抗冲聚丙烯微结构的研究

利用¹³C NMR对抗冲聚丙烯的微结构进行了研究.结果表明,由于抗冲聚丙烯聚合工艺的差别,4个抗冲聚丙烯样品中的乙烯链段的序列分布也不同.根据抗冲聚丙烯的¹³C NMR谱,计算出了丙烯段的次甲基和甲基的峰强度,由此建立了表征抗冲聚丙烯共聚物中丙烯链段的立构规整度的方法.     

无规共聚聚丙烯中硬脂酸钙的测定

采用傅里叶变换红外光谱法(FTIR)对无规共聚聚丙烯(PP-R)中的硬脂酸钙进行快速定性分析,通过考察硬脂酸钙含量变化的系列PP-R的FTIR图,确定了对硬脂酸钙进行定性的特征吸收峰为1561cm-1;对无规共聚聚丙烯样品中的硬脂酸钙进行初步的定量分析.采用电感耦合等离子体-原子发射光谱法(ICP-AES)间接测定硬脂酸钙含量;钙元素校准曲线在5.0-70.0mg/L浓度范围内的线性相关系数r=0.998;该方法定量分析PP-R中的钙的加标回收率在91.0%-104%之间,相对标准偏差在0.47%-1.21%之间,方法的准确性和精密度满足定量的要求.     

聚丙烯压电驻极体膜的压电和声学性能研究

以多孔聚丙烯(PP)膜为原材料, 通过压缩气体膨化工艺和电晕极化方法成功制备出PP压电驻极体膜, 并研究了该功能膜的压电和声学性能. 结果表明PP压电驻极体膜厚度方向和横向的杨氏模量分别为1.4和480 MPa, 因此压电系数d₃₃比d₃₁和d₃₂高2个量级以上, d₃₃是该类压电膜压电效应的主要性能指标, 而 d₃₁和d₃₂可以忽略不计. PP压电驻极体膜的准静态压电系数d₃₃在15-35 kPa的压强范围内具有良好的线性度. 在2-300 Hz的测试频率范围内, 300 Hz 下的d₃₃是2 Hz下的81%, 这主要是由PP膜的杨氏模量随频率增大而增强引起的. 在100 Hz-100 kHz 的音频和超声波频率范围内, PP压电驻极体膜具有平坦的频响曲线; 在1 kHz下其开路电压灵敏度和压电系数d₃₃分别为0.85 mV/Pa和164 pC/N. 关键词： 聚丙烯压电驻极体 压电效应 声学性能     

电子能谱法研究改性的聚丙烯纤维性能与结构关系

本文讨论了聚丙烯纤维(PPF)在Ar、N_2、O_2和空气等离子体作用时,改变时间和功率对PPF表面进行等离子体处理,发现处理后纤维的吸湿性变化很大,回潮率是未处理样品的120-400%,染色性能从5级提高到1级标准。这一变化的光电子能谱法研究结果表明:PPF表面的结构发生较大变化。表面大量引入含O、N极性基团。经谱图拟合可知,这些基团是亲水性的极性结构,应归属于C-OH、C=O、COOH、C-NH_2和CONH_2基团。     

交联聚丙烯压电驻极体的压电性能及振动能量采集研究

以电子束辐照交联聚丙烯(IXPP)泡沫薄板为原材料, 首先利用热压工艺对微观结构进行改性, 然后采用电晕充电方法对样品实施极化处理, 使之具有压电效应, 成为压电驻极体. 通过准静态和动态压电系数d₃₃、复电容谱, 以及等温衰减的测量, 研究了IXPP压电驻极体膜的机电耦合性能; 同时考察了基于IXPP压电驻极体膜的振动能量采集器在{3-3}模式下对环境振动能的俘获. 结果表明, IXPP压电驻极体的准静态压电系数d₃₃可高达620 pC/N; 厚度方向的杨氏模量和品质因数(FOM, d₃₃·g₃₃)分别是0.7 MPa和11.2 GPa^-1; 在50, 70和90℃下进行等温老化, 经过24 h后, IXPP压电驻极体膜的准静态压电系数d₃₃分别降低到初始值的54%, 43%和29%; 采用面积为3.14 cm²的IXPP压电驻极体膜为换能元件, 当振子质量为25.6 g, 振动频率为820 Hz时, 振动能量采集器在匹配负载附近可以输出高达65 μW/g²的功率.     

蓝光锆（Ⅳ）配合物的合成及光致发光性能研究

合成了一系列蓝光锆（Ⅳ）配合物 Cl[Zr（NN）（DBM）₃]（DBM=二苯甲酰基甲烷,NN=1,10-邻菲罗啉 1;2,9-二甲基-1,10-邻菲罗啉 2;4,4'-二甲基-2,2'-联吡啶 3;1-乙基-2-（1-萘基）-1H-咪唑-4,5-f-1,10-邻菲罗啉4）,以波长为355 nm的紫外光激发,4个配合物的最大发射峰均位于445 nm左右,半峰宽只有36~45 nm。在相同的测试条件下,配合物 1 的蓝光发射强度最大,量子效率最高,其原因是结构刚性强,能够有效地减少非辐射跃迁造成的能量损失。而且,配合物 1~3 的热稳定性很好,分解温度均在200℃以上,可以用于制作有机发光器件,不会在器件的制作过程中发生分解。     

Schif f碱配合物荧光粉的合成及光谱性能研究

有机电致发光材料具有主动发光、视角广、对比度高等显著特点。稀土有机配合物电致发光材料目前备受广大研究者的关注。以水杨醛和苯甲酸衍生物为原料,经酯化、肼化及希夫碱缩合合成了水杨醛对甲氧基苯甲酰腙(1-H₂L)、水杨醛对甲基苯甲酰腙(2-H₂L)、水杨醛对溴基苯甲酰腙(3-H₂L) 3种配体,以Pr(NO₃)₃为原料,合成了水杨醛酰腙系列镨稀土配合物,经红外光谱、紫外光谱等分析手段对该类配合物的结构进行表征,配体在3 136～3 141 cm-1出现羟基ν(OH)伸缩振动峰,在配合物的红外光谱中消失,配合物在3 330～3 368 cm-1之间的吸收峰归属为结晶的H₂O的ν(O-H)羟基弯曲振动吸收峰,配合物在与配体对应的3 140 cm-1均不出现羟基吸收峰,三种配体及配合物的吸收波形相似,反映出配体及配合物的结构基本一致,但配体与配合物的吸收波峰相差较大,据此可推测配体已经配位。采用荧光分光光度计测定了该类配合物的荧光光谱,并讨论了配体取代基的变化对荧光强度的影响。配体分别在352,369,365和417 nm波长监测下,于517 nm处出现发射峰。其中3-H₂L的荧光强度最高。配合物均在470 nm的蓝光激发下,分别于608和617 nm出现镨的电偶极跃迁特征发射峰,归属于3P₀→3F₂跃迁。配合物均可被470 nm蓝光激发,在608～617 nm处有较好的红光发射,该类荧光粉有望应用于OLED上进行应用。     

铕-苯甲酸-邻菲咯啉掺杂配合物体系的合成与荧光性能研究

合成了Eu_1-xLn_x(BA)₃ Phen(Ln： Gd,La,Y;BA： 苯甲酸;Phen： 1,10-邻菲咯啉)系列固体粉末配合物。红外光谱的研究表明该系列配合物具有相似的结构;荧光光谱表明该类配合物均能发出强的铕离子的特征荧光,并且掺杂元素能增强配合物的发光性能,起到共发荧光作用。     

C60Pd(Ph2PCH2PPh2)配合物的合成及光电性能研究

在氮气氛下 ,采用配体取代法 ,即以C60 取代Pd(Ph2 PCH2 PPh2 ) 2 中一个Ph2 PCH2 PPh2 合成出富勒烯金属配合物C60 Pd(Ph2 PCH2 PPh2 ) ,采用元素分析、红外光谱、紫外可见光谱、光电子能谱以及X射线粉末衍射等手段对产物进行表征 .同时研究了产物的光电性能、氧化还原性能及热稳定性能 .光伏效应研究结果表明 ,产物具有优良的光电转化性能 ,尤其是在BQ/H2 Q介质电对中 ,光生电压最大达到 174mV ;当C60 Pd(Ph2 PCH2 PPh2 )薄膜厚度为 1μm时 ,光伏效应值最大 .     

含d^10过渡金属配合物的结构及发光性能对比研究

采用恒温磁力搅拌和水热合成方法,以Zn(Ⅱ)和Cd(Ⅱ)为配位中心,以烟酸(HNA),异烟酸(HINA),2,2'-联吡啶(2,2'-bipy),1,10-菲咯啉(phen)为配体合成了五种配合物,通过X射线单晶衍射确定了它们的晶体结构.室温下,测定了化合物的IR,UV-Vis-NIR和荧光光谱,并对比分析了它们的光物理性能.五种化合物的固态粉末在室温紫外光照射下,均可产生较强的发光,而且化合物(5)还具有常温磷光发射.由于有机配体的不同,使得化合物的发光来源于不同类型的电荷转移跃迁.化合物(1)和(3)的荧光发射与相应配体相比,发生蓝移,其发光是以ILCT为主,但掺杂L→M(4S)跃迁的部分;化合物(2)和(4)的荧光发射比配体异烟酸的发射发生红移,其发光来自于LMCT跃迁;而化合物(5)的发射峰型及位置与有机配体phen差别很大,应归属于LLCT和LMCT的共同贡献.     

Mechanical,Thermal, and Surface Properties of Ultrahigh Molecular Weight Polyethylene/Polypropylene Blends

Various compositions of ultrahigh molecular weight polyethylene/polypropylene (UHMWPE/PP) blends were prepared in decalin, with the rheological, mechanical, thermal, and surface properties of the blends being determined using the solution cast film. Viscosity and mechanical properties of the blends decreased below the additivity value with increasing PP content implying that PP molecules disturb the entanglement of UHMWPE. Contact angle of the blend films with a water drop increased with increasing content of PP. The atomic force microscope (AFM) images showed that the surface of cast UHMWPE was very smooth whereas that of cast PP was very uneven. For blends, the surface became rough and uneven with increasing content of PP. The melting temperature of PP (T _mP) decreased in the blends with increasing UHMWPE content while that of UHMWPE (T _mU) remained almost constant in blends.     

Investigation of Pendant Group and Chain Segment Motions in P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly(methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M_η ～2×10⁵) with different mass percentages of MMA were synthesized by the method of solution polymerization. Thermally stimulated depolarization current (TSDC) technique was used to investigate the effect of copolymerization on pendant group and chain segment motions. Three TSDC peaks were observed over the temperature range from 310 to 400 K. The highest temperature, ρ peak originates from the detrapping of trapped charge carriers. The lower temperature, α peak corresponds to the glass transition. The activation energy of the α relaxation decreases from 1.2 eV for PMMA to 0.98 eV for MMA(75)/BA(25). In the fitting process, another peak, β′, is separated on the low temperature side. The apparent energy barrier of the β′ for PMMA is 0.80 eV. The β′ relaxation is thought to correspond to the motion of pendant groups including intra‐ and inter‐molecular interactions. All three peaks move to lower temperatures with an increase in BA component, and the activation energy for the α and β′ relaxations also decreases with the increase of BA component in copolymers, indicating that the flexible side groups of BA have an effect of plasticization on the glass transition and motion of pendent groups. The temperatures of the α and β′ peaks of P(MMA/BA) copolymers follow the Fox equation. Fitting results gives the α peak at 238 K and β′ peak at 225 K for polybutyl acrylate (PBA).     

Effect of Injection Parameters and Addition of Nanoscale Materials on the Shrinkage of Polypropylene Copolymer

The effect of variation of injection conditions and addition of nano-calcium carbonate (CaCO₃), nano-silicon dioxide (SiO₂) and full-vulcanized nano-powdered styrene butadiene rubber (PSBR) on the shrinkage of injection-molded polypropylene-ethylene copolymer (90/10, co-PP) were investigated. The results showed that the shrinkage was different for different locations along the flow path. The shrinkage in the length direction of the injection-molded sample varied with the adjustment of the processing parameters, while the shrinkage in the width and thickness direction was almost unchanged. The addition of nano-CaCO₃ and PSBR decreased the shrinkage of co-PP, while the shrinkage of co-PP/ SiO₂ composite was almost unchanged.     

Effect of β-Nucleating Agent on the Crystallization,Mechanical Properties,and Heat Resistance of Injection-Molded Isotactic Polypropylene

Injection-molded β-isotactic polypropylene (β-iPP) was prepared with a commercial β-nucleating agent (NT-A). The effect of NT-A on the crystallization, mechanical properties, and heat resistance of β-iPP was investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM), and mechanical and heat deflection tests. DSC and WAXD analysis showed that the content of β-crystals in the nucleated iPP was higher than that of pure iPP, and the content of β-crystals of the core was higher than that of the skin. PLM observations showed that injection-molded iPP had an obvious skin-core structure. NT-A induced abundant β-crystals and resulted in small spherulites which improved the Izod notched impact strength. When the content of NT-A was 0.075wt%, the Izod notched impact strength reached a maximum, 2.6 times more than that of pure iPP. The heat distortion temperature was also improved by NT-A.     

Crystallization kinetics, glass transition kinetics, and thermal stability of Se70−xGa30Inx (x=5, 10, 15, and 20) semiconducting glasses

Crystallization and glass transition kinetics of Se_70−xGa₃₀In_x (x=5, 10, 15, and 20) semiconducting chalcogenide glasses were studied under non-isothermal condition using a Differential Scanning Calorimeter (DSC). DSC thermograms of the samples were recorded at four different heating rates 5, 10, 15, and 20 K/min. The variation of the glass transition temperature (T_g) with the heating rate (β) was used to calculate the glass transition activation energy (E_t) using two different models. Meanwhile, the variation of the peak temperature of crystallization (T_p) with β was utilized to deduce the crystallization activation energy (E_c) using Kissinger, Augis-Bennet, and Takhor models. Results reveal that E_t decreases with increasing In content, while both T_g and E_c exhibit the opposite behavior, and the crystal growth occurs in one dimension. The variation of these thermal parameters with the average coordination number <Z> was also discussed, and the results were interpreted in terms of the type of bonding that In makes with Se. Assessment of thermal stability and glass forming ability (GFA) was carried out on the basis of some quantitative criteria and the results indicate that thermal stability is enhanced while the crystallization rate is reduced with the addition of In to Se-Ga glass.     

Influence of the Polymer/Inorganic Filler Interface on the Mechanical,Thermal, and Flame Retardant Properties of Polypropylene/Magnesium Hydroxide Composites

The relationship between the interface structure and the macroscopic properties of composites composed of isotactic polypropylene (iPP) and magnesium hydroxide (MH) was investigated with a focus on mechanical properties, thermal stability, and flame retardancy. Surface treatment of MH was carried out using dodecanoic acid (DA) and dodecylphosphate (DP), both of which interacted with MH to form submonolayer coverages. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed that both organic reagents adhere to the MH surface via ionic interactions. Even low amounts of organic reagents on the MH surface were sufficient to improve the mechanical, thermal, and flame retardant properties of the composites. The incorporation of 1.8 wt% of DP in (70/30) iPP/MH-DP composite decreased the peak heat release rate (PkHRR) to 39% compared with that of neat iPP. Since the effects of DA with the same dodecyl chains were not significant, it is concluded that the phosphate groups in DP provide flame retardancy.     

Effect of different plasticizers on the secondary relaxation of poly(vinyl chloride)

Samples of poly(vinyl chloride) plasticized with variable amounts of either dibutyl phthalate (DPB) or dicyclohexyl phthalate (DCHP) were investigated by dynamic-mechanical measurements in the β relaxation temperature range. In this range of temperature, a superposition of the relaxation due to the cyclohexyl group with the PVC β peak was found for the samples plasticized with DCHP. By studying the dependence of the activation energy and of the peak broadness on the DCHP concentration it was possible to show that the PVC β relaxation is reduced to zero at the critical plasticizer weight fraction W₁ = 0.2. For the PVC-DBP series the β peak disappears at the same plasticizer content. These results strengthen the hypothesis that the β peak of PVC is due to a kind of cooperative motion since 1 mole of plasticizer for every 20 repeating units of the polymer is sufficient to suppress the PVC β relaxation.     

The Effect of Zinc Oxide and Calcium Carbonate Nanoparticles on the Thermal Conductivity of Polypropylene

The thermal conductivity (TC) of compression-moulded polypropylene (PP) and PP filled with 5–15% zinc oxide (ZnO) or calcium carbonate (CaCO₃) nanoparticles, prepared by extrusion, was studied using a thermal conductivity analyzer (TCA). The effect of nanoparticle content and crystallinity on the thermal conductivity was investigated using conventional methods, including SEM, XRD, and DSC. The incorporation of nanoparticles improved the crystallinity and thermal conductivity simultaneously. The experimental TC values of the PP nanocomposites with different level of nanoparticles concentration showed a linear increase with an increase in crystallinity. The TC improvement in PP/ZnO nanocomposite was greater than that of PP/calcium carbonate nanocomposites. This fact can be attributed to the intrinsic, better thermal conductivity of the ZnO nanoparticles. Several models were used for prediction of the TC in the nanocomposites. In the PP/ZnO nanocomposites the TC values correlated well with the values predicted by the Series, Maxwell, Lewis and Nielson, Bruggeman, and De Loor models up to 10 wt%.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.