γ‐Irradiation effects on the thermal and structural characteristics of modified,grafted polypropylene

The effects of both the degree of grafting and γ irradiation on the thermal stability and structural characteristic of polypropylene‐graft‐polyvinylpyrrolidone and polypropylene‐graft‐polyvinylpyrrolidone modified with α‐cyano‐δ‐(2‐thienyl) crotononitrile were investigated. The employed techniques were thermogravimetric analysis, differential thermogravimetry, and X‐ray diffraction. The thermal stability of various polymeric substrates was investigated through the determination of the degradation temperature and activation energy of degradation. The effects of different parameters on the structural characteristics of different films were investigated through the determination of possible changes in the degree of ordering of the polymeric substrates. The results revealed that the thermal stability of the trunk polymer, grafted polymer, and polymer modified by α‐cyano‐δ‐(2‐thienyl) crotononitrile increased progressively with an increasing degree of grafting. The increase was, however, more pronounced for the sample undergoing the lowest degree of grafting. The activation energy of the thermal degradation process remained almost unchanged, and this indicated that the degradation processes of the different films followed almost the same mechanism. The γ irradiation at a dose of 60 kGy of the sulfur‐treated polymeric films [i.e., the polymeric films treated with α‐cyano‐δ‐(2‐thienyl) crotononitrile] reduced their thermal stability. This conclusion was reached by the consideration of the changes observed in the pre‐exponential factor of the Arrhenius equation due to different chemical and γ‐irradiation treatments. The degree of ordering, evidenced by X‐ray diffraction measurements of the trunk polymer, grafted polymer, and modified polymer, suffered a significant drop. This drop was much more pronounced for the sulfur‐containing polymeric materials. The observed drop in the degree of ordering of the polymeric substrates was taken as a measure of the structure collapse due to a certain treatment (degree of grafting and sulfur inclusion). The γ irradiation of the sulfur‐containing polymeric materials greatly increased their degree of ordering, which reached a value greater than that measured for the trunk polymer. Therefore, it was concluded that the thermal stability increased as the degree of ordering decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 506–515, 2006     

Preparation and properties of magnetorheological elastomers based on silicon rubber/polystyrene blend matrix

Magnetorheological (MR) elastomers, which are mainly composed of magnetic particles and elastic polymer, are a new kind of smart materials whose modulus can be controlled by changing the strength of magnetic fields. In this article, MR elastomers based on immiscible silicon rubber/polystyrene (SR/PS) blend matrix were fabricated successfully via cosolvent method and the MR effect, electric and mechanical properties, and the microstructures of the corresponding materials were studied. SEM studies showed that the dispersion of iron particles in blend matrix were different from that in single polymer, which could be further proved by the different electric conductivity. The MR effect of MR elastomers based on blend matrix varied with the different ratios of SR and PS, which was discussed in detail from the special dispersion of iron particles and of zero‐modulus of MR elastomers. In addition, the MR elastomers based on SR/PS blend matrix had enhanced mechanical properties, which made them more hopeful to be applied in practice. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3143–3149, 2007     

不同氧磷比对磷酸盐包边玻璃性质的影响规律

包边技术是提高大尺寸激光玻璃饱和增益系数的关键技术.采用传统的方法熔制玻璃,研究了P2O5含量对P2O5-Al2O3-B2O3-CuCl-Na2O-ZnO磷酸盐包边玻璃的折射率、热膨胀系数、玻璃转变温度、膨胀软化温度以及化学稳定性的影响.结果表明:当P2O5的摩尔分数为60%左右,玻璃样品具有最高的折射率(1.5220)、最低的玻璃转变温度(352.4℃)、较好的化学稳定性[0.52mg/(cm2·d)]和适宜的热膨胀系数(128.427×10-7/℃),是用作钕磷酸盐激光玻璃硬包边的理想材料.     

水性聚氨酯的合成与改性

以甲苯二异氰酸酯(TDI)、聚醚二元醇(N220)和二羟甲基丙酸(DMPA)为主要原料,采用三羟甲基丙烷(TMP)进行交联改性合成了水性聚氨酯(WPU),研究了n(-NCO)/n(-OH)、DMPA及TMP对WPU的耐水性、稳定性和力学性能的影响。研究发现,改性后的乳液常温贮存稳定性好,适度交联可提高胶膜的拉伸强度及耐水性。     

Production of finely ground natural graphite particles with high electrical conductivity by controlling the grinding atmosphere

Natural graphite particles with high crystallinity sieved to obtain a particle size range of under 63 μm were ground with a ball mill, under various well-controlled grinding atmospheres such as N₂, O₂, He, H₂, and vacuum. The ratio, X_dif50/X_st50, i.e. between the 50 wt.% Stokes diameter and the 50 wt.% laser diffraction diameter, of the ground particles, was used as an index of the flakiness of the particles. The specific resistance of films composed of the ground graphite particles was systematically measured. The rate of reduction in the size of the particles by grinding was slow under an O₂-rich atmosphere such as 100% O₂ and dry air. On the other hand, it was relatively fast in vacuum, or under an N₂ or He atmosphere, and a gas mixture of 99% N₂ and 1% O₂. The rate of size reduction by grinding under a H₂ atmosphere was intermediate. In our experimental conditions, the flakiness of the ground particles increased with the decrease in the particles’ sizes. The electrical conductivity of the ground particles, however, tended to decrease with the decrease in their sizes. Under the condition that the Stokes diameter of the ground particles remains constant, the electrical conductivity of films made from the ground particles increases with the increase in the flakiness of the particles. It was finally determined from our systematic grinding experiments that small flaky particles, which had a size, X_st of ∼1 μm, with a high electrical conductivity can be produced by grinding in a gas mixture of 99% N₂ and 1% O₂. In this case, the flaky shape of the ground particles was visually confirmed by scanning electron microscopy.     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Improvement of mechanical properties for PP/PS blends by in situ compatibilization

The effect of the in situ compatibilization on the mechanical properties of PP/PS blends was investigated. The application of Friedel-Crafts alkylation reaction to the PP/PS-blend compatibilization was assessed. Styrene/AlCl₃ was used as catalyst system. The graft copolymer (PP-g-PS) formed at the interphase showed relatively high emulsifying strength. Scission reactions, occurring in parallel with grafting, were verified for PP and PS at high catalyst concentration, but no crosslinking reactions were detected. Tensile tests were performed on dog-bone specimens of the blends. Both elongation at break and toughness increased with catalyst concentration. At 0.7% AlCl₃, a maximum was reached, which amounted to five times the value of the property for the uncompatibilized blend. At higher catalyst concentrations these properties decreased along with the PP molecular weight due to chain-scission reactions. On the other hand, the tensile strength did not change with the catalyst concentration. The in situ compatibilized blends showed considerable improvement in mechanical properties, but were adversely affected by chain scissions at high catalyst contents.     

An improved prediction result of entropic‐FV model for vapor–liquid equilibria of solvent–polymer systems

In this work, entropic expressions of UNIFAC‐FV and Entropic‐FV models were evaluated by using an extensive database of infinite dilution vapor–liquid equilibrium (VLE) data of athermal systems containing polypropylene, polyethylene, and polyisobutylene. For the infinite dilution athermal systems, performance of the Entropic‐FV model was better than that of the UNIFAC‐FV model. Then, finite concentration VLE data of non‐athermal systems that consisted of 16 polymers and 36 solvents containing a large variety of solvent–polymer systems ranging from nonpolar to polar substances were considered to optimized 46 pairs of group interaction parameters of the Entropic‐FV model. For systems containing polar solvents of three types of solvents studied, revised group interaction parameters gave significant improvements from 17.9 to 13.0% average absolute deviation (AAD) of solvent activities. For overall results, improvements were achieved from 15.1 to 12.4% AAD. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1145–1153, 2005     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

New associative systems based on alkylated hyaluronic acid. Synthesis and aqueous solution properties

This paper concerns the preparation of new water-soluble alkylated derivatives of hyaluronan (HA); these derivatives were synthesized under mild aqueous and well controlled conditions. The first step was to prepare a HA derivative selectively modified with adipic dihydrazide (HA-ADH) with a substitution degree of 0.08; then, alkyl chains with different chain lengths were introduced with a substitution degree around 0.05. These polymers being still water-soluble exhibit associating properties in the presence of external salt. Formation of hydrophobic domains is demonstrated from fluorescence measurements in the presence of pyrene as a probe. Then, it is shown that the viscosity of polymer solutions in 0.1 M NaCl becomes non-Newtonian for HA grafted with C-10 and C-12 chains and increases rapidly with the polymer concentration over 1 g/L. When the polymer concentration increases, a gel-like behaviour was observed from rheological measurements with the G′ modulus larger than G″ in all the frequency range covered. The dependence of the shear stress on shear rate applied according to a continuous linear ramp provided evidence of the deformation or rupture of aggregates. The latter were shown to reform slowly. At the end, the influence of temperature was examined: first a slight increase in the modulus was observed followed by a decrease corresponding to reinforcement of the hydrophobic interactions.