³⁺ were investigated by dynamic rheological methods. The steady-shear viscosity and stress, the zero-shear viscosity, the complex viscosity, and the dynamic shear modulus have been determined as a function of the surfactant and salt concentrations. Some interesting and noticeable results have been obtained, which can express the micellar growth and structure. The formation of wormlike micelles or network structure in surfactant solutions becomes much easier with increasing surfactant and salt concentrations. The Cox-Merz rule and the Cole-Cole plot are not applicable perfectly to the systems studied. The nonlinear viscoelasticity and non-Newtonian behavior can be found in all solutions according to the comparison with the simple Maxwell model. The technique of freeze-fracture transmission electron microscopy (FF-TEM) was also applied to confirm the formation of these interesting structures.     

阳、阴、非离子表面活性剂胶束对酯碱性水解的影响

应用紫外分光光度法和热动力学方法研究了芳香酸酯和正脂肪酸酯在表面活性剂ＤＴＡＢ、ＴＴＡＢ、ＣＴＡＢ、ＳＤＳ、Ｂｒｉｊ３５、ＴｒｉｔｏｎＸ－１００胶束中的碱性水解反应。阳、阴、非离子表面活性剂胶束对酯的碱性水解均有禁阻作用。讨论了胶束对酯碱性水解禁阻作用的原因。     

CO2-Responsive Wormlike Micelles Based on Pseudo-Tetrameric Surfactant

Wormlike micelles, which are linear aggregates created by the self-assembly of surfactants, may entangle to form dynamic three-dimensional network-like structures, endowing solutions with considerable macroscopic viscoelasticity. Recently, a pressing need has arisen to research a novel stimuli-responsive worm-like micelle that is efficient and environmentally friendly. CO₂ is an inexpensive, abundant, non-toxic, biocompatible, and non-combustible gas, and it is anticipated that CO₂ may serve as the trigger for stimuli-responsive worm-like micelles. In this paper, the formation of CO₂-switchable pseudo-tetrameric surfactants, which subsequently self-assemble into CO₂-switched wormlike micelles, is accomplished using a simple mixing of two commercial reagents, such as stearic acids and cyclen. The rheological characteristics switched by the use of CO₂ are cycled between that of a low-viscosity (1.2 mPa·s) fluid and a viscoelastic fluid (worm-like micelles, 3000 mPa·s). This article expands the field of study on stimuli-responsive worm-like micelles.     

Rheology of viscoelastic anionic micellar solutions in the presence of a multivalent counterions

The growth and structure of anionic micelles sodium dodecyl trioxyethylene sulfate (SDES) in the presence of a multivalent counter-ion, Al³⁺, were investigated by means of rheological methods and the technique of freeze-fracture transmission electron microscopy. It was found that wormlike micelles and network structures could be formed in SDES/AlCl₃ aqueous micellar solutions, according to the measurements of the zero-shear viscosity, the complex viscosity and the dynamic moduli (storage modulus and loss modulus), and the application of the Cox–Merz rule and a Cole–Cole plot. The cyclic shear test, the plateau modulus and the relaxation time were also studied to express the rheological properties of the wormlike micellar solutions. The structure was of a character of a nonlinear viscoelastic fluid and departed from the simple Maxwell model. Received: 23 November/2000 Accepted: 31 January 2001     

介孔SiO2孔道内Gemini分子有序自组装构筑正相胶束辅助传递OH-离子

利用Gemini型阳离子表面活性剂(顺丁烯二酸二乙酯撑基双[辛烷基二甲基氯/溴化铵], G_8-2-8)在有机反离子水杨酸根(Sal^-)的诱导作用下, 于介孔SiO₂孔道内有序组装, 构筑表面带有季铵基团的正相蠕虫胶束. 胶束外表面有序排布的季铵基团与介孔SiO₂孔道内壁布满的硅羟基共同作用形成环形保水腔室, 即构筑了OH^-传递的有序通道. 通过对G_8-2-8/NaSal 胶束体系的流变学性质研究, 结果表明, 胶束网络结构已经形成. 将G_8-2-8/NaSal胶束网络形成过程引入聚砜(PSF)体系中, 制备出有序OH^-迁移通道的高耐碱性的阴离子导电膜. 相关性能测定结果表明, 随着G_8-2-8质量分数的增加, 电导率、 含水率及离子交换量均呈现上升趋势, 特别是在离子交换量和含水率均较低的情况下, OH^-的迁移效率得到明显提升. 经过400 h的耐碱性测试, 结果表明, 该系列膜的电导率降幅仅为1.5%左右, 且外观形貌无明显变化, 表现出优异的耐碱稳定性.