Numerical simulation of flat-tip micro-indentation of glassy polymers: Influence of loading speed and thermodynamic state

Flat-tip micro-indentation tests were performed on quenched and annealed polymer glasses at various loading speeds. The results were analyzed using an elasto-viscoplastic constitutive model that captures the intrinsic deformation characteristics of a polymer glass: a strain-rate dependent yield stress, strain softening and strain hardening. The advantage of this model is that changes in yield stress due to physical aging are captured in a single parameter. The two materials studied (polycarbonate (PC) and poly(methyl methacrylate) (PMMA)) were both selected for the specific rate-dependence of the yield stress that they display at room temperature. Within the range of strain rates experimentally covered, the yield stress of PC increases linearly with the logarithm of strain rate, whereas, for PMMA, a characteristic change in slope can be observed at higher strain rates. We demonstrate that, given the proper definition of the viscosity function, the flat-tip indentation response at different indentation speeds can be described accurately for both materials. Moreover, it is shown that the model captures the mechanical response on the microscopic scale (indentation) as well as on the macroscopic scale with the same parameter set. This offers promising possibilities of extracting mechanical properties of polymer glasses directly from indentation experiments.     

Jamming and crystallization in athermal polymer packings

Dense packings of chains of hard spheres possess characteristic features that do not have a counterpart in corresponding packings of monomeric spheres especially near the maximally random jammed (MRJ) state. From the modelling perspective the additional requirement that spheres keep their connectivity while maximizing the occupied volume fraction imposes severe constraints on generation algorithms of dense chain configurations. The extremely sluggish dynamics imposed by the uncrossability of chains precludes the use of deterministic or stochastic dynamics to generate all but dilute polymer packings. As a viable alternative, especially tailored chain-connectivity-altering Monte Carlo (MC) algorithms have been developed that bypass this kinetic hindrance and have actually been able to produce packings of hard-sphere chains in a volume fraction range spanning from infinite dilution up to the MRJ state. Such very dense athermal polymer packings share a number of structural features with packings of monomeric hard spheres, but also display unique characteristics due to the constraints imposed by connectivity. We give an overview of the most relevant results of our recent modeling work on packings of freely-jointed chains of tangent hard spheres about the MRJ state, local structure, chain dimensions and their scaling with density, topological constraints in the form of entanglements and knots, contact network at jamming, and entropically driven crystallization.     

High pressure study of the 2D polymeric phase of C60 by means of raman spectroscopy

Abstract

The effect of high hydrostatic pressure, up to 12GPa, on the intramolecular phonon frequencies and the material stability of the two-dimensional tetragonal Cm polymer has been studied by means of Raman spectroscopy in the spectral range of the radial intramolecular modes (200-800cm^?1). A number of new Raman modes appear in the spectrum for pressures ～ 1.4 and ～ 5.0 GPa. The pressure coefficients for the majority of the phonon modes exhibit changes to lower values at P=4.0 GPa, which may be related to a structural modification of the 2D polymer to a more isotropic phase. The peculiarities observed in the Raman spectra are reversible and the material is stable in the pressure region investigated.     

Zinc oxide nanoparticles reinforced conducting poly(aniline-co-p-phenylenediamine) nanocomposite

Zinc oxide (ZnO) nanoparticles were synthesized by thermal decomposition method and formation of composite with conducting copolymer via in situ chemical oxidative polymerization. Transmission electron microscopy showed that the nanoparticles with an average diameter of 15–25?nm were dispersed in the copolymer matrix. The comonomer molecules were adsorbed on the surface of ZnO particles and then polymerized to form core–shell nanocomposite. The obtained nanocomposite showed a significant improvement in the thermal behavior as indicated by thermogravimetric analysis. The nanocomposite was also confirmed by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and X-ray diffraction. Room temperature conductivity of nanocomposite was higher than the value obtained for the pure copolymer. Photocatalytic activity of the nanocomposite was evaluated by measuring the degradation of methylene blue dye under UV irradiation.     

Optical properties of polyvinyl alcohol doped (Se80Te20)100–xAgx (0 ≤ x ≤ 4) composites

Polyvinyl alcohol (PVA) doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) thin films were prepared by the spin-coating technique on a quartz substrate. The optical parameters of PVA-doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) composites at the same chalcogen concentration (S₀ = 0.1 mg ml^?1) and PVA/(Se₈₀Te₂₀)₉₆Ag₄ composites at three different chalcogen concentrations viz. S₁ = 0.3 mg ml^?1, S₂ = 0.6 mg ml^?1 and S₃ = 1 mg ml^?1 have been studied. The semi-crystalline nature of the as-deposited thin filmsisdetermined by X-ray diffraction. The transmission and reflection spectra of PVA-doped Se–Te–Ag thin films were obtained in a 350–650 nm spectral region. The optical-band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical-band gap increases, but the refractive index, extinction coefficient, and the real and imaginary parts of the dielectric constant decrease, with increase in Agcontent in PVA-doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) thin films. Such type of behavior is explained on the basis of decrease in density of the defect states. However, the optical-band gap has been found to be decreased and all other optical parameters show increase in their values with increase in concentration of (Se₈₀Te₂₀)₉₆Ag₄ glass in PVA-doped composites. The results have been explained on the basis of cluster-size formation at the time of dissolution. This study shows that the optical properties of new composites are affected by the change in silver and chalcogen concentration.     

2,6-双(三甲基锡)-4,8-双(2-乙基己氧基)苯并[1,2-b∶4,5-b']二噻吩的合成与多核NMR研究

以苯并[1,2-b∶4,5-b´]二噻吩-4,8-二酮为原料合成了一种聚合物太阳能电池材料的单体2,6-双(三甲基锡)-4,8-双(2-乙基己氧基)苯并[1,2-b∶4,5-b´]二噻吩. 通过多核1D和2D NMR技术（包括1D ¹H、¹³C、¹¹⁹Sn、¹¹⁷Sn NMR、DEPT、选择性1D TOCSY及2D¹H-¹H COSY、gHSQC、gHMBC）表征了目标分子结构,完成了 ¹H、¹³C、¹¹⁹Sn 与¹¹⁷Sn NMR化学位移归属,并探讨了该化合物的NMR谱线特征.     

Resonance Light Scattering Study on the Formation of a Manganese (II) Coordination Supramolecular Polymer and Its Analytical Application

The formation of a manganese (II) coordination supramolecular polymer was studied by resonance light scattering spectra for manganese (II) detection. Bis-sulfosalophen (a ditopic tetradentate Schiff base ligand) and bis-phenanthroline-glutaraldehyde (a ditopic bidentate ligand) were prepared for the construction of the supramolecular polymer. In a procedure of manganese (II) detection, manganese (II) ion reacts with bis-sulfosalophen to form a binuclear manganese (II) complex. The binuclear complex then self-assembles with bis-phenanthroline-glutaraldehyde to form the supramolecular polymer, resulting in the production of strong resonance light scattering signal. The amount of manganese was detected by measuring the resonance light scattering intensity. Under optimal conditions, a linear range was found to be 0.5–50.0 ng/mL, with a detection limit of 0.1 ng/mL. The method has been successfully applied to determine manganese in vegetable and tea samples with relative standard deviations of less than 5% and recoveries of 95.8–105.7%.     

Spectroscopic Studies of the Stability of Doped Polythiophenes Under Air

Abstract

The stability of the doped state of conductive polythiophenes under air was investigated by the use of Infrared (IR) and UV-visible (UV) spectroscopies. Poly(3-methyl thiophene) doped with BF₃-ethyl ether (BFEE). shows higher stability due to its stereoregularity-chain structure. While the doped polythiophene (PT) degrades easily under the moisture.     

金属表面镀高分子膜对真空击穿阈值的影响

探索提高金属表面真空击穿阈值的方法,对脉冲功率技术的发展和应用具有重要意义。在金属表面电子发射理论分析的基础上,采用有限元法计算阴极杆表面电场随二极管电压的变化规律,设计了实验系统,并开展了实验研究。实验对比了在脉宽约30 ns、阴极杆与阳极筒间隙12 mm时,钛合金TC4阴极杆在不同种类高分子膜（膜厚30～60 μm）下真空击穿阈值的变化情况。在表面粗糙度R_z（轮廓最大高度）为0.8 μm的TC4阴极杆表面分别镀环氧树脂膜和丙烯酸膜,实验结果表明,镀丙烯酸膜阴极杆的击穿阈值约505 kV/cm,相对于不镀膜阴极杆,击穿场强提高了约20.6%;在表面粗糙度R_z为0.2 μm的TC4阴极杆表面分别镀聚酰亚胺膜和聚醚醚酮膜,实验结果表明,镀聚酰亚胺膜阴极杆的击穿阈值为584 kV/cm,相对于不镀膜阴极杆,击穿场强提高了约28.1%。因此,在金属表面镀丙烯酸膜、聚酰亚胺膜可以有效提高金属表面的真空击穿阈值。     

一个二维梯状化合物[Ni(μ1，5-dca)2(en)]n的合成，结构和磁性(英)

A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)₂(en)]_n (1) (dca=dicyanamide anion, [N(CN)₂]^-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P2₁/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm³. In this compound, the adjacent nickel atoms are connected by dca all in μ_1，5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276.