Preparation of hydrophobic organic-silicanano composites

In this paper, we use silica nanoparticles modified by methacryloxy propyl trimethoxylsilane (KH570) as the core material, and employ polymers including hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and acrylic ester as the shell materials to prepare the hydrophobic inorganic–organic hybrid nanocomposites with a seed emulsion polymerization strategy. The size, morphologyandproperties of the core-shell structured nanoparticles are investigated by TEM and SEM. The results showthat the polymer nanocomposite has three concentric layers with silica nanoparticles in the center, acrylic polymer as the internal shell and fluorosilicone polymer as the outmost shell. By controlling the ratio of the silica nanoparticles and monomers, we can achieve each composite particle has the core-shell structure with silica nanoparticles as the core and the thin layer of fluorosilicone polymer as the shell. Compared with the traditional polymer film, the nanocomposite film shows a hydrophobic property with a contact angle of up to 100 degree. Therefore, it is feasible to prepare hydrophobic organic–inorganic nanocomposites using the method proposed here.     

Switching behavior of thermochromic copper and silver tetraiodomercurate embedded in silica hybrid materials

Thermochromic silica hybrids containing copper or silver mercuric iodides and cetyltrimethylammonium bromide (CTAB) were obtained and characterized. The color and switching behavior of the materials was studied in relationship with the structure of the thermochromic composites and silica network modifiers. In order to evidence the presence of the components and possible interactions governing the thermochromic transition, ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis – DR), Fourier transform infrared spectroscopy – attenuated reflection (FTIR-ATR), X-ray diffraction spectroscopy (XRD) and X-ray fluorescence (XRF) analysis were performed. The dynamic behavior was studied by UV–Vis reflectance spectra, FTIR and differential thermal analysis (DTA) analysis. Results confirm that during the embedding of thermochromic compounds in silica hybrid matrices, in the presence of CTAB, some interactions are established between thermochromic compounds and CTAB. These interactions determine the parameters of thermochromic transition in all cases of thermochromic composites. Hysteresis during the repetitive heating–cooling cycles was also observed. Thermal stability of the thermochromic compounds was enhanced after embedding in silica hybrids.     

硅丙乳液包覆Mg(OH)2核壳结构纳米粒子的制备与表征

为有效提高Mg(OH)_2纳米粒子在硅丙乳液中的相容性与分散稳定性,在油酸修饰Mg(OH)_2纳米粒子的基础上,以甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸与乙烯基三乙氧基硅烷为共聚单体,通过乳液聚合法制备出具有核壳结构的硅丙乳液包覆Mg(OH)_2复合材料。利用傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、透射电子显微镜(TEM)等测试手段对样品结构、形貌进行了表征。通过燃烧实验,研究了硅丙乳液包覆Mg(OH)_2纳米粒子对水性防火涂料阻燃性能的影响。结果表明,油酸通过酯化作用修饰在Mg(OH)_2纳米粒子表面,借助油酸分子中双键结构,丙烯酸类混合单体在纳米Mg(OH)_2表面完成聚合过程,形成以Mg(OH)_2纳米粒子为核、硅丙乳液为壳的复合材料。XRD与热分析表明经硅丙乳液包覆的纳米Mg(OH)_2晶体结构与热稳定性能未受影响。此外,掺杂0.1%(质量分数)的硅丙乳液包覆Mg(OH)_2可使水性防火涂料阻燃时间延长至113 min,较未掺杂水性涂料阻燃时间(91min)提高约23%。     

A comprehensive study of soft magnetic materials based on FeSi spheres and polymeric resin modified by silica nanorods

A novel soft magnetic composite (SMC) based on spherical FeSi particles precisely covered by hybrid phenolic resin was designed. The hybrid resin including silica nano-rods chemically incorporated into the phenolic polymer matrix was prepared by the modified sol–gel method. A chemical bridge connecting silica nano-rods with the base polymeric net was verified by FTIR, ¹³C and ²⁹Si NMR spectroscopy, whereas the shape and size of silica nano-rods were determined by TEM. It is shown that the modification of polymeric resin by silica nano-rods generally leads to the improved thermal and mechanical properties of the final samples. The hybrid resin serves as a perfect insulating coating deposited on FeSi particles and the core–shell particles can be further compacted by standard powder metallurgy methods in order to prepare final samples for mechanical, electric and magnetic testing. SEM images evidence negligible porosity, uniform distribution of the hybrid resin around FeSi particles, as well as, dimensional shape stability of the final samples after thermal treatment. The hardness, flexural strength and density of the final samples are comparable to the sintered SMCs, but they simultaneously exhibit much higher specific resistivity along with only slightly lower coercivity and permeability.     

Studies on preparation and properties of the multi-walled carbon nanotubes (MWNTs)/epoxy nanocomposites

The MWNTs were coated with polyaniline (PANI) by in situ chemical oxidation polymerization method. FTIR spectroscopy, scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated that the MWNTs were coated with PANI. The MWNTs/epoxy nanocomposites were fabricated by using the solution blending method. Differential scanning calorimetry (DSC), tensile testing, HP 4294A impedance analyzer and SEM were used to investigate the properties of the nanocomposites. The results showed that the modified carbon nanotubes were well dispersed in the polymer matrix. The nanocomposites have enhancements in mechanical, thermal and dielectric properties compare with the neat epoxy resin. The nanocomposites were proven to be a good polymer dielectric material.     

Use of precipitated silica with silanol groups as an inorganic chain extender in polyurethane

In this study, novel polyurethane/silica (PU/SiO₂) hybrid materials, prepared without an external crosslinking agent, were developed via the chemical reaction between urethane groups of PU prepolymer and hydroxyl groups at the surfaces of silica. The added inorganic filler-silica thus played the dual roles not only inorganic chain extender but also reinforcing agent in the preparation of the hybrid. Two different blending methods, were compared with respect to the mechanical properties of the PU/SiO₂ hybrid materials: stirring mixing and three-roller shear mixing. The hybridization mechanism was confirmed using Fourier-transform infrared spectroscopy (FT-IR), solid-state ²⁹Si NMR spectroscopy and X-ray diffraction (XRD). The dispersion of silica particles in the PU matrix was investigated by scanning electron microscopy (SEM). Because of the shear effect of three-roller shear process, the size of the silica aggregates tended to be more uniform. The tensile strength and elongation at break of the PU/SiO₂ hybrid were 51 MPa and 590%, respectively, which represent increases of fourfold and 39% compared to those of neat PU. The thermogravimetric analysis (TGA) results for the PU/SiO₂ hybrids indicated greater thermal stabilities and lower decomposition rates after hybridization. This work contributes new insights into the preparation of high-performance PU/SiO₂ hybrids.     

Small-angle X-ray scattering and FTIR characterization of nanostructured poly (vinyl alcohol)/silicate hybrids for immunoassay applications

In the present work we aimed to develop and characterize hybrid organic–inorganic materials based on poly(vinyl alcohol) (PVA) polymer chemically modified by organosilanes and crosslinked network to be tested as solid support on immunoassay application. Hybrids were synthesized by reacting PVA with 5 different alkoxysilanes modifying chemical groups: tetraethoxysilane (TEOS), 3-mercaptopropyltriethoxysilane (MPTES), 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-(triethoxysilyl)propylisocyanate (TESPI), and 3-aminopropyltriethoxysilane (APTES). PVA-derived hybrids were also modified by chemically crosslinking with glutaraldehyde (GA) during the synthesis reaction. In order to investigate the structure in the nanometer-scale, PVA-derived hybrids were characterized by using small-angle X-ray scattering synchrotron radiation (SAXS). Fourier transform infrared spectroscopy (FTIR) was used to investigate PVA hybrids chemical functionalities and their interaction with bovine herpesviruses. The morphology of silane modified PVA films were also analyzed by SEM coupled to EDX. The bioactivity assays were tested through Enzyme Linked Immunosorbent Assay (ELISA) with bovine herpesvirus (BoHV). SAXS results have indicated nano-ordered disperse domains for PVA hybrids with different X-ray scattering patterns for PVA polymer and PVA-derived hybrids. FTIR spectra have clearly showed that the proposed modifications of PVA by organosilanes were obtained. The chemical crosslinking of PVA polymer chain by GA was verified by FTIR. The immunoassay results have showed that PVA hybrids with chemically functionalized structures have played an important role on regulating to some extent the interaction of herpesvirus and solid substrate at the interface. These results have given strong evidence that PVA-derived hybrid nanocomposites were successfully formed with GA crosslinked network. Also, such PVA based material could be advantageously used in immunoassays with enhanced specificity for diagnosis.     

Synthesis and characterization of novel hyperbranched polyimides/attapulgite nanocomposites

Novel hyperbranched polyimides/attapulgite (HBPI/AT) nanocomposites were successfully synthesized by in situ polymerization. HBPI derived from novel 2,4,6-tri[3-(4-aminophenoxy)phenyl]pyridine (TAPP) and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA). 4,4′-diphenylmethane diisocyanate (MDI) modified AT copolymerized with HBPI and the nanocomposites formed multilinked network. Chemical structure, morphology, thermal behavior, and mechanical properties of nanocomposites were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and tensile testing et.al. Results indicated that modified AT was homogeneously dispersed in matrix and resulted in an improvement of thermal stability, mechanical properties and water resistance of HBPI/AT nanocomposites.     

细乳液聚合制备纳米二氧化硅-丙烯酸酯复合乳液的研究

采用硅溶胶和丙烯酸酯单体通过细乳液聚合制备纳米二氧化硅/丙烯酸酯复合高分子乳液。考察了聚合过程中硅溶胶量对于单体转化率和聚合物粒子粒径的影响,并用GPC、XPS表征所得的复合乳液。实验结果表明:二氧化硅的引入提高了聚合反应速率,增加聚合物的分子量并使分子量分布变窄;在复合乳液粒子中,二氧化硅主要以分散相分布在连续的丙烯酸酯相内部;复合乳液的力学性能明显优于不含二氧化硅的纯丙烯酸酯聚合物乳液。     

Preparation and characterization of epoxy nanocomposites by using PEO-grafted silica particles as modifier

EP/SiO₂ nanocomposites, which contained PEO flexible chain, have been prepared via epoxy resin and PEO-grafted silica particles. The PEO-silica particles were obtained by endcapping PEO-1000 with toluene 2,4-diisocyanate (TDI), followed by a reaction with silica sols. The chemical structure of the products was confirmed by IR measurements, and the mechanical properties of composites such as impact strength, flexural strength, dynamic mechanical thermal properties were investigated. The results showed that the addition of the PEO-grafted silica particles to the epoxy/DDS curing system, the impact strength is 2 times higher than that of the neat epoxy. While the storage modulus and the glass transition temperature are a little changed. The morphological structure of impact fracture surface and the surface of the hybrid materials were observed by scanning electron microscope (SEM) and atomic force microscopy (AFM), respectively.     

聚氨酯/环氧树脂互穿聚合物网络半硬泡沫的结构与性能

采用同步法合成了聚醚型聚氨酯/环氧树脂互穿聚合物网络半硬泡沫.通过FTIR,DMA,SEM研究了IPN半硬泡沫的化学结构、动态力学性能以及微观结构形态.FTIR分析表明了聚氨酯和环氧树脂的网络间存在接枝反应.很宽组成比范围内IPN半硬泡沫均显示出单一的宽温域玻璃化转变,而且该转变随着环氧树脂含量的增加向高温方向移动.通过SEM发现IPN半硬泡沫泡孔结构形状都比较均一.循环加载压缩发现所有IPN泡沫不仪压缩性能好而且具有很好的回弹性,大变形压缩后泡沫儿乎不变形,重复使用性能好.     

废印刷电路板非金属粉负载二氧化硅杂化填料的制备及其在不饱和聚酯中的应用

为增强废印刷电路板非金属粉(WPCBP)与聚合物基体之间的界面结合作用,采用溶胶-凝胶法在WPCBP表面原位负载了一层纳米二氧化硅粒子(SiO2),制备了一种新型的WPCBP-SiO2杂化填料.SEM、TGA和FTIR证明SiO2通过化学键成功负载到了杂化填料的表面.采用含双键的界面改性剂对杂化填料进行改性后,应用于不饱和聚酯树脂基体,探讨了未改性杂化填料及表面改性杂化填料对不饱和聚酯复合材料的力学性能、界面结合作用和热稳定性能的影响.结果表明,新型的杂化填料WPCBP-SiO2能够与不饱和聚酯基体形成强的界面结合作用,显著提高不饱和聚酯复合材料的力学性能和热稳定性能,且表面改性后复合材料的各项性能得到进一步提高.     

丙烯酸树脂/TiO2有机-无机杂化材料的力学、热学和光学性能研究

采用溶胶-凝胶法成功制备了均匀透明的丙烯酸树脂/TiO2有机-无机杂化材料.通过动态力学分析仪(DMA)、电子拉力机(Instron Tester)、热失重分析仪(TGA)和紫外可见光谱(UV-VIS)等手段表征了杂化材料的力学、热学和光学性能.结果发现丙烯酸树脂与TiO2杂化后,聚合物的力学性能、热稳定性和紫外屏蔽性能均有显著提高.与原位聚合法相比,共混法合成该杂化材料可获得更优异的力学性能.增加丙烯酸树脂中的丙烯酸含量能显著降低相分离,从而使其各种性能,特别是力学性能得以提高.     

Influence of addition of silica particles on reaction-induced phase separation and properties of epoxy/PEI blends

Polyether imides (PEI)/silica nanocomposites, prepared by sol–gel process, were used to modify the epoxy resin (ER), and the effect of silica particles on reaction-induced phase separation and mechanical properties of these systems were investigated. SEM images of the fracture surface of ER/PEI/silica composites showed an interesting morphology transformation with the increase of silica particle content. SEM–EDX results indicated that silica particles once formed in the PEI gradually migrated and concentrated in epoxy-rich region during the phase separation because of the better affinity between silica particles and epoxy resin. FTIR measurement and rheological test confirmed that the silica particles make the polymerization reaction of epoxy faster and the dynamic DSC results demonstrated that the activation energy of these systems decreased with the increase of the silica particles. Mechanical measurements approved that the introducing of PEI/silica nanocomposites into the epoxy could lead to great improvement of the impact strength and storage module.     

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.     

Nanocomposites of poly(ε-caprolactone) doped with titanium species

Organic–inorganic hybrid nanocomposites were prepared via in situ sol–gel process. The organic phase is a biodegradable polymer, poly(ε-caprolactone) (PCL), while the tetrabutyl titanate (TBT, Ti(OBu)₄) was used as inorganic precursor. Synthesis parameters like acidity medium and precursor amount were investigated in order to assess their influence on hybrid properties. The obtained nanocomposites were characterised by thermal analysis, spectroscopic techniques, transmission electronic microscopy (TEM) and X-ray diffraction to gather information on the structure of the nanocomposites. Mechanical properties and biodegradability were also evaluated. A reaction mechanism based on Fourier transform infrared spectroscopy and NMR results was proposed using methyl acetate as model compound. TEM micrographs of the nanocomposites show a fine good nanoparticles dispersion. Acidic conditions and 10 wt% of precursor lead to a nanocomposite with higher mechanical properties and biodegradability than PCL.     

Organic/inorganic hybrid nanospheres based on hyperbranched poly(ethylene imine) encapsulated into silica for the sorption of toxic metal ions and polycyclic aromatic hydrocarbons from water

Organic–inorganic hybrid silica nanospheres were prepared through a biomimetic silicification process in water at ambient conditions by the interaction of low cost poly(ethylene imine) hyperbranched polymer with silicic acid. The characterization of these nanoparticles by FTIR spectroscopy, scanning electron microscopy (SEM), zeta-potential and dynamic light scattering (DLS) experiments confirmed that the dendritic polymer was incorporated into the silica network. Preliminary experiments show that these hybrid nanoparticles can be employed for the removal of toxic water contaminants. Hybrid nanospheres’ sorption of two completely different categories of pollutants, i.e. metal ions such as Pb²⁺, Cd²⁺, Hg²⁺, Cr₂O₇²⁻, and polycyclic aromatic hydrocarbons such as pyrene and phenanthrene, was largely enhanced in comparison with the corresponding polymer-free silica nanospheres. This was attributed to the to the formation of conventional metal-ligand and charge-transfer complexes proving that although integrated into the silica network poly(ethylene imine) retains its chemical properties.     

Preparation of poly(acrylic)/SiO2/EuL3 x 2H2O, hybrid thin films from monodispersed colloidal silica

In this study, poly(acrylic)/SiO2/EuL3 x 2H2O hybrid thin films were prepared from various acrylic monomers (MMA and EDMA/TMPTA), lanthanide metal complexes (EuL3 x 2H2O, L = pyridine carboxylic acid), and monodispersed colloidal silica with a coupling agent, 3-(trimethoxysilyl)propyl methacrylate (MSMA). It is a combination of the sol-gel reaction, thermal polymerization, and spin coating. The silica content in the hybrid thin films is fixed at 20 wt%, and the EuL3 x 2H2O content is varied from 0.01 g to 0.07 g. FTIR and EA analysis confirms the chemical structure of the prepared EuL3 x 2H2O and poly(acrylic)/SiO2/EuL3 x 2H2O hybrid thin films. UV-Vis spectra and n&k analysis shows that the hybrid thin film has good transparency in visible light. The refractive index of hybrid thin films can be effectively controlled through the EuL3 x 2H2O content. The PL spectra shows that the strongest emission peak occurs at 615 nm and the emission intensity increases to the peak maximum at an EuL3 x 2H2O content of 0.05 g. Both TGA and PL analysis show that the prepared hybrid thin films from the crosslinked acrylic polymer moiety have much better film uniformity, thermal stability, and fluorescence properties. The TEM diagram shows that the MSMA/SiO2/EuL3 x 2H2O particles with a size 15-20 nm are well dispersed in the reaction solution. The SEM diagram shows that the particle distribution in the prepared hybrid thin films is uniform and no phase separation is observed. Finally, AFM analysis indicates that the prepared hybrid thin films have an excellent surface planarity.     

Thermophysical and rheological behavior of polystyrene/silica nanocomposites: Investigation of nanoparticle content

In this work, solvent blending in combination with extruding are applied to provide polystyrene/silica nanocomposite specimens. Transmission electron microscope (TEM) and scanning electron microscope (SEM) show same nanoparticle dispersion in PS matrix in low to high filler loadings. Differential scanning calorimetry (DSC), dynamic mechanical thermal analyzer (DMTA) and thermogravimetric analyzer (TGA) were used to study the thermophysical characteristic of the nanocomposites in solid state. In addition, the melt state rheological behavior of the samples was investigated under constant and zero shear rates. Interestingly, different behaviors were detected in nanocomposites in low and high nanoparticle loadings. In addition, rheological characteristics of molten polymer are dramatically affected in samples with low nanosilica concentration while stabilized in high filler loadings.     

丙烯酸树脂/蒙脱土纳米复合材料的制备与鞣制性能

通过原位插层聚合法制备了两种丙烯酸树脂/蒙脱土纳米复合材料,采用X射线衍射、透射电镜及核磁共振等方法对纳米复合材料的结构进行了表征。研究结果表明,所制备的两种纳米复合材料均为剥离型纳米复合材料,纳米复合材料的热性能较相应聚合物提高20℃左右。应用结果表明,两种纳米复合材料均具有鞣制性能,其应用性能较相应聚合物有所提高。