Viscoelastic behaviour of butyl acrylate/styrene/2-hydroxyethyl methacrylate/acrylic acid latices thickened with associative thickeners

The rheological behaviour of butyl acrylate/styrene/acrylic acid latices thickened with a hydrophobically modified ethoxylated polyurethane (HEUR) or hydrophobically modified alkali-soluble polyacrylate emulsion (HASE) was investigated. While the pseudoplastic character of frequency dependence of complex viscosity was similar for both thickeners, viscoelastic behaviour, expressed as the ratio of loss and storage moduli, significantly differed, indicating that the HEUR molecules, unlike swollen HASE particles, create a viscoelastic space structure. The increase in hydrophilicity of the particle surface, achieved by incorporation of 2-hydroxyethyl methacrylate (HEMA) monomer into the latex copolymer reduced the viscoelasticity of latices thickened with HEUR, but not of those thickened with HASE. This confirms that adsorption of hydrophobic end-groups on particle surface is important for thickening of latices with HEUR and that a physical network of latex particles interconnected by the thickener macromolecules is formed. To cite this article: O. Quadrat et al., C. R. Chimie 6 (2003).     

Thickening effect of dispersions of ethyl acrylate-methacrylic acid copolymer prepared by different polymerization routes

Thickening of latices (particle diameters 105, 157 and 221 nm) by model dispersions of ethyl acrylate-methacrylic acid copolymer (15 wt.% of the acid) prepared by both non-seeded and seeded semicontinuous emulsion copolymerizations was investigated. Using viscometry and dynamic and steady shear measurements, we found that the thickening effect of the dispersions strongly depends on their particle structure and the intensity of interactions between the components in the system. In weakly interacting systems (lower latex concentrations, large latex particles) the thickening effect of the dispersions is controlled by effective volume fraction of swollen particles. This leads to a higher viscosity of systems thickened by more swollen (less crosslinked) particles obtained by the non-seeded process. On the other hand, in strongly interacting systems (high latex concentrations, small latex particles) lower deformability of more crosslinked particles prepared by the seeded process causes a higher flow resistance of the systems thickened by this dispersion.     

SAXS研究四臂聚氧化乙烯片晶的增厚

使用小角X光散射（SAXS）方法研究了每臂分子量为5000的四臂聚氧化乙烯在从熔点以上的温度淬火到室温后,在室温到熔点前的温度区域里片晶的增厚过程.采用一维相关函数分析方法分析了SAXS数据,获得了样品的长周期、线性结晶度、结晶层和无定形层厚度随温度的变化.按照这些参数在升温过程中的演变规律,确定了3个特征区域.Ⅰ区约在26~45 ℃内,存在着3种不同厚度的片晶,最厚的片晶层厚度为9.3 nm,线性结晶度、长周期、结晶层和无定形层厚度等参数基本不变,称为不变区.Ⅱ区约在45~52 ℃之间,这些参数都发生变化,SAXS的主峰分化为两个主要的峰,长周期、结晶层和无定形层厚度开始增加,但是,线性结晶度升高后又降低,称为转变区.Ⅲ区约在52~60 ℃之间,体系中只有单一厚度的片晶,其厚度不断增厚,到60 ℃结晶层厚度达15.8 nm,称为增厚区.从分子运动和片晶亚稳定本质分析,可以解释实验上观察到的3个区域发生变化的本质：在不变区里,主要的分子运动几乎被冻结,不可能发生可检测到的片晶结构变化.在转变区里,分子运动开始起作用,未结晶的分子开始结晶.同时,薄片晶会熔融,尔后又重新结晶.在增厚区里,线性结晶度和结晶层厚度增加,也意味着熔融-重结晶过程还在继续,直至达到这个样品可能形成的最厚片晶的熔点.实验观察到的熔融-重结晶过程的本质是聚合物片晶的亚稳态特性,稳定性低的薄片晶向稳定性高的厚片晶转变,即一个典型的奥斯瓦尔德熟化（Ostwald ripening）.     

Synthesis and characterization of cubic cobalt oxide nanocomposite fluids

Narrow size distribution cubic Co₃O₄ nanoparticles were synthesized and rheological properties of suspensions of the cubes in oligomeric polyethylene glycol (PEG) were explored over a range of particle volume fractions and rotational shear flow conditions. At low and high particle volume fractions, the relative viscosity of the suspensions is described by a Krieger–Dougherty formula with an intrinsic viscosity consistent with expectations for suspensions of ideal cuboids. At intermediate to high particle loadings, the suspensions manifest complex rheological behavior, including shear thinning and shear-thickening features. These observations are discussed in terms of the charge carried by the cubes and the shear rate/volume fraction dependency of the transition from shear thinning to shear thickening.     

Effect of thickening agents on the penicillin fermentation

The effects of thickening agents (polyethylene glycol [PEG] 20000 and carboxymethylcellulose [CMC]) on the penicillin fermentation byPenicillium chrysogenum were investigated. By adding the thickening agents to the fermentation medium, the growth form of the mold can be manipulated. Depending on the amount of thicking agent added, the change in morphology is from compact smooth pellets to various intermediate forms, and finally to filamentous mycelia. It was found that better penicillin production was obtained when the mold was in small, fluffy, loose pellets. The penicillin fermentation is not only affected by the thickening agents, but also the status of inoculum and agitation. Under the condition that the mold will otherwise grow in large pellets (e.g., under a low level of spore inoculum), the enhancement in the penicillin production through addition of the thickening agents may be more significant. In tank fermentation, the thickening agent was introduced in the stage of preculture, rather than main culture. The increase in the broth viscosity caused by addition of the thickening agent resulted in a decrease in dissolved oxygen level, which could be compensated in the case of PEG 20000.     

Heat Storage Performance of Disodium Hydrogen Phosphate Dodecahydrate： Prevention of Phase Separation by Thickening and Gelling Methods

Disodium hydrogen phosphate dodecahydrate （Na2HPO4·12H2O） is an attractive candidate for phase change materials. The main problem for its practical use comes from incongruent melting character during thermal cycling. Experimentally, heat of fusion of the pure salt decreased from 200 to 25 jog 1 in a four-run freeze-thaw cycling. Additives such as thickening agent or in-situ synthesized polyacrylate sodium in the molten salt can prevent its phase separation to some extent. In the test, sodium alginate 3.0%-5.0% （w/w） thickened mixture containing Na2HPOn·12H2O and some water showed constant heat storage capacities. Polyacrylate sodium gelled salt was synthesized through polymerizing sodium acrylate in the melt of Na2HPOn·12H2O and some extra water at 50 ℃. Optimum conditions composed of sodium acrylate 3.0%-5.0% （w/w）, cross-linking agent N,N-methylenebis-acrylamide 0.10%-0.20% （w/w）, K2S208 and Na2SO3 （mass ratio 1 ; 1） 0.06%-0.12% （w/w）. As opposed to normal large crystals of pure Na2HPOn·12H2O in solid state, the gelled salt existed in a large number of tiny particles dispersed in the gel network at room temperature, commonly less than 2 mm. But only those sample particles with sizes less than 0.2 mm may have relatively stable thermal storage property. A problem encountered was the poor reproducibility of the synthesis method： heat storage capacity of the product was often very different even though the synthesis was carried out in the same conditions. An alternative gelling method by sodium alginate grafted sodium acrylate was tried and it showed a fairly good effect. Heat capacities and heat of fusion of Na2HPO4·12H2O were measured by an adiabatic calorimeter.     

分散介质和温度对纳米二氧化硅胶体剪切增稠行为的影响

对分散介质和温度对纳米二氧化硅胶体剪切增稠行为的影响进行了系统研究. 用四种液体分散介质(乙二醇, 聚乙二醇400, 丙二醇, 聚丙二醇400)制备的纳米二氧化硅胶体表现出不同的连续剪切增稠或者跳变剪切增稠行为. 温度上升降低了分散介质的黏度, 进而降低了胶体的表观黏度. 剪切增稠的临界黏度与温度的关系符合“Arrhenius”公式的描述. 胶体黏度与分散介质黏度的比值用来归一化不同温度下的稳态剪切流变曲线. 在低剪切速率的剪切变稀阶段, 剪切变稀现象与分散介质黏度没有明显相关性, 而与分散介质的化学性质密切相关. 在高剪切速率的剪切增稠阶段, 分散介质黏度越高, 胶体剪切增稠现象越强烈.     

氧化石墨烯对聚乙烯醇/硼酸水凝胶流变性能的影响

研究了氧化石墨烯(GO)对聚乙烯醇(PVA)/硼酸(borate)水凝胶线性及非线性流变性能的影响。 通过扫描电子显微镜、硼谱核磁共振波谱以及流变研究了水凝胶的流变性能。 结果表明,GO质量浓度在稀溶液区时,GO片层与PVA链间通过硼酸根离子形成了具有弹性活性的缔合点,有效地提高了水凝胶的平台模量、松弛时间和零切粘度;当GO进一步增加到亚浓溶液区,部分的交联剂被GO的团聚体捕获并处于非弹性活性的缔合状态,处于有效缔合状态的交联剂变少,导致平台模量、松弛时间和零切粘度降低。 稳态剪切测试下,样品在剪切增稠区的粘度增加随着GO添加量的增加明显加强,这与剪切场下取向的氧化石墨烯片层参与网络结构的重排有关。