乳液共混法制备纳米SiO_2/BIIR复合材料及其性能研究

采用溶液乳化法制备出了溴化丁基胶乳,并通过乳液共混法制备纳米SiO2/溴化丁基橡胶(BIIR)复合材料。结果表明,改性的纳米SiO2可以很好的分散在溴化丁基橡胶胶乳(BIIRL)中;通过涂布成型硫化后,纳米SiO2/BIIR复合材料具有良好的物理性能,其断裂伸长率、拉伸强度和拉伸断裂应力都得到了较大提高;在SiO2用量很少的情况下,气密性得到了显著的提高。     

电子显微镜对纳米SiO2/NR复合材料结构的分析

控制制备工艺条件,利用Na2SiO3.9H2O与HCl在助剂作用下,先制备纳米SiO2乳液,然后再将其与天然胶乳共混共凝制备纳米SiO2/NR复合材料。采用SEM、TEM分析研究不同工艺条件下制备的纳米SiO2粒子的表面结构及粒径大小和纳米SiO2/NR复合材料的拉伸断面。结果表明,本方法制备的纳米SiO2粒子的粒径在25 nm~40 nm之间,其在NR基体中分散均匀,复合材料具有较好的综合力学性能。     

低填充SiO2/聚丙烯纳米复合材料的拉伸特性

通过对纳米SiO2辐照接枝聚合改性,结合熔融共混工艺制备了低填充SiO2/PP纳米复合材料,发现在一定拉伸速度和粒子含量下,经辐照改性的SiO2/PP纳米复合韧性得到显著提高,同时强度也有所增加,随拉伸速度的升高,纳米复合材料的模量和强度逐渐增大,而韧性则随之下降,断面扫描电镜观察表明,改性纳米粒子填充复合材料韧性提高的机理以空化和基体大面积剪切屈服为主。     

ATRP法在纳米SiO_2表面接枝PBA及其对PVC的改性

采用原子转移自由基聚合法(ATRP)在纳米二氧化硅(SiO2)粒子表面接枝聚丙烯酸丁酯(PBA),并以此对聚氯乙烯(PVC)进行改性。红外光谱(FT-IR)、透射电镜(TEM)、扫描电镜(SEM)及力学性能等测试结果表明,所制备的SiO2-g-PBA纳米复合粒子在PVC中分散均匀,使PVC/SiO2-g-PBA复合材料的缺口冲击强度及拉伸强度均明显高于PVC及PVC/SiO2复合材料。当SiO2-g-PBA纳米复合粒子的质量分数为5%时,PVC/SiO2-g-PBA复合材料的冲击强度达到9.5kJ/m2,较纯PVC提高了280%,同时拉伸强度也有一定的提高,达到了65.3MPa。     

纳米SiO_2/聚甲基丙烯酸甲酯透明复合材料的制备及透光率

首先利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)对纳米SiO_2进行表面改性(SiO_2-MPS),再通过原位聚合法在SiO_2-MPS表面接枝聚甲基丙烯酸甲酯(PMMA)。采用熔融共混法将未改性和改性SiO_2与PMMA共混制成预分散母料,再分别与PMMA熔融共混制备纳米SiO_2/PMMA透明复合材料。用FTIR、TG和SEM对不同表面处理的纳米SiO_2和纳米SiO_2/PMMA复合材料的结构进行表征,并对其冲击强度、接触角和透光率进行表征。结果表明:SiO_2-MPS/PMMA复合材料中纳米SiO_2与MPS、MPS与PMMA间形成化学键,接枝率分别达到10.01%和22.95%,SiO_2-MPS-PMMA在PMMA中分散性最好,团聚现象明显减少,与纯PMMA相比,SiO_2/PMMA、SiO_2-MPS/PMMA和SiO_2-MPS-PMMA/PMMA复合材料的冲击强度、与水接触角均略有提升,透光率达到90%左右,最高可达94.2%。     

聚丙烯(PP)/纳米二氧化硅SiO2复合材料的制备及其性能研究

纳米材料因其独特的性能而广泛应用于聚丙烯(PP)等高分子材料的改性.本文用纳米二氧化硅与PP共混进行改性,利用双螺杆共混方法制备聚丙烯(PP)/纳米二氧化硅(SiO2)复合材料,研究了聚丙烯(PP)/纳米二氧化硅(SiO2)复合材料的力学性能,采用熔融流变仪、XRD、SEM对熔体流动速率、PP物相情况等进行了研究.实验结果表明,2%含量的纳米二氧化硅聚丙烯纳米复合材料综合性能最佳,提高了PP的综合力学性能.在本文中对纳米SiO2改性PP的机理进行了初步探讨,利用X射线衍射图谱分析,结果表明纳米SiO2的加入对PP中β晶型的产生有诱导作用.     

SiO2含量和共混方法对NR/PP共混型热塑性弹性体的影响

采用两种共混方法制备天然橡胶(NR)/聚丙烯(PP)/纳米二氧化硅(SiO2)热塑性弹性体,采用透射电镜(TEM)、动态热机械(DMA)分析、橡胶加工分析仪(RPA)和力学性能测试研究了共混方法和SiO2的填充量对NR/PP/SiO2热塑性弹性体力学性能、形态结构和流变行为的影响。研究结果表明,当纳米SiO2的填充量较低(<3phr),共混方法对SiO2的分散影响较大,当SiO2主要分散在PP基体相中时,其对热塑性弹性体的补强作用明显;随着纳米SiO2的填充量的增加(≥3phr)时,SiO2趋向于分散在NR相中,共混方法对SiO2的分散影响不大。     

偶联剂对EVOH/纳米SiO_2复合材料结构与性能的影响

采用不同的偶联剂KH550、KH560、KH570和KH8431对纳米SiO2进行表面改性,采用熔融共混法将未改性和改性纳米SiO2(5%(质量分数)SiO2)与EVOH共混制成复合材料,并吹塑成薄膜。利用FT-IR、TEM、SEM对不同偶联剂处理的纳米SiO2和复合材料的结构进行表征,并对复合材料的流变性能、阻隔性能、力学性能、耐热性能和透明性进行了表征。结果表明,纳米SiO2与4种偶联剂均形成化学键合,改性纳米SiO2比未改性纳米SiO2在EVOH中分散性好,加工时熔体的流动性更好。用KH550处理的纳米SiO2在EVOH中分散性最好,与EVOH能形成较大界面相互作用力,与EVOH/未改性纳米SiO2复合材料相比,EVOH/改性纳米SiO2复合材料的拉伸强度和储能模量分别提高17.2%和136%,透湿、透氧系数分别下降11.2%和9.5%,透光率达到74.9%,雾度为14.9%。     

PP-g-MAH对PP/SiO2纳米复合材料力学性能的影响

为了进一步提高聚丙烯的力学性能,以马来酸酐接枝聚丙烯(PP-g-MAH)为聚丙烯/二氧化硅(PP/SiO2)纳米复合材料的界面相容剂,研究了PP-g-MAH添加量对PP/SiO2的力学性能、微观形态以及结晶行为的影响,并研究了其增容机理.研究表明:PP-g-MAH的加入使纳米PP/SiO2纳米复合材料的力学性能得以全面提高,使纳米二氧化硅与聚丙烯的界面粘结得到改善,并且,由于PP-g-MAH导致复合材料的界面强度提高和界面层厚度增加,使KH-570与PP-g-MAH并用的PP/PP-g-MAH/纳米SiO2复合材料比单用KH-570的PP/SiO2纳米复合材料的改性效果更加明显;PP-g-MAH对PP的结晶过程具有较明显的成核作用,使改性PP的结晶温度提高.     

嵌段齐聚物修饰纳米SiO2对PET结晶性能的影响

采用溶液聚合法在纳米 SiO2表面接枝两种不同性质的齐聚物聚乙二醇(PEG)和聚对苯二甲酸乙二酯低聚物(LMPET),通过 FTIR、1 H-NMR、XPS 和 HR-TEM 对其结构形貌进行表征。采用熔融共混制备 PET 纳米复合材料,并利用 DSC 和 XRD 对改性纳米 SiO2对 PET 结晶性能的影响进行研究。结果表明,LMPET 通过 PEG 成功接枝到 SiO2表面,粒径尺寸为40~50 nm;纳米 SiO2可作为成核剂诱导 PET 的结晶提高结晶速率,当添加量为2%(质量分数)时,结晶温度得到明显提高。     

Thermal degradation kinetics and morphology of natural rubber/silica nanocomposites

A novel natural rubber/silica (NR/SiO2) nanocomposite with a SiO2 loading of 4 wt% is developed by incorporating latex compounding with self-assembly techniques. The SiO2 nanoparticles are homogenously distributed throughout the NR matrix as spherical nano-clusters with an average size of 75 nm. In comparison with the host NR, the thermal resistance of the nanocomposite is significantly improved. The degradation temperatures (T), reaction activation energy (E), and reaction order (n) of the nanocomposite are markedly higher than those of the pure NR, due to significant retardant effect of the SiO2 nanoparticles.     

Effect of grafted polymer species on particle monolayer structure at the air-water interface

We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass substrate.     

Synthesis of SiO2-coated ZnMnFe2O4 nanospheres with improved magnetic properties

A core-shell structured composite, SiO2 coated ZnMnFe2O4 spinel ferrite nanoparticles (average diameter of approximately 80 nm), was prepared by hydrolysis of tetraethyl orthosilicate (TEOS) in the presence of ZnMnFe2O4 nanoparticles (average diameter of approximately 10 nm) synthesized by a hydrothermal method. The obtained samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FESEM). The magnetic measurements were carried out on a vibrating sample magnetometer (VSM), and the measurement results indicate that the core-shell samples possess better magnetic properties at room temperature, compared with paramagnetic colloids with a magnetic core by a coprecipitation method. These core-shell nanospherical particles with self-assembly under additional magnetic fields could have potential application in biomedical systems.     

水性聚氨酯为表面活性剂的SiO2-聚甲基丙烯酸甲酯复合微球的细乳液法制备

采用异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇N210和二羟甲基丙酸(DMPA)为主要反应原料, 合成出羧酸型水性聚氨酯, 并以甲基丙烯酸羟乙酯(HEMA)对其进行C=C封端, 然后使用该水性聚氨酯作为可聚合表面活性剂, 采用双原位细乳液法, 不同引发剂体系引发聚合, 制备出SiO₂-聚甲基丙烯酸甲酯复合微球。通过TEM、FTIR和TGA等测试方法对所得产物进行了表征分析。结果表明, 使用水性聚氨酯表面活性剂(PUS)所制备的SiO₂-聚甲基丙烯酸甲酯复合微球形貌, 不同于传统小分子表面活性剂所制得产物的形貌, 而且引发剂类型对SiO₂-聚甲基丙烯酸甲酯复合微球形貌有较大影响。     

多孔壳/磁核结构光催化剂的制备及表征

以聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物(P123)为结构导向剂,钛酸丁酯(TBOT)为钛源,SiO2/NiFe2O4为核,制备了具有多孔结构可磁分离的Ti O2/SiO2/NiFe2O4光催化剂。采用N2吸附-脱附、TEM、HRTEM、SEM、XRD和VSM等手段对样品进行分析表征。样品颗粒呈球形,分布均匀,平均粒径约为40nm,具备良好的磁分离性能。以硝基苯为模拟物测定其光催化活性,UV光照条件下,240min内硝基苯污染物降解完全,表明该光催化剂具有良好的光催化活性。     

PMMA/SiO_2-TiO_2杂化纤维的制备与表征

以正硅酸乙酯和钛酸四丁酯为前驱体,乙烯基三乙氧基硅烷为偶联剂,采用溶胶凝胶原位聚合法制备了聚甲基丙烯酸甲酯/二氧化硅-二氧化钛(PMMA/SiO2-TiO2)杂化溶胶,陈化后用提拉法制得杂化纤维。研究了溶胶的杂化反应机理;使用红外光谱(IR)、扫描电子显微镜(SEM)、紫外-可见光谱(UV-Vis)、荧光光谱(FL)和热重分析(TGA)分析了杂化纤维的结构与性能。结果表明,PMMA与SiO2-TiO2之间通过化学键连接;纤维直径为150μm,在纤维内部有机无机相间形成均一的连续相;TiO2的引入增加了其抗紫外性;杂化纤维具有荧光性能;其耐热性能优于纯PMMA。     

SiO2纳米粒子填充PS/PMMA共连续共混物的应力松弛行为

采用流变测试和扫描电子显微镜技术,考察了亲水性SiO2纳米粒子对具有共连续结构的聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)(体积比50/50)共混物在步阶剪切应变下应力松弛行为的影响。研究表明,PS/PMMA共混物呈现两步应力松弛行为,即来源于本体聚合物的较快的松弛以及来源于界面的较慢的松弛。SiO2粒子的加入细化了共混物的形态尺寸,加速了共混物第二阶段的松弛行为。同时,实验结果进一步表明,填充共混物应力松弛行为的加快主要是由于SiO2的加入引起形态细化造成的,而并非组分粘弹性的变化。     

Template guided self-assembling two-dimensional array of Au@SiO2 core-shell nanoparticles for room-temperature single electron transistors

The composite nanoparticles of a gold core capped by a SiO2 shell with well-controlled thickness have been synthesized and fabricated into two-dimensional array on silicon surface by a simple self-assembly method combined with an AFM nanolithography technique. Current-voltage measurements of the Au@SiO2 composite nanoparticles (shell thickness of 6 nm) show a well-pronounced Coulomb staircase with a period of 300 mV at room temperature, demonstrating single electron transistor behavior. The step width of the Coulomb staircase can be tuned by controlling the thickness of SiO2 shell. The tunable single electron tunneling properties make the 2D array of Au@SiO2 composite nanoparticles an ideal candidate for planar single electron transistor devices.     

Optical properties of titanium dioxide nanoparticles/3-(2-benzothiazolyl)-7-N,N-diethylaminocoumarin/polymethyl methacrylate composite films

3-(2-benzothiazolyl)-7-N,N-diethylaminocoumarin organic laser dye-polymethyl methacrylate (PMMA) composite films doped with inorganic titanium dioxide (TiO₂) particles are fabricated by spin-coating technique. TiO₂ nanoparticles exhibit a strong influence on optical properties of the organic laser dye/PMMA composite films. The refractive index and absorbance (absorption intensity) of organic laser dye/PMMA composite film with micro- and nanoparticles of TiO₂ are reduced, compared to those without TiO₂ particles. The organic laser dye/PMMA composite film with TiO₂ nanoparticles has the lowest refractive index and absorbance values. Photoluminescence intensities of all systems exhibit a maximum peak around the excitation wavelength, close to that of the organic laser dye, at 450 nm and the minimum around the excitation wavelength of 350 nm. Photoluminescence intensity of the organic laser dye/PMMA composite film with TiO₂ microparticles is always the lowest at all excitation wavelengths. However, the photoluminescence intensity of the organic laser dye/PMMA composite film with TiO₂ nanoparticles has the highest value at excitation wavelengths of 330 and 380 nm, while the photoluminescence intensity of composite film without TiO₂ particles is more than that with nanoparticles at other excitation wavelengths.     

Low-temperature Preparation of Photocatalytic TiO2 Thin Films on Polymer Substrates by Direct Deposition from Anatase Sol

Anatase TiO2 sol was synthesized under mild conditions （75℃ and ambient pressure） by hydrolysis of titaniumn-butoxide in abundant acidic aqueous solution and subsequent reflux to enhance crystallization. At room temperature and in ambient atmosphere, crystalline TiO2 thin films were deposited on polymethylmethacrylate （PMMA）, SiO2-coated PMMA and SiO2-coated silicone rubber substrates from the as-prepared TiO2 sol by a dip-coating process. SiO2 layers prior to TiO2 thin films on polymer substrates could not only protect the substrates from the photocatalytic decomposition of the TiO2 thin films but also enhance the adhesion of the TiO2 thin films to the substrates. Field-emission type scanning electron microscope （FE-SEM） investigations revealed that the average particle sizes of the nanoparticles composing the TiO2 thin films were about 35-47 nm. The TiO2 thin films exhibited high photocatalytic activities in the degradation of reactive brilliant red dye X-3B in aqueous solution under aerated conditions. The preparation process of photocatalytic TiO2 thin films on the polymer substrates was quite simple and a low temperature route.