用混合乳化剂UE20/PVA制备的水包油型生漆乳液的性能

以漆酚基乳化剂(UE20)和聚乙烯醇(PVA)为混合乳化剂制备了水包油(O/W)型生漆乳液(RLE), 研究了UE20与PVA的质量比、混合乳化剂质量分数(wME)、水与天然生漆(RL)的质量比、温度和贮存时间对RLE性能的影响, 并用透射电镜观察了wME对RLE粒子的大小及形态的影响. 结果表明, RLE的黏度随着PVA的增加而增大; 当wME≤6.7%时, RLE表现出假塑性流体的特征, 其黏度随着wME的增大而增大, 乳液的稳定性增强; 而当wME≥10.0%时, RLE则表现出膨胀型流体的特征, 乳液的黏度较低; 随着温度的升高及水的用量增加, RLE粒子间相互作用减弱, 乳液的稳定性降低. 正交实验结果表明, 影响RLE的黏度及稳定性的顺序为wME＞mH2O∶mRL＞mUE20∶mPVA＞乳化温度. 随着wME的增大, RLE粒子的粒径减小, 其形态也由不规则的形状转变为球形粒子.     

Mg-Al MMH对除虫脲水悬浮剂流变性的影响

研究了Mg-Al型混合金属氢氧化物(MMH)质量分数(w)、温度和无机电解质对除虫脲水悬浮剂流变性的影响, 并采用Herschel-Buckley模型对流变曲线进行拟合. 实验结果表明, 稠度指数(KH)及屈服值(τH)均随w的增大而增大, w越大, 体系假塑性越明显, 且当w达到一定值后体系产生正触变性; 温度升高, KH和τH增大, 但不影响体系“剪切变稀”的假塑性特征和正触变性; 不同浓度的电解质对体系KH和τH的影响程度不同, 对于相同浓度的NaCl 和CaCl2, CaCl2对体系的影响更为显著, 但电解质的加入不改变体系“剪切变稀”的假塑性特征及正触变性.     

煤加氢液化残渣的流变特性研究

采用从煤直接液化实验装置取得的液化残渣,研究了它的流变性及温度和油、沥青质、固体含量对其流变性的影响。液化残渣是剪切变稀的非牛顿型假塑性流体,非牛顿指数随温度升高而不断减小,温度越高越接近牛顿流体行为。液化残渣对温度非常敏感,在升温过程中其表观黏度下降很快,且没有出现黏度峰。在液化残渣中加入少量的循环油后其表观黏度大幅下降;而在加入少量沥青质后则表现出低温下黏度变大,高温下黏度变小的现象;固体含量则始终是黏度增大的因素,表明其黏度与油、沥青质和固体含量关系密切。液化残渣的黏度－温度关系符合Arrhenius关系式,但在升温过程中出现了拐点,低温段的黏流活化能比高温段的要大。     

稳态荧光探针法研究复配乳化剂的聚集行为

采用荧光探针技术,根据芘的第一振动峰I₁(373 nm)与第三振动峰I₃(384 nm)荧光强度的比值(I₁/I₃)随乳化剂浓度的变化,对十二烷基磺酸钠(AS)与壬基酚聚氧乙烯醚(Oπ-10)复配乳化剂的CMC值进行了测定,并与十二烷基磺酸钠(AS),壬基酚聚氧乙烯醚(Oπ-10)的CMC值进行了比较,结果表明复配乳化剂的CMC介于两者之间.以二苯甲酮为猝灭剂,用稳态荧光法测定了不同比例复配乳化剂的胶束聚集数,实验结果表明,复配乳化剂浓度为4—9倍CMC时,测定的胶束聚集数随复配乳化剂浓度的增大而线性增大;且Oπ-10:AS<2:1时,随着复合乳化剂中Oπ-10比例的增大,复配乳化剂胶束聚集数增大.利用芘的I₁/I₃值,结合胶束微环境的极性变化规律,探讨了复配乳化剂的聚集行为对硅丙乳液聚合物的影响.     

油焦浆流变特性的研究

利用减压不同和石油焦制备成浆体燃料,然后考察了其流变性及温度、浓度和原料油对流变性的影响。结果表明,浆体为屈服假塑性流体并具有触变性,屈服应力值和粘度随着温度升高、浓度的降低而减小。原料油中的胶质和沥青质组分对浆体的流变特性和度有很大的影响,含有较多的胶质和沥青质原料油的浆体表现出更强的屈服假塑性和更高的粘度。     

荧光探针法研究乳化剂对硅/丙核壳乳液聚合行为的影响

用荧光探针(芘)法测定了十二烷基硫酸钠(SDS)、烷基酚聚氧乙烯醚(OP-10),以及复配乳化剂的临界胶束浓度(CMC),并首次把荧光探针技术应用到硅/丙核壳乳液聚合反应的研究中.利用芘的I₁/I₃值,结合胶束微环境的极性变化规律和乳液聚合机理,探讨了乳化剂对聚合反应的影响.结果表明,荧光探针(芘)法可用于研究硅/丙乳液的聚合行为和确定乳化剂配比.通过粒径分析、透射电镜(TEM)对产品的结构进行了表征.     

蓝藻与神府煤共成浆性的研究

考察了预处理方法对含水蓝藻表观黏度的影响,以及蓝藻对神府煤浆成浆浓度、流变性和静态稳定性的影响。结果表明,采用添加化学药剂、高速搅拌、加热等方法对含水蓝藻进行预处理,可以使表观黏度从72mPa·s降低到21.8mPa·s(剪切速率100s^-1)。蓝藻结构受到破坏是表观黏度降低的主要原因。含水蓝藻表观黏度的降低有利于蓝藻煤浆成浆浓度的提高。当添加水质量与含水蓝藻质量比为1∶1时,蓝藻煤浆的成浆浓度达到60%。蓝藻的加入提高了神府煤浆的稳定性,使稳定性从4h提高到72h以上。蓝藻煤浆为假塑性流体,剪切变稀。     

盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白,用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDSPAGE)确定为Ⅰ型胶原;红外及紫外光谱表明胶原分子中存在三螺旋结构.分别采用小幅振荡剪切法、恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响.研究表明,随盐酸胍浓度的增大及作用时间的延长,盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体.在所研究的盐酸胍浓度范围(0~6.0 mol/L)内,盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变;随盐酸胍作用时间的延长(6~48 h),盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变.本文的研究结果有助于加深对触变性产生机理的认识.     

聚苯乙烯磺酸钠在1-烯丙基-3-甲基咪唑氯盐中的流变行为

研究了聚苯乙烯磺酸钠(Na PSS)在1-烯丙基-3-甲基咪唑氯盐(AmimCl)中的流变行为,并与其在AmimCl/H_2O混合溶剂中的流变行为进行了对比.聚合物浓度单位为每升溶剂中所含链段单元的摩尔数(mol/L).研究发现,Na PSS在AmimCl中表现出与其在无盐、有盐水溶液以及中性聚合物在离子液体(ILs)溶液中不同的流变行为.Na PSS在AmimCl含量不同的AmimCl/H_2O混合溶剂中的流变行为也不相同,随着AmimCl含量的增加,Na PSS在混合溶剂中的特性黏数[η]逐渐降低,表明分子线团逐渐塌缩,溶液的增比黏度随Na PSS浓度变化的标度所表现出的性质由聚电解质无盐水溶液特点逐渐变为中性聚合物溶液在θ状态下特点.当溶剂为纯AmimCl时,0.007~0.8 mol/L的浓度范围在0.29 mol/L处被分成2个浓度区.动态流变行为研究表明c0.29 mol/L浓度区为稀溶液区,溶液的增比黏度和弛豫时间随Na PSS浓度变化的标度关系为:ηsp~c1.4p和τ~c0p,与无盐聚电解质水溶液在缠结区的行为相似;c0.29 mol/L浓度区为溶液的亚浓非缠结区,溶液在该浓度区内增比黏度和弛豫时间随Na PSS浓度变化的标度关系为:ηsp~c3.5p和τ~c1.9p,接近于中性聚合物良溶液在亚浓缠结区的行为.这一特殊现象可能由混合体系中强烈的长程静电耦合作用引起.     

核/壳乳液聚合工艺中乳化剂的定量研究

以十二烷基硫酸钠(SDS)为乳化剂,采用多步种子乳液聚合方法制备了核/壳结构乳液,研究了乳化剂加入量以及加料速率对核壳乳液聚合的影响,并推导了核及壳乳液聚合阶段所需乳化剂量的计算公式.研究表明,当种子、核、壳乳液聚合阶段单体量分别为12g、50g和50g,种子乳液聚合阶段加入的乳化剂量为0.44g时,控制核、壳乳液聚合阶段乳化剂的加入量分别在0.64～2.07g及0.04～2.12g之间,且预乳化单体的滴加速度低于2.3g/min时,可以防止二次成核及新乳胶粒子的形成,制得粒径分布窄、核/壳结构明显的乳胶粒子.利用透射电镜(TEM)对所制备的核壳结构乳胶粒子的结构形态进行了验证,试验结果与理论预测结果一致.     

Dynamics of shear-thinning suspensions of core-shell structured latex particles

The rheological behavior and microstructure of shear-thinning suspensions of core-shell structured carboxylated latex particles were examined. The steady shear viscosity of the suspension increased with increasing dissociation of the carboxyl groups or increasing particle concentration, however the critical shear stress sigma(c) and inter-particle distance xi of the microstructure did not change. With increasing particle diameter, sigma(c) increased and xi decreased. These results were consistent with a Brownian hard sphere model, in which competition exists between the bulk mass transfer due to the applied field and diffusion of the particles. We confirmed that sigma(c) depends on xi, as expressed by sigma(c) = 3kT/4pi xi3. This relationship is consistent with the dynamics of a Brownian hard sphere model with particle diameter xi. Thus the dynamics of shear-thinning suspensions of core-shell particles can be explained by a Brownian thermodynamic model.     

On the emulsion polymerization of styrene in the presence of a nonionic emulsifier

The batch emulsion polymerization kinetics of styrene (St) initiated by a water-soluble peroxodisulfate in the presence of a nonionic emulsifier was investigated. The polymerization rate versus the conversion curves showed two nonstationary rate intervals, two rate maxima, and Smith–Ewart Interval 2 (nondistinct). The rate of polymerization and number of nucleated polymer particles were proportional to the 1.4th and 2.4th powers, respectively, of the emulsifier concentration. Deviation from the micellar nucleation model was attributed to the low water solubility of the emulsifier, the low level of the micellar emulsifier, and the mixed modes of particle nucleation. In emulsion polymerizations with a low emulsifier concentration, the number of radicals per particle and particle size increased with increasing conversion, and the increase was more pronounced at a low conversion. By contrast, in emulsion polymerizations with a high emulsifier concentration, the number of radicals per particle decreased with increasing conversion. This is discussed in terms of the mixed models of particle nucleation, the gel effect, and the pseudobulk kinetics. The formation of monodisperse latex particles was attributed to coagulative nucleation and droplet nucleation for the polymerizations with low and high emulsifier concentrations, respectively. The effects of the continuous release of the emulsifier from nonmicellar aggregates and monomer droplets, the close-packing structure of the droplet surface, and the hydrophobic nature of the emulsifier on the emulsion polymerization of St are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4422–4431, 1999     

Rheology of hydrophobically modified polyacrylamide-co-poly(acrylic acid) on addition of surfactant and variation of solution pH

Constant shear and shear dependent viscosity measurements are reported in aqueous systems of co- and terpolymers of acrylamide (AM), N-n-alkylacrylamide (C10, C12, and C14 alkyl groups), and acrylic acid (AA) with added anionic surfactant sodium dodecyl sulfate (SDS). The results are presented as three-dimensional plots of viscosity vs surfactant concentration and pH at constant shear rate or viscosity vs shear rate and surfactant concentration at constant pH. For terpolymers incorporating AA, a strong viscosity maximum is observed at intermediate pH values (pH 4-6) where the AA groups are partially ionized and at SDS concentrations close to the critical micelle concentration. At high pH, all AA incorporating terpolymer solutions with SDS are strongly shear thinning, but at pH 3-4 the systems of terpolymers with SDS are strongly shear thickening at low shear, followed by a shear-thinning region at high shear. These results are explained in terms of surfactant-mediated network formation with polymer coil expansion and hydrogen bonding between partially ionized AA groups as additional factors.     

Simulation of nonlinear shear rheology of dilute salt-free polyelectrolyte solutions

Brownian dynamics simulations are used to conduct a systematic analysis of the nonlinear shear rheology of dilute polyelectrolyte solutions, exploring its relationship to shear rate, Bjerrum length, and concentration. A simple coarse-grained bead-spring chain model that incorporates explicit counterions is used. It is found that the polyelectrolyte chains exhibit a shear thinning behavior at high shear rate (as characterized by bead Peclet number Pe) that is independent of the electrostatic strength due to the stripping of ions from close proximity to the chain caused by the flow. In contrast, at low values of Pe, the viscosity increases monotonically with increasing Bjerrum length over the range studied here, in contrast to the nonmonotonic trend displayed by the chain size. Furthermore, at fixed Bjerrum length, the reduced viscosity increases monotonically with concentration. The mechanism underlying these observations is essentially the primary electroviscous effect; the ion cloud surrounding a polyelectrolyte chain deforms in flow, causing a significant increase in viscosity as concentration increases. Finally, the authors have also considered the role of hydrodynamic interactions in these simulations, finding that for low concentration studies in shear flow, these do not qualitatively affect the results.     

Experimental Investigation of Rheological and Morphological Properties of Water in Crude Oil Emulsions Stabilized by a Lipophilic Surfactant

Rheological behavior of two crude oils and their surfactant-stabilized emulsions with initial droplet sizes ranging from 0.5 to 75 µm were investigated at various temperatures under steady and dynamic shear testing conditions. In order to evaluate the morphology and Stability of emulsions, microscopic analysis was carried out over three months and average diameter and size distribution of dispersed droplets were determined. The water content and surfactant concentration ranged from 10 to 60% vol/vol and 0.1 to 10% wt/vol, respectively. The results indicated that the rheological properties and the physical structure and stability of emulsions were significantly influenced by the water content and surfactant concentration. The crude oils behaved as Newtonian fluids over a wide range of shear rates, whereas the emulsions behaved as non-Newtonian fluids, indicating shear-thinning effects over the entire range of shear rates. The viscosity, storage modulus and degree of elasticity were found to be significantly increased with the increase in water content and surfactant concentration. The maximum viscosity was observed at the point close to the phase inversion point where the emulsion system changes from water-in-oil emulsion to oil-in-water emulsion. The results also indicated that the rheological properties of crude oils and their emulsions are significantly temperature-dependent.     

Viscoelastic Drag of Particles Settling in Wormlike Micellar Solutions of Varying Surfactant Concentration

Wormlike micellar octadecyl trimethyl ammonium chloride (OTAC) solution is a self-assembled fracturing fluid used to carry proppants into fractures in oil recovery. Slow settling velocity of proppant is desirably resulted from the viscoelastic drag with low viscosity of fracturing fluids for fracturing work. Steel spheres, as a substitute for proppants, fall into three semi-dilute OTAC solutions. The steady rheology demonstrates that OTAC solutions are divided into shear-thickening and shear-thinning regimes by the critical shear rate. The applied steel spheres always lie in the shear-thickening regime of the 2.8 wt% OTAC solution with aggregated micelles as their characteristic shear rates are less than the critical shear rate of the solution. Strong shear-thickening viscous drag results in lower settling velocity of steel spheres. Most of the applied steel spheres, on the other hand, lie in the shear-thinning regime of the 4 wt% OTAC solution with orientated micelles. Although the latter solution has small dissipation coefficient, high Weissenberg number, and consequently high elastic effect, the shear-thinning viscosity results in higher settling velocity of steel spheres.     

Rheological behavior of silica suspensions in aqueous solutions of associating polymer

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups. The aqueous solutions show viscoelastic responses above some critical concentrations because a three-dimensional structure is formed by association of hydrophobic groups. When the associating polymers are added to silica suspensions at low concentrations, the flocculation is induced by bridging mechanisms, and the flow of suspensions become shear-thinning. For suspensions prepared with polymer solutions in which the associating network is developed, the viscosity decreases, shows a minimum, and then increases with increasing particle concentration. The viscosity decrease may arise from the breakdown of associating network due to adsorption of polymer chains onto the silica surfaces. As the particle concentration is increased, the polymer concentration in solution is decreased, and finally, all polymer chains are adsorbed on the surfaces. Beyond this point, the partial coverage of particle surfaces takes place and strong interactions are generated between particles by polymer bridging. Since the stable suspensions are converted to highly flocculated systems, the viscosity is increased and the flow becomes shear-thinning. The concentration effect of silica particles on the viscosity behavior of suspensions can be explained by a combination of viscosity decrease in solution due to polymer adsorption and viscosity increase due to flocculation.     

丙烯酰胺双水相聚合体系稳定性研究

通过浊点滴定法测定了不同温度下PAAmPEGH2O双水相体系相图,发现分相浓度随着温度的升高先增后降,55℃时分相浓度最低.双水相聚合体系微观结构显示,分散相以砾状液滴形式均匀分散在连续相中.研究了聚合过程中聚合体系粘度的变化,以及聚合温度、分散介质、单体、引发剂及乳化剂等对聚合体系最终粘度的影响,聚合体系最终粘度在一定范围内随分散介质和单体浓度增加变化不大,但是超过某一浓度后聚合体系粘度急剧增加;聚合体系中加入少量乳化剂对体系粘度影响不大,但加入大量乳化剂后体系稳定性变差,聚合体系粘度急剧增加;聚合体系最终粘度随着聚合温度升高先降后增,与相图的预测结果一致.