Charge density effects in salt‐free polyelectrolyte solution rheology

Solution rheology of 2‐vinyl pyridine and N‐methyl‐2‐vinyl pyridinium chloride random copolymers in ethylene glycol was studied over wide ranges of concentration and effective charge. The fraction of quaternized monomers α and the fraction of monomers bearing an effective charge f of these copolymers were measured using counterion titration and dielectric spectroscopy, respectively. Ethylene glycol is a good solvent for neutral poly(2‐vinyl pyridine), with very few ionic impurities. The viscosity η and relaxation time τ of dilute and semidilute unentangled solutions exhibit the scaling with concentration and effective charge expected by the Dobrynin model. Reduced viscosity data are independent of concentration in dilute solution, giving an intrinsic viscosity that depends on effective charge, and the experimental data obey the Fuoss law in the semidilute unentangled regime. Scaling concentration with the overlap concentration (c/c*) reduces these data to common curves, and c* ～ f ^?12/7 as predicted by the Dobrynin model, where f is the fraction of monomers bearing an effective charge. While the overlap concentration depends strongly on effective charge until counterion condensation occurs, the entanglement concentration c_e is surprisingly insensitive to effective charge, indicating that entanglement effects are not understood using the Dobrynin model. The terminal modulus G = η/τ depends only on the number density of chains G = ckT/N for c* < c < c_e, and G ～ c^3/2 for c > c_e independent of the effective charge. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2001–2013, 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     

甲醇与蓖麻油混合物运动粘度的实验研究

利用改型的乌别洛特毛细管粘度计,本文对243～353K温度范围内对质量配比为98.8:1.2的甲醇与蓖麻油混合物的运动粘度进行了实验研究,运动粘度测量结果的不确定度为1.06%,利用得到的实验数据拟合了甲醇 蓖麻油二元混合物的运动粘度方程.方程与实验数据最大偏差为3.31%,平均偏差为1.11%.     

无相移滤波技术用于分析化学信号处理

把无相移滤波技术引入了分析化学信号处理领域。其方法为：先将输入序列按顺序滤波，然后将所得结果逆转后反向通过滤波器，再将所得结果逆转后输出。通过对色谱信号的实验研究表明，与普通的数字滤波方法相比较，无相移滤波不但具有普通数字滤波的优点，而且不会产生滤波前后的相位偏移，具有良好的应用前景，尤其对于需要准确计算保留时间的场合，用此预处理方法非常适合。     

Sorption properties of freshly precipitated alumogels

The influence of the pH of precipitation and the ionic medium nature on the composition, surface charge, and kinetic sorption characteristics of aluminum oxyhydroxides formed by alkaline hydrolysis of an aqueous solution of aluminum nitrate was studied. The methods of drop titration with alkali, argentometric titration, point of zero charge, and indicator reactions of heterogeneous hydrolysis were used. The composition of the freshly precipitated hydrogels of aluminum(iii) oxyhydroxide, rate constants of heterogeneous hydrolysis of the IrCl₆ ^2– ions as indicator reactions, and the pH of the point of zero charge were determined. The rate of indicator reactions (as for other oxyhydroxide hydrogels) depends strongly on the pH of precipitation. However, it is lower than the rates characteristics of iron(iii) and chromium(iii) oxyhydroxides obtained under similar conditions. The pH of the point of zero charge for the alumogels in a chloride medium is 8.3 and that in a sulfate medium is 9.5.     

Magnetic phase transitions in nanostructures induced by shear stress under high pressure

Magnetic phase transitions of the first and second order were revealed by Mössbauer spectroscopy in nanosystems of - and -ferric oxides and metallic europium subjected to shear stress (240°) under high pressure (20 kbar). For - and -ferric oxide nanoclusters, the Curie (Neel) points decreased to 300 K, whereas for nanostructured europium the Neel point increased from 90 to 100 K. The thermodynamic model of magnetic phase transitions predicting a change in the character of magnetic phase transitions and a decrease (increase) in the critical Neel (Curie) points in nanoclusters was developed. The type of magnetic phase transitions and the change in the critical points were caused by defects in nanoclusters, whose maximum concentration was observed for the clusters with the 20—50 nm size range.     

表面膨胀粘度的测定研究

用不同浓度的NaCl和表面活性剂直链的十二烷基苯磺酸钠(LAS)、稳定剂聚丙烯酰胺和水所组成的泡沫体系为研究对象,通过表面压松弛的方法,利用计算机数据拟合,得到了计算表面膨胀粘度的方法。     

Molecular aggregation in the ternary system deca glycerol dioleate/heptane/water

The phase diagram for the ternary system deca glycerol dioleate(DGD)/heptane/water was established at 25 °C. In this phase diagram it was seen that the reverse micellar solution phase extends in its area until the water content reaches 35–45 wt%, at which a liquid crystalline phase begins to appear. On the basis of the experimental results of specific conductivity, viscosity, etc. for the samples containing a definite amount of DGD (0,1 M), and varying relative amounts of heptane and water, the mechanism of the transition of reverse micellar structures to liquid crystalline phase is discussed.     

Theory of oscillatory experiments with a coaxial cylinder viscometer

Equations are derived for the coaxial cylinder system in the combined oscillatory and steady-state shear mode. The limitations of the use of the various equations are presented. If the usual linear equations are used, the main limitation, in the case of oscillatory shear only, is that the frequency of measurement should be below 0.016 | ^*|/(r ₂ –r ₁ )². Here | ^*| is the modulus of the complex viscosity, is the density of the liquid andr ₁ andr ₂ are the radii of the cylinders. Furthermore it is shown that there is a small error in the numerical factor of the usually applied equations. The calculations are set up in such a way that extension to higher harmonics follows in a natural way. An experimental example illustrates the use of the derived equations.     

羟丙基甲基纤维素作为水泥添加剂研究(四)

以萘磺酸甲醛缩合物为分散剂，水溶性羟丙基甲基纤维素衍生物为粘稠剂，研究了它们的混合物对混凝土材料的分散性与粘稠性及其它性能的影响，并探索了其作用机理。