Orientation and relaxation of polymer–clay solutions studied by rheology and small-angle neutron scattering

The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay [montmorillonite, i.e., Cloisite NA+ (CNA)] was investigated with rheology and small-angle neutron scattering (SANS). The steady-state viscosity and SANS were used to measure the shear-induced orientation and relaxation of the polymer and clay platelets. Anisotropic scattering patterns developed at much lower shear rates than in pure clay solutions. The scattering anisotropy saturated at low shear rates, and the CNA clay platelets aligned with the flow, with the surface normal parallel to the gradient direction. The cessation of shear led to partial and slow randomization of the CNA platelets, whereas extremely fast relaxation was observed for laponite (LRD) platelets. These PEO–CNA networklike solutions were compared with previously reported PEO–LRD networks, and the differences and similarities, with respect to the shear orientation, relaxation, and polymer–clay interactions, were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3102–3112, 2004     

Thermal stability of shear-induced precursor structures in isotactic polypropylene by rheo-X-ray techniques with couette flow geometry

Combined in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) studies using couette flow geometry were carried out to probe thermal stabilty of shear-induced oriented precursor structure in isotactic polypropylene (iPP) at around its normal melting point (162 °C). Although SAXS results corroborated the emerging consensus about the formation of “long-living” metastable mesomorphic precursor structures in sheared iPP melts, these are the first quantitative measures of the limiting temperature at which no oriented structures survive. At the applied shear, rate = 60 s⁻¹ and duration t_s = 5 s, the oriented iPP structures survived a temperature of 185 °C for 1 h after shear, while no stable structures were detected at and above 195 °C. Following Keller's concepts of chain orientation in flow, it is proposed that the chains with highly oriented high molecular weight fraction are primarily responsible for their stability at high temperatures. Furthermore, the effects of flow condition, specifically the shear temperature, on the distributions of oriented and unoriented crystals were determined from rheo-WAXD results. As expected, at a constant flow intensity (i.e., rate = 30 s⁻¹ and duration, t_s = 5 s), the oriented crystal fraction decreased with the increase in temperature above 155 °C, below which the oriented fraction decreased with the decrease in temperature. As a result, a crystallinty “phase” diagram, i.e., temperature versus crystal fraction ratio, exhibited a peculiar “hourglass” shape, similar to that found in many two-phase polymer–polymer blends. This can be explained by the competition between the oriented and unoriented crystals in the available crystallizable species. Below the shear temperature (155 °C), the unoriented crystals crystallized so rapidly that they overwhelmed the crystallization of the oriented crystals, thus depleting a major portion of the crystallizable species and increasing their contribution in the final total crystalline phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3553–3570, 2006     

Acrylic acid level and adhesive performance and peel master‐curves of acrylic pressure‐sensitive adhesives

Three series of pressure‐sensitive adhesives were prepared with constant glass‐transition temperature, using emulsion polymerization. The monomers chosen were butyl acrylate, 2‐ethylhexyl acrylate (EHA), methyl methacrylate (MMA), and acrylic acid (AA). Within each polymer series, the proportion of AA monomer was held constant for each polymer preparation but acrylic ester monomer levels were varied. Adhesion performance was assessed by measurement of loop tack, static shear resistance, and through the construction of peel master‐curves. Peel master‐curves were generated through peel tests conducted over a range of temperatures and peel rates and through application of the time–temperature superposition principle. Bulk effects dominated by polymer zero shear viscosity change as AA and EHA levels were varied were attributed to the observed effect on static shear resistance and the horizontal displacements of peel master‐curves. Static shear resistance was found to strongly correlate with log(a_C), a parameter introduced to horizontally shift peel master‐curves to form a superposed, “super master‐curve”. An interfacial interaction was proposed to account for deviations observed when loop tack was correlated with log(a_C). Surface rearrangements via hydrogen bonding with the test substrate were suggested as responsible for the interfacial interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1237–1252, 2006     

An accurate method to predict the stress concentration in composite laminates with a circular hole under tensile loading

The paper presents a theoretical-numerical hybrid method for determining the stresses distribution in composite laminates containing a circular hole and subjected to uniaxial tensile loading. The method is based upon an appropriate corrective function allowing a simple and rapid evaluation of stress distributions in a generic plate of finite width with a hole based on the theoretical stresses distribution in an infinite plate with the same hole geometry and material. In order to verify the accuracy of the method proposed, various numerical and experimental tests have been performed by considering different laminate lay-ups; in particular, the experimental results have shown that a combined use of the method proposed and the well-know point-stress criterion leads to reliable strength predictions for GFRP or CFRP laminates with a circular hole. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 43, No. 4, pp. 531–570, July–August, 2007.     

环形线电荷的电场分布

给出了圆环形线电荷电场分布的理论公式，并利用计算机计算出其具体分布规律。     

Mg-Nd-Zr-Zn合金的制备及钕对合金组织性能的影响

在RJ-2溶剂和Be的联合保护下制备了Mg-Nd-Zr-Zn系合金. 通过对合金组织的分析, 以及Nd对组织性能影响的研究, 试制出了Nd添加量合理的Mg-Nd-Zr-Zn合金. 经过测试, 认为Nd添加量的增加提高了合金的250 ℃高温抗拉强度, 当Nd添加量超过2.8%时, 合金的高温强化作用不十分显著. Mg-Nd-Zr-Zn合金在250 ℃时的拉伸断裂方式主要是韧性断裂.     

碱改性γ－Al_2O_3催化剂表面碱强度分布与COS水解活性的研究

用非水滴定法和Ｈａｍｍｅｔｔ系列指示剂测定了ＣＯＳ水解碱改性γ－Ａｌ_２Ｏ_３催化剂的表面碱强度分布．发现表面碱强度分布不均匀与表面能量分布不均匀相呼应．采用零点酸碱强度（Ｈ_（０，ｍａｘ））及碱中心区域分析法，Ｂｒｏｎｓｔｅｄ催化定律，进一步证实ＣＯＳ水解反应具有明显碱催化特征，较高活性催化剂的Ｈ_（０，ｍａｘ）一般为１０左右，对ＣＯＳ水解反应起主要作用的碱性中心的碱强度（Ｈ_０）为４．８≤Ｈ_０≤９．８．对碱金属氧化物改性后的γ－Ａｌ_２Ｏ_３催化剂，Ｂｒｏｎｓｔｅｄ规律在每个碱强度分区域内是适用的．     

Early-stage flocculation kinetics of polystyrene latex particles with polyelectrolytes studied in the standardized mixing: Contrast of excess and moderate polyelectrolyte dosage

Standardized mixing procedure was applied to the analysis of flocculation of polystyrene latex (PSL) particles with polyelectrolytes. After confirming the initial enhancement of flocculation rate in the very beginning followed by abrupt stop with excess dosage, attention was shifted to the system of moderate dosage. In the former, effects of ionic strength were further analyzed to find the consistency with adsorption isotherm. In the latter, flocculation started slowly in the beginning, sometime slower than salt-induced rapid coagulation, however, the rate gradually increases in the middle stage. Often, the increased rate exceeds that of salt-induced rapid coagulation. This behavior emerged more clearly in the case of lower ionic strength. This is the indication that the rate of relaxation of polymer on the colloidal surface is a function of surface coverage and ionic strength. The ultimate degree of flocculation is usually higher than that observed for excess dosage. The size distribution of flocs was also examined, however, no clear difference between different experimental conditions was confirmed for the same degree of flocculation.