改性纳米SiO2/硅橡胶复合材料的制备及性能

为提高纳米SiO₂在硅橡胶（SR）基体中的分散性及两相间的界面结合力,设计以羟基硅油（HSO）和γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）为纳米SiO₂的表面封端改性剂,并将改性SiO₂与双组份加成型液体SR复合得到改性纳米SiO₂/SR复合材料。通过一系列表征手段对改性纳米SiO₂的形貌结构及其在乙醇中的分散性等进行分析,研究了改性纳米SiO₂对纳米SiO₂/SR复合材料的断面形貌、力学性能及热稳定性的影响。结果表明:KH570成功接枝到纳米SiO₂表面并与SR基体间形成化学键。当HSO协同KH570改性纳米SiO₂时,可有效改善纳米SiO₂在SR基体中的分散性能及纳米SiO₂与SR两相间的界面结合性能,并显著提高纳米SiO₂/SR复合材料的力学性能和热稳定性。将SiO₂∶HSO∶KH570以质量比为2.0∶0.2∶0.6处理的改性纳米SiO₂粒子,得到的改性纳米SiO₂/SR复合材料起始热分解温度提高了230℃。当SiO₂∶HSO∶KH570质量比为2.0∶0.2∶0.45时,改性纳米SiO₂/SR复合材料的拉伸强度和断裂伸长率分别提高了约1倍。      

乙烯-醋酸乙烯酯共聚物增强硅橡胶复合材料的黏弹阻尼性能

在密炼机中将醋酸乙烯基（VA）含量为18%（质量比）的乙烯-醋酸乙烯酯共聚物（EVA）与硅橡胶（SR）共混,再在开炼过程中加入橡胶其他组分混合得到EVA/SR混炼胶,硫化形成EVA/SR宽温域黏弹阻尼复合材料。采用毛细管流变仪、橡胶加工分析仪（RPA）、动态力学热分析仪（DMA）和DSC研究了EVA含量对EVA/SR复合材料的力学性能、加工性能、阻尼性能和热性能的影响。结果表明:加入较多EVA可更明显地改善SR的硬度和模量及撕裂强度,并使其拉伸强度和断裂伸长率仍然较高,保持在SR使用要求范围内。EVA/SR混炼胶剪切变稀,增大剪切应变幅值显示明显的Payne效应,用Kraus模型可分析EVA含量和硫化的影响。EVA分散于白炭黑填充的SR化学交联网络中形成多重结构;SR降低了EVA的结晶温度,添加EVA起到了增强和增黏SR的作用。纯SR损耗因子大于0.1的温度范围为-42~-28℃;对于EVA:SR质量比为40:100的EVA/SR复合材料,其最大损耗因子从0.125提高到0.18,有效阻尼温域为-23~37℃。这明显拓宽了SR有效阻尼温域,可应用于较高温度减震降噪工程。      

SiO2 / Ni 核壳结构纳米粒子的制备及其磁性能

以硅酸钠为主要原料, 通过液相沉淀法在纳米镍粉表面包覆了一层SiO₂ 。应用XRD、FTIR、TEM、TGA、DSC 和VSM 对复合粉体的结构、形貌和磁性能进行了研究。结果表明, SiO₂ 以非晶态的形式包覆在纳米镍粒子表面, 形成了核壳结构, 降低了纳米粉体的团聚现象。TGA 和DSC 结果表明, SiO₂ 的包覆提高了纳米粉体的抗氧化性。磁性分析结果表明, 粉体包覆前由于表面氧化层(NiO) 的存在, 粉体的磁滞回线偏移; 包覆后的粉体由于SiO₂的存在, 饱和磁化强度降低, 矫顽力升高。      

Preparation and characterization of nano-hydroxyapatite/silicone rubber composite

To take advantage of the merits for both hydroxyapatite (HA) and silicone rubber (SR) in medical applications, we developed a novel method to produce a new nano-composite of these two widely used biomaterials. In this work, n-HA (nano-hydroxyapatite) slurry, which was modified by silane coupling agent, was mixed with silicone gum and the nano-composite could therefore be achieved. It is found that the dispersion states of the n-HA particles in SR are homogeneous and the mechanical properties of the composite can be improved significantly. The composites with micrometer HA (μ-HA) and SR were taken as the contrast for comparison. We find that the tensile strength of the n-HA/SR composite can be enhanced greatly in comparison with that of the μ-HA/SR composite.     

超导YBa2Cu3O7 +δ/硅橡胶复合材料的压敏与介电特性

采用YBa₂Cu₃O_{7 +δ}(简称YBCO)多晶陶瓷超导粉末与硅橡胶(110型)按不同质量比进行配料,经过特殊的制备工艺,合成不同含量的超导 YBCO/硅橡胶高分子复合材料,分别测量样品的压敏效应和介电特性。结果表明,在不同应力作用下,样品电阻值的变化范围在1～4个数量级。样品电阻值随测量温度的降低(300~50K)呈下降趋势,测量温度降到90K时,样品电阻值发生突变,但在9050K没有观察到超导零电阻现象。室温下,样品的介电常数随频率的增加(1 kHz~5 MHz)而减小,介电损耗随测量频率的增大先增大后减小。随着YBCO含量的增加,形成的超电容网络微观结构也就越多,样品的电阻逐渐减小电流加大,导致超电容中电解质的极化强度有所增加,两者共同作用的结果导致样品的介电常数、介电损耗均随着YBCO含量的增加而增大。     

A Decomposition Method for the Analysis of Viscoelastic Structural Dynamics with Time‐Dependent Poisson's Ratio

Abstract: This paper presents a decomposition method for the dynamic analysis of elastic–viscoelastic composite (EVC) structures with time‐dependent Poisson's ratio. The analysis splits the viscoelasticity matrix with time‐dependent Poisson's ratio into two matrices in a simple form in which the time‐dependent Poisson's ratio does not appear. The decomposition simplifies the process of dynamical analysis for EVC structures with time‐dependent Poisson's ratio. The approach also makes it possible to apply existing analysis methods for constant Poisson's ratio structures directly to structures with time‐dependent Poisson's ratio. Based on the numerical results of three case studies, it is found that the time‐dependent Poisson's ratio has little influence on the structure's natural frequencies and damping properties. Therefore, it could be concluded that the effect of time‐dependency in Poisson's ratio may be ignored in the EVC structural dynamic analysis without introducing notable errors.     

Elastic properties of cement-stabilised mixes with steel slag

In this study, we evaluated the elastic and mechanical properties of a new type of cement-stabilised material made with steel slag, varying the content of cement and steel slag. To study the elastic properties of these mixes, we measured their density, compressive strength and ultrasound pulse velocity at curing ages of 7, 28 and 90 days. The aggregate type and curing age greatly affected the elastic properties and varied much depending on the cement content. The Poisson's ratio chosen in analyses had little influence on the dynamic modulus. Various expressions given by building codes were used to predict the elastic properties of the mixtures. These codes generated very different values of the static modulus of elasticity, making most of them unsuitable for predicting the elastic properties of cement-stabilised materials. Using our experimental data, we provide the best combination of existing equations to predict elastic properties, and we conclude that measuring the ultrasound pulse velocity is a suitable way to predict the mechanic and elastic properties of cement-stabilised materials.     

Thermal evolution and optical properties of Cu nanoparticles in SiO2 by ion implantation

SiO₂ samples were implanted by 45 keV Cu ions at a dose of 1 × 10¹⁷ /cm², and subjected to furnace annealing at temperatures ranging from 200 to 600 °C in nitrogen atmosphere. The results indicate that the Cu nanoparticles have been synthesized by Cu ion implantation, and subsequent annealing induces the diffusion and nucleation of nanoparticles partially. The results from XPS measurements show that the Cu⁰ is the dominate charge state in the implanted and subsequent annealed samples. With increasing annealing temperature, the size and distribution of Cu nanoparticles have been modified gradually. The surface plasmon resonance (SPR) of Cu nanoparticles at 570 nm has been observed by optical transmission spectroscopy. The strongest SPR signal at 400-600 °C indicates that lots of Cu nanoparticles have grown and show good optical properties. Moreover, the luminescence has been investigated in Cu implanted and subsequent annealed samples. Possible luminescence mechanisms, such as radiation induced defects, Cu (ions or atoms) related luminescence centers, etc., have been discussed.     

Cryogenic properties of SiO2/epoxy nanocomposites

SiO₂/epoxy nanocomposites were prepared using diglycidyl ether of bisphenol-F (DGEBF) type epoxy and tetraethylorthosilicate (TEOS) via the sol-gel process. Silica nanoparticles were collected after burning off the matrix resin and the silica nanoparticles were observed using TEM. The cryogenic tensile properties at 77 K and thermal expansion coefficient of the nanocomposites were studied. The tensile properties at room temperature were also given to compare with the cryogenic tensile properties. The fracture surfaces were examined with scanning electron microscopy (SEM). The effects of silica nanoparticle content have been studied on the cryogenic tensile and thermal properties of the nanocomposites. In addition, the dependence of the glass transition temperature on the silica nanoparticle content has also been examined.     

Preparation and characterization of sol-gel derived Er-Yb codoped SiO2/TiO2 core-shell nanoparticles

The Er³⁺-Yb³⁺ codoped silica/titania core-shell nanoparticles were prepared by hydrolysis of titanium alkoxide precursors in the presence of lanthanide ions via sol-gel method. The structure of the particles was characterized by field emission scanning electron microscopy and transmission electron microscopy. The diameter of the silica core is about 50 nm. The thickness of the titania shell is about 4 nm. A typical doping density of Er³⁺ in the titania shell is 4.51 at.%, and the one of Yb³⁺ is 12.20 at.%. The UV-vis-NIR absorption spectra and the photoluminescence spectra were also investigated.     

Hydrophilic and photocatalytic properties of the SiO2/TiO2 double layers

The hydrophilic and photocatalytic properties of the SiO₂/TiO₂ double layers composed of a 20-nm-thick porous SiO₂ layer on the 200-nm-thick columnar anatase TiO₂ layer were studied. The hydrophilicity of the double layers was strictly determined by the relative coverage of organic contaminants. The intrinsic hydrophilicity of 0° of SiO₂ in terms of the water contact angle was restored by the photocatalytic decomposition of organic contaminants under the UV light irradiation.Electron spin resonance measurements revealed the generation of OH radicals under the UV light irradiation onto the SiO₂/TiO₂ double layers. Photoconductivity measurements showed that the current decay in O₂ gas atmosphere was remarkably fast in comparison with that in H₂O vapor. These observations support our view that the generation of OH radicals effective for decomposing organic contaminants on the surface begins with the reaction between O₂ molecules and the photoexcited electrons. We propose together with other experimental facts herein that OH radicals would be generated via O₂⁻ and H₂O₂ in the double layer system.     

Synthesis and properties of chitosan/SiO2 hybrid materials

This study primarily aims to explore the strength and thermal properties of various hybrid materials that are made of tetraethoxysilane/vinyltriethoxysilane (TEOS/VTES) and chitosan in different weight ratios. It is confirmed, from micro Fourier transform infrared (micro FT-IR) and nuclear magnetic resonance (NMR) analysis, that hydrogen bonds emerge between chitosan and SiO₂ in hybrid materials. With the addition of more VTES and TEOS, the surface of the hybrid material features thick granules. In addition, the mechanical performance and thermostability of both types of hybrid are better than pure chitosan. The former is enhanced with an increasing amount of TEOS until it exceeds 2.4 g and the latter is also improved with an increasing amount of TEOS.     

Fabrication and characterization of transparent ZnO–SiO2/silicone nanocomposites with tunable emission colors

ZnO quantum dot-SiO₂ (Z–S) nanocomposite particles with tunable photoluminescence were obtained via hydrolyzing tetraethoxysilane in the ZnO quantum dots containing ethanol solution with further calcinations. The nanocomposite particles were introduced into a transparent silicone matrix and the ratio of ZnO to SiO₂ was adjusted to maintain the transmittance in terms of the filler-matrix refractive index matching principle. Finally, transparent Z–S/silicone nanocomposites with tunable emission colors were successfully fabricated which may find potential applications as encapsulating materials for highly bright LED lamps.     

Hierarchical electrospun SiO2 nanofibers containing SiO2 nanoparticles with controllable surface-roughness and/or porosity

Herein we report that hierarchical electrospun SiO₂ nanofibers incorporated with SiO₂ nanoparticles with fiber diameters being ∼ 500 nm and particle sizes being tens of nanometers were developed through the combination of sol-gel process and electrospinning technique followed by high-temperature pyrolysis; and their morphologies and BET surface areas were examined. The study revealed that the pre-gelation of tetraethyl orthosilicate (TEOS) in spin dopes was important to achieve the morphological consistence of the electrospun precursor nanofibers and the resulting final SiO₂ nanofibers; additionally, SiO₂ nanoparticles appeared to be enriched on the fiber surface, while the surface-roughness and/or porosity of the nanofibers could be controlled through adjusting the incorporation amount of SiO₂ nanoparticles. The developed hierarchical electrospun SiO₂ nanofibers are expected to have important applications in composites (particularly dental composites) as well as catalyst support and adsorption.     

纳米TiO2/液体硅橡胶直流电缆附件绝缘复合材料的介电性能

高压直流电缆附件在电力系统运行中,由于复合绝缘电导率不匹配极易导致电场畸变引发绝缘故障。针对这一问题,采用直接共混法制备了不同掺杂浓度的纳米TiO₂/液体硅橡胶（LSR）复合材料,并对其微观形貌和介电性能进行了测试研究。结果表明:纳米TiO₂粒子在LSR基体中分散较均匀,随着TiO₂掺杂含量的增加,纳米TiO₂/LSR复合材料试样的相对介电常数和介质损耗因数增大。当纳米TiO₂粒子添加量为4wt%时,纳米TiO₂/LSR复合材料的电导率与电缆主绝缘交联聚乙烯（XLPE）的电导率近似相等,且随着电场强度的增大,两者的电导率变化趋势也基本一致。电声脉冲法（PEA）测量结果表明,添加4wt% TiO₂的纳米TiO₂/LSR复合材料内积聚的空间电荷最少。纳米TiO₂粒子的掺杂,提高了TiO₂/LSR复合材料电缆附件绝缘电导率对电场强度的响应依赖特性,使其能与XLPE绝缘电导率较好地匹配,同时一定程度地抑制了空间电荷的积累,有助于直流电缆附件内复合绝缘电场的均匀分布。      

SiO2 / 氰酸酯纳米复合材料的力学性能和热性能

采用高速均质剪切法制备了SiO₂ / 氰酸酯(CE) 纳米复合材料, 并对该体系的静态力学性能、动态力学性能和热稳定性进行了研究。结果表明, 纳米SiO₂的加入提高了复合材料的冲击强度和弯曲强度。当SiO₂ 含量为0. 30 wt %时, 复合材料的冲击强度达最大, 增幅为88. 9 %; 当SiO₂含量为0. 15 wt %时, 材料的弯曲强度达最大, 增幅为2010 %。复合材料的储能模量和高温损耗模量较纯CE 树脂有明显提高, 玻璃化转变温度比纯CE 提高了31. 2 ℃, 热分解温度在SiO₂含量为0. 30 wt %时达最大, 失重为10 %时的热分解温度提高了25. 7 ℃。      

Preparation of SiO2/TiO2 composite fibers by sol-gel reaction and electrospinning

Submicron scale composite fibers of SiO₂/TiO₂ with various compositions have been prepared by electrospinning a sol-gel precursor of tetraethyl orthosilicate(TEOS) and titanium(IV) isopropoxide(TiP), followed by calcination. Any gelator or binder has not been used in this direct preparation process for composite fibers, and the maximum amount of titania for suitable fiber formation was about 50 mol%. The sintered composite fibers were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) spectroscopy. Our results show that the surface morphology and crystallization behavior of electrospun fibers are largely influenced by the calcination temperature and the content of TiO₂. XRD results also reveal that the anatase phase in composite fibers can be preserved even after high temperature processing at lower content (x = 0.1, 0.2) of titania.     

纳米纤维素增强SiO2气凝胶力学性能与微观结构

为克服SiO₂气凝胶强度低、易破碎等缺点,通过原位溶胶-凝胶法制备纳米纤维素（CNF）增强SiO₂气凝胶,并对SiO₂气凝胶的化学结构、微观形貌和力学、物理性能进行表征分析,探讨了CNF对SiO₂气凝胶力学性能的增强机制。结果表明：CNF独特的纳米级网络结构可增强SiO₂颗粒之间的联结强度;Si-OH（960 cm^-1）和Si-O-Si（1 225 cm^-1、1 056 cm^-1和800 cm^-1）等特征吸收峰的出现表明,CNF与SiO₂之间形成稳定的化学键联结;采用不同含量CNF气凝胶作为SiO₂增强相均可达到增强力学性能的效果,同时仍能保持SiO₂气凝胶本身质轻、高孔隙率、高比表面积等特性;当以CNF质量分数为6wt%的溶液制备气凝胶时,CNF增强SiO₂气凝胶具有最优的力学性能,压缩模量和压缩强度分别为12.43 MPa和2.59 MPa。     

液体天然橡胶对湿法混炼制备白炭黑/天然橡胶复合材料界面相互作用的影响

采用液体天然橡胶（LNR）作为增容剂,通过湿法混炼工艺制备白炭黑/天然橡胶（SiO₂/NR）复合材料。利用SEM、橡胶加工分析仪（RPA）、差示扫描量热分析仪（DSC）、溶胀法和核磁共振交联密度仪分别对改性前后SiO₂/NR复合材料的界面形态、Payne效应、玻璃化转变温度（T_g）、结合胶含量及交联密度进行分析,研究LNR对NR与SiO₂相互作用的影响。结果表明,采用LNR改性后,SiO₂/NR复合材料中SiO₂与NR结合紧密,两相界面变得模糊,断面表现为韧性断裂。一定SiO₂用量下,SiO₂/NR复合材料Payne效应明显减弱。当SiO₂与NR质量比为60：100时,玻璃化转变温度（T_g）由-59.57℃提高到-56.61℃,结合胶含量由40.24%增加到44.02%。Lorenz-Park方程定量计算表明,经LNR改性后,SiO₂/NR复合材料界面相互作用增强。核磁共振测试结果表明,改性后,SiO₂/NR复合材料交联密度增加,横向松弛时间（T₂）减小,SiO₂与NR质量比分别为30：100、50：100和70：100时,T₂分别缩短4.20 ms、5.84 ms和7.86 ms,SiO₂与NR相互作用增强,NR分子链运动受限。LNR具有较好的增容效果,经LNR改性的SiO₂/NR复合材料界面相互作用增强。