氧气氛中紫外光辐照官能化HDPE的结构与性能研究

采用FT－IR，XPS，WAXD，DXC，凝胶和表面自由能力分析，研究了氧化氛中紫外辐照官能化高密度聚乙烯（HDPE）的化学结构、晶体结构和表面自由能的变化。与空气相比，在氧气氛中紫外辐照HDPE能提高C－O，C（＝O）O和C＝O等含氧基团的引入速度，同时又能降低HDPE中的凝胶含量，在空气和氧气氛中紫外辐照后，HDPE的晶型没有发生变化，仍为正交晶系；HDPE的晶胞参数a,b,c以及（110），（200），（020），（011），（111）等晶面间距基本保持不变；HDPE的熔融温度下降，但熔融热焓升高，结晶度增大，表面自由能增大，且在氧气氛中辐照HDPE的变化幅度较大。     

The surface modification of carbon fiber for thermoplastic HDPE composites

The interfacial adhesion strength between the fiber and the matrix greatly affects the properties of the carbon fiber (CF)–reinforced composite. The presence of surface functional groups on the fiber and changes in surface roughness were determined by X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), and Raman spectroscopy. The effect of surface modification of CF on the mechanical properties and tribological properties of the composites is enhanced. The performance has been significantly improved. SEM analysis showed that modification had a positive effect on the interface between fiber and matrix. In the paper, the method of CF modification and the treatment of enhanced high-density polyethylene have simple and effective characteristics, which can be widely used and have guiding significance for industrial production.     

紫外线辐照光强对HDPE化学结构及对HDPE/PC共混体系增容效应的影响

采用FT-IR,XPS,凝胶分析以及熔融指数、接触角和力学性能测定,研究了不 同紫外辐照光强对高密度聚乙烯（HDPE）的化学结构、流动性、亲水性和辐照改性 HDPE在HDPE/聚碳酸酯（PC）共混体系中的增容效应的影响。在相同辐照时间下, 随紫外光强提高,引入HDPE分子链的含氧基团数量增加;在辐照过程中,紫外光强 对HDPE的交联有显著影响,在较低光强（32W/m~2）下辐照24h的HDPE无凝胶生成, 便在较高光强（45和78W/m~2）下辐照24h后,HDPE产生凝胶,其含量随紫外光强提 高而增多;与未辐照HDPE相比,较高光强下辐照HDPE的熔融指数有所下降,但其亲 水性得到明显改善;紫外辐照改性HDPE对HDPE/PC体系有增容作用,随紫外光强提 高其增容效应明显增强。与未增容HDPE/PC（80/20）体系相比,加入20%辐照 24hHDPE（光强78W/m~2）的HDPE/PC共混物的拉伸屈服强度从26.3MPa提高到30. 2MPa,缺口冲击强度从51J/m提高到158J/m。     

Synthesis and characterization of C60/polyaniline composites from interfacial polymerization

C₆₀/polyaniline (PANI) nanocomposites have been synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in the presence of C₆₀ by using an interfacial reaction. When compared with the pure PANI nanofibers from the similar process, the diameter of the obtained C₆₀/PANI nanofibers was increased because of the encapsulation of C₆₀ into PANI during aniline polymerization, which resulted from the charge‐transfer interactions between C₆₀ and aniline fragment in PANI. In addition, the resulting C₆₀/PANI nanocomposites synthesized from the low initial C₆₀/aniline molar ratio (less than 1:25) showed the homogenous morphology composed of fiber network structures, which has an electrical conductivity as high as 1.1 × 10^?4 S/cm. However, the C₆₀/PANI nanocomposites from the higher initial C₆₀/aniline molar ratio (more than 1:15) showed the nonuniformly distributed morphology, and the electrical conductivity was decreased to 3.5 × 10^?5 S/cm. Moreover, the C₆₀/PANI nanocomposites from the interfacial reaction showed a higher value of electrical conductivity than the mechanically mixed C₆₀/PANI blends with the same C₆₀ content, because of the more evenly distributed microstructures. FTIR, UV–vis, and CV data confirmed the presence of C₆₀ and the significant charge‐transfer interactions in the resultant nanocomposites, which was responsible for the morphology development of the C₆₀/PANI and the variation of the electrical conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Effect of Ultraviolet Irradiation on Structure and Properties of HDPE and HDPE/STC Blends

Abstract

Some oxygen‐containing groups such as C?O and C–O were introduced onto high‐density polyethylene (HDPE) chains by an ultraviolet irradiation technique without the addition of any additives, and this method causes no chemical pollution to the environment. This groups content increases with irradiation time. Gelation took place in the HDPE irradiated for 16?hr, and the gel content also increases with irradiation time. After irradiation, the crystal shape and crystalline plane spacing of HDPE remained unchanged; the melting temperature decreased, whereas the crystallinity and hydrophilicity increased. Due to the introduction of polar groups, the interfacial interaction between sericite–tridymite–cristobalite (STC) particles and irradiated HDPE, and the mechanical properties of irradiated HDPE/STC (60/40) blend were improved. Compared with the yield and impact strength of HDPE/STC (60/40) blend, those of the corresponding blend irradiated for 16?hr were increased from 25.1?MPa and 56?J/m to 29.1?MPa and 283?J/m, respectively.     

Ultraviolet weathering of HDPE/wood-flour composites coextruded with a clear HDPE cap layer

This study examined the effect coextruding a clear HDPE cap layer onto HDPE/wood-flour composites has on the discoloration of coextruded composites exposed to accelerated UV tests. Chroma meter, FTIR-ATR, XPS, SEM, and UV vis measurements accounted for the analysis of discoloration, functional groups, and degree of oxidation of both uncapped (control) and coextruded composites before and after UV exposures. Two separate discoloration characteristics occurred in the discoloration of composites. For uncapped WPCs (control), chemical changes due to photooxidation resulted in darkening followed by physical changes, including loss of colored wood components from the surface, as well as increased roughness on the surface, which led to lightening of WPCs. By contrast, because a hydrophobic cap layer prevented the loss of colored components from the surface, coextruding a clear hydrophobic HDPE cap layer over WPCs significantly decreased the discoloration during the weathering process. Photooxidation of wood components at the interface accounted for the discoloration of coextruded WPCs before the failure of cap layer. Moreover, as the cap layer absorbed a specified amount of UV light and reduced oxygen available to interface, it decreased the photooxidation rate at the interface compared to that at the WPCs surface.     

高密度聚乙烯/石墨导电复合物的PTC行为及其热循环稳定性

研究了高密度乙烯／石墨导电复合物的PTC行为及其影响因素,揭示了内应力随温度升高而松驰对PTC效应的贡献。复合物的导电性能与PTC行为是电导网络的总体结构及其随温度的变化所决定的,与材料组分性质以及各组分之间的相互作用关系不大。当环境温度趋于基体熔点时,复合物热学性质的变化造成导电网络的大规模破坏,是PTC行为产生的根源。热处理等物理手段可改变导电网络的微观结构,但不影响PTC行为赖以产生的物理机制,也不能有效改善PTC行为的热循环稳定性。     

HDPE／NBR共混物结构和性能的研究

本文对高密度聚乙烯(HDPE)/丁腈橡胶(NBR)共混物的组成、结构、性能和相互作用进行了研究。实验结果表明:少量的NBR能大幅度提高HDPE的冲击韧性和耐环境应力开裂性能。WAXD显示NBR在共混物中呈现一定程度的取向;TEM显示NBR能以平均粒径为0.2 μm的尺寸分散于HDPE中,且形成较牢固的结合;DMA分析发现HDPE与NBR间相互作用而引起α、γ、T_(?)转变温度发生变化。本文对HDPE与NBR相互作用的机理进行了讨论。     

Effect of Electron Beam Irradiation and Ethylene Vinyl Acetate Copolymer on the Properties of NBR/HDPE Blends

The mechanical and physical properties of blends based essentially on nitrile butadiene rubber (NBR) and different ratios of high density polyethylene (HDPE) up to 25 parts per hundred part of rubber (phr) before and after electron beam irradiation were investigated. The values of tensile strength (TS), tensile modulus at 50% elongation (M₅₀), hardness and gel fraction % (GF%) of NBR/HDPE blends were increased with both irradiation dose and by increasing the content of HDPE in the blends. On the other hand, the values of elongation at break (E _b ) were decreased with both irradiation dose and the content of HDPE in the blends. By loading NBR/HDPE (100/25) blend with ethylene vinyl acetate (EVA) copolymer the mechanical and physico-chemical properties were improved. Moreover, the degree of improvement is proportional to the loading content of EVA.     

Synthesis and Characterization of Composite Materials HDPE/HA and PMMA/HA Prepared by Sonochemistry

Summary : In the present work, the synthesis and characterization of composite materials based on HDPE, and PMMA with nanometric hydroxyapatite, are studied. Composites preparation was carried out by dilutions of the commercial polymers, using decaline as solvent for the polyolefin and 2-butanone for PMMA. In the synthesis of Hydroxyapatite (HA), ammonium phosphate [(NH₄)₂HPO₄] and calcium hydroxide [Ca(OH)₂] were used as precursors. Composites with 20, 30 and 40 wt% of HA were prepared. The polymer dilutions and the precursors of the HA were placed simultaneously in a reactor under ultrasonic radiation at 20 kHz, for periods of 15, 25 and 35 min. The products obtained were characterized by FTIR, TGA, TEM, XRD and biocompatibility studies were also carried out. The results showed the presence of nanometric HA and clear interactions between HA and PMMA polymers were observed by FTIR. These results were corroborated by TEM showing that nanometric HA particles are encapsulated into the polymeric PMMA matrix. For the composites of HDPE, these interactions were not observed.     

环境温度对紫外辐照HDPE结构与性能的影响研究

采用元素、XPS、GPC分析，凝胶和力学性能测定，研究了空气中不同环境温度下紫外辐照官能化HDPE的结构、粘着性以及紫外辐照官能化HDPE对HDPE/聚乙烯醇(PVA)体系的增容作用。实验结果表明，提高环境温度可显著提高引入C-O、C(=O)O和C=O等含氧基团的速度。在相同辐照时间下，随环境温度提高，辐照HDPE的分子量下降、分子量分布变宽以及剥离强度提高的幅度增大，并在70℃时产生凝胶。较高环境温度下辐照的HDPE对HDPE/PVA共混体系有较好增容作用，在HDPE/PVA(83/17)体系中加入10%(质量分数)的70℃环境温度下辐照24h的HDPE，共混物的拉伸屈服强度和缺口冲击强度分别从30.8MPa和110J/m提高到34.9MPa和142J/m。     

MWNTs/HDPE复合体系在太赫兹波段的光电性质

利用太赫兹时域光谱技术和电导测量研究了多壁碳纳米管/高密度聚乙烯(MWNTs/HDPE)复合体系的光电性质. 直流电导率结果表明, 复合体系的逾渗阈值在5%左右; 交流电导率则随频率的变化出现一个拐点, 拐点的位置与颗粒浓度以及导电颗粒的存在状态密切相关. 加入碳纳米管后, 复合体系在太赫兹波段的吸收系数和折射率均有很大的提高. 通过假定在此波段导电颗粒在聚合物中的介电行为类似于偶极子的弛豫, 利用Cole-Cole理论对复合材料的介电性质进行了解释.     

Surface modification of magnetic metal nanoparticles and its influence on the performance of polymer composites

To control the interfacial interaction in magnetic metal nanoparticles‐filled polymer composites, surfaces of iron, cobalt, and nickel nanoparticles were grafted by irradiation‐induced polymerization. On the basis of the study of dynamical mechanical behavior, thermal stability, and magnetic performance of the composites prepared by either solution mixing or in situ polymerization, the structure–property relationships of the composites are a function of interfacial interaction and the dispersion state of the nanoparticles. In addition, grafting of polymers onto the surface of the metal nanoparticles changed the surface magnetic state, leading to the possibility of purposely tailoring the magnetic behavior of the composites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1070–1084, 2003     

iPP/HDPE/CB复合材料的制备及反常的温度-电阻效应

本文利用普通熔融挤出法制备了iPP/HDPE/CB复合材料, 分别采用注射成型及压制成型方法得到测试试样. 通过研究复合材料体积电阻率随温度的变化, 考察注塑试样和压制试样的PTC特性及复合材料形态结构与试样PTC特性之间的关系.     

Acyclovir release from its composites with silica as a function of the silica matrix modification and the drug loading

Acyclovir release from its composites with unmodified silica at pH 1.6 and 7.4 follows zero order kinetics for two days. Modification of the silica matrix with phenyl groups leads to dramatic decrease in the drug release level at pH 7.4 compared with pH 1.6 as well as to heterogeneous phase state of acyclovir in the phenyl modified composite with high loading of the drug.     

Effects of plasma treatment of carbon fibers on interfacial properties of BMI resin composites

High performance continuous fiber surface modification by inductively coupled RF plasma (ICP) and dielectric barrier discharge (DBD) low temperature plasma were conducted. X-ray photoelectron spectroscopy (XPS) and other analytical testing methods systematically studied plasma treatment time, discharge power, discharge pressure, etc, on fiber surface state, surface composition, and surface shape changes in the appearance and wetting properties. The results show that after plasma treatment the surface of the fiber is grafted with a large number of polar functional groups such as carboxyl groups and hydroxyl groups. The surface roughness increases, the surface free energy increases, and the fiber wetting property is significantly improved, resulting in improvement in interlaminar shear strength (ILSS) between the fiber and the resin matrix. Finally, the surfaces of the fibers and its relationship with interfacial properties of fiber reinforced bismaleimide composites are also discussed.     

电子束辐照交联CB/HDPE凝胶复合物的阻温特性

对电子束辐照交联并经溶剂抽提得到的炭黑/高密度聚乙烯(CB/HDPE)凝胶复合物的阻温特性进行了研究.结果表明,凝胶复合物与未抽提的交联试样和未交联试样相比,其PTC强度显著增大,并伴有明显的NTC现象.经热冷循环后,表现出很好的阻温特性稳定性,并且NTC现象消失.表明阻温特性的稳定性及NTC现象的消除强烈依赖于CB/HDPE导电复合材料凝聚态结构的稳定性     

Thermal Behaviour of Blends of HDPE with Long-chain Branched HBPE

The thermal behaviour of new blends on the base of high-density polyethylene (HDPE) and of long-chain branched polyethylenes (HBPE) made by means of new metallocene catalysts has been studied by DSC in relation to the melting and crystallisation characteristics and discussed in the phase behaviour of the mixtures. While HBPE's with 7.5 to 12 per cent by mass of octene as comonomer in the blends with HDPE are relevant for the formation of homogeneous composition regions. Especially, with higher HBPE contents, the phase separation and splitting of the melting and crystallisation peaks is observed. This behaviour has not been observed with 2 per cent by mass of octene in HBPE. The dependence of the melting and crystallisation temperatures of HDPE/HBPE blends on the octene content of the HBPE's for constant composition of mixtures have been shown for both the homogeneous and heterogeneous mixing. Blends of a high-molecular HDPE and a HBPE resulted in a reduction of the composition range not effected by phase separation. This revised version was published online in July 2006 with corrections to the Cover Date.     

The influence of hydroxyapatite modification on the cross-linking of polydimethylsiloxane/HAp composites

Hydroxyapatite (HAp) was modified by the action of various hydrophobic agents based on silicon-containing compounds. The influence of the type of applied agent on the thermodynamic and kinetic parameters of the cross-linking of poly(dimethyl siloxane)/HAp composites was investigated. All the modified HAp particles became hydrophobic and these samples were used to synthesize the polysiloxane/hydroxyapatite composites (PDMS/HAp). The possible modes of interaction between the hydroxyapatite and hydrophobing agents were discussed. The most probable interaction between hydroxyapatite and the applied hydrophobing agents is hydrogen bonding. PDMS/HAp composites were formed directly in the cell of the DSC and cross-linking was investigated in situ. It was determined that the introduction of hydroxyapatite into polysiloxane matrices changed the enthalpy of cross-linking, as well as the activation energy of cross-linking and reaction order, while the introduction of modified HAp led to thermodynamic and kinetic parameters more similar to those of the cross-linking of unfilled elastomer.     

Cocontinuity and phase inversion in HDPE/PS blends: Influence of interfacial modification and elasticity

In this work the level of continuity and cocontinuity for blends of HDPE/PS prepared on a twin-screw extruder have been studied by both morphology and dissolution studies. Addition of SEBS as an interfacial modifier results in a shift of the percolation threshold for dispersed PS to higher concentrations. The region of phase inversion, however, is maintained at 70% PS. The shift in the percolation threshold to higher values is related to reduced elongation of the PS dispersed phase after interfacial compatibilization. These results indicate that an interfacial modifier significantly influences percolation phenomena without shifting the region of phase inversion. Models based on viscosity ratio have failed to predict the region of phase inversion in this study. Elastic effects are shown to be able to describe the basic tendencies. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1889–1899, 1998