Tailoring HASE rheology through polymer design: Effects of hydrophobe size, acid content, and molecular weight

Hydrophobically modified alkali-soluble emulsion (HASE) polymers are an important class of rheology modifiers for waterborne coatings applications. They are typically prepared as terpolymers by emulsion polymerization of ethyl acrylate (EA), methacrylic acid (MAA), and an associative macromonomer. The viscosity development and shear responses of HASE solutions depend on a number of factors. This article presents rheological data reflecting the impacts of three key variables: hydrophobe size, acid content, and molecular weight, on model HASE thickening and rheological performance. The relative contributions of hydrophobic association, chain expansion, and polymer chain length are discussed. In steady shear flow, all thickener solutions approached some constant low-shear viscosity at small deformation rates. At the same molar composition, larger hydrophobe size resulted in higher viscosity development and greater shear thinning behavior. The amount of acid monomer in HASE polymers can influence the balance between hydrophobic attraction and electrostatic repulsion forces. It was found that a minimum of 15 wt% MAA was required to effect dissolution and thickening of the model HASE polymers. Increasing the MAA level yielded higher zero-shear viscosity and storage modulus G’ with maximal values being obtained at 40% MAA. The molecular weight of the model thickeners was controlled by the amount of chain transfer agent (CTA) added during polymerization. When the CTA level was below 0.1 wt% based on total monomers, the polymer solutions displayed shear-thinning behavior. A small increase in CTA concentration beyond 0.1% resulted in a dramatic change to Newtonian flow, and the solution viscosity was nearly two orders of magnitude lower. The model thickeners were also tested in a vinyl acrylic architectural paint formulation. The effects of each individual factor on paint thickener efficiency, high-shear, and low-shear properties are discussed and compared with solution rheology for predictive relationships. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 11–12, 2003, in Philadelphia, PA.     

Rheological properties of ethylcellulose latex

Because of their large specific surface area, aqueous‐based pseudolatex systems of ethylcellulose can absorb large amounts of drugs. In addition, the stability of polymeric particles in biological fluids delays the release of the drug as in controlled drug delivery systems. The aim of the present study was to characterize the rheological properties of latex particles as a measure of their colloidal stability. Here, we report the effect of three variables: pH, electrolyte concentration, and temperature. The rheograms clearly show that the polymer suspensions displayed Bingham plastic behavior. Internal structuring of the latex was greatest at acid and natural pH values, particularly at the highest ionic strength. In acid solutions, only temperature appeared to play a fundamental role; both the shear stress corresponding to the onset of nonlinear viscoelasticity and the elastic modulus at all frequencies were higher at 37°C than those at room temperature. This is assumed to be a consequence of deformation of the polymer particles upon heating. The effect of ionic strength was noticeable only at the natural pH (pH ? 6.5). At high concentrations of sodium chloride, the particles aggregated because of the decrease in double layer repulsion, and as a result, the latex became structured and its elastic modulus subsequently increased. Interestingly, when the temperature was increased further, this structure presumably broke, down, at least partially, and the storage modulus was reduced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 847–851, 2006     

注塑用聚氯乙烯干混粉料流变性能的研究

用国产注塑机直接采用聚氯乙烯(PVC)干混粉料注塑硬质聚氯乙烯(RPVC)管件是一个新课题。本文着重介绍在美国哈克(HAAKE)EU-5型转矩流变仪上筛选配方,对PVC干混粉料在加强稳定化、阻止热分解、改善加工性能和实现内外润滑的平衡等方面,进行初步探讨;同时结合生产实践,阐述了干混粉料的制备,机筒模具温度、塑化注塑压力等工艺全过程的控制条件,以及注塑管件在出现缺陷时的解决办法。     

Evaluation and characterization of ammoniumpolyphosphate–pentaerythritol‐based systems for intumescent coatings

Intumescent coatings are increasingly used as a method of passive fire protection on steel constructions. By forming a carbon network and releasing a blowing agent, the thin intumescent film swells 100‐fold at elevated temperatures. The highly insulating foam effectively prevents the load bearing steel from reaching its critical temperature at which it looses its mechanical properties and collapses. The role of the carbon donor in intumescent coatings has been studied. Comparison in temperature development, foaming ratios, and rheological behavior has been performed between formulations containing pentaerythritol (penta), di–penta, and tri–penta. A simulated fire test, in which the temperature development during intumescence was studied, showed that the formulations containing penta were considerably more efficient in keeping a low temperature throughout the process. A more rapid temperature development was displayed when using di–penta and tri–penta as the carbon donor. Rheometer tests indicate that penta formulations enter the intumescent process at a lower temperature and stays in it for a longer time than di–penta and tri–penta formulations. Furthermore, the crossover temperature and maximum phase angle are shifted towards higher temperatures by replacing penta with di–penta and with tri–penta in the formulations, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 748–753, 2007     

The prediction of transport parameters in filamentous fermentation broths based on results obtained in pseudoplastic polymer solutions

Transport phenomena studies on single phase “model” fluids are of limited value in biochemical engineering if they cannot be translated to the heterogeneous systems encountered in real fermentation processes. In this paper we discuss the utility of polymer solutions as models of filamentous fermentation broths for evaluation of: pipeline friction factors and impeller power numbers (turbine and helical ribbon). To a first approximation, polymer solutions can serve as suitable models for the prediction of laminar flow pressure drop in pipelines and turbulent power consumption in stirred tanks. However, results obtained on polymer solutions do not directly apply to filamentous fermentation broths for predictions of laminar flow impeller power consumption and the transition point for turbulent flow in stirred tanks. These discrepancies are believed to result from the existence of a time dependent yield stress in filamentous fermentation broths.     

Rheological properties and compatibility of NR/EPDM and NR/brominated EPDM blends

Ethylene–propylene–diene terpolymer (EPDM) was modified by bromination reaction. Blending the resulting brominated EPDM with natural rubber (STR5L) and blending the unmodified EPDM with STR5L at various compositions were carried out. The rheological properties of the blends were investigated using a capillary extrusion. Shear flow curves of the pure rubbers and their blends illustrated the pseudoplastic property as shear thinning behavior with a power law index n < 1. True shear viscosity of all blends showed the negative deviation in relation to their additive values. Rheological behavior and two T_g's found from the DSC thermograms at all blend compositions indicated blend incompatibility for both sets of blends. The incompatibility of the vulcanized blends was also found by measuring the spin–spin relaxation time T₂ by pulsed NMR. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 837–847, 2003     

Rheological properties of bitumen in water emulsions with added solids

Experimental work was carried out to investigate the rheological properties of bitumen in water emulsions containing solids of different shape and size. The bitumen volumetric concentration was varied up to 60%, solids free basis, and the solids volume fraction (total volume basis) was varied up to 0.2. Irregular-shaped silica sand (average diameter: 9 and 33 μm) and smooth spherical glass beads (average diameter: 27 and 44 μm) were used as the added solids. In the low shear stress range, shear thinning behavior was observed for bitumen in water emulsions. At high shear stress, the viscosity of the emulsions became fairly independent of the shear stress. The addition of solids to the bitumen emulsions increased the mixture viscosity. The addition of irregular-shaped silica sand gave a higher viscosity than a similar addition of the spherical glass beads. The viscosity of the emulsion/solids mixtures was influenced by the solids size as well; the smaller size particles gave a higher viscosity. The addition of solids to the bitumen emulsions also induced shear thickening (dilatancy) behavior at high solids volume fraction. The degree of the shear thickening increased with the oil concentration.     

表面活性剂聚集体的流变性质

以流变学基础知识为出发点，系统综述了胶束、微乳液，溶致液晶（层状、六角状、立方状），囊泡、虫状胶束等表面活性剂聚集体的流变性质及其剪切诱导结构转变现象的研究现状，总结了自流变性质的特点和理论模型，对具有黏弹性的表面活性剂活性剂聚集体进行了较为详细的论述，胶束稀溶液和微乳液多为牛顿流体；溶致液晶为非牛顿流体，有应力服价值和较高的黏弹性，囊泡的弹性性质比较突出，；虫状胶束体系具有非线性黏弹性，易形成网络结构；层状液晶、囊泡和虫状胶束等结构在剪切作用下能发生变化。这些结论对指导表面活性剂的研究和应用有重要意义。     

Sharkskin mechanism of high‐impact polystyrene (HIPS) and rheological behavior of HIPS/TiO2 composites

The rheological behaviors of high‐impact polystyrene (HIPS) and HIPS/TiO₂ composites were investigated by use of a rheometer in the present article. HIPS exhibited a constant critical stress of the sharkskin in various temperatures, and the analysis indicated that the mechanism of sharkskin of HIPS was wall–slip and its special temperature dependency was determined by weak wall–melt adsorption. The experimental results also showed that the introduction of TiO₂ into HIPS only slightly influenced the apparent viscosity (η_a) of the composites. Moreover, TiO₂ exhibited an unusual effect on the non‐Newtonian index of the composites at high shear rate. Both phenomena indicated the increase of inner free volume induced by TiO₂ in molecularly rigid HIPS. Moreover, it was noteworthy that a featured stress could be used to label the dispersion of TiO₂ in the HIPS matrix, and the numeric affinity of this featured stress and the critical stress of sharkskin revealed that both processes were relevant to the same molecular relaxation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 802–807, 2005     

保护胶体稳定的丙烯酸酯乳液流变性

分别采用常规乳化剂和羟乙基纤维素为保护胶体制备丙烯酸酯乳液。通过TEM分别观察乳胶粒的形态。利用流变仪测定剪切速率（Ds）-剪切应力（τ）关系、剪切速率（Ds）-黏度（η）关系。结果表明：采用羟乙基纤维素为保护胶体制备的乳液与常规乳液具有不同结构，该结构使其乳液体系流变性能不同。在相同剪切速率下，保护胶体制备的丙烯酸酯乳液的剪切力明显大于常规乳液的剪切力，该乳液在一定剪切速率范围内有剪切稀化现象。