The influence of orientation on the radiation-induced crosslinking/oxidative behavior of different PEs

This paper studies the influence of orientation and structural peculiarities on the radiation-induced oxidation/crosslinking changes in different polyethylenes (PEs). For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) were oriented via solid-state stretching at an elevated temperature. Later on, oriented samples were gamma-irradiated in air to various absorbed doses (up to 700 kGy). In order to investigate orientation- and radiation-induced changes in morphology, surface microstructures were analyzed by optical (OM) and scanning electron microscopy (SEM). Differential scanning calorimetry (DSC), IR spectroscopy and gel measurements were used to determine changes in crystallinity, oxidative degradation and degree of network formation, respectively. Conclusions derived according to these methods were compared. The differences in morphology, crystallinity, oxidation and gel behavior are caused primarily by the structural peculiarities of different types of PEs, the heterogeneous nature of radiation effects in semicrystalline polymers and, in the case of oriented samples, by the molecular orientation as well. The presented results reveal complicate crosslinking behavior with orientation while increase/decrease in crystallinity/oxidation with draw ratio was clearly evident.     

辐射交联聚氯乙烯绝缘材料的研究Ⅱ.添加一缩三乙二醇二丙烯酸酯的影

本文研究了聚氯乙烯(PVC)在添加一缩二乙二醇二丙烯酸酯双官能团单体(DGDA)条件下的辐射交联效应。辐射初期PVC的交联反应速度较快,当剂量达到40kGy以后,凝胶含量达到最大值。在相同剂量条件下,PVC的凝胶含量、交联G值随DGDA添加量的增加而提高。交联PVC比未交联PVC的体积电阻系数有明显的提高,说明PVC辐射交联后的电绝缘性能得到很大改善。交联后,它的机械性能也有一定的提高。辐射交联PVC的热老化失重比未交联的PVC有较大的减少,而拉伸强度残留率K_1和断裂伸长率残留率K_2比未交联的PVC有较大提高,也就是说PVC交联后的耐温性提高了。     

辐射交联法制备微孔化硅橡胶的研究

采用辐射交联法制备微孔化硅橡胶材料,实现硫化与发泡分步进行,是探索射线技术用于制备高性能微孔材料的一种新方法。以二氧化硅为填料,以电子加速器为射线源辐照实现硅橡胶的硫化,再经高温发泡为微孔材料。主要研究辐照条件、填料含量等关键因素对硅橡胶性能与结构的影响,并用扫描电镜观察泡孔的形态结构。结果表明,通过控制吸收剂量和填料含量等条件,实现了硅橡胶材料微孔化。微孔化硅橡胶材料表面光滑,接近橡胶形态,而材料内部具有丰富的μm级小孔,孔壁完整,孔与孔间彼此不贯通,泡孔细小,胞体尺寸（平均）最小达14 μm,泡孔的均匀性好,其力学性能较好。     

Thermal characterization of the HDPE/LDPE blend (10/90) irradiated using γ-rays

Gamma irradiation effect over the properties of slow cooled and fast cooled HDPE/LDPE 10/90 blend was studied. The blend and the neat polyethylenes were irradiated at room temperature in the presence of air using the following doses (4.8 kGy/h): 0, 50, 150, 400 and 1000 kGy. Differential scanning calorimetry (DSC) experiments were carried out using the following heating rates: 5, 10 and 20 °C/min. DSC results for the slow and fast cooled blend showed traces with three melting peaks and with increasing irradiation dose two melting peaks were obtained, i.e. the high melting peak shifts toward lower temperatures to merge with the intermediate melting peak into one endotherm. No changes in crystal structure by X-ray diffraction were found as a result of samples irradiation. Radiation crosslinking prevents crystal rearrangements during heating in the DSC. Gel content and melt flow index (MFI) measurements showed that radiation induced a high degree of crosslinking for all samples; gel content values were above 50% and a drop of more than 90% in the MFI was found. Irradiation of slow cooled samples resulted in larger values of gel content and lower MFI values than for fast cooled samples, mainly because of the higher degree of crosslinking for the former.     

γ辐照羧基丁苯胶乳的研究

研究了以丙烯酸－2－乙基己酯（2－EHA）为交联酶化剂，γ辐照对羧基丁苯胶乳（CS－BRL）的交联行为，粒径大小、分布以及化学结构和热性能的影响，并推测了CSBRL辐射硫化的反应机理，结果表明，一率对CSBRL的交联行为影响不大；随着吸收剂量增大，交联密度急剧增大，体积溶胀度迅速减小，交联点间平均分子量减小，交联密度还随着敏化剂用量增加而增大。动态光散射仪的测试表明，吸收剂量＜25kGy时，胶乳的流体力学半径与辐照前相比变化不大，当吸收剂量增大到102kGy时，流体力学半径与辐照前相比稍有增加。显微傅立叶红外光谱证实CS－BRL不仅被辐射交联，还接枝上了丙烯酸酯，DSC分析表明，未加敏化剂的CSBRL玻璃化温度随剂量增加变化不大，而加入3％敏化剂的CSBRL的DSC曲线变化很大。     

Synthesis and properties of radiation modified thermally cured castor oil based polyurethanes

Thermally cured polyurethanes were prepared from castor oil and hexamethylene diisocyanate (HMDI). Due to the long aliphatic chain of the castor oil component of polyurethane, thermal curing of castor oil based polyurethane (COPU) is limited by increasing polymer viscosity. To enhance further crosslinking, COPUs were exposed to doses up to 3.0 MGy produced by the mixed ionizing radiation field of a SLOWPOKE-2 research nuclear reactor. The physico-mechanical properties of castor oil based polyurethanes (COPU), unirradiated and irradiated, were characterized by mechanical tensile tests. A four-fold increase in modulus and tensile strength values from 0.930 to 4.365 MPa and 0.149 to 0.747 MPa, respectively, suggests improved physico-mechanical properties resulting from radiation. The changing areas of the carbonyl and the NH absorbance peaks and the disappearance of the isocyanate peak in the FTIR spectra as radiation progressed, indicates increased hydrogen bonding and intermolecular crosslinking, which is in agreement with the mechanical tests. Unchanging ¹³C solid state NMR spectra imply limited sample degradation with increasing radiation.     

γ射线辐照改性聚碳硅烷提高热解陶瓷产率

在N2气中用γ射线对聚碳硅烷(Polycarbosilane,PCS)进行辐照,利用傅里叶红外光谱分析、凝胶渗透色谱分析和热重分析等手段研究了不同吸收剂量下PCS的化学结构、分子量和热分解特性。结果显示,经γ射线辐照处理后的PCS轻微失重,分子量和软化点随着吸收剂量的增加而增加,说明PCS经辐照后发生了分子间的交联反应。红外分析表明,PCS的交联主要是通过Si-H键和C-H键的断裂产生新的Si-C-Si结构实现的。热重分析表明,PCS热解为碳化硅的陶瓷产率随吸收剂量的增加显著升高,剂量达到1.5 MGy后PCS样品的陶瓷产率基本提高到稳定值,此时,陶瓷产率从改性前的61.9%提高到80.0%。     

Radiation effects on styrene-butadiene-styrene copolymer

Styrene-butadiene-styrene copolymer (SBS) of different configuration and block ratio were irradiated by ⁶⁰Co γ-rays at 20 °C and 120 °C. The gel fraction and thermal properties before and after irradiation were discussed. The gel fraction increased with both absorbed doses and temperature. This means higher crosslinking efficiency was obtained at higher temperature. The radiation chemical yields were calculated according to the Charlesby-Pinner equation. The DSC analysis indicated that the crosslinking had taken place in the polybutadiene (PB) block while the chain scission of polystyrene (PS) block was dominant when irradiated at elevated temperature.     

The effect of radiation on the properties of silicone rubber

As a result of -radiation, silicone rubber undergoes a series of changes due to radiation cross-linking. The modulus of elasticity increases linearily with a dose up to 150–200 megarads. The vitrification temperature (– 120 to- 125 ° C) hardly changes up to 100 megarads and at 270 megarads it is –110 to –115 ° C. With cross-linking, the rate of crystallization and degree of crystallinity decrease. The melting point falls from – 35 ° C for the initial material to – 55 ° C for rubber Irradiated with a dose of 40 megarads. A dose of 100 megarads practically completely eliminates crystallization. This dose produces rigid rubbers with a modulus of 200– 250 kg/cm² and a high degree of frost resistance, (Tg –125 ° C), but with a very small breaking stretch (15–20%) with a strength of 30–40 kg/cm².     

Improvement of poly(vinyl alcohol)/poly(vinylpyrrolidone) blended hydrogel by radiation crosslinking

1IntroductionHydrogelisapolymericmaterial(syntheticornaturaJ)whichswellswhenplacedincontactwithwaterbutisnotsolubleandhastheabililtytoretainwaterwithinitsstructare.InIecentyears,muchattentionhasbeenfocusedontheresearchanddevelopmentofthepolymerhydIogelsforbiomaterials,suchascontactlenses,wounddressing,enzymeimmunoassay,cathetersanddIugdeliverysystems[1~3].Adressingisoftencoveredonthewotmdtoaccelerateitshealing.TheIearetwokindsofdiessings:drytypeandwettype.Ithasbeenreportedthatheallngwithawe…