Quantification of radiation induced crosslinking in a commercial, toughened silicone rubber, TR55 by H MQ-NMR

Radiation induced degradation in a commercial, filled silicone composite has been studied by SPME/GC-MS, DMA, DSC, swelling, and multiple quantum NMR. Analysis of volatile and semi-volatile species indicates degradation via decomposition of the peroxide curing catalyst and radiation induced backbiting reactions. DMA, swelling, and spin-echo NMR analysis indicate an increase in crosslink density of near 100% upon exposure to a cumulative dose of 250 kGray. Analysis of the sol fraction via Charlesby-Pinner analysis indicates a ratio of chain scission to crosslinking yields of 0.38, consistent with the dominance of the crosslinking observed by DMA, swelling and spin-echo NMR and the chain scissioning reactions observed by MS analysis. Multiple quantum NMR has revealed a bimodal distribution of residual dipolar couplings near 1 krad/s and 5 krad/s in an approximately 90:10 ratio, consistent with bulk network chains and chains associated with the filler surface. Upon exposure to radiation, the mean 〈Ω_d〉 for both domains and the width of both domains increased. The MQ-NMR analysis provided increased insight into the effects of ionizing radiation on the network structure of silicone polymers.     

Why does poly(acrylic acid) addition improve the quality of holograms recorded in dichromated poly(vinyl alcohol)?

Holographic measurements have shown that the addition of 0.5% of poly(acrylic acid) (PAA) can improve the quality of holograms recorded in poly(vinyl alcohol) (PVA) doped with ammonium dichromate (ADC). The purpose of this paper is to explain this improvement. First, an analytical approach investigated the structural and architectural modification of the polymeric matrix and the fate of the various chromium species within PVA/PAA/ADC films. The addition of PAA in dichromated PVA led to a pre-reticulation of the polymeric matrix. This process increased with the amount of PAA.Second, an analytical approach focused on the evolution of PVA/PAA/ADC films upon irradiation at 365 nm, which is representative of hologram formation. The improvement brought by the presence of 0.5% of PAA in PVA/ADC was assigned to an additional source of crosslinking through the formation of covalent bonds. This process paralleled the crosslinking through coordination bonds involving Cr(V) and PVA units. At 0.5% of PAA, the mobility of the medium before exposure was sufficient to allow the migration of the species involved in the reticulation process during hologram formation, whereas higher concentrations of PAA inhibited this migration.     

Morphology development in thermoplastic vulcanizates (TPV): Dispersion mechanisms of a pre-crosslinked EPDM phase

The fragmentation and dispersion in molten polypropylene (PP) of several pre-crosslinked and plasticized ethylene–propylene–diene terpolymer (EPDM) networks was studied. Thus, the morphologies and mechanical properties of PP/EPDM blends having similar compositions but made from either un-crosslinked, pre-crosslinked or dynamic-crosslinked EPDMs were compared. The results first highlight the importance of the gel fraction of the pre-crosslinked EPDMs, as well as the impact of the thermoplastic matrix proportion on the quality of the dispersion of such networks. As a result, pre-crosslinked EPDM having a gel fraction below g_EPDM = 0.7 can be finely and homogeneously fragmented and dispersed in presence of PP. It can be then admitted a collision–coalescence–separation type erosion mechanism of the EPDM domains. Nevertheless, contrarily to some theoretical model expectations, a partial fragmentation of the chemical networks was always observed even at very high crosslink density (g_EPDM > 0.7). Finally, the blends crosslinked under shearing (dynamic-crosslinked) showed a clear mechanical property synergy due to their fine and homogeneous morphology coupled with the full crosslinking of the elastomer. In the end, these results brought significant information on TPV morphology stabilization and their related mechanical properties.     

芳醚酮大环封端聚酰亚胺的合成与交联

本文制备了一种含硫醚键环状芳醚酮单体, 并将其引入聚酰亚胺中, 在不存在引发剂的条件下, 能开环交联反应制备出全芳香高热稳定的可交联聚酰亚胺.     

无皂乳液聚合法制备非球形聚苯乙烯粒子研究

采用苯乙烯(St)、二乙烯基苯(DVB)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为单体,在乙醇和水混合介质中通过无皂乳液聚合法制备了非球形聚苯乙烯(PS)粒子。通过FT-IR、TEM和激光粒度及电位分析仪对粒子的结构、形貌、粒径以及Zeta电位进行了表征。结果表明,所合成PS粒子均含三种单体结构单元,且形貌上均为非球形;随着DVB用量的增加,PS粒子形貌更趋于球形,粒径和单分散系数均逐渐增加;随DMC用量增加,PS粒子粒径随之增加,单分散系数逐渐减小,表面Zeta电位也逐渐增加;KHCO3用量的增加能使PS粒子粒径和单分散系数均增加;随着醇水比的减小,PS粒子粒径逐渐减小,而单分散系数则逐渐增加。     

电化学阻抗谱研究聚合物凝胶电解质对染料敏化太阳能电池性能的影响

用甲基丙烯酸β-羟乙酯(HEMA)与N-乙烯基吡咯烷酮(NVP)共聚物P(HEMA-NVP)、甲基丙烯酸甲酯(MMA)与N-乙烯基吡咯烷酮共聚物P(MMA-NVP)为原料制备了聚合物凝胶电解质, 用电化学阻抗谱(EIS)研究了聚合物凝胶电解质中聚合物基质的结构与组成对准固态染料敏化太阳能电池(DSSCs)光伏性能的影响. 不同交联剂用量、不同HEMA用量的P(HEMA-NVP)共聚物及不同MMA用量的P(MMA-NVP)吸收液态电解质后分别形成HGelI、HGelII、MGel凝胶电解质. 结果发现, 随共聚物P(HEMA-NVP)中交联剂由0.1%(w, 下同)增大到0.6%时, 形成的HGelI 组装的DSSCs的光电转化效率(η)先增大后降低, 交联剂用量为0.4%时, DSSCs的η为最大, 为5.54%(光强100 mW·cm^-2). 同时, 比较HGelII 系列和MGel 系列DSSCs的光电性能参数发现, 含有羟基的HGel 系列的η要高于MGel 系列, 而后者的开路电压(V_oc)值高于前者. 在HGelII 系列中, HEMA含量为60%(w)时, DSSCs的η最高. 电化学阻抗谱分析表明共聚物中交联结构的不同影响了电池内部的界面阻抗及离子的传输, 引入羟基有利于降低界面阻抗. 通过调整共聚物中交联剂用量和羟基含量可改善DSSCs的光伏性能.     

红外光谱分析用于双酚A型环氧树脂的实验教学

通过红外光谱的实验教学,学生掌握了在高温和空气中氧的共同作用下,环氧树脂会发生一系列化学变化,从而发生老化甚至失效。通过特定官能团的跟踪分析,学生全面学习和掌握了环氧树脂从固化到老化红外光谱分析的全过程。     

不同热交联气氛对含氟聚芳醚近红外光学吸收的影响

光波导材料对于光通信及光互联产业的发展起着至关重要的作用,例如可用来制作波分复用系统中的光衰减器,热光开关,阵列波导光栅复用／解复用器,光滤波器等．聚合物材料由于其容易加工,与无机材料相比有相对较低的制作成本,而从众多光波导材料中脱颖而出．目前光通讯材料与器件的研究应用主要集中在1．3和1．55μm两个波长上,然而随着波分复用(WDM)技术的发展,     

Monoacylation of unprotected symmetrical diamines with resin-bound benzoic acids

A protocol for monoacylation of unprotected symmetrical diamines with a resin-bound benzoic acid is described. The nature of the resin (gel-based polystyrene vs highly crosslinked macroporous polystyrene) was found to play a minor role in acylation selectivity. Rather, the concentration of the diamine dictates the ratio of mono- and diacylated products. Thus, by employing a high concentration of symmetrical diamine (e.g., 1 M, 20 equiv), monoacylation can be selectively achieved for a variety of unprotected symmetrical alkyl and aryl diamines.     

Crosslinked carboxymethyl cellulose-sodium borate hybrid binder for advanced silicon anodes in lithium-ion batteries

Hybrid gel binder with deformable network and strong adhesive capability on silicon particles can effectively accommodate the large volume change of silicon anodes upon cycling, leading to an excellent cycling stability and high Coulombic efficiency.