Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

新型合成聚合物重金属离子吸附剂及其吸附性能

阐述了新型聚合物重金属离子吸附剂的合成与改性及其对水溶液中Cd(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)、Hg(Ⅱ)等重金属离子的吸附性能。这些聚合物重金属离子吸附剂对低浓度的重金属离子表现出了较好的吸附能力，其中聚合物吸附剂PGHyFeO—COOH对mg／L级的Pb(Ⅱ)、Cd(Ⅱ)、Hg(Ⅱ)的最大吸附量分别为211．4mg／g、155．0mg／g、147．2mg／g。这些吸附剂的吸附速度也较快，平衡吸附时间一般在60min左右，有的甚至只有几分钟。新型聚合物重金属离子吸附剂在水处理工业中具有广阔的应用前景。     

Recycled poly(ethylene terephthalate) and its short glass fibres composites: effects of hygrothermal aging on the thermo-mechanical behaviour

This paper reports on the effects of hygrothermal aging at 70 °C in water and at 80% relative humidity, on the thermo-mechanical properties, molar mass and microstructure of recycled poly(ethylene terephthalate) (rPET) and its short glass fibres composites.For all the investigated materials, the elastic mechanical properties (tensile and storage moduli) determined at low strain levels resulted practically unaffected by hygrothermal aging under the selected conditions. On the other hand, a marked reduction of the tensile strength and apparent fracture toughness has been observed for rPET matrix and its composites during hygrothermal aging, more markedly for materials immersed in water than for those aged at 80% RH. Both properties resulted to be related on the molar mass of the rPET matrix, that decreased during hygrothermal aging as a consequence of the hydrolysis process.The materials glass transition, evaluated as the temperature of the loss factor peak, increased during hygrothermal aging due to the progressively restricted mobility of the amorphous phase caused by a concurrent crystallinity increase. This crystallization process (chemicrystallization) is favoured by temperature, by the plasticizing effect of water and by the reduction of molar mass.Consistently with the mechanical measurements, the morphology of fracture surfaces exposed to hygrothermal aging in water revealed a reduction of plastic deformation of the rPET matrix and a weakening of the fibre-matrix interface for rPET composites.     

Fluoroelastomers-dependence of relaxation phenomena on composition

The dynamic-mechanical properties of some fluoroelastomers were determined as a function of composition at low frequency (≈ 1 Hz), by means of a free oscillation torsion pendulum, between −180°C and the softening point. Vinylidenefluoride (VDF)-hexafluoropropene (HFP) copolymers of molar composition 0–39% HFP and terpolymers of VDF and HFP with up to 30mol% tetrafluoroethylene (TFE) and a constant VDF to HFP molar ratio of 3.4 were considered. Two relaxation processes typical of the amorphous phase were found. The first, located at about −87°C, is related to local motions and the transition temperature was found to be independent of composition for copolymers, while it depends on TFE molar content for terpolymers. The second is related to the glass transition and the transition temperature depends on the composition. However, for semicrystalline copolymers the double glass transition phenomenon was observed. When crystallinity goes to zero at about 20 mol% HFP, only one transition is observed. It was also found that ordered structures can take place for terpolymers when TFE molar concentration exceeds 20%. The crystal disorder transition of pure PVDF (75°C) is observed also for low HFP concentrations but the transition temperature is strongly reduced. Analogies between the VDF-HFP and E-P systems are also discussed.     

Nucleophilic substitution onto poly(methylmethacrylate): 4. Dilute solution properties of substituted polymethacrylates

The morphological and hydrodynamic properties of a series of homogeneous fractions of substituted poly(methylmethacrylate) (A units) bearing keto-β-functional groups (B units) of the general structureCOCH₂R, with R = SO_xCH₃ (x = 1,2) or SO₂N(CH₃)₂, were investigated by intrinsic viscosity, light scattering and partial specific volume measurements in dimethylformamide (DMF) solution at 25°C. For molar substitution degrees $\text{DS}{}_{\mathrm{m}}\text{< 0.5}$, the copolymers behave as flexible random coils. The Stockmayer-Fixman-Yamakawa analysis of the $\text{[η]-}\text{M}\text{?}{}_{\mathrm{w}}$ data leads to slightly higher unperturbed dimensions K_o and steric factor σ than those for PMMA, and to stronger chain expansion as a result of the weak hydrogen bonding between DMF and COCH₂R units and a positive X_AB interaction parameter. For $\text{DS}{}_{\mathrm{m}}\text{> 0.5}$ however, copolymers bearing COCH₂SO₂N(CH₃)₂ groups behave as worm-like chains, as derived from the Fujii-Yamakawa analysis of the $\text{[η]-}\text{M}\text{?}{}_{\mathrm{w}}\text{-}\text{v}\text{?}$ data: the persistence length increases from 380 to 570 Å within the $\text{DS}$_m range 0.57–0.75. This transition from a random coil to a worm-like chain for $\text{DS}{}_{\mathrm{m}}\text{> 0.5}$ was tentatively correlated with the accumulation of B units in sterically hindered and self-associated short blocks of average length l_B ? 1.6 which provide drastically increased rigidity to the copolymer chain.     

支化型水性聚氨酯胶黏剂的合成及性能

采用异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇2000(PTMG2000)为原料,二月桂酸二丁基锡、1,4-丁二醇和2,2-二羟甲基丙酸分别为催化剂、小分子扩链剂和亲水单体,制得水性聚氨酯预聚体(PPU);接着以丙烯酸甲酯、二乙醇胺和三羟甲基丙烷为原料合成了超支化聚(胺-酯)(HPAE);最后制备出不同HPAE含量(以IPDI与PTMG2000的总质量为基准,下同)的支化型水性聚氨酯(WPU)胶黏剂.采用FTIR和1HNMR对HPAE及胶黏剂的结构进行了表征;通过TGA、多功能材料试验机考察了胶膜的热力学性能和机械性能.结果表明,HPAE用量为IPDI与PTMG2000的总质量的1.0％时,制备的WPU2乳液及胶膜综合性能较好,其乳液固含量为33.67％,胶膜吸水率为11.22％,水接触角为90.32°;胶膜机械拉伸强度为10.33 MPa,断裂伸长率为533.73％;其粘结性能良好,剥离强度为4.063 N/mm.     

Methods to determine solubility parameters of polymers using inverse gas chromatography

Experimental values of the Flory–Huggins parameter, χ, between polymers and solvents, are frequently used to determine the solubility parameters of the polymers. A method using nonlinear curve fitting of RTχ/V was compared to the linear regression method commonly used. It was found that the formulas for the solubility parameter were the same, but the linear method produced a slightly different entropy term. The nonlinear method gave a lower correlation coefficient and wider confidence intervals and was more effective at distinguishing systems than the linear model. The effect of the deviation of probes in the solubility parameter model is discussed. Using probes with low solubility parameters to measure the polymer solubility parameter gave wider confidence intervals. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2894–2902, 2004     

Competitive removal of Pb2+, Cd2+, and Zn2+ by poly(acrylamide‐co‐maleic acid) hydrogels/differential pulse polarographic determination

Poly(acrylamide‐co‐maleic acid) [P(AAm/MA)] hydrogels, with various compositions, were prepared from ternary mixtures of acrylamide (AAm)/maleic acid (MA)/water by using ⁶⁰Co γ‐rays. The effect of composition of these hydrogels, on the competitive removal of Pb²⁺, Cd²⁺, and Zn²⁺ ions from aqueous solution, was investigated. The hydrogel compositions and their adsorption behaviors were determined by use of differential pulse polarography, a very sensitive electroanalytical technique. It was observed that the external stimuli of pH, temperature, and ionic strength have an important role on the adsorption. The increments of MA content in P(AAm/MA) hydrogels caused a significant increase in the adsorption these ions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2401–2406, 2004     

3-十二烷氧基-2-羟丙基三甲基氯化铵水溶液与烷烃的动态界面张力

用旋转滴法测定了3-十二烷氧基-2-羟丙基三甲基氯化铵（R12TAC）水溶液与系列烷烃的动态界面张力（DIFT），考察了浓度、温度和烷烃链长对DIFT的影响，并详细表征了DIFT随时间的变化过程。根据修正的Word-Tordai方程计算了DIFT的有关参数。结果表明：R12TAC浓度越大，DIFT曲线越低，DIFT下降越快，达平衡值的时间越短；随R12TAC浓度的增大，表观扩散系数Da从2．02×10^-10m^-2·s^-1减小到0．14×10^10m^-2·s^-1，吸附势垒Ea从2．60kJ·mol^-1增大到9．32kJ·mol^-1；温度升高，DIFT降低，表观扩散系数Da升高，而吸附势垒降低；固定一种表面活性剂溶液，测定R12TAC／系列烷烃溶液的动态界面张力，发现R12TAC／正己烷体系的DIFT最低，这与表面活性剂在水和油中的溶船度有关。     

Phase characterization and mechanical and flame‐retarding properties of nano‐CaSO4/polypropylene and nano‐Ca3(PO4)2/polypropylene composites

An in situ deposition approach was used for the synthesis of nano‐CaSO₄ and nano‐Ca₃(PO₄)₂. The nanosize particles were confirmed with an X‐ray diffraction technique. Composites of polypropylene (PP) with 0.1–0.5 wt % nano‐ or commercial CaSO₄ or nano‐Ca₃(PO₄)₂ were prepared. The transition from the α phase to the β phase was observed for 0.1–0.3 wt % nano‐CaSO₄/PP and nano‐Ca₃(PO₄)₂/PP composites. This was confirmed by Fourier transform infrared. A differential scanning calorimetry analysis was carried out to determine the thermal behavior of the nanocomposites with increasing amounts of the nano‐CaSO₄ and nano‐Ca₃(PO₄)₂ fillers. Increases in the tensile strength and Young's modulus were observed up to certain loading and were followed by a decrease in the tensile strength. A continuous decrease in the elongation at break (%) was also observed for commercial CaSO₄ and larger nano‐Ca₃(PO₄)₂. A decrease in the mechanical properties after a certain loading might have been due to the agglomeration and phase transition of PP in the composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 670–680, 2007