表面活性剂胶团水溶液性质的黏度研究方法

综合归纳散见于众多文献中的关于表面活性剂溶液性质与分子聚集体结构的实验研究方法，并将分篇发表。在此篇中介绍了表面活性剂胶团水溶液性质的黏度研究方法，涉及特性黏度[η]、Huggins常数KH、Kramer常数Kk、胶团表面水化度W、胶团引流体力学半径Rx以及胶团球形形状和尺寸分散性的判定等。     

疏水缔合型阳离子聚丙烯酰胺的合成及絮凝性能

以甲基丙烯酸三氟乙酯(TFEMA)为疏水单体、丙烯酰胺(AM)为主单体、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为阳离子单体,以过硫酸铵和亚硫酸氢钠为复合引发剂,采用自由基胶束聚合法合成了共聚物P(AM-DMC-TFEMA)。分别考察了反应温度、引发剂用量、单体总质量分数及反应时间对P(AM-DMC-TFEMA)的产率及阳离子度的影响。确定较佳工艺条件为:反应温度65℃,引发剂用量占单体总质量的2%,单体总质量分数26%,反应时间3 h。采用红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)和环境扫描电镜(ESEM)对其结构进行了表征。同时考察了P(AM-DMCTFEMA)对硅藻土悬浮液的絮凝效果,结果表明,其对硅藻土具有良好的絮凝效果,絮凝时间仅为20 s,合成的共聚物上清液透过率为97.31%。     

The concentration dependence of the angular dissymmetry of light scattered by micellar solutions

A light scattering investigation was made of micelles formed from a polystyrene-poly(ethylene/propylene) two-block copolymer in n-nexane. n-Hexane is a selectively bad solvent for polystyrene and so polystyrene blocks formed the cores of the micelles. The light scattering measurements were made at 25°C for concentrations up to 0.015 g cm^?3. The dissymetry ratio ($\text{I}{}_{\mathrm{45°}}\text{I}{}_{\mathrm{135°}}$) was found to decrease with increase in concentration and it was below unity for measurements at c > 4.8 × 10^?3 g cm^?3. The effect of concentration on the dissymmetry ratio was predicted quite well by assuming the micelle packing could be described by radial distribution functions for hard spheres.     

New anionic alkylaryl surfactants based on olefin sulfonic acids

A new family of anionic surfactants has been produced by the simultaneous sulfonation and alkylation of aromatic compounds using olefin sulfonic acid(s). This new process does not require the conventional alkylation unit and the strong acid catalysts, such as AlCl₃ or HF, normally used for alkylation. The resulting alkylaryl sulfonic acids differ from existing prodeucts by having the sulfonate group attached to the alkyl chain rather than the aromatic ring. This allows for further derivatization of the aromatic compounds by leaving more positions open on the ring. Aromatic compounds that lend themselves to the new process include benzene, toluene, xylene, alkylbenzenes, phenol, alkylphenols, alkoxylated phenols, alkoxylated alkylphenols, alkoxylated alkylphenol/formaldehyde resins, naphthalene, and alkylnaphthalenes. Any type of olefin that can be sulfonated can be used as the starting material. These include internal and α-olefins, linear and branched olefins, polyolefins, and vinylidenes. Mono- and disulfonated compounds, as well as geminitype surfactants, are easily prepared.     

Aggregate structures formed via a bridging flocculation mechanism

A high molecular weight cationic polyelectrolyte has been used to flocculate a colloidal dispersion of anionic polystyrene latex particles. The polymer used had a high charge density and the flocculation occurred at a solution pH where both the polymer and the particles were fully charged. Under these conditions, flocculation is expected to occur through a bridging flocculation mechanism. Low angle laser light scattering has been used to follow the flocculation process as a function of time; parameters of interest were the aggregate sizes, size distributions, and aggregate mass fractal dimensions. The light scattering measurements showed that the flocs formed had a mass fractal character. All the systems examined here were overdosed with respect to the optimum flocculation concentration of polymer. Under these conditions, decreasing the polymer concentration was seen to result in an increased flocculation efficiency. A secondary growth process was also observed whereby initially formed fractal aggregates can subsequently aggregate again. These larger aggregates are also expected to be mass fractals although this cannot be determined from the light scattering measurements due to the superposition of Fraunhofer diffraction effects. This type of fractal-in-fractal character is unusual.     

Homopolymer influence on micellar solutions of block copolymer

The influence of polystyrene on the formation of poly(styrene-b-ethylene/propylene) micelles in 5-methyl-2-hexanone was investigated. This solvent is selective for the polystyrene blocks. Static and dynamic light scattering and viscosity measurements were carried out to determine whether polystyrene chains in the micellar solutions cause any change in the thermodynamic functions of micellization or in the structural parameters of the micelles. Two homopolystyrenes of different molar mass were used at a concentration of 10⁻²g cm⁻³. Homopolystyrene seems to slightly favour micelle formation, the lower mass polystyrene having a larger effect. The polystyrene chains do not significantly affect the hydrodynamic size and molar mass of the poly(styrene-b-ethylene/propylene) micelles.     

Clouding phenomenon in ionic micellar solutions: Role of the counterion

Clouding is rarely observed with ionic surfactants. Herein we report the occurrence of clouding in sodium dodecyl sulfate (SDS, an anionic surfactant) solutions on addition of different symmetrical and unsymmetrical quaternary phosphonium bromides (tetra-n-butylphosphonium, tetraphenylphosphonium, and n-propyltriphenylphosphonium). Cloud point (CP) measurements were made with solutions having different SDS/salt combinations. The nature of the counterion had a crucial role in the occurrence of the phenomenon, whereas substitution of an alkyl chain by a phenyl ring made the salt more effective near ambient temperature. A linear relationship between the SDS and salt concentrations was obtained. It is proposed that both the electrostatic charge and the hydration state of the headgroup region are influenced by counterion addition and that the net charge or volume of the counterion has a key role to play in the overall phenomenon. The effect of the addition of some hydroxy compounds on CP variations in these SDS+salt systems was also studied, and the data were interpreted on the basis of incorporation of these compounds in the micellar headgroup region. The nature of the counterions influenced this incorporation.     

Interfacial activity and micellar morphology of an imidazolium ring containing zwitterionic surfactants

Zwitterionic surfactants based on 3-(1-alkyl-3-imidazolio) propane-sulfonate ([ImS3-R] where R is octyl or dodecyl) is an emerging and important class of amphiphile due to their relevance as nano reactors for the synthesis of metallic nanoparticles and accelerated acid hydrolysis. The physicochemical properties of such synthesized imidazolium ring-containing zwitterionic surfactants have been characterized by surface tension and small-angle neutron scattering (SANS) techniques. Surface tension measurements were used to calculate several thermodynamic parameters over a range of concentrations and temperatures (298–313 K). The results obtained showed a weak signature representing the critical micelle concentration (CMC) for ImS3-8, however, by increasing the alkyl length of the hydrophobic group to dodecyl, that is, ImS3-8 to ImS3-12, the signature of the CMC was much more evident. As expected, the CMC for ImS3-12 shifted to a lower concentration. An increase in temperature increased the surface activity and decreased the CMC of both zwitterionic surfactants, although the changes were small. Compared to classical surfactants, that is, sodium dodecyl sulfate and dodecyl trimethylammonium bromide, the CMC of ImS3-12 is much lower. Modeling of SANS data demonstrated that the morphology of the micelles formed by these amphiphiles may be described by the “classical” model, a central hydrophobic core, with a shell of hydrated headgroups. Due to their widespread applications in colloidal and interfacial science, the present study adds new insight to the fundamental understanding of these interesting imidazolium-based surface-active ionic liquids (ImS3-R).     

机械絮凝和网格絮凝处理低浊度水源水的性能对比中试研究

针对某市第三水厂的三期工程建设,用中试规模试验来选择絮凝方式。试验结果表明,在相同的源水、相同加药量和相同的进水量的情况下,网格絮凝的沉淀效果优于机械絮凝。随着PAC投加量的增加,沉淀出水的浊度和大于2μm的颗粒数呈下降趋势。源水水质和投药量是影响沉淀池出水水质的最重要因素,最佳投药量的范围为21~28mg/L。     

Quaternary salts as solubilization site modifiers of organic compounds in anionic micellar solutions

The effects of the addition of different salts (quaternary bromides or NaBr) on the viscosity (measured under Newtonian flow conditions) of sodium dodecylbenzenesulfonate (SDBS) micellar solutions were studied at 30°C. Tetra-n-butylammonium bromide (Bu₄NBr) was found most effective in increasing the viscosity (due to possible change in micellar shape) at fairly low SDBS concentration (50 mM). The effectiveness of Bu₄NBr may be due to the presence of four butyl chains and to the positive charge on its counterion (Bu₄N⁺) which can subsequently interact with anionic SDBS micelles electrostatically as well as hydrophobically; owing to solubility/steric problems, other salts were ineffective. Organic additives such as cyclohexylamine and cyclohexanol had marginal effects on viscosity when added to 50 mM SDBS solutions having no Bu₄NBr. However, in the presence of Bu₄NBr, the effect was dependent on salt concentration and the nature of the additive. The overall effect is discussed on the basis of change in the solubilization site of the additive in the presence of Bu₄NBr.     

Surfactant precipitation in aqueous solutions containing mixtures of anionic and nonionic surfactants

The salinity tolerance (precipitation phase boundary) is measured for a mixed anionic/nonionic surfactant system above the CMC. For any total surfactant concentration, the salinity tolerance is shown to increase as the percentage of nonionic surfactant in the system is increased. A model is developed which can predict the phase boundaries for the mixed surfactant system from the pure anionic surfactant phase boundary and information about mixed micelle formation. In the model, precipitation is viewed as a solubility product relationship between the anionic surfactant monomer and the total unassociated counterion. The reason that salinity tolerance (or counterion concentration necessary to cause precipitation) increases with addition of nonionic surfactant is that mixed micelle formation reduces the anionic surfactant monomer concentration. For the experimental studies, sodium dodecyl sulfate is the anionic surfactant, a polyethoxylated nonylphenol is the nonionic surfactant, and sodium chloride is the added salt.     

水厂格栅反应池絮凝工艺的优化措施

金陵石化烷基苯水厂格栅反应池存在设计参数及格栅布局不合理的现象,造成混凝效果差,混凝剂单位消耗过高,通过对格栅反应池的水力计算分析,提出了工艺改造和参数调整的方案,使格栅反应池的水力条件得到改善,混凝剂单位消耗量大幅下降,为老水厂的格栅反应池改造提供了较好的借鉴。     

基于胶束强化超滤的金属离子去除技术研究进展

胶束强化超滤技术(MEUF)作为一种新兴的含金属废水处理技术,有着较好的应用前景.通过总结前人的研究结果,综合讨论了影响金属离子截留效果的各个因素,为优化MEUF提出了一些建议.并就当前采用胶束强化超滤法处理金属离子技术的最新发展与表面活性剂的循环再利用作了简要的介绍.     

基于分形学的絮凝理论研究进展

絮凝过程中形成的絮体具有自相似性和标度不变性等特点,是一个典型的分形体。但传统的絮凝理论并未考虑絮体的分形结构,因而存在一定的缺陷。本文主要介绍了引入分形理论后,絮凝形态学和絮凝动力学的发展状况,重点阐述了絮体分形结构与其粒径、强度、密度、沉降速度等之间的关系,以及分形理论对Smoluchowski方程、传统絮体生长模式理论的改进。此外,本文同时指出分形学与絮凝理论的结合在很多方面尚未总结出系统的普适规律,尤其是非线性絮凝动力学仍需进一步完善。     

胶束催化的丁苯橡胶氯甲基化反应

以SDS和NP-10为乳化剂,采用胶束催化法研究了丁苯橡胶的氯甲基化反应,结果表明,反应时间、乳化剂种类和浓度、四丁基溴化铵等对丁苯橡胶的氯甲基化程度有着明显的影响,当反应条件为[NP-10]=10CMC,T=60℃,t=4h,[TBAB]=0.04mol.L-1时,丁苯橡胶的氯甲基化程度可达到50%左右.     

Removal of Organic Compounds Containing a Benzene Ring from Water by Adsorptive Micellar Flocculation

The removal of low-molecular-weight benzoic acid (benzoic acid, p-toluic acid, and salicylic acid)-derived and aniline (aniline, 4-chloroaniline, and 2,6-dimethylaniline)-derived organic compounds through adsorptive micellar flocculation (AMF) with anionic surfactants (sodium dodecyl sulfate, SDS) and aluminum sulfate was demonstrated. The interactions between SDS and the organic compounds were studied using ¹H nuclear magnetic resonance (NMR) spectroscopy. Batch AMF experiments were conducted to study the influence of several factors on target pollutant removal. For benzoic acid derivatives, the removal rate was improved by increasing the SDS and Al concentrations, while increases in the concentrations of the organic pollutant tended to decrease the removal rate. The highest removal efficiencies were observed with p-toluic acid (95.4%) > salicylic acid (84.5%) > benzoic acid (76.5%) under weakly acidic conditions due to the greater hydrophobicity of p-toluic acid and the complexation of the Al salts and the salicylic acid. The removal rates of the aniline derivatives were positively related to the SDS concentration and negatively related to the pH. At a pH of 3.0, the highest removal rates of aniline, 4-chloroaniline, and 2,6-dimethylaniline (91.3%, 98.0%, and 97.6%, respectively) were observed. For aniline compounds, charge neutralization between the SDS anions and aniline cations dominated the removal process. These findings provide new insights for the development of further applications of AMF for the removal of benzoic acid and aniline derivatives.     

Electrochemical degradation of anionic surfactants

This study was performed to investigate the electrochemical oxidation of anionic surfactants. In particular, a synthetic solution of sodium dodecyl benzene sulfonate and a real car wash wastewater were treated by galvanostatic electrolysis using a Ti–Ru–Sn ternary oxide and a boron-doped diamond (BDD) anode. Measurements of the Chemical Oxygen Demand (COD) and the concentration of the anionic surfactants were used to follow the oxidation. Using the Ti–Ru–Sn ternary oxide anode, the complete removal of COD and sodium dodecyl benzene sulfonate was obtained only in the presence of chloride ions that act as inorganic mediators. The oxidation rate was almost independent of current density and electrolyte flow rate. In the case of BDD the mineralisation of the sodium dodecyl benzene sulfonate was achieved in all experimental conditions due to reaction with hydroxyl radicals electrogenerated on the diamond surface during electrolysis. The COD removal rate increased with increase in electrolyte flow rate, indicating that the oxidation was mass-transfer controlled. Comparison of the results of the two electrodes showed that chlorine mediated oxidation at the Ti–Ru–Sn ternary oxide anode allowed a faster COD removal of both the synthetic solution and real car wash wastewater.     

紊流絮凝动力初探

根据紊流水力特征研究絮凝动力学问题,分析絮凝动力因素,得出了主要作用力及主导作用力。认为紊流运动可以看成是各种不同尺度的涡旋运动迭加于平均速束的结果,涡旋运动产生的剪切力和离心惯性力是絮凝颗粒产生接触碰撞的主要作用和,而涡旋剪切力是絮凝反应的主导动力。为提高絮凝效率提供了技术途径。     

Solubilization of phospholipid bilayer caused by surfactants

The interaction of surfactants with liposomes eventually leads to the rupture of such structures and the solubilization of the phospholipid components. In this paper, solubilization is regarded as a decrease in light scattering of liposome suspensions. To this end, in accordance with the nomenclature, adopted by Lichtenberg, three parameters were considered as corresponding to the effective surfactant/lipid molar ratios (Re) at which light scattering starts to decrease, Re_sat; reaches 50% of the original value, Re₅₀; and shows no further decrease, Re_sol. These parameters corresponded to the Re at which the surfactant (i) saturated the liposomes, (ii) resulted in a 50% solubilization of vesicles and (iii) led to a total solubilization of liposomes. The surfactants tested were the nonionic surfactant octylphenol ethoxylated with 10 units of ethylene oxide or Triton X-100 (OP-10EO), two anionic surfactants, sodium dodecyl sulfate and sodium dodecyl ether sulfate, and an amphoteric surfactant dodecyl betaine (D-Bet). Unilamellar liposomes formed by egg phosphatidylcholine containing increasing amounts of phosphatidic acid were used. The Re parameters were the lowest for D-Bet, followed by OP-10EO, whereas the anionic surfactants always showed the highest values regardless of the electrical charge of the lipid bilayers. These parameters seem also to be inversely related to the critical micelle concentration (CMC) of the surfactant, except for OP-10EO. Moreover, the CMC values of the surfactant/lipid systems at 0.5 mM lipid concentration corresponded in all cases to the surfactant concentration at which liposomes were saturated by surfactants. As a consequence, this ratio can be regarded as an interesting parameter associated with the mixed micelle formation in liposome solubilization.     

生物絮凝剂γ-PGA絮凝性能的研究

目前,以γ-聚谷氨酸(γ-PGA)为主要成分的生物絮凝剂广泛应用于环保、医药、食品领域.主要考察了γ-PGA的絮凝性能,实验结果表明,γ-PGA絮凝活性较高,热稳定性较高,具有较强的抗pH冲击能力.但其投加量偏大,且对溶解性有机物的去除效率不高,比较适合应用于处理低浓度工业废水以及河流水体的净化.