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.     

Rheological behavior of mixed system of ionic liquid [C8mim]Br and sodium oleate in water

We report on the rheological behavior of wormlike micelles constructed by ionic liquid surfactant [C₈mim]Br (1-octyl-3-methylimidazolium bromide) and anionic surfactant sodium oleate (NaOA) in aqueous solution. The effects of surfactant composition, total surfactant concentration, added salts, and temperature were investigated. The prevailing surfactant effect at lower concentration and the leading cosolvent effect at higher concentration of [C₈mim]Br may be the main reasons for appearance of well-established maximum in key rheological parameters with variation of surfactant composition and total surfactant concentration. The Cole-Cole plots demonstrate that the systems (total surfactant concentration falls within 0.17–0.35 mol·L^-1 and molar ratio 0.33≤R≤0.50) fit the Maxwell’s mechanical model as linear viscoelastic fluid. The addition of NaBr or sodium salicylate decreases significantly the viscosity and the relaxation time of the wormlike micelle solution but cannot change the value of plateau modulus G₀. The present system has low rheological tolerance to temperature. The increase of temperature decreases the average contour length and viscosity of wormlike micelles and thus strengthens the relaxation progress of diffusion and weakens the relaxation progress of reptation. Increasing the temperature also decreases the value of plateau modulus G₀ and shifts the minimum value of the loss modulus G^″_min to higher frequencies.     

油酸钠蠕虫状胶束的性质及驱油效率研究

分别通过稳态、动态流变的方法和冷冻蚀刻透射电镜、室内模拟驱油实验和平板夹砂微观模型驱油实验,研究了由碳酸钠诱导形成的油酸钠蠕虫状胶束的流变学性质及形貌和蠕虫状胶束驱油配方的驱油效果及驱油微观机理。结果表明,在油酸钠(NaOA)溶液中,加入一定量的Na2CO3能够形成蠕虫状胶束;孤岛东区稠油注聚驱后,蠕虫状胶束驱油配方(w/%,1.83 NaOA 4.24 Na2CO3)的室内模拟驱油可提高采收率25%原始石油地质储量(OO IP);平板夹砂微观驱油模型显示蠕虫状胶束驱油体系进入模型中,能够使注聚后束缚残余油重新启动、变形,渐渐形成油墙向出口处运移,蠕虫状胶束驱油体系能够有效扩大波及体积,提高洗油效率,从而提高驱油效率。     

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.     

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.     

Rheological Properties and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant and Salts in Sorbitol/H2O Solvent: 2. Effect of Salts and Sorbitol

The impact of mixed salts and sorbitol on the viscoelastic properties of a multi‐component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS) and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, saccharin and sodium fluoride) in sorbitol/H₂O mixed solvent are systematically investigated by steady state and dynamic rheology. As reported previously, the viscosity of the mixed system passes through a maximum with increase in the SLSS mass fraction (X_SLSS) at a fixed total surfactant concentration, salt concentration (C_salt) and mass ratio of sorbitol in mixed solvent (R). The shape of the X_SLSS‐dependent viscosity curve does not change regardless of C_salt and R, but adding salts or sorbitol has different effects on the rheological properties of this system. The former due to a high screening effect plays an important role in the elongation and entanglement of the wormlike micelles, facilitating the enhancement of rheological properties and the formation of Maxwell fluids. The latter has a dual effect on the rheological properties and phase behavior of the mixtures. A certain amount of sorbitol can promote the formation entangled wormlike micelles, while the effect is reversed if the sorbitol content is too large. The electrostatic and hydrophobic interaction between CAPB and SLSS are the prerequisite for the aggregate formation and transition. Meanwhile, the aggregation behaviors are strongly influenced by the balance between low dielectric constant, strong solvophobic interaction and steric effect of sorbitol with the ability to form hydrogen bonds which favors the growth of micelles, and appearance of aqueous two‐phase systems with smaller amounts of wormlike micelles in CAPB‐rich regions which oppose enhancement of rheological properties. Our findings provide a new insight and approach to control and adjust the phase behavior of such a complicated applied multi‐component system.     

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.     

阳离子双子表面活性剂C18-4- C18•2Br的流变性

对阳离子双子表面活性剂四亚甲基-1,2-双(十八烷基二甲基烷基溴化铵)(C18-4-C18.2Br)的流变特性进行了研究,考察了表面活性剂质量分数、水杨酸钠质量分数及温度对表面活性剂溶液黏度和黏弹性的影响。C18-4-C18.2Br溶液的黏度随着质量分数的增加而增加。随着水杨酸钠质量分数的增加,C18-4-C18.2Br溶液的黏度和黏弹性出现先增加后下降的过程。温度对C18-4-C18.2Br溶液的黏度有较大影响,水杨酸钠的加入可明显提高C18-4-C18.2Br溶液的抗温性。TEM结果表明,适量的水杨酸钠能够促进C18-4-C18.2Br胶束从球形向蠕虫状转变,过量的水杨酸钠又会使蠕虫状胶束向囊泡转变。     

水相和特殊介质中有序聚集体的结构、性质和应用(Ⅱ)——表面活性剂蠕虫状胶束

综述了近来关于表面活性剂蠕虫状胶束相态、平衡状态和动态的理论和实验结果以及应用冷冻蚀刻电镜照片直接观察到其结构。在一定条件下,表面活性剂在溶液中能可逆地缔合成为一种长的、有柔性的、甚至网状的蠕虫状胶束。它们具有类似柔软的高聚物溶液的线性黏弹性质,然而蠕虫状胶束经历裂解和再组合过程而表现复杂的流变性。最后介绍了蠕虫状胶束在油田、减阻剂和日用化工等方面的应用。     

环保型MES粘弹性胶束溶液的流变性

用流变学方法研究了可生物降解阴离子表面活性剂脂肪酸甲酯磺酸钠（MES）在NaCl溶液中从球状胶束转变成蠕虫状胶束的生长过程,分析了两性表面活性剂十二烷基甜菜碱（BS-12）对MES胶束溶液流变行为的影响机制。首先,测量了MES粘弹性胶束体系剪切粘度（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τs）等物理量;应用Cox-Merz规则和Cole-Cole图,证实了MES（3.0%～5.0%）/NaCl（3.0%～5.0%）/BS-12（0.5%～0.9%）体系形成蠕虫状胶束,且蠕虫状胶束的动态粘弹性在MES（3.5%～5.0%）/NaCl（3.5%～5.0%）/BS-12（0.5%～0.9%）范围是符合Maxwell模型的线性粘弹性流体。     

Application of pH-Responsive Viscoelastic Surfactant as Recyclable Fluid at High Temperature

A pH-responsive amphiphilic surfactant stearic amide 3-(N,N-dimethylamino)propylamide (SAA) was synthesized and served as a thickener in aqueous solution to construct a switchable viscoelastic surfactant fluid (VES fluid). The structure of SAA was studied by ¹H NMR, and the viscoelastic behavior of VES fluid was studied in detail by rheological measurements. The viscosity of this VES fluid can be switched reversibly from low to high immediately by adjusting system pH value. Even at high shear rate (170 s⁻¹) and high temperature (90 °C), excellent viscoelastic behavior of this VES fluid can be observed, which is a key performance for fracturing applications. Meanwhile, the recycled VES fluid can still maintain good pH-responsive behavior even after more than three cycles. These unique performances of this VES fluid not only enhanced our understanding of the transformation of wormlike micelles at high temperature, but also enriched a large potential of VES fracturing fluid in the development of oil and gas reservoirs.     

Development of a Stimuli-Responsive Gemini Zwitterionic Viscoelastic Surfactant for Self-Diverting Acid

A Gemini zwitterionic viscoelastic surfactant named self diverting acid - gemini sulfonated surfactant (SDA-GS), which has double quaternary ammonium groups, double sulfonate groups, and two hydrophobic tails, was synthesized from oleylamidopropyl dimethylamine, 1,3-propanesultone, and 2, 2-bis(bromomethyl)propane-1, 3-diol. The viscosity of an SDA-GS aqueous solution varies with acid and calcium chloride concentrations. With a decrease in the HCl concentration, the viscosity of the acid solution prepared with SDA-GS increases to a maximum value, followed by a decrease, which results from the aggregation of the surfactant into wormlike micelles and the following disaggregation. Calcium ions generated by the reaction of acid and calcium carbonate can enhance the aggregation of the surfactant to increase the peak viscosity of the acid solution. The peak viscosity of the acid solution prepared by 5 wt.% SDA-GS without calcium ions could only reach 73.2 mPa.s when the HCl concentration was 4 wt.%, but that of the acid solution with calcium carbonate powder added could reach over 200 mPa.s when the HCl concentration was consumed to 4 wt.% and the calcium chloride concentration 21.6 wt.%. The viscoelastic measurements proved that calcium ions can drive the growth of the wormlike micelle. The acid and Ca²⁺ response of SDA-GS can be applied in self-diverting acid to improve the acid displacement in the heterogeneous reservoir. Experimental evaluation showed that the acid solution prepared by SDA-GS and the selected corrosion inhibitor showed a good corrosion inhibition performance and a viscosity variation that makes it an efficient self-diverting acid. The spent acid (21.6 wt.%) with 4 wt.% HCl retained high viscosity over 80 mPa.s at a 170 s⁻¹ shearing rate and at 120°C after 90 min. The parallel core flood tests to simulate in situ application of SDA-GS acid showed that the permeability improvement ratios (K₁/K₀) of the cores could reach 182.3 and 278.4 at 60 and 90°C, respectively.     

Synergistic Behavior and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant,and Salts in Sorbitol/H<Subscript>2</Subscript>O Solvent: 1. Effect of Surfactant Compositions

The phase behavior and rheological properties of a multi-component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS), and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, sacharrin, and sodium fluoride) in sorbitol/H₂O mixed solvent at different mass fraction of SLSS (X _SLSS) were systematically investigated by steady and dynamic rheology, dynamic light scattering, and diffusion ordered spectroscopy (DOSY). When fixing the salt concentration and the mass ratio of sorbitol in mixed solvent (R), the zero-shear viscosity increases first and then decreases showing a maximum with increasing X _SLSS, resulting from the formation and entanglement of wormlike micelles. Especially when X _SLSS is between 0.33 and 0.80, the mixture is dominated by entangled wormlike micelles coexisting with small micelles and separated wormlike micelles, and shows high viscoelasticity. The maximum of the zero-shear viscosity is ca. 5 orders of magnitude larger than that of sorbitol/H₂O mixed solvent or the CAPB/SLSS aqueous solution. The characteristic structural parameters for the micellar solutions at different X _SLSS are also estimated from further analysis of the rheological results, and indicate the stronger network structures of the wormlike micelles are formed in our systems compared with the wormlike micelles formed by a traditional zwitterionic/anionic surfactant aqueous solutions. The great improvements of rheological properties are attributed to the strong screening effects of the mixed salts and the strong solvophobic effect of sorbitol on the electrostatic and hydrophobic interaction between the CAPB and SLSS molecules. The present work has improved our understanding about the aggregation behavior of zwitterionic/anionic mixed surfactants with salts in less polar solvent/H₂O mixture, which would be of widely practical importance to optimize the formulation of products for personal care and household cleaning.     

芥酸钾/三羟乙基苄基氯化铵蠕虫状胶束的黏度行为

以阴离子表面活性剂芥酸钾(KEU)与有机反离子三羟乙基苄基氯化铵(BTHEAC)通过自组装形成的蠕虫状胶束为主要研究对象,苯乙烯与N,N-孪尾取代丙烯酰胺(DiC_nAM)为可聚合单体,偶氮二异丙基咪唑啉盐酸盐(VA-044)为引发剂,在一定温度下,合成了系列增溶单体并聚合的蠕虫状胶束,通过黏度法研究了该合成条件对蠕虫状胶束表观黏度的影响。结果表明,当单体增溶并聚合后,蠕虫状胶束表观黏度显著增大。当苯乙烯的浓度为0.02mol/L、摩尔比n(KEU):n(BTHEAC)=5:3、n(苯乙烯):n(DiC₈AM)=5:2时,合成的蠕虫状胶束表观黏度最大,为1320mPa·s,明显大于KEU/BTHEAC蠕虫状胶束的表观黏度,且耐温性能良好。     

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.     

Effect of a Hydrophilic PEO–PPO–PEO Copolymer on Cetyltrimethyl Ammonium Tosylate Solutions in Water

Cetyltrimethyl ammonium tosylate (CTAT) in water forms long flexible wormlike micelles at concentrations above 10 mM, leading to highly viscous solutions and viscoelastic stiff gels above 100 mM. In the presence of a nonmicellar hydrophilic PEO–PPO–PEO triblock copolymer F87 (TBC-F87, Total mol.wt. = 7,700, EO = 70%) these wormlike micelles RE transformed into smaller structures, as evident from a sharp decrease in viscosity and increase in specific conductance. These results are quantified by small angle neutron scattering (SANS) measurements. The PPO middle block of TBC-F87 gets inserted in the CTAT micelle, the size and total aggregation number of CTAT/TBC-F87 mixed micelles decreased but the number of TBC-F87 molecules in the mixed micelles increased with an increase in [TBC-F87]. Two break points in the typical specific conductance versus CTAT concentration plot at various [TBC-F87] amounts represent interactions between CTAT and TBC-F87. The penetration of PPO of TBC-F87 inside CTAT micelles decreases hydrophobicity of the core while the presence of PEO end blocks enhances hydrophilicity each favoring smaller micelles.     

温度和剪切协同作用对十六烷基三甲基氯化铵溶液表观黏度的 影响

深入研究表面活性剂的流变特性，对于理解湍流减阻机理和改进制药、化工等领域的产品质量具有重要意义。本文研究了相同升温速率、不同剪切速率以及相同剪切速率、不同升温速率对阳离子表面活性剂十六烷基三甲基氯化铵（CTAC）溶液表观黏度的影响。研究表明：当温度较低时，剪切速率对表面活性剂溶液表观黏度的影响起主导作用；随着温度的升高，高温对胶束的影响增强导致溶液在高温处出现剪切稀化现象。当浓度为0.3125mmol/L时，溶液临界温度随剪切速率的升高保持恒定；但当浓度升高至0.6250～1.2500mmol/L时，在高温和高剪切的作用下，黏度曲线出现“平台”和短暂的增稠现象。对于中等浓度表面活性剂溶液，浓度升高导致蠕虫状胶束出现分支并抑制了“平台”的产生；随着升温速率的增大，胶束结构的响应时间滞后于升温速率，但当γ=150s^?1时，滞后效应减弱，高剪切对胶束结构的破坏占主导作用。     

Rheological Investigation of Wormlike Micelles Based on Gemini Surfactant in EG–Water Solution

The self‐assembly behavior of gemini surfactants in ethylene glycol (EG)‐water (5/95, v/v) mixed solvent was investigated by rheological measurements at 10 °C. The influence of molecular structure of the gemini surfactant and added hydrotrope on the solution properties was studied. Sodium salicylate (NaSal) showed stronger ability to induce 2‐hydroxyl‐propanediyl‐α,ω‐bis‐(dimethyldodecylammonium bromide), referred to as 12‐3(OH)‐12, to form wormlike micelles than sodium benzoate. Less NaSal is required to promote a sphere to rod transition and to reach the peak viscosity. Moreover, the concentrations of hydrotrope and gemini surfactant are both lower than conventional single‐chain surfactant systems to reach a comparable viscosity. The strong hydrophobicity of gemini surfactants and hydrotropes is responsible for the high efficiency in forming wormlike micelles in EG/water systems. The geometric structure of gemini surfactants also plays a vital role in self‐assembly into wormlike micelles. Dimethylene‐1,2‐bis‐(dodecyl dimethylammonium bromide), referred to as 12‐2‐12, shows absolute superiority over 12‐3(OH)‐12 in constructing wormlike micelles. The present study will be helpful for developing de‐icing fluids and anti‐freezing solutions, which need rheology control in EG‐aqueous medium at low temperature.     

Drag Reduction by Wormlike Micelles of a Biodegradable and Non-Biodegradable Surfactants

This study describes the effects of wormlike micelles formed by the commercial surfactants tallowalkylamidopropyl dimethylamine oxide (Aromox APA-TW) and oleyl methyl bis(2-hydroxyethyl) ammonium chloride (Ethoquad O/12) as drag reducers. Ethoquad O/12 is immune to degradation by heat and microorganisms. Conversely, Aromox APA-TW is biodegradable in the environment, and its susceptibility to heat-induced degradation was previously assessed. This work considers the effects of temperature, salt, and time on the drag-reduction capacity (in different Reynolds number) of wormlike micelles of these two surfactants. Wormlike micelles formed by Aromox APA-TW are able to reduce drag at higher temperatures compared to wormlike micelles formed by Ethoquad O/12. However, Aromox APA-TW can degrade after being heated to 80 °C and also after storage of the wormlike micelle solutions. Ethoquad O/12 does not undergo degradation after being heated or stored. These surfactants have the potential to be used as additives in industrial operations, as the wormlike micelles formed are able to reduce drag in systems with long pumping distances or recirculation, even in solutions with high salt concentrations (brine) and high temperatures.     

The Formation of pH-Sensitive Wormlike Micelles in Ionic Liquids Driven by the Binding Ability of Anthranilic Acid

Wormlike micelles are typically formed by mixing cationic and anionic surfactants because of attractive interactions in oppositely charged head-groups. The structural transitions of wormlike micelles triggered by pH in ionic liquids composed of N-alkyl-N-methylpyrrolidinium bromide-based ILs (ionic liquids) and anthranilic acid were investigated. These structures were found responsible for the variations in flow properties identified by rheology and dynamic light scattering, and account for the structures observed with cryogenic transmission electron microscopy (Cryo-TEM). High-viscosity, shear-thinning behavior, and Maxwell-type dynamic rheology shown by the system at certain pH values suggested that spherical micelles grow into entangled wormlike micelles. Light scattering profiles also supported the notion of pH-sensitive microstructural transitions in the solution. Cryo-TEM images confirmed the presence of spherical micelles in the low-viscosity sample and entangled wormlike micelles in the peak viscosity sample. Nuclear magnetic resonance spectroscopy analysis revealed that the pH sensitivity of ionic liquid systems originated from the pH-dependent binding ability of anthranilic acid to the cationic headgroup of ionic liquids.