简述离子表面活性剂构筑蠕虫状胶束的研究现状

粘弹性蠕虫状胶束具有特殊的微观结构,其流变性能在不同领域具有重要的应用。本文介绍了表面活性剂构筑的蠕虫状胶束的结构特点、应用及研究现状。传统离子表面活性剂构筑蠕虫状胶束通常需要一些外加作用,Gemini表面活性剂因其结构优势,可以自身形成蠕虫状胶束。     

Wormlike Micelles in Mixed Amino Acid‐Based Anionic Surfactant and Zwitterionic Surfactant Systems

The formation of wormlike micelles in aqueous solutions of an amino acid‐based surfactant, sodium lauroyl sarcosinate (LS) and a zwitterionic surfactant, cocamidopropyl betaine (CAPB) has been investigated. Holding the total concentration of LS and CAPB constant at 12 wt%, the synergistic effects of mass ratio of CAPB and LS and pH of the micelle solution on rheological behaviors of CAPB/LS micelles were studied. The viscosity of CAPB/LS micelle systems with a mass ratio from 4:8 to 9:3 increases to maximum values and then decreases as pH increases from 4.0 to 5.6. The maximum viscosity of the transparent CAPB/LS micelle solution is nearly 5500 mPa·s with a mass ratio of CAPB/LS = 8:4 at pH 5.10. It is suggested that the proper pH for CAPB and LS to form wormlike micelles should be close to the isoelectric point of the CAPB/LS solution. The results of thixotropy measurements show that the appropriate mass ratio of CAPB/LS can improve the stability of the network structure of wormlike micelles. In addition, viscosity curves of CAPB/LS wormlike micelles follow a nonlinear co‐rotational Jeffreys model, and the linear viscoelasticity of CAPB/LS wormlike micelles can be described by a linear viscoelastic Jeffreys model. The network of wormlike micelles is confirmed by Cryo‐TEM images.     

NaSal/NaCl诱导阳离子蠕虫状胶束的形成及流变性研究

以阳离子三联表面活性剂双(2-羟基-二亚甲基醚)-α,ω,γ-三(十六烷基二甲基氯化铵)(TrimerC16)为主剂,水杨酸钠(Na Sal)为有机反离子,氯化钠(Na Cl)为无机反离子,制备了阳离子蠕虫状胶束体系。利用电导率-表观黏度法研究了TrimerC16的相行为,考察了不同有机反离子Na Sal、苯甲酸钠(Na BENZ)及甲酸钠(Na FM)对TrimerC16克拉夫特温度(Tk)的影响,通过动态流变手段研究了TrimerC16/Na Sal/Na Cl的流变行为,并采用表观黏度法考察了温度(T)及剪切时间(ts)对该体系表观黏度(ηa)的影响。结果表明:TrimerC16的临界囊泡浓度(CVC)为0.015 mmol?L?1,临界胶束浓度为0.042mmol?L?1;三种有机反离子对TrimerC16的Tk影响大小顺序为:Na SalNa BENZNa FM;剪切速率(r′)为100 s?1时,TrimerC16/Na Sal/Na Cl体系的黏度仍高达70 m Pa·s;T=100℃时,转速为50 r?min?1下,TrimerC16/Na Sal/Na Cl体系的ηa为61.8 m Pa?s,而同一测试条件下,相同摩尔浓度的单链表面活性剂胶束体系的ηa已接近水的黏度。TrimerC16/Na Sal/Na Cl蠕虫状胶束体系耐较高温、耐剪切且破胶彻底。     

蠕虫状胶束的黏弹性及其应用

文章主要叙述了在流变性上具有其特有性质的一种非常重要的表面活性剂聚合结构,即黏弹性蠕虫状胶束的重要应用。其内容包括了由阴离子,两性离子和高分子表面活性剂形成的相应体系。应用范围更是涉及了油田化学品,药物减水剂和个人护理品及家居用品的增浓等。     

Effect of Silica Nanoparticles on Wormlike Micelles with Different Entanglement Degrees

Enhancing the viscoelastic properties of wormlike micelles by adding nanoparticles has been widely reported. Various mechanisms have been proposed to explain how nanoparticles strengthen the network formed by wormlike micelles. It remains unclear whether nanoparticles produce the same effect on systems with different entanglement degrees. To clarify this issue, the concentration of potassium chloride was used to control the entanglement degree of wormlike micelles. The rheological behavior of different nanoparticle-enhanced wormlike micellar systems (NEWMS) was investigated using rheology. Three critical parameters including zero-shear viscosity (η₀), relaxation time (τ_R), and contour length (L) were calculated to analyze the effect of nanoparticles on the different wormlike micellar systems. An appropriate mechanism describing the interaction between nanoparticles and wormlike micelles with different structures was proposed.     

Electrostatic Effect on Synergism of Wormlike Micelles and Hydrophobically Modified Polyacrylic Acid

The electrostatic effects on the synergism between wormlike micelles and hydrophobically modified polyacrylic acid (HMPA) have been investigated by rheological measurements and dissipative particle dynamics molecular simulation (DPD). Both cationic surfactants, cetyltrimethylammonium bromide (CTAB), and anionic surfactant, sodium oleate (NaOA), were employed to construct wormlike micelles, and the influences of both simple salts, NaBr or NaAc, and hydrophobic salts, sodium benzoate (NaBen) and benzyltrimethyl ammonium bromide (BTAB), were discussed. The synergistic effects vary with the headgroup charge and the counterions property of surfactants. For the NaOA system, the obvious viscosity maximum was observed only at low NaAc content, while a monotonous viscosity increase appeared at a high content of BTAB. However, the optimal synergism can be only observed in the presence of concentrated NaBen in CTAB system. DPD molecular simulation provides a support and favorable illustration for the synergism mechanism. It suggests that not only the hydrophobic interaction but also the electrostatic interaction has an important impact on the synergism between ionic wormlike micelles and HMPA.     

In‐Situ Formation of Viscoelastic Wormlike Micelles in Mixtures of Non‐Surface‐Active Compounds

Viscoelastic fluids based on surfactant self‐assembled wormlike micelles have been in focus over the past decade. In this work, we report wormlike micellar solutions formed in situ by simply mixing two non‐surface‐active compounds, N‐(3‐(dimethylamino)propyl)palmitamide (C16AMPM) and salicylic acid (HSal), without specialized organic synthesis of a surfactant. In the absence of HSal, C16AMPM is poorly soluble in pure water; after introducing HSal, C16AMPM is protonated into quaternary ammonium, behaving like a cationic surfactant with a low critical micellar concentration (0.25 mM) and a small area per molecule, which favors the formation of long cylindrical wormlike micelles. Above the overlapping concentration (~28 mM), the wormlike micelles formed entangle each other into viscoelastic networks, enhancing the viscosity by several orders of magnitude. In contrast to the worms formed by a single ultra‐long‐chain surfactant, the current system shows the advantages of a smaller flow activation energy and end‐cap energy, simpler formulation and lower cost, which make it more suitable for practical use.     

Rheological Properties of Wormlike Micelles Formed in Aqueous Systems of 3‐Alkoxy‐2‐hydroxypropyl Trimethyl Ammonium Bromides in the Presence of Sodium Octanoate

The rheological properties of aqueous systems composed of each of the four homologous cationic surfactants (3‐alkoxy‐2‐hydroxypropyl trimethyl ammonium bromides, C_nHTAB, n = 12, 14, 16 and 18) in the presence of an anionic surfactant, sodium octanoate (SO), have been studied by using steady state and frequency sweep rheological measurements. The effects of surfactant concentration, hydrophobic chain length and temperature were investigated. In C₁₄HTAB solution, the viscosity shows shear thinning in the concentration range of C_C14HTAB >320 mmol/kg. Addition of SO promotes the micellar growth and results in the generation of wormlike micelles. Zero‐shear viscosity (η₀) of the binary surfactant system exhibits a maximum point in the investigated concentration range, suggesting the interaction between C₁₄HTAB and SO molecules is strongest at the optimal ratio of C₁₄HTAB with SO. The decrease in viscosity was attributed to be the transition from entangled wormlike micelles to branching micelles after the maximum point, cryo‐TEM images revealed the changes in the structure of the wormlike micelles.     

溶剂对聚合物减阻剂流变行为和减阻性能的影响

采用博力飞旋转粘度计测定了减阻剂在不同溶剂中溶液的流变性能,通过减阻剂室内模拟环道评价装置测定了不同溶剂合成的聚合物的减阻率。结果表明,减阻剂属于典型的剪切增稠型非牛顿流体;减阻剂在不同溶剂中溶液的粘度随着温度升高而降低;当环己烷与减阻剂的溶度参数相等时,减阻剂在环己烷中的溶解性能最好。并探讨了剪切增稠流体的减阻机理,分析了不同溶剂合成的减阻剂对减阻性能的影响。     

The Use of Drag Reduction Agent and a Detergent for Drag Reduction in Circulatory Vertical Pipe Flow

This paper describes the results of an experimental study of drag reduction in a circulatory vertical pipe system for both upward and downward flows using a drag reduction agent, corrosion inhibitor, and a cheap detergent (washing-up liquid) with various concentrations for different flow rates.

It was found that the corrosion inhibitor did not produce any drag reduction effect for both upward and downward flows while the drag reduction agent was effective for both flows; whereas, the detergent was effective only for upward flow. A comparison of the effectiveness of the drag reduction agent against the detergent showed that the effectiveness of the drag reduction agent is much higher than that of the detergent. The effect of liquid detergent is only noticeable if a large concentration is used. A 1000-ppm of detergent produces the same results as 25 ppm of drag reduction agent, which undermined the lower cost of the detergent. Over the range of Reynolds numbers tested the maximum drag reduction for upward flow is 35% while for the downward flow is 42%.     

Prediction of Field Drag Reduction by a Modified Practical Pipe Diameter Model

Slick water fracturing is a successful stimulation technology for gas shales. Due to the high pumping rates associated with slick water fracturing, drag reduction (DR) is critical to the success of field operations. In this study, three drag‐reducing agents were tested in a laboratory setup and the results were compared with data from numerous slick water fracturing treatments in the field in China. The results show that, as long as the slopes of effective pipe radius versus velocity from the laboratory‐scale tubes and from the field pipes are close, field drag reduction can be predicted by a modified correlation between DR and velocity established in the laboratory. The modified practical pipe diameter model should be useful in the design of slick water fracturing treatments and the selection of drag‐reducing agents in the laboratory.     

溶液聚合合成减阻剂及其特征对减阻的影响

油相减阻剂的合成方法主要分为本体聚合法和溶液聚合法.对溶液聚合法合成的α-烯烃聚合物进行室内模拟环道评价装置、凝胶渗透色谱、核磁共振及红外光谱测试,分析结果表明,溶液聚合转化率高达97.92%,产物为超高分子质量聚合物,减阻率达到56.45%接近于美国固体产品的减阻率.     

表面活性剂蠕虫状胶束缔合体系研究进展

介绍了表面活性剂蠕虫状胶束体系的研究进展情况,包括蠕虫状胶束的生长,稀溶液向亚浓溶液的过渡、粘弹体系的动态特性和非线性粘弹性以及剪切诱导粘弹性。     

Synthesis and Properties of Dicephalic Cationic Surfactants Containing a Quaternary Ammonium and a Guanidine Group

Novel dicephalic surfactants containing a quaternary ammonium and a guanidine group were synthesized, and the effect of the alkyl chain length on micellization and antimicrobial activity were investigated. Surface tension and conductivity were applied to study the self-aggregation of the amphiphilic molecule in aqueous solution. The results indicated that these compounds reduce the surface tension to a level of 30–36 mN/m at the air/water interface and that there is a characteristic chain length dependence of the micellization process of surfactants. The antimicrobial activity was evaluated against Gram-negative, Gram-positive bacteria and fungi, indicating strong antibacterial activity against tested strains.     

pH对油酸钠/盐酸三乙胺蠕虫状胶束流变性质的影响

用流变学方法研究了pH对油酸钠/盐酸三乙胺(NaOA/Et3NHCl)蠕虫状胶束溶液流变性质的影响。通过稳态剪切和动态流变实验发现,30℃时,NaOA(0.12 mol/L)/Et3NHCl(0.2 mol/L)溶液在pH=8.20~9.40循环变化时,pH对溶液黏度的改变具有"开关"效应,可实现黏度在3~27 649 mPa·s时反复变化3次以上。体系在pH=8.55~9.02时为蠕虫状胶束,其流变行为符合Maxwell模型。这种溶液流变性对pH的响应行为是由于pH对反离子Et3NH+与NaOA的相互作用影响而产生的。当pH降低时,反离子Et3NH+的离子势增大,导致胶束表面电荷密度降低,蠕虫状胶束进一步增长。当pH=8.64,胶束因相互吸引而析出。而在初始条件下,升高pH=9.40,反离子Et3NH+从胶束中解吸出来,蠕虫状胶束受到破坏。     

Synthesis and Micellization of Organosilicon Gemini Quaternary Ammonium Surfactants

A novel class of organosilicon gemini quaternary ammonium surfactant alkyl‐α, ω‐bis(diethyl‐methyl‐dimethoxy‐silopropyl ammonium bromide) (α, ω = 1,4; 1,6; 1,8) was synthesized and characterized by ¹H‐nuclear magnetic resonance (NMR) and elemental analysis. It is found that the quaternization reaction has two steps: first single quaternization and then double quaternization. The effect of solvent on convert ratio has the following sequence: polar aprotic solvents > polar protic solvents > aromatic solvents. The electrical conductivity of aqueous solution was measured at 20, 25, 30 and 35 °C, and the thermodynamic properties of , and were calculated according to the mass action model and Gibbs equation. It is shown that the enthalpy driven and entropy driven are almost equal in the micellization of [SiC₃‐4‐SiC₃]Br₂ and [SiC₃‐6‐SiC₃]Br₂, but in the micellization of [SiC₃‐8‐SiC₃]Br₂, the enthalpic contribution becomes significant and the effect of thermal is greater than the degree of order in the micellization.     

羧酸盐型表面活性剂对功能化Gemini表面活性剂流变性质的影响

利用稳态和动态剪切实验考察了功能化Gemini表面活性剂1,3双-(二羟乙基十二烷基溴化铵)-丙烷[简写为12(2OH)-3-12(2OH)·2Br]与传统阴离子表面活性剂(十二酸钠、十四酸钠和十六酸钠)混合体系在25℃下的流变性质。12(2OH)-3-12(2OH)·2Br的浓度为50 mmol/L时,十二酸钠、十四酸钠和十六酸钠均可以增强溶液的黏弹性。十二酸钠与12(2OH)-3-12(2OH)·2Br的混合摩尔比β为0.3时,溶液的零剪切黏度η0出现最大值,为12.35 Pa·s,平台模量G'∞为31.88 Pa;β=0.4时,G'∞值为14.67 Pa。混合体系的黏弹性顺序为:十二酸钠/12(2OH)-3-12(2OH)·2Br十四酸钠/12(2OH)-3-12(2OH)·2Br十六酸钠/12(2OH)-3-12(2OH)·2Br。改变12(2OH)-3-12(2OH)·2Br的浓度到60 mmol/L且十二酸钠/12(2OH)-3-12(2OH)·2Br的混合摩尔比β为0.3时,零剪切黏度η0和平台模量G'∞均增大,分别为33.92 Pa·s和46.41 Pa。     

Synthesis,Surface Activity,and Antimicrobial Efficacy of Hydrogenated Cardanol-Derived Positively Charged Asymmetric Gemini Surfactants

Nine different hydrogenated cardanol-based quaternary ammonium compounds including one conventional single-tale single-head surfactant, one bicephalic single-tale double-head surfactant, and seven asymmetric Gemini surfactants were synthetized using a simple process with high yields. Their structures were characterized using ¹H NMR, ¹³C NMR, and high-resolution mass spectral studies. Their surface active properties were evaluated by the wilhelmy plate method at 25 °C and physical parameters like CMC, γ_CMC, π_CMC, C₂₀, τ_CMC, and A_min were calculated. The Krafft temperature values of C-BP-1, C-BP-4, and C-BP-6 are lower than 0 °C, suggesting high-potential industrial application. All synthesized compounds but C-BP-F exhibit great antimicrobial ability against Gram-positive bacteria (S. aureus [ATCC 25923] and C. glutamicum [ATCC 13032]) while inadequate antimicrobial ability against Gram negative strains (E. coli [ATCC 25922] and P. aeruginosa [ATCC 27853]).     

非离子表面活性剂的加入对水基纳米微流体在小直径管中的减阻作用(英文)

The goal of this research was to determine the impact of nonionic surfactants on drag reduction effect in water and metal oxide nanofluid. Two nonionic surfactants (Rokacet O7 and Rokanol K7) and copper(Ⅱ) oxide water-based nanofluid were examined. Friction factors in a 4 mm diameter pipe for the Reynolds number between 8000 and 50000 were determined. Results showed that addition of nonionic surfactants caused the decrease of friction factor in water and nanofluid. The drag reduction effect was similar in both cases. Presence of nanoparticles in the system has no great influence on drag reduction effect.     

反胶束法纳米TiO_2的UV-vis和TEM研究

用石油醚为溶剂的反胶束体系溶胶-凝胶法合成了纳米TiO2,采用UV-vis光谱跟踪纳米TiO2粒子粒径的变化,研究了影响纳米TiO2溶胶粒子大小的因素,采用TEM表征了纳米TiO2的粒子大小及其粒径分布。结果表明,合成的反胶束纳米TiO2的UV-vis光谱吸收边λonset为344.8~363.2 nm,与锐钛型纳米TiO2的吸收边λonset=385 nm相比,紫外可见光谱发生“蓝移”,反胶束纳米TiO2粒子的半径为5~6.5 nm;TEM表明,纳米TiO2粒子的粒径为15~55 nm,粒径分布较窄,粒径分布指数SD I为1.19~1.29;FTIR谱图表明,TiO2粒子为表面具有一定数量钛羟基的水合TiO2。