Electrical and thermal properties of polyimide/silica nanocomposite

The electrical and thermal properties of thin films of polyimide/silica nanocomposites prepared via sol–gel process were studied as a function of nanosilica particles content, temperature and applied field frequency. It was found that the dielectric constant and dielectric loss of the nanocomposites decrease with both the frequency and the nanosilica content, while increase with temperature. The AC-conductivity measured in frequency range 200?kHz–1.5?MHz decreases with the filler concentration and increases with increasing temperature. For the (25?wt%) nanocomposite, it was found that the AC-conductivity increases with temperature, and the Cole–Cole plots showed that the calculated activation energy and relaxation time decrease with temperature. The observed thermal conductivity increases gently with temperature. The empirical universal law was used to fit the observed electrical data under the measuring conditions.     

剥离型纳米蒙脱土/聚酰亚胺复合材料的制备与表征

利用二苯基甲烷-4,4’-二异氰酸酯（MDI）与酸化的蒙脱土（MMT）表面的羟基进行反应制得了MMT-MDI;进一步利用己内酰胺（CPL）对MMT-MDI进行插层并对多余的异氰酸酯端基进行封端,制得了MMT-MDI-CPL。采用预聚体溶液插层法,利用聚酰胺酸（PAA）在二甲基乙酰胺（DMAC）溶剂中分别对MMT-MDI和MMT-MDI-CPL进行预聚体插层,制得了剥离型纳米MMT/聚酰亚胺（PI）复合材料。通过电感耦合等离子体发射光谱（ICP-OES）、FTIR、TG、XRD和SEM对改性MMT和纳米MMT/PI复合材料进行了表征。结果表明：MDI与MMT表面羟基反应而被成功接枝于MMT上;MDI对MMT的改性、CPL对MMT-MDI的插层和封端使MMT层间距得到逐步扩大;MMT/PI复合材料的XRD和断面SEM表明,MMT在PI基体中得到了充分剥离。     

无机掺杂改性聚酰亚胺薄膜的制备及表征

采用聚酰亚胺为树脂基体,甲基三乙氧基硅烷、异丙醇铝和钛酸四丁酯为无机前驱体,在N,N-二甲基乙酰胺溶液中进行溶胶-凝胶反应,制备聚酰亚胺／SiO2／Al2O3和聚酰亚胺／SiO2／TiO2两种无机掺杂聚酰亚胺薄膜,采用红外光谱仪、热重分析仪、扫描电镜等测试方法对薄膜的化学结构和表面形貌及其热稳定性进行了表征分析．结果表明：在一定的无机组分含量范围内,无机相均匀的分散在有机基体中,但两种杂化薄膜的分散形态及粒径尺寸不同,热性能均较未掺杂的聚酰亚胺薄膜有所提高。     

明胶/锂藻土纳米复合材料的制备与性能研究

通过溶液共混和溶剂蒸发的方法制备了明胶/锂藻土纳米复合材料,利用衰减全反射傅立叶红外光谱(ATR-FTIR)、广角X射线衍射(WAXD)、紫外-可见光谱(UV-Vis)、差示量热扫描(DSC)和热重分析(TGA)等仪器方法对材料的结构与性质进行了研究。结果表明:ATR-FTIR曲线中,除Si-O键外,各基团特征峰强度都随锂藻土含量增加而降低。WAXD谱图中未发现锂藻土的层状衍射峰,说明锂藻土完全剥离。锂藻土还对明胶的结晶性和结晶结构产生影响,在2θ=27.1°发现了新的衍射峰,并随着锂藻土含量增加峰强度变强。明胶/锂藻土纳米复合膜表现出良好的透明性,锂藻土含量对材料透明度影响不大。随着锂藻土含量的增加,明胶的熔点(Tm)先增加后降低,含5%锂藻土的纳米复合膜有最高的熔点。纳米复合膜的热稳定性明显好于纯明胶膜,并且随着锂藻土含量的增多,材料的热稳定性也提高,少量锂藻土即可大幅改善明胶的热稳定性。     

Preparation and characteristic of a new class of silica/polyimide nanocomposites

A new class of silica/polyimide nanocomposites was successfully prepared by the sol-gel reaction, tetraethoxysilane, (TEOS), was hydrolyzed by the water released from imidization at low and high temperature. Silica particles with diameter of around 30–50 nm were observed in the hybrid films by scanning electron microscopy. The flame retardance, decomposition temperature and glass transition temperature of the film increased with increasing silica content. The tensile strength increased slightly while the elongation at break of the films decreased with increasing silica content.     

Preparation and characterization of hollow silica nanocomposite functionalized with UV absorbable molybdenum cluster

The nanoparticle-based material technology has recently opened a new heat shielding material generation for window applications such as aerogel, vacuum insulation panel or nanospace materials. Aiming to prepare a nanospace-based heat insulation material functionalized with an ultraviolet (UV) absorbent, the Mo₆ cluster-deposited hollow silica nanoparticles (HSNs) were prepared by the vacuum impregnation process (VIP). The pore channels of the hollow silica wall filled with the Cs₂[Mo₆Iⁱ₈(OCOC₂F₅)^a₆] octahedral cluster (CMIF) were confirmed by an HR-TEM coupled EDX device, ICP-OES and BET analysis. The retention of the octahedral structure or the typical optical property of the Mo₆ cluster in the pores of the HSNs was demonstrated by ultraviolet (UV) light absorption and photoluminescence spectroscopes even though the powders were heated to 200 °C. The multi-functional CMIF@HSNs nanocomposite could adsorb the UV rays under 400 nm and scatter the NIR light through the pores of the silica wall in order to reduce the heat passing a window. For this purpose, the film preparation based on the CMIF@HSNs nanocomposite was performed by dip coating in the commercially available top coat suspension (TCS) on soda lime glass. Excellent mechanical and optical properties of the CMIF@HSNs-based thin film were visibly obtained with a relative transmittance. This study suggests a potential insulation material prepared by a high efficiency and simple method for reducing the air temperature in buildings.     

磺化聚酰亚胺/SiO2复合膜的制备及其质子交换性能研究

制备了具有不同硅含量的磺化聚酰亚胺/二氧化硅(SPI/SiO2)复合膜,研究了SiO2的引入对复合膜的力学性能、耐热性能、尺寸稳定性以及抗氧化和耐水解稳定性的影响规律,并对其质子传导率和甲醇渗透率进行了评价。结果表明,与商业化的Nafion115膜相比,复合膜表现出更优异的阻醇特性和选择透过性,其中SPI/SiO2-2复合膜具有更突出的高温质子传导特性。     

Directly ultraviolet photochemical deposition of silver nanoparticles on silica spheres: Preparation and characterization

A simple method was developed to directly deposit silver nanoparticles on the surface of silica spheres. The photochemical reduction was carried out by ultraviolet irradiation in air atmosphere at room temperature. The [Ag(NH₃)₂]⁺was reduced to silver atoms upon ultraviolet irradiation. Silver atoms subsequently deposited on the surface of silica spheres and agglomerated into silver nanoparticles. Silica spheres with silver nanoparticles of different size and density can be simply controlled by adjusting the UV-light irradiation time. The silver nanoparticles deposited on silica spheres were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and field emission scanning electron microscopy.     

Preparation and characterization of hydroxyapatite/collagen nanocomposite gel

The self-organized hydroxyapatite/colagen (HAp/Col) nanocomposite fiber (79.6/20.4 weight ratio) was synthesized by a co-precipitation method using Ca(OH)2, H3PO4, and Col as starting substances. The gelation of the nanocomposite is essential in the application of the scaffold for bone tissue engineering. We successfully prepared HAp/Col nanocomposite gels by a facile novel method using a sodium phosphate buffer at pH 6.8. The water-insoluble nanocomposite was homogeneously dispersed in the buffer to form a viscous mixture, and gels were obtained after incubating of the mixture at 37 degrees C. The mechanical strength of the gels was analyzed against the incubation time. The demineralized gel with EDTA had the typical nanostructure of native type I Col fibers from the results of scanning electron microscopy (SEM) and atomic force microscopy (AFM); the dense network of type I Col nano-fibers below 100 nm in diameter, and the periodic pattern of 68.8+/-4.4 nm (mean +/- SD) along the fibers were observed. The gelation of the HAp/Col nanocomposite in the buffer is attributed to the physical cross-linking through entanglement of the reconstituted Col fibrils.     

聚乳酸/蒙脱石纳米复合材料的制备与表征

对纳基蒙脱石(MMT)有机改性后,采用溶液插层薄膜塑造工艺制备蒙脱石/聚乳酸(PLA)纳米复合物,采用X-Ray粉晶衍射(XRD)、综合热分析(TGA&DSC)、红外吸收光谱(IR)等方法对复合材料进行表征,讨论了蒙脱石对插层结果的影响.结果表明,PLA能够插入MMT层间;MMT的层间距由1.40nm增大到2.16nm;复合材料的热稳定性能得到改善.     

有机硅丙烯酸酯/蒙脱土纳米复合乳液的制备及表征

以十二烷基苯磺酸(DBSA)为插层剂改性蒙脱土(MMT),制得了有机蒙脱土(OMMT)。采用原位插层聚合法,以OMMT、八甲基环四硅氧烷、乙烯基三甲氧基硅烷以及甲基丙烯酸酯甲酯、丙烯酸丁酯和丙烯酸为原料,制备了有机硅丙烯酸酯/蒙脱土纳米复合乳液。考察了OMMT用量对乳胶粒径及乳胶膜性能的影响,并对OMMT及乳胶膜的结构进行了表征。结果表明:当OMMT的用量为2.0%时,乳胶粒子尺寸为纳米级,乳胶膜的耐热性以及各项物理机械性能均得到明显改善。XRD分析表明,MMT变为OMMT后,其层间距从1.23nm增大至1.54nm。FT-IR分析表明,有机硅和丙烯酸酯单体在OMMT层间发生接枝聚合反应。     

Preparation of silica/polyacrylamide/polyethylene nanocomposite via in situ polymerization

SiO₂/polyacrylamide (PAM) composite was prepared via the polymerization of acrylamide in the presence of silica sol in water/hexane emulsion, and pure SiO₂ was also prepared without the use of acrylamide in the same way. Field emission scanning electron micrographs (FESEM) showed that PAM covered the silica nanoparticles to form SiO₂/PAM nanospheres, which loosely agglomerated to form SiO₂/PAM secondary particles, while SiO₂ secondary particles were made up of tightly agglomerated silica nanoparticles. Metallocene catalyst was then immobilized over SiO₂ and SiO₂/PAM respectively to prepare supported metallocene catalyst for ethylene polymerization. Transmission electron micrographs (TEM) showed that support particles broke up to smaller particles and even nanoparticles in polyethylene (PE) matrix when the support particles were the fragile SiO₂/PAM secondary particles, which shows a novel way to prepare silica/polyacrylamide/polyethylene nanocomposite.     

Preparation of ultra-low dielectric constant silica/polyimide nanofiber membranes by electrospinning

Ultra-low dielectric constant silica/polyimide (SiO₂/PI) composite nanofiber membranes are prepared by the combined sol–gel and electrospinning techniques. The emulsion composed of partially hydrolyzed tetraethoxysilane (TEOS) and polyamic acid (PAA) is spun to yield the precursor of the SiO₂/PI fibers with a core–shell structure due to phase separation. The dielectric constant (k) of the composite membranes varies from 1.78 to 1.32 with increasing content of SiO₂. The fibers accumulate and form the film with a large amount of pores leading the lower k. In addition, the interfacial reaction between SiO₂ and the PI matrix reduces the value of k as the SiO₂ concentration is increased. The thermal stability of PI increase after mixing with SiO₂ and the SiO₂/PI composite fibers have large commercial potential in the electronics industry.     

Synthesis and characterization of CuO containing mesoporous silica spheres

A new series of mesoporous silica spheres containing nanodispersed copper oxides were synthesized in H₂O/EtOH/ammonia solution at room temperature. The mesoporous structures were characterised using X-ray powder diffraction and N₂ adsorption-desorption techniques. Scanning electron micrograph and transmission electron micrograph revealed that the MCM-41 particles have spherical morphologies. The DTA curve of pure MCM-41 exhibited a sharp single exothermic peak between 290°C and 340°C, while a broad peak with several shoulders in the temperature range between 180°C and 380°C was observed for Cu-MCM-41, indicating the possible complexation of Cu²⁺ with surfactants adhering to the inner surfaces of the mesopores. Electron paramagnetic resonance spectra of uncalcined samples revealed that Cu²⁺ ions are in an octahedral or distorted octahedral coordination with nitrogen ligands of the surfactant while in the calcined samples they are coordinated with oxygen of the MCM-41 framework. The redox properties of samples were examined by a temperature-programmed reduction and N₂O passivation method. The results indicate that CuO with increasing particle size could be formed in the mesoporous materials with increasing Cu contents, and this decreased the reducibility of the resulting CuO.     

单分散聚酰亚胺粒子的制备与表征

采用均苯四甲酸二酐(PMDA),4,4’-二氨基二苯醚(ODA)为单体,甲醇、四氢呋喃组成的混合溶液为溶剂,进行缩聚反应合成聚酰亚胺(PI)的预聚体聚酰胺酸,经过两步法亚胺化得到PI粒子。红外光谱(FT-IR)对聚合物进行表征,表明经过两步法亚胺化(化学亚胺化和热亚胺化)才能使聚酰胺酸完全亚胺化;扫描电镜(SEM)图片显示,当四氢呋喃/甲醇(THF/MeOH)比例为7∶3可得到粒径为5～10μm且分散性好的PI粒子;利用热失重分析(TGA)可知T5d为530℃,T10d在560℃,PI粒子具有优良的热稳定性。     

聚酰亚胺/纳米SiO2杂化膜的制备和表征

以均苯四酸二酐、4,4＇-二氨基二苯基甲烷和正硅酸乙酯为原料,采用溶胶-凝胶法制备聚酰亚胺／纳米SiO2杂化膜,利用FT—IR、XPS、AFM对杂化膜的制备过程及杂化膜的结构进行了表征．证实聚酰胺酸加热亚胺化较为完全,杂化膜中有SiO2粒子生成,并以纳米尺度均匀地分布于聚酰亚胺中．采用综合热分析仪对杂化膜的热性能进行了分析,结果表明杂化膜的热性能优于聚酰亚胺膜,其热分解温度比聚酰亚胺膜提高了17．8℃．     

Preparation and characterization of polyimide/ladder like polysiloxane hybrid films

Novel polyimide (PI)/ladder like polyphenylsilsesquioxane (PPSQ) hybrid films was prepared. PI was made from poly(amide acid) of 4, 4′’-diaminodiphenylether and pyromellitic dianhydride. PPSQ was prepared from phenyltrimethoxysilane through sol-gel process. The chemical structure of PPSQ was characterized by Fourier transform infrared and nuclear magnetic resonance. The coefficients of thermal expansion for the hybrid films decrease with the increasing content of PPSQ. The thermal and mechanical properties of the hybrid films were essentially similar to the neat PI.     

Preparation and characterization of carbon nanotube/polyetherimide nanocomposite films

Multi-walled carbon nanotube (MWCNT)/polyetherimide (PEI) nanocomposite films have been prepared by casting and imidization. A homogeneous dispersion of MWCNTs throughout the PEI matrix is observed by scanning electron microscopy of fracture surfaces, which shows not only a fine dispersion of MWCNTs but also strong interfacial adhesion with the matrix, as evidenced by the presence of many broken but strongly embedded carbon nanotubes (CNTs) in the matrix and by the absence of debonding of CNTs from the matrix. Differential scanning calorimetry and dynamic mechanical analysis show that the glass transition temperature of PEI increases by about 10 °C by the addition of 1 wt% MWCNTs. Mechanical testing shows that for the addition of 1 wt% MWCNTs, the elastic moduli of the nanocomposites are significantly improved by about 250% while the tensile strength is comparable to that of the matrix. This improvement is due to the strong interfacial interaction between the MWCNTs and the PEI matrix which favors stress transfer from the polymer to the CNTs.     

Preparation and characterization of γ-MnO2/CNTs nanocomposite

A layer of manganese dioxides (γ-MnO₂) was adsorbed upon carbon nanotubes (CNTs) surface by using a chemical deposit process. The morphologies of the MnO₂/CNTs composite were characterized using transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD) and laser Raman spectroscopy (RS). It is found that the adsorbed layer belongs to the γ-MnO₂ nanoparticles in the size of about 10 nm, and coated homogeneously around the CNTs. It is expected that this γ-MnO₂/CNTs composite will be applied to make supercapacitors.