动态硫化法PP/EPDM/纳米SiO_2双重粒子协同增韧改性研究

以三元乙丙橡胶 (EPDM)作弹性粒子 ,以纳米SiO2 作刚性粒子 ,通过动态硫化方法制备了PP/EPDM/纳米SiO2 三元改性材料 ,并采用力学性能测试、动态力学试验、DSC分析和偏光显微镜观察等方法 ,研究了该材料的结构与性能。结果表明 ,纳米SiO2 与EPDM对PP具有协同增韧和增强效应 ,这种效应与 2种粒子的浓度比相关 ,当纳米SiO2 质量分数为 3 %、EPDM质量分数为 1 0 %时 ,协同作用最明显。 2种粒子使PP出现较大的低温损耗模量峰 (E″)和内耗峰 (tanδ) ,并具有成核作用 ,使PP结晶温度提高 ,结晶速率加快 ,形成的球晶细小而均匀 ,并同时提高结晶度和熔点。     

β成核剂和纳米SiO_2复合改性PP/POE复合材料研究

研究了纳米SiO2和β成核剂对PP/POE复合材料力学性能的影响,并用广角X射线衍射仪(WAXD)对其进行了表征。结果表明:纳米SiO2的加料方式影响PP/POE复合材料的力学性能,先将PP和纳米SiO2共混挤出,再与POE共混制备得到的复合材料冲击强度最高。当纳米SiO2含量为4%时,PP/POE/纳米SiO2复合材料的综合力学性能最好。在PP/POE/纳米SiO2复合体系中的加入β成核剂后,复合材料的拉伸强度和弯曲强度下降,而韧性进一步提高,当β成核剂含量为0.4%时,复合材料的缺口冲击强度和断裂伸长率达到最大值,拉伸强度也明显提高。XRD表明,β成核剂在纳米SiO2改性PP/POE复合体系中能显著诱导β晶的生成。     

反应性增容对PP/纳米SiO2中填料成核活性的影响

采用示差扫描量热法研究PP/纳米二氧化硅(SiO2)复合材料的非等温结晶动力学.研究结果表明:纳米SiO2起到异相成核的作用,使PP的结晶峰温升高;反应性增容增强了纳米SiO2的威核活性;添加纳米SiO2使PP的结晶活化能增大,反应性增容使复合材料的结晶活化能减小,与纯PP的结晶活化能相近;但反应性增容使PP的结晶总速率小于未增容填充体系.     

PP-g-MAH对PP/纳米SiO_2复合材料性能的影响

采用熔融共混法制备了聚丙烯(PP)/纳米SiO2复合材料,研究了相容剂马来酸酐接枝聚丙烯(PP-g-MAH)对复合材料力学性能、结晶性能及界面作用的影响。结果表明:PP-g-MAH能有效地增强纳米SiO2与PP基体间的界面作用,提高复合材料的力学性能;同时,PP-g-MAH增强了纳米SiO2的成核活性,使PP的结晶温度升高,球晶细化。     

反应性增容对PP/纳米SiO2性能的影响

研究了反应性增容对聚丙烯(PP)／纳米SiO2复合材料结晶和流变性能的影响。反应性增容使PP的结晶峰温明显提高,结晶速率增大,球晶细化;复合材料的储能模量、损耗模量和复数黏度明显增大,熔体流动速率减小。在环氧功能化纳米SiO2质量分数为3％,反应性增容剂氨基化PP质量分数为10％时,复合材料的结晶峰温从115.8℃升到125．6℃,熔体流动速率从11．0g/10 min降到8．5 g/10 min。     

PP/纳米SiO2/POE复合材料的研究

采用熔融共混法制备PP/纳米SiO2/POE复合材料,并通过力学性能测试、DSC分析以及材料断面形貌分析等手段,对增强增韧效果进行研究.结果表明纳米SiO2和POE微粒显现了比较明显的协同增韧效果,当PP/纳米SiO2/POE为100/4/15时,综合力学性能最优.纳米SiO2的成核作用提高了PP的结晶温度和结晶速率.两种微粒在PP基体中达到均匀分散,其中纳米SiO2粒子平均粒径为150nm,与其二次粒子直径相当,表明熔融过程并未造成纳米粒子的团聚.     

PP/纳米SiO2复合材料制备与结晶性能的研究

通过熔融共混法制备了聚丙烯(PP)/纳米SiO2复合材料。研究了纳米SiO2含量对PP/SiO2力学性能的影响。结果表明:当纳米SiO2含量为2份时,复合材料的力学性能最优;与纯PP相比,V形缺口冲击强度提高了90%,拉伸强度提高了5%,弯曲强度提高了23%。扫描电镜(SEM)观察表明纳米SiO2均匀无团聚地分散于PP中;差示扫描量热法(DSC)和X射线衍射法(XRD)实验结果发现均匀分散的纳米SiO2使PP的结晶度变大,晶体尺寸分布变窄,晶体体积变小。改善了的PP球晶是聚丙烯性能提高的重要原因之一。     

PP/纳米SiO2复合材料的非等温结晶动力学

采用差示扫描量热法研究了聚丙烯（PP）/纳米SiO2复合材料的非等温结晶动力学,研究了纳米粒子的成核活性及复合材料的结晶有效能垒。研究结果表明,纳米SiO2起到异相成核的作用,使PP的结晶峰温升高,结晶总速率增大;增容剂马来酸酐接枝聚丙烯(PP-g-MAH)提高了纳米SiO2的成核活性;添加纳米SiO2使复合材料的结晶有效能垒降低,PP-g-MAH使复合材料的结晶有效能垒增大,但低于纯PP的结晶有效能垒。     

四针状氧化锌晶须填充改性聚丙烯研究

以乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)为增容剂,利用熔融共混法制备了聚丙烯(PP)/POE-g-GMA/四针状氧化锌晶须(T-ZnOw)复合材料,借助于SEM、DSC和其他测试手段对复合材料的结构和性能进行了考查。DSC测试结果表明:T-ZnOw对PP基体的结晶有一定的诱导作用,使体系出现了双熔融峰和双结晶峰,但对PP的结晶能力和结晶度影响不大。力学性能测试结果表明:在POE-g-GMA的协同作用下,T-ZnOw对PP基体有较强的增韧作用,但增强作用不明显。     

纳米SiO2粒子对PP结晶行为的影响

通过X-射线光电子能谱（XPS）对经偶联剂处理的纳米SiO2粒子（简称烷基化SiO2纳米粒子）和聚甲基丙烯酸甲酯（PMMA）接枝包覆SiO2纳米粒子（简称SiO2-g-PMMA复合纳米粒子）的表面组成进行分析。将纳米SiO2粒子，烷基化SiO2纳米粒子，复合纳米粒子分别与基体PP复合制备复合材料，通过DSC，WAXD和TEM等测试方法详细研究了PP/SiO2复合材料的结晶行为与力学性能，结果发现：纳米SiO2粒子与烷基化SiO2纳米粒子并不改变基体PP的结晶形态，而复合纳米粒子诱发了基体PP的β晶型结晶，复合纳米粒子比较均匀地分散于PP基体中，对复合材料的力学性能有较大的改善。     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Participation of lewis base on vinyl chloride polymerization with Al(C2H5)3CCl4 catalyst system

The polymerization of vinyl chloride has been investigated using an $\text{Al}\text{(}\text{C}{}_2\text{H}{}_5\text{)}{}_3\text{CCl}{}_4$ catalyst system in the presence of various Lewis bases. Effective Lewis bases are γ-butyrolactone, diglyme and diethylenetriamine which are multidentate. The rate of polymerization is dependent not only on the basicity of the Lewis base used but also on a coordination number of one. The latter is the predominant factor. For the effect of polymeric amines, a tentative hypothesis is discussed.     

Synthesis and Characterization of Ti0.33Ta0.33Nb0.33C and Ti0.33Ta0.33Nb0.33CxN1-x Whiskers

Ta_0.33Ti_0.33Nb_0.33C and Ta_0.33Ti_0.33Nb_0.33C _x N_{1− x} whiskers were synthesized via a carbothermal vapor-liquid-solid growth mechanism in the temperature range 900°-1450°C in Ar or N₂. The optimum temperature was 1250°C. Whiskers were obtained in a yield of 70-90 vol%. The whiskers were 0.5–1 µm in diameter and 10–30 µm in length. The starting materials that produced the highest whisker yield were: TiO₂, Ta₂O₅, Nb₂O₅, C, Ni, and NaCl. C was added to reduce the oxides, and Ni to catalyze whisker growth. NaCl was used as a source of Cl for vapor-phase transportation of Ta and Nb oxochlorides and Ti chlorides to the catalyst. The catalyst metal was recycled several times during the synthesis and was transported as NiCl₂( g ) according to thermodynamic calculations. The rate of formation and the chemical composition of the whiskers depended on the synthesis temperature, the choice of catalyst, and the atmosphere. At low temperatures, the whiskers were enriched in Nb and Ta, whereas the Ti content increased with increased synthesis temperature.