表面修饰纳米SiO2增强增韧聚氯乙烯

用过量的2 , 4-甲苯二异氰酸酯(TDI)对纳米SiO₂表面进行修饰合成含—NCO 的功能化SiO_2,再用丙烯酸羟丙酯(HPA)对其表面进行修饰合成出HPA修饰纳米SiO₂(SiO₂-HPA)。用共混法制备了SiO₂-HPA/PVC纳米复合材料,研究了不同 SiO₂含量及不同界面特性时复合材料的力学性能。结果表明: SiO₂-HPA/PVC复合材料的力学性能和加工性能等方面均优于未修饰的样品。在纳米SiO₂质量分数为0%～5%时,SiO₂-HPA/PVC的拉伸强度和冲击强度随着填充量的增加呈先上升后下降的趋势并在3%～4%达到最大值。表面修饰纳米SiO₂与PVC基体之间具有很强的界面结合作用,其相容性得到大大改善,填充表面修饰纳米SiO₂达到了增强增韧双重效果。此外,对纳米粒子增强增韧机制进行了深入的探讨。     

原位接枝改性纳米二氧化硅/ 聚丙烯复合材料Ⅱ: 性能测试

通过熔融共混过程中原位接枝的方法制得聚丙烯酸丁酯接枝改性纳米二氧化硅/ 聚丙烯(SiO₂-g- PBA/PP) 复合材料, 探讨了材料制备的最佳工艺条件, 研究了复合材料的机械性能、结晶性能、微观形貌以及动态黏弹行为。结果表明, 少量纳米粒子(体积分数≤1.36 %) 的加入即可对PP 起到同时增强增韧的作用, 制备SiO₂-g- PBA/PP 的适宜工艺条件为熔融共混温度180 ℃, 共混时间10 min , 转子转速60 r/ min。对复合材料结晶行为的研究表明, 纳米粒子的成核效应使PP 的结晶速率加快。微观形态观察表明, 纳米粒子与聚合物基体间具有良好的界面结合, 这一点从对材料动态黏弹行为的研究中得到进一步证明, 从而阐明了纳米粒子增韧增强聚合物的机理。     

纳米SiO2/纤维素复合材料的非均相制备及其性能

采用硅酸四乙酯(TEOS)作为无机前聚物,纤维素为有机组分,利用溶胶-凝胶法在非均相乙醇溶液中制备了纳米SiO₂/纤维素复合材料。通过傅里叶红外光谱(FTIR)、透射电镜(TEM)和热重分析(TGA)对复合材料的形貌、结构以及热稳定性进行表征。讨论了SiO₂含量对材料力学性能的影响。研究了主要因素碱催化剂氨水对纤维素与SiO₂复合效果的影响。结果表明,纳米复合材料的弹性模量、拉伸强度随SiO₂含量的增加先增加后减少,质量分数分别为3.1％、10.6％时弹性模量、拉伸强度达到最大。氨水加入量为3.70×10-4 mol/L时,纤维素与SiO₂的复合效果最佳。非均相制备的纳米SiO₂/纤维素复合材料同样也明显提高了纤维素材料的疏水性、热稳定性和力学性能。     

偶联剂对PI/SiO2 纳米复合材料形态结构及性能的影响——Ι

用溶胶2凝胶法成功地合成了PI/SiO₂ 纳米复合材料, 并用紫外-可见光谱、红外光谱、扫描电子显微镜等手段对硅烷偶联剂对其微观形态结构以及密度、溶解性等性能的影响进行了研究。研究结果表明, 偶联剂的加入对两相间起到很好的增容作用, 使得二氧化硅无机粒子的粒径大大减小, 分散更加均匀, 在宏观上表现为透明性提高, 所得P I/SiO₂ 纳米复合材料的溶解性有明显改善, 而且随偶联剂加入量的增加, 效果更加显著。另外, PI/SiO₂ 纳米复合材料的密度也随偶联剂量的增加而增大。     

纳米SiO2/尼龙66复合材料的力学性能和热性能

采用熔融共混的方法在双螺杆挤出机上制备出纳米SiO₂/尼龙66复合材料,并对其力学性能和热性能进行了研究。结果表明：复合材料的拉伸强度和弹性模量随纳米SiO₂含量的增加而提高。当SiO₂质量分数为3％时,复合材料的拉伸强度达到最大,增幅为11.2％;当SiO₂质量分数为5％时,弹性模量达到最大, 增幅为30.1％。复合材料的储能模量和玻璃化转变温度较纯尼龙66也有明显提高。差示扫描量热法（DSC）分析显示,纳米SiO₂的加入一方面阻碍了尼龙66的结晶过程,降低了材料的结晶温度;另一方面它又能作为形核剂,增加尼龙66的形核位置,提高形核率。     

纳米填料改性丁基橡胶复合材料的力学性能、芥子气防护性能和燃烧性能

以有机蒙脱土、纳米级SiO₂气凝胶和沉淀法白炭黑等具有不同粒子形状和结构特性的纳米粒子为增强填料,采用熔体共混法制备了丁基橡胶复合材料。采用SEM和XRD对复合材料的微观结构进行了表征,并研究了不同纳米填料对复合材料的力学性能、芥子气防护性能和燃烧性能的影响。结果显示：纳米级SiO₂气凝胶/丁基橡胶复合材料的力学性能最优,填充15 wt% SiO₂气凝胶的复合材料的拉伸强度和撕裂强度分别比丁基橡胶硫化胶提高了9倍和2.2倍。复合材料的芥子气防护性能与纳米填料的粒子形状有密切的关系,填充15 wt%层片状结构有机蒙脱土的复合材料的芥子气防护时间达到了21h以上,明显优于填充近似球形粒子的纳米级SiO₂气凝胶和白炭黑的复合材料的防护性能。然而纳米填料使复合材料的氧指数和氧化分解温度只有少量提高,阻燃性能改善有限。     

TiO2/环氧树脂纳米复合材料的研究

以纳米TiO₂作为增强材料,制备纳米复合材料,研究了不同的纳米 TiO₂含量对纳米复合材料性能的影响,采用透射电镜对纳米 TiO₂粒子的分布进行了表征,采用正电子湮没技术(PALS),测试了自由体积的尺寸及浓度。结果表明,纳米粒子均匀分散于环氧树脂中,使环氧树脂的拉伸强度、拉伸模量、冲击强度得以提高;也使环氧树脂的自由体积尺寸增大。     

弹性体修饰纳米SiO2粒子改性PBT

选用乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯(E-MA-GMA)三元共聚物对纳米SiO₂表面进行修饰包覆改性,考察改性后纳米SiO₂在聚对苯二甲酸丁二醇酯(PBT)基体中的分散情况及对PBT复合材料力学性能的影响。FTIR、TEM、SEM结果表明,E-MA-GMA的环氧基团与纳米SiO₂的—OH 基团发生反应,破坏了SiO₂的链状团聚结构,降低了纳米粒子间氢键等作用力。质量分数为10%～20% E-MA-GMA 改性的纳米SiO₂在PBT基体中的分散性及其与基体的相容性均得到明显改善,从而提高了PBT基复合材料的弯曲和拉伸性能。与纯PBT相比,SiO₂/PBT复合材料的拉伸强度提高了9%,而弯曲强度和模量分别提高了14%和20%。     

纳米SiO2表面接枝聚合改性及其聚丙烯基复合材料的力学性能

分别用苯乙烯和丙烯酸乙酯对纳米SiO₂进行辐照接枝聚合改性,通过两步熔融共混工艺与聚丙烯(PP)共混制备了SiO₂/PP复合材料。研究了SiO₂添加量和表面接枝不同聚合物的SiO₂对复合材料力学性能的影响。结果表明,接枝改性的SiO₂对PP有较好的增强增韧效果;拉伸断面观察显示复合材料韧性的提高主要由基体剪切屈服所致。对断面上个别较大团聚体分析发现,经辐照接枝聚合改性的纳米粒子团聚体的结构变得更加紧凑、结实,且随粒子表面聚合物的性质不同,团聚体与基体树脂的界面粘结也随之不同,导致其拉伸破坏形状有所差异,但与基体树脂的界面粘结都得到较好的改善。     

少层石墨烯负载纳米SiO2复合材料对水润滑性能的影响

采用液相超声直接剥离法制备了少层石墨烯负载纳米SiO₂复合材料,采用TEM对其形貌进行了表征,利用多功能往复摩擦磨损试验仪考察了少层石墨烯负载纳米SiO₂复合材料对水润滑性能的影响。通过SEM、XPS分别分析了磨损表面的形貌、元素组成及典型元素的化学状态,初步探讨了石墨烯负载纳米SiO₂复合材料在水中的润滑机理。结果表明:纳米SiO₂均匀分布于少层石墨烯片层表面和层间;其作为水润滑添加剂具有良好的减摩抗磨性能,这主要是由于石墨烯负载纳米SiO₂复合材料在磨损表面形成的摩擦化学反应膜与纳米SiO₂的自修复效应发生协同作用,抑制了Fe的氧化,并填补和修复了磨损表面,使磨痕表面的摩擦磨损减轻。     

Microemulsion processing of silica-polymer nanocomposites

Silica-polymer nanocomposites have been synthesized via polymerizable bicontinuous microemulsions to disperse functionalized/nonfunctionalized SiO2 nanoparticles uniformly in a polymerized microemulsion system as revealed by transmission electron microscopy. The effect of both types of SiO2 nanoparticles in the polymerized microemulsion increased its glass transition temperature (Tg) from 90 to 128 degrees C. TgS of functionalized silica nanocomposites were about 15 degrees C higher than those of nonfunctionalized samples. As expected, both hardness and modulus of the nanocomposites increased with the loading of both types of silica from 2 to 6 wt%. In the case of nonfunctionalized silica, the improvement of properties may be simply exerted by the conventional filler effect due to the better dispersion of nanoparticles of silica in fluid microemulsion prior to the polymerization. The additional effect for the functionalized silica containing a terminal vinyl group is that It could be grafted to the polymer matrix through cross-polymerization with microemulsion-formed polymer to establish strong nanocomposite networks.     

Poly(vinyl alcohol)/silica nanocomposites: morphology and thermal degradation kinetics

The morphology of self-assembled poly(vinyl alcohol)/silica (PVA/SiO2) nanocomposites is investigated with atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is found that the SiO2 nanoparticles are homogenously distributed throughout the PVA matrix in a form of spherical nano-cluster. The average size of the SiO2 clusters is below 50 nm at the low contents (SiO2 < or =5 5 wt%), while particle aggregations are clearly observed and their average size markedly increases to 110 nm when 10 wt% SiO2 is loaded. The thermogravimetric analysis (TGA) shows that the nanocomposite significantly outperforms the pure PVA in the thermal resistance. By using a multi-heating-rate method, the thermal degradation kinetics of the nanocomposite with a SiO2 content of 5 wt% is compared to the PVA host. The reaction activation energy (E) of the nanocomposite, similar to the pure PVA, is divided into two main stages corresponding to two degradation steps. However, at a given degradation temperature, the nanocomposite presents much lower reaction velocity constants (k), while its E is 20 kJ/mol higher than that of the PVA host.     

Dispersion stabilization of yttria-stabilized zirconia slurry for spray coating by PVB polymeric adsorption

In this study, the dispersion stabilization characteristics of the poly(vinyl butyral) (PVB) adsorbed yttria-stabilized zirconia (YSZ) was investigated. The addition of PVB showed remarkable dispersion effect to the YSZ slurry prepared with isopropyl alcohol (IPA) and toluene as a bi-solvent system, PVB as a dispersant medium and YSZ powders. The agglomerated YSZ particle size decreased with PVB addition until 3 wt% and PVB added more than 3 wt% acted as a binder. The smallest particle size was obtained at 3 wt% PVB and the more PVB addition causes reflocculation of YSZ particles. The relative amount of adsorbed PVB onto the YSZ surface increased with increasing PVB contents. It turns out that the YSZ slurry dispersion stabilization was improved by the interaction between the hydroxyl group of YSZ surface and O-H group in PVB which is newly formed Zr-O-C bonding.     

Epoxidised natural rubber/silica hybrid nanocomposites by sol-gel technique: Effect of reactants on the structure and the properties

This paper reports the effects of various reaction parameters such as solvent, mole ratio of water to tetraethoxysilane and temperature on the structure and the properties of epoxidised natural rubber/silica organic-inorganic hybrid nanocomposites, prepared by sol-gel technique. The sol-gel reaction was conducted at a constant concentration of tetraethoxysilane (45 wt% with respect to the rubber), used as the precursor for silica under a constant pH of 1.5. Infrared spectroscopic studies and the ash content data indicated the maximum silica generation in tetrahydrofuran compared to chloroform and carbon tetrachloride, which are less polar and had low affinity towards water than the former. The silica particles prepared from tetrahydrofuran were scattered within the rubber matrix with an average dimension of 100 nm, as evident from the transmission electron microscopic study. Dispersion of nanosilica within the composites was obtained when the tetraethoxysilane to water mole ratio was maintained up to 1:2, beyond which the resultant composites showed phase separation due to the agglomeration of the silica particles. High gelling temperature of the hybrids also resulted in phase separated morphology, probably due to the accelerated condensation reaction in the composites. All the phase separated composites showed higher infrared optical density and transmission loss compared to the nanocomposites. Poor mechanical reinforcement was observed from the dynamic mechanical analysis of the uncured composites having larger silica particles. On the contrary, better mechanical properties were achieved with the nanocomposites containing 90–100 nm silica. The nanocomposite prepared with 1:2 tetraethoxysilane to water mole ratio in tetrahydrofuran under room temperature showed the highest tensile strength and 100% tensile modulus, probably due to better polymer-filler interaction, in the uncrosslinked state and after crosslinking.     

Effect of polyvinyl butyral on the microstructure and laser damage threshold of antireflective silica films

Silica antireflective films modified by polyvinyl butyral (PVB) were deposited on fused silica substrates by sol-gel process. The effects of PVB on the microstructure and laser damage threshold (LIDT) of films were investigated. The results of the nano particle analyzer and scanning probe microscope revealed that PVB molecules surrounded silica particles and controlled the particle growth, which resulted in a stable sol with uniformly distributed silica particles. Therefore, the films deposited from these modified sols possessed more uniform microstructures than the films without PVB. The adhesive-resistance test indicated that the strength of the modified silica films increased due to the bond reaction between PVB molecules and silica particles. The introduction of PVB into silica sols had also increased the LIDT of films. The LIDT of films increased from 30.0 J/cm² to 40.1 J/cm² after 1.0 wt.% PVB was added. The increase in LIDT was attributed to the increased strength and uniform microstructures of films as an effect of the PVB modification.     

聚氨酯/二氧化硅包覆多壁碳纳米管复合材料的导热与电绝缘性能

通过溶胶-凝胶法制备了厚度为30nm-50nm的二氧化硅(SiO2)包覆多壁碳纳米管(SiO2-MWNTs),并与聚氨酯(PU)复合制备了PU/SiO2-MWNT复合材料。研究了SiO2-MWNTs对PU导热电绝缘性能的影响。结果表明,SiO2包覆层增强了MWNTs与PU之间的界面相互作用,促进了MWNTs在PU中的分散。由于SiO2包覆层的电绝缘作用,PU/SiO2-MWNT复合材料保持了PU的电绝缘性能。同时SiO2包覆层作为过渡层,降低了PU与MWNTs间的模量失配,减少了声子的界面散射,提高了PU/SiO2-MWNT复合材料的导热性能。当SiO2-MWNTs的质量分数为0.5%和1.0%时,PU/SiO2-MWNT复合材料的热导率分别提高了53.7%和63.8%。     

共混型石墨烯-nanoSiO_2/TPU复合材料的制备与性能

采用熔融共混技术制备了氧化石墨烯(GO)-nano SiO_2杂化材料填充改性的形状记忆热塑性聚氨酯(GO-nano SiO_2/TPU)复合材料,探讨了GO-nano SiO_2杂化材料对复合材料力学性能、熔融指数及形状记忆性能的影响。结果表明:GO-nano SiO_2含量对GO-nano SiO_2/TPU复合材料的力学性能有明显的影响,其含量为0.5wt%~1wt%时,GO-nano SiO_2/TPU复合材料的综合力学性能较好。熔融指数分析表明,填料的加入会降低材料的加工流动性能。形状记忆性能研究表明,加入GO-nano SiO_2杂化材料使得GO-nano SiO_2/TPU复合材料的形状固定率先降低后上升,在含量为1wt%后上升趋势更加明显;而形状回复率随填料含量的增加而呈降低趋势,并且在100℃高温这种变化趋势更加明显和稳定,回复温度越高,形状回复率越好。     

纳米ATO/PVB隔热透明原位复合材料的制备及性能

利用超声波将经表面预处理的纳米氧化锡锑(ATO)粒子均匀分散到聚乙烯醇(PVA)水溶液中,与正丁醛缩合反应,原位法制备了一系列纳米ATO/聚乙烯醇缩丁醛(PVB)复合材料。采用FTIR、UV/VIS/NIR、TG、TEM及AFM等对所制备的原位纳米ATO/PVB复合材料的结构、微观形貌及性能进行了研究。结果表明: 在合成PVB树脂的阶段添加少量纳米ATO粒子,能更均匀地分散在PVB基质中,所制备的复合材料薄膜的紫外线及近红外光透过率大幅度下降,而可见光透过率降低幅度较小,且随纳米ATO用量增加,紫外屏蔽及隔热性能不断提高。在纳米ATO用量(与PVB质量比为2.76%)较低时,纳米ATO/PVB复合材料的力学性能尤其韧性得到明显提高,断裂伸长率达到纯PVB的7.3倍; 在ATO与PVB质量比为1.74%时,可见光透过率高于70%,紫外光透过率低于10%,近红外光热辐射透过率低于28%,导热系数为0.23 W(m·K)^-1,与纯PVB相比,用纳米ATO/PVB复合材料胶膜所制盖板的隔热空腔内温度下降5.5℃,具有良好的透明度、紫外屏蔽及隔热性能。     

Structure-property relationship in sol-gel derived polymer/silica hybrid nanocomposites prepared at various pH

This paper reports a comparative study on structure-property relationship of acrylic rubber (ACM)/silica, epoxidised natural rubber (ENR)/silica and poly (vinyl alcohol) (PVA)/silica hybrid nanocomposites prepared by sol-gel technique under different pH levels (pH = 1.0–13.0), probably for the first time. The initial concentration of tetraethoxysilane (TEOS) (used as the precursor for silica) was kept at 45 wt%, and tetrahydrofuran (THF) for ACM/silica and ENR/silica while water for PVA/silica were taken as solvents. TEOS to water mole ratio was maintained at 1:2 for the rubber/silica systems to accomplish the sol-gel reaction. The structure of the resultant hybrid composites was determined by using electron microscopy, Fourier Transform infrared spectroscopy and solubility. Dynamic mechanical and mechanical properties were also investigated. The silica particles were found to exist as nanoparticles (average diameter <100 nm) at low pH (≤ 2.0) beyond which these aggregate, although the amount of silica generation was not strictly influenced by the various pH conditions in all the systems. These nanocomposites were optically clear and showed superior mechanical reinforcement over the micro-composites containing aggregated silica structures with lower optical clarity. The nanocomposites exhibited higher storage modulus both at the glassy and the rubbery regions as compared to those micro-composites. The loss tangent peak heights were also minimum and the Tg shifted to higher temperature for those nanocomposites. The maximum improvement of mechanical properties was observed with the PVA/silica nanocomposites due to higher level of interaction between the hydroxyl groups of PVA and the silanol groups of the silica phase.