DSC monitoring of supermolecular structure damage of polyethylene products

Investigated materials were produced from polyethylene of low density (PE-LD) and a filler: carbon black or chalk. A part of the samples was kept in ambient temperature over several months in order to study the effect of material ageing. The qualitative conclusions were drawn based on a precise analysis of shape of DSC curves and the basic investigations of PE morphologies known from literature. The influence of the thermal history and the filler contents on the amount and kind of crystal phase was established. Additionally, the effect of the measurement technique, in our case it was positron annihilation lifetime spectroscopy (PALS), on the morphological feature changes was found. The paper serves selected examples of problems solved by DSC. However, from the other hand, the authors discuss critically the opportunity given by this method.     

聚苯基单醚喹噁啉薄膜的性能与物理老化

研究了物理老化对聚苯基单醚喹啉薄膜的结构与力学性能的影响 .用差示扫描量热计 (DSC)及正电子湮没寿命谱 (PALS)方法表征了两种不同物理老化条件试样的凝聚结构以及自由体积的差别 .结果表明 ,物理老化使聚苯基单醚喹啉薄膜玻璃化转变温度移向高温 ,在其末端出现热焓吸收峰 ,分子链堆砌紧密使自由体积减小 ,分子可动性降低 .用动态力学分析 (DMTA)以及静态拉伸性能测试等方法研究了两类试样的力学性能 ,结果表明 ,物理老化后 ,试样的动态储能模量稍有增加 ,力学损耗降低 .而静态拉伸实验的断裂应变降低 ,屈服应力增加 ,断裂能降低 ,试样在宏观上由韧性断裂变为明显的脆性断裂 .     

Physico-mechanical and free volume behaviour of guar gum filled polyurethane/polyacrylonitrile biodegradable composites

A series of different weight ratios of guar gum viz. 5, 10, 20 and 30 were incorporated into polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi interpenetrating polymer networks (SIPNs) using polyethylene glycol-400, 4,4′-diphenyl methane diisocyanate, acrylonitrile, benzoyl peroxide and new metallic catalyst. The obtained polymer composites were subjected to biodegradation studies using specific fungi Aspergillus niger. The composites are characterized for physico-mechanical properties like density and tensile behaviour of the specimens before and after biodegradation. The positron annihilation lifetime spectroscopy (PALS) was used to monitor the content of free volume before and after biodegradation. The extent of degradation was examined by change in tensile behaviour and surface morphology. The influences of fungi on mechanical and morphological behaviour of filled IPNs are found to be interesting. The free volume changes in the composite systems correlates well with the mechanical properties.     

Research activities at the PALS research infrastructure

The Prague Asterix Laser System (PALS) Research Infrastructure (RI) in Prague, one of only four kJ-class laser facilities in EU, has been offering its beam time to European researchers for already 14 years, since 2004 in the framework of the LASERLAB-Europe consortium. Till June 2014, the PALS RI has provided 4313 experimental days for a total of 41 projects with 303 international users from 42 different research institutions. Its principal experimental facility is a terawatt sub-ns iodine laser (1315?nm) with an optional plasma-based zinc XUV laser (21.2?nm), and an auxiliary Ti:Sapphire fs laser (1?J, 70?fs) exploited for femtosecond plasma probing and experiments with synchronised femtosecond and sub-nanosecond laser pulses at mean laser intensities of up to 30?PW/cm². The lasers are equipped with several target facilities and rich sets of instruments for both active and passive plasma diagnostics. The PALS main research areas include development and applications of secondary laser sources of high-energy ions and both coherent and non-coherent high-intensity XUV radiation, laboratory astrophysical and inertial fusion-relevant studies. In this paper, the main results having been achieved at PALS in the framework of LASERLAB-EUROPE international access activities during the last four years are highlighted.     

Correlation between nanohole volume and mechanical properties of amine‐cured epoxy resin blended with poly(ethylene oxide)

A set of diglycidylether of bisphenol‐A (DGEBA)/4,4′‐diaminodiphenylmethane (DDM) epoxy matrix modified with poly(ethylene oxide) (PEO), pre‐cured at two different temperatures, was examined by positron annihilation lifetime spectroscopy (PALS). The aim was to investigate the correlation between local free volume and mechanical properties. A negative deviation from the linear additivity rule of the local free volume is observed at both cure schedules. Using together the local free volume and mechanical results allows to conclude that the cure temperature makes small contribution to the flexural strength and modulus of blends but is responsible for the composition‐dependent rise of the fracture toughness. It is proposed that this behavior is a consequence of the nearest‐neighbor intrachain contacts or self‐association of the epoxy‐OH groups during cure leading to a non‐uniform space distribution of the DGEBA–PEO contacts, which causes the deflection of the crack path. Copyright © 2008 John Wiley & Sons, Ltd.     

纳米ZnO／环氧树脂复合材料的力学性能和摩擦学性能

在超声波作用下，利用偶联剂将ZnO纳米微粒同环氧树脂进行复合，制备了纳米ZnO／环氧树脂复合材料，用M-2000型摩擦磨损试验机评价了复合材料在干摩擦条件下同不锈钢对摩时的摩擦学性能，测定了复合材料的力学性能，并用正电子湮没寿命技术(PALT)分析了试样的微观结构．结果表明：纳米ZnO／环氧树脂复合材料的耐磨性优于环氧树脂；当纳米ZnO的质量分数为10％时，复合材料的磨损率最小，仅为环氧树脂的15％，且摩擦系数也有所降低；摩擦后复合材料试样的自由体积孔穴尺寸有所增大，而且随着ZnO含量的增加，自由体积孔穴尺寸呈增大趋势．     

Addition-type polynorbornene with Si(CH3)3 side groups: Detailed study of gas permeation and thermodynamic properties

Polymerization of norbornene bearing Si(CH₃)₃ groups in the five position with the opening of double bonds was performed. By accurate selection of the ratios catalyst/co-catalyst and monomer/catalyst the samples with increased molecular mass (about 400,000) were obtained. Transport parameters of this, addition type poly(trimethylsilyl norbornene) (PTMSN) were measured using the gas chromatographic and mass spectrometric methods for different gases (H₂, He, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈ and n-C₄H₁₀). Temperature dependence of the permeability coefficients (P) indicated that low activation energies of permeation (E_P) and diffusion (E_D) are characteristic for PTMSN. In some cases (CO₂, C₂H₆) negative E_P values were observed. Thermodynamics of vapor sorption in this polymer was studied using the inverse gas chromatography method. It was shown that PTMSN is characterized by very large solubility coefficients S similar to those of poly(trimethylsilyl propyne) (PTMSP). The comparison of the P, D, and S values of these highly permeable polymers showed that the greater permeability of PTMSP is determined by the larger D values. Application of different approaches for the determination of the size of microcavities in PTMSN indicated that this polymer is characterized by large size of microcavity (800–1200 ?³).     

Effect of KOH molarity and annealing temperature on ZnO nanostructure properties

In this work, ZnO nanorods (NRs) were fabricated using a low cost chemical bath deposition (CBD) method. The effect of the potassium hydroxide concentration on the fabricated ZnO nanostructures was studied in depth. The optical, structure, and surface morphology properties of the fabricated ZnO nanostructures were investigated using Uv-vis spectroscopy, XRD, and SEM. The results indicate that the formation of hexagonally structured ZnO nanorods with different lengths and diameters was dependent on the KOH concentration. The sample prepared with 2 M of KOH was the best one for optoelectronic applications, since it has the smallest diameters. This sample was annealed at different temperatures (473 K–1073 K). Positron Annihilation Lifetime Spectroscopy was used to determine the defects in the ZnO nanorods. The results show that the positron mean lifetime (τ_m) decreased as the annealing temperature increased, which means that the overall defects in the ZnO nanorods decreased with increasing temperature. Consequently, higher performance semiconductor devices based on ZnO nanorods could be fabricated after high annealing of the ZnO nanorods.     

明胶大分子中的正电子湮没行为

利用正电子湮没寿命谱 ,从分子尺度上对两种分别从深海鱼皮和牛骨提取的明胶大分子的微观结构性能进行了研究 .正电子湮没寿命谱的长寿命组分给出了关于明胶大分子中自由体积空穴的信息 .结果表明 ,鱼明胶大分子中自由体积空穴的尺度与数量均低于骨明胶大分子 .同时 ,用鱼明胶和骨明胶作为成核分散介质的乳剂试验表明 ,鱼明胶可以改善卤化银颗粒的单分散性并抑制晶核的生长和聚结 .由此认为 ,明胶作为保护性胶体的功能与其微结构特征相关 .鱼明胶在控制卤化银颗粒成核与生长中的功能强于骨明胶 .     

Free volumes evolution during desorption of n-heptane from silica with regular pore geometry. Positron annihilation study

The mechanism of n-heptane evaporation from mesoporous MCM-41 silica was investigated by positron annihilation lifetime spectroscopy (PALS). Experiments were performed in situ during desorption of hydrocarbon under stepwise lowered pressure. Desorption is a quasicontinuous process that corresponds to emptying various types of free volumes in the silica/n-heptane system, including mesopores. Insight into the kinetics of desorption was derived from the changes of PALS spectra associated with succeeding stages of pore emptying. For the investigated system emptying of pores and formation of bubbles in the n-heptane condensate present in regular pores were found to take place at various bulk saturating vapour pressure of the fluid.