Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Sustainable biocarbon as an alternative of traditional fillers for poly(butylene terephthalate)-based composites: Thermo-oxidative aging and durability

Sustainable biocomposites have gained considerable interest as an alternative to conventional composites in recent years due to their cost-effectiveness and environmental friendliness. The aim of this study was to investigate the performance and durability behavior of biocomposites from sustainable biocarbon (BC) as compared to conventional established fillers. The poly(butylene terephthalate) (PBT) and its composites reinforced with BC, talc, and glass fiber (GF) were prepared and the durability performances was investigated. The study showed that BC/PBT biocomposites provided a lighter weight alternative to traditionally used fillers. After undergoes thermo-oxidative aging, the mechanical properties of BC/PBT biocomposite were deteriorated. The GF/PBT showed the most stable in retaining its mechanical properties in comparison to the talc/PBT and BC/PBT. The aging behavior and mechanism of the PBT composites were discussed. This study provides further insight on the durability-related properties progression of biocomposites as compared to traditional used fillers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47722.     

Staining of poly(ethylene terephthalate) by ruthenium tetroxide

The staining of poly(ethylene terephthalate) (PET) by ruthenium tetroxide (RuO₄) is used to obtain a contrast at the crystalline lamellar scale in transmission electron microscopy. This paper demonstrates the efficiency of this technique conducted in vapor phase on ultracut bulk samples. Advantages of this method against other contrast enhancing techniques and the parameters of staining are discussed. The depth of attack is measured and is shown to be limited by a crosslinking process. The chemical mechanisms are investigated by grazing infrared spectroscopy and involve the oxidation of the aliphatic moeities of PET.     

甲醇氧化羰化制碳酸二甲酯产物气相色谱分析

以Chromosorb 10 1为固定相 ,气相色谱法分析甲醇氧化羰化制碳酸二甲酯产物中水、甲醇、乙酸甲酯和碳酸二甲酯等组份的含量 ,考察了柱温 ,载气流量对分离度的影响 ,确定了适宜的分析条件 ,并用校正面积归一化法定量。该方法操作简便 ,快速 ,精度高 ,重现性好     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

有机羧酸钠盐对PET结晶和熔融行为的影响

采用差示扫描量热仪研究了5种具有不同取代基的苯甲酸钠盐作为结晶成核剂对聚对苯二甲酸乙二醇酯（HET）结晶和熔融行为的影响，并同滑石粉进行了对比。结果表明，成核剂的加入能明显改变PET的结晶和熔融行为。苯甲酸钠、对苯二甲酸甲酯单羧酸钠和对羟基苯甲酸钠提高既汀的熔融结晶温度（Tc）分别达22．93、21．7和19．37℃，但使PET降解严重；对苯酚钠甲酸钠能够提高Tc达17．75℃且对PET相对分子质量影响很小；对苯二甲酸二钠成核作用最差。低于滑石粉。此外，成核剂的成核能力越强，PET双熔融峰中的低温峰顶温度就越高。     

4，4＇－二苯醚二甲酸改性PET的热性能研究

采用示差扫描量热和热重分析的方法对合成的不同４，４＇－二苯醚二甲酸（ＯＢＢＡ）含量的共聚酯的热性能进行了研究。结果发现共聚酯的熔点和热结晶温度与ＰＥＴ相比有所降低；而冷结晶温度则升高。随着ＯＢＢＡ添加量的增加，在恒温热重分析中热失重速率常数减小；在升温热重分析中，热失重活化能则增加。所有的实验结果皆表明，芳族醚键的引入对提高共聚酯的热性能有重要作用。     

Light scattering studies on crystallization in polyethylene terephthalate

The light scattering from the spherulites of polyethylene terephthalate grown near the glass transition temperature has been investigated. The Hv scattering profiles can be reproduced by the sum of the ideal spherulite scattering with the distribution of spherulite radius and the isotropic scattering from randomly oriented crystallites. The ratio of optical anisotropies in the isotropic scattering to the ideal spherulite scattering is obtained by the method established to eliminate the effects of the number density of spherulites and the coefficient depending on the experimental conditions. It is found that the anisotropy ratio is almost independent of the crystallization time and of temperature above 106 °C, while it is larger at a crystallization temperature of 103 °C. The spherulitic structure is discussed in terms of the anisotropy ratio.