Surface modification of an epoxy resin with polyamines via cyanuric chloride coupling

The presence of polyamine groups on the surface of dielectric resins potentially improves the adhesion with electrochemically deposited metals. In this article, first cyanuric chloride is covalently bound to the surface hydroxyl groups of the epoxy resin. The remaining reactive sites on the coupled cyanuric chloride molecule are then used to anchor polyamines. New data on the triazine coupling is presented. The surface reactions are monitored and characterized by means of ATR-IR, SEM-EDS, XPS and ToF-S-SIMS.     

环氧树脂的等离子体表面梯度刻蚀及沿面闪络性能研究

结合等离子体表面刻蚀方法与梯度改性方法,实现了氧化铝/环氧树脂表面的等离子体梯度刻蚀。利用扫描电子显微镜(SEM)、表面轮廓仪、X射线光电子能谱分析(XPS)、高阻计、闪络电压和表面电位测试系统,对比了未处理、等离子体均匀刻蚀、等离子体梯度刻蚀三种情况的样片表面形貌、化学元素和电气参数,研究了等离子体梯度刻蚀对沿面闪络性能的提升机理。结果表明,等离子体表面刻蚀可提升环氧树脂表面粗糙度、提高样片表面电导率、浅化陷阱能级以及提升沿面闪络电压。等离子体梯度刻蚀对闪络电压的提升效果要优于等离子体均匀刻蚀,相比于未处理样片最大可提升26.5%。分析认为针-针电极的电场分布可划分为三结合点处附近的高场强区和电极之间的低场强区,加快高场强区的表面电荷消散速率并适当控制低场强区表面电荷迁移速率,可以最大程度地提升样片整体的沿面闪络性能。     

等离子体表面梯度硅沉积对环氧树脂电气性能的影响

环氧树脂作为常见的绝缘材料,在高压直流电场作用下易在其表面积累电荷,发生电场畸变,导致材料绝缘性能下降,影响电力系统运行可靠性。为改善气固界面的电荷特性和绝缘性能,在大气压等离子体射流技术的基础上,对环氧树脂表面进行等离子体梯度硅沉积处理。对改性前后环氧树脂表面理化特性、表面电导率、表面电荷消散和沿面耐压特性进行了多参数测量。实验结果表明,梯度改性对材料表面的物理形貌和化学组分均有明显影响,不同区域的电导率实现了梯度分布,加快了表面电荷消散速度,表面陷阱能级变浅;梯度改性后的样品沿面闪络电压提升幅度可达30.16%。通过等离子体表面梯度硅沉积处理能够改善环氧树脂表面电气性能,在高压直流设备的绝缘设计方面具有广阔的应用前景。     

Electroless deposition of silver on synthesized calcite via surface modification

Metallic silver was deposited on the surface of synthesized calcite via a simple electroless deposition method. Calcite with cubic morphology was prepared first by homogeneous precipitation and it was subsequently surface modified using ammonium oxalate. The electroless deposition was carried out using formaldehyde as the reducing agent and silver nitrate as the silver source. Both calcite and the silver deposited calcite were characterized by different techniques. Surface modification of calcite with ammonium oxalate is necessary for the deposition of silver and the size of the deposited silver particles could be controlled by changing the deposition parameters such as concentration of the reagents and the deposition time. Lower concentration of silver ions (e.g. 0.01 M AgNO₃) and shorter deposition times (e.g. 30 min) lead to the formation of silver nanoparticles on calcite.     

Surface modification of PVDF membrane via AGET ATRP directly from the membrane surface

This contribution demonstrates a method for PVDF microporous membrane modification via surface-initiated activators generated by electron transfer atom transfer radical polymerization (AGET ATRP) directly from the membrane surface. Three hydrophilic polymers, poly(2-(N,N-dimethylamino) ethyl methacrylate) (PDMAEMA), poly(2-oligo (ethylene glycol) monomethyl ether methacrylate) (POEGMA), and poly(2-hydroxyethyl methacrylate) (PHEMA), were grafted from the PVDF membrane surface in aqueous solution at room temperature. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the successful covalent tethering of the polymer chains onto the PVDF membrane surface. The gravimetry results indicated an approximately linear increase of the graft yields, up to about 330 μg/cm² for DMAEMA and 470 μg/cm² for both HEMA and OEGMA, with the polymerization time. Block copolymer brushes were prepared by chain extension. Water contact angle decreased over 50% for high yields, indicating improved surface hydrophilicity. The effects of the graft polymerization on membrane surface morphology, pore structure and permeability were investigated. It was found that the surface roughness was decreased and the pore size distribution was narrowed. The membrane permeability increased at low graft yields due to the enhanced hydrophilicity and decreased at high graft yields due to the overall reduction of the pore diameters.     

Hydrophilic modification of polyethersulfone porous membranes via a thermal-induced surface crosslinking approach

A thermal-induced surface crosslinking process was employed to perform a hydrophilic surface modification of PES porous membranes. Difunctional poly(ethylene glycol) diacrylate (PEGDA) was used as the main crosslinking modifier. The addition of trifunctional trimethylolpropane trimethylacrylate (TMPTMA) into the reaction solutions accelerated the crosslinking progress of PEGDA on PES membranes. The membrane surface morphology and chemical composition were characterized by scanning electron microscopy (SEM) and FTIR-ATR spectroscopy. The mass gains (MG) of the modified membranes could be conveniently modulated by varying the PEGDA concentration and crosslinking time. The measurements of water contact angle showed that the hydrophilicity of PES membranes was remarkably enhanced by the coating of crosslinked PEGDA layer. When a moderate mass gain of about 150 μg/cm² was reached, both the permeability and anti-fouling ability of PES membranes could be significantly improved. Excessive mass gain not only contributed little to the anti-fouling ability, but also brought a deteriorated permeability to PES membranes.     

Effects of moisture absorption and surface modification using 3-aminopropyltriethoxysilane on the tensile and fracture characteristics of MWCNT/epoxy nanocomposites

In this study, we examined the tensile and fracture behaviors of multi-walled carbon nanotube (MWCNT) reinforced epoxy nanocomposites with and without moisture absorption. The MWCNT/epoxy nanocomposites were fabricated using 0.1 wt.% unmodified, oxidized, and silanized MWCNTs and were kept in seawater for over 15 weeks. Silane-modified specimens demonstrated greater tensile strength, elastic modulus, and transmittance than unmodified or acid-modified specimens, irrespective of moisture absorption. Compared to dry nanocomposites, moisture absorption decreased the tensile strength and elastic modulus for each surface modification. Fracture behavior showed similar tendencies as tensile test results. However, the fracture toughnesses of oxidized and silanized MWCNT/epoxy nanocomposites were not notably different, whereas unmodified specimens had much lower fracture toughnesses, irrespective of moisture absorption. Moisture absorption may have caused degradation resulting in weak interfacial bonding due to epoxy swelling.     

氟化时间对环氧树脂绝缘表面电荷积累的影响

为抑制环氧树脂绝缘的表面电荷积累、研究处理时间对表面电荷积累的影响, 使用氟/氮混合气在实验室反应釜中对环氧试样进行了不同时间(10 min, 30 min和60 min)的表面氟化处理. 衰减全反射红外分析与SEM断面和表面观察表明随氟化时间的增加, 氟化层的氟化度和厚度增大, 表面微观粗糙度降低、表面组织变得致密. 与开路热刺激放电电流测量所表明的、未氟化(原)试样有深的表面电荷陷阱和稳定的表面电荷相比, 这些氟化试样的表面不能存储电荷. 沉积在它们表面上的电晕电荷于室温下分别约在2 min, 10 min和15 min内快速衰减为零, 展现随氟化时间的延长而减慢的电荷释放速率. 表面电导率和接触角测量及表面能计算表明氟化引起表面电导率和表面润湿性与极性的显著增加, 但它们随氟化时间的延长而减小. 氟化试样表面电导率的显著增大归因于表面电荷陷阱的非常可能的实质变浅和表面吸附的水分. 表面充电电流测量进一步地表明, 与原试样几乎为零的稳态表面电流相比, 这些氟化试样在连续充电期间显现大的稳态表面电流. 这意味着这些氟化试样在充电期间比原试样有少得多的表面电荷积累.     

Effect of the surface roughness on interfacial properties of carbon fibers reinforced epoxy resin composites

The effect of the surface roughness on interfacial properties of carbon fibers (CFs) reinforced epoxy (EP) resin composite is studied. Aqueous ammonia was applied to modify the surfaces of CFs. The morphologies and chemical compositions of original CFs and treated CFs (a-CFs) were characterized by Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS). Compared with the smooth surface of original CF, the surface of a-CF has bigger roughness; moreover, the roughness increases with the increase of the treating time. On the other hand, no obvious change in chemical composition takes place, indicating that the treating mechanism of CFs by aqueous ammonia is to physically change the morphologies rather than chemical compositions. In order to investigate the effect of surface roughness on the interfacial properties of CF/EP composites, the wettability and Interfacial Shear Strength (IFSS) were measured. Results show that with the increase of the roughness, the wettabilities of CFs against both water and ethylene glycol improves; in addition, the IFSS value of composites also increases. These attractive phenomena prove that the surface roughness of CFs can effectively overcome the poor interfacial adhesions between CFs and organic matrix, and thus make it possible to fabricate advanced composites based on CFs.     

直流电晕充电下环氧树脂表面电位衰减特性的研究

介质材料表面电荷的积累和衰减行为是制约众多高压直流电力设备研制的关键因素. 薄片状介质试样的表面电荷密度与表面电位近似呈线性关系, 因此常通过表面电位衰减行为研究表面电荷的衰减特性. 基于电晕充电、表面电荷沉积和脱陷、介质体内单极性电荷输运等3个物理过程, 建立表面电位动态响应的物理模型. 通过计算环氧树脂的表面电位衰减行为, 得到栅极电压、相对介电常数和体电导率等对其表面电位衰减特性的影响. 栅极电压越高, 表面电位的衰减速度越快; 环氧树脂材料参数典型值(相对介电常数3.93, 体电导率10^-14 S· m^-1)下, 归一化表面电位的衰减速率随时间变化的曲线可拟合为分段幂函数, 其中, 分段幂函数的特征时间、指数系数与栅极电压分别呈幂函数和线性变化关系. 相对介电常数越大, 表面电位的衰减速度越慢; 环氧树脂相对介电常数典型范围(3–4)内, 表面电位衰减时间常数由1720 s增大到2540 s, 两者呈线性关系. 体电导率越大, 表面电位的衰减速度越快; 环氧树脂体电导率典型范围(10^-15–10^-13 S· m^-1)内, 表面电位衰减时间常数由24760 s 减小到260 s, 两者呈幂函数变化关系.     

Surface modification of ceria nanoparticles and their chemical mechanical polishing behavior on glass substrate

To improve their chemical mechanical polishing (CMP) performance, ceria nanoparticles were surface modified with γ-aminopropyltriethoxysilane (APS) through silanization reaction with their surface hydroxyl group. The compositions, structures and dispersibility of the modified ceria particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), laser particle size analyzer, zeta potential measurement and stability test, respectively. The results indicated that APS had been successfully grafted onto the surface of ceria nanoparticles, which led to the modified ceria nanoparticles with better dispersibility and stability than unmodified ceria particles in aqueous fluids. Then, CMP performance of the modified ceria nanoparticles on glass substrate was investigated. Experimental results showed that the modified ceria particles exhibited lower material removal rate (MRR) but much better surface quality than unmodified ceria particles, which may be explained by the hardness reduction of ceria particles, the enhancement of lubrication of the particles and substrate surfaces, and the elimination of the agglomeration among the ceria particles.     

Micro double tapered optical fiber sensors based on the evanescent field-effect and surface modification

A double tapered optical fiber sensor based on evanescent field-effect and surface modification technology was introduced in this work. Whether the liquid and gas molecules had polarities or not, they all could be detected by the sensors modified in different silane coupling agents. At the same time, the sensing characters of the single mode optical fiber with three different tapering lengths were researched, and it came to a conclusion that the optical fiber sensor had stronger evanescent field effect and higher sensitivity when length of tapered fiber was 30 mm. The functionalized tapered fibers modified by 3-aminopropyltrimethoxy silane (APTES) or 3-methylpropenylacyloxy propyltrimethoxy silane (MPAPTES), were employed to detect the polar or nonpolar molecules which had corresponding features. Further, the results of quantitative tests showed that the fiber optic sensor was sensitive to the change of the ethanol concentration and the characteristic peaks of the absorption power spectra could reach to 3–5 dB.     

Formation of amine groups on the surface of GaN: A method for direct biofunctionalization

Gallium nitride has attracted significant interest as a material for biosensors; however, techniques for biofunctionalizing GaN surfaces have received limited attention. Here, we present a method for producing amine groups directly on GaN surfaces through exposure to a glow discharge plasma fed with humidified air, thereby eliminating the need for complex organic functionalization chemistry. Amine formation is tracked via X-ray photoelectron spectroscopy (XPS) by labeling the plasma-formed surface groups with a fluorinated probe that binds specifically to primary amines. These amine groups can subsequently couple covalently to a wide range of biomolecules. The covalent immobilization of a NeutrAvidin layer is demonstrated using Fourier transform infrared spectroscopy (FT-IR) and fluorescent biotin-binding assays. Finally, we show that plasma exposure times sufficient for the formation of amine groups do not significantly alter the conductivity of the GaN substrate.     

Effects of plasma surface modification on the mechanical properties of carbon fiber and carbon fiber/epoxy composite

_The effect of surface treatment on mechanical properties of carbon fibers has been investigated by application of plasma polymerization of selected monomers in the vapor phase. The role of the fiber-matrix interface on carbon fiber-reinforced epoxy resin composites has also been studied. Composites have been prepared separately by the use of plasma-modified and unmodified carbon fibers in the epoxy resin matrix. The mechanical properties of carbon fibers (Hercules and Grafil) as well as of fiber/epoxy composites were examined by using single filament and three-point bending tests, respectively. It was observed that plasma polymerization treatment at selected plasma conditions led to significant improvement of interlaminar shear and flexural strength values of composites.     

Studies on surface modification of poly(tetrafluoroethylene) film by remote and direct Ar plasma

Poly(tetrafluoroethylene) (PTFE) surfaces are modified with remote and direct Ar plasma, and the effects of the modification on the hydrophilicity of PTFE are investigated. The surface microstructures and compositions of the PTFE film were characterized with the goniometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results show that the remote and direct plasma treatments modify the PTFE surface in morphology and composition, and both modifications cause surface oxidation of PTFE films, in the forming of some polar functional groups enhancing polymer wettability. When the remote and direct Ar plasma treats PTFE film, the contact angles decrease from the untreated 108-58° and 65.2°, respectively. The effect of the remote Ar plasma is more noticeable. The role of all kinds of active species, e.g. electrons, ions and free radicals involved in plasma surface modification is further evaluated. This shows that remote Ar plasma can restrain the ion and electron etching reaction and enhance radical reaction.     

H MAS and H[Na] double resonance NMR studies on the modification of surface hydroxyl groups of γ-alumina by sodium

The modification of surface hydroxyl groups with sodium in a series of Na₂CO₃-γ-Al₂O₃ catalysts was investigated as a function of both the Na₂CO₃ loading and the calcination temperature by means of ¹H magic angle spinning (MAS) and ¹H[²³Na] spin-echo double resonance NMR techniques. The ¹H NMR experiments revealed that sodium ions are homogeneously distributed over the alumina surface and closely coordinated with the surface hydroxyl groups. In the catalysts calcined at 250 °C, the acidic hydroxyl groups (with a chemical shift of 2.0 ppm) are preferentially associated with sodium ions at low Na₂CO₃ coverages (5 and 10%), while both the acidic and the basic (0 ppm) hydroxyl groups are accessible for sodium ions at high coverages (15 and 20%). The coordination causes a low-field shift of about 2 ppm in the ¹H MAS spectra, and a broad signal at 4.5 ppm appears. It is interesting that the 4.5 ppm signal is completely suppressed in the ¹H[²³Na] MAS experiments, providing direct evidence that a strong interaction exists between adsorbed sodium ions and the surface hydroxyl groups. Increasing the calcination temperature to 450 °C results in preferential removal of the acidic hydroxyl groups, and only the most basic hydroxyl groups remain when the calcination temperature is raised to 600 °C. This is attributed to the formation of the coordinated species which enhances the acidity of the surface hydroxyl groups and prompts their dehydroxylation, especially at high calcination temperature. Correlation of the ¹H MAS NMR results and catalytic activity measurements indicates that the basic hydroxyl groups are essential for the carbonyl sulfide hydrolysis reaction.     

Role of surface modification of CdS nanoparticles on the performance of hybrid photovoltaic devices based on p-phenylenevinylene derivate

The role of organic capping ligand of semiconductor nanoparticles in dictating the interfacial charge transfer processes in hybrid semiconductor nanoparticles/polymer-based photovoltaic devices is investigated. Morphology, optical and structural study of the CdS nanoparticles and the hybrid material were accomplished using X-ray diffraction (XRD), absorption (UV–vis), atomic force microscopy (AFM), transmission electron microscopy (TEM), photoluminescence (PL) and time resolved photoluminescence spectroscopy (PLRT). A broad band absorption in UV–visible region and considerable fluorescence quenching of MEH-PPV in the composites are noted indicating a photo-induced charge transfer and dissociation of excitons. Time-resolved photoluminescence measurements indicating decreased lifetime further confirm this process. The solar cells open-circuit voltage and short-circuit current were improved using thiophenol modified CdS nanoparticles as electron acceptor in comparison to MEH-PPV only device demonstrating a promising approach to enhance charge transport in the hybrid nanoparticles–polymer composite photovoltaic cells (PV).     

Studies on the surface modification of diatomite with polyethyleneimine and trapping effect of the modified diatomite for phenol

The adsorption isotherm of polyethyleneimine (PEI) on diatomite was studied using UV spectrophotometry, the surface of diatomite was modified with polyethyleneimine by using impregnation method, and the trapping behavior of the modified diatomite for phenol was investigated by using 4-aminoantipyrine (4-AAP) spectrophotometric method. The experiment results show that negatively charged diatomite particles have very strong absorption effect for cationic macromolecule PEI, the adsorption isotherm fits in Freundlich equation. The character that there is a maximum value after intitial sharp increase of adsorption capacity on the adsorption curve indicates that there is strong affinity between diatomite particles and polyethyleneimine macromolecules, and it attributes to the strong electrostatic interaction. After modification with PEI, the electric property of diatomite particle surface changes essentially, and the isoelectric point of diatomite particles moves from pH 2.0 to 10.5. In acidic solution, phenol exists as molecular state, and the modified diatomite particles adsorb phenol through hydrogen bond interaction. However, the hydrogen bond interaction between nitrogen atoms on PEI chains and phenol is weaker because of high degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is lower. In basic solution, phenol exists as negative benzene–oxygen ion, and the modified diatomite particles adsorb phenol through electrostatic interaction. However, the electrostatic interaction between PEI and negative benzene–oxygen ion is very weak because of low degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is much lower. The modified diatomite particles produce very strong trapping effect for phenol in neutral aqueous solution via the cooperating of strong electrostatic interaction and hydrogen bond interaction, and the saturated adsorption capacity can attain to 92 mg g⁻¹.     

Rapid synthesis of water-glass based aerogels by in situ surface modification of the hydrogels

The objective of the present research was to reduce the processing time of water-glass based aerogels synthesized via an ambient pressure drying. For this purpose we employed a co-precursor method for the surface modification in hydrogels using trimethylchlorosilane (TMCS) and hexamethyldisilazane (HMDS). The surface modification resulted in the displacement of pore water from the hydrogels and thereby absolutely avoiding the time-consuming solvent exchange step. The attachment of trymethylsilyl (Si(CH₃)₃) groups to the silica surface was confirmed by the presence of SiCH₃ peaks at 2900, 1400, 1255 and 845 cm⁻¹ in the Fourier Transform Infrared (FTIR) spectra. The differential thermal analysis (DTA) revealed that the aerogels maintain their hydrophobic behavior up to a maximum temperature of 500 °C above which they become hydrophilic. The physical and textural properties of the silica aerogels have been reported and the results have been discussed by taking into account the surface modification and the amounts of the pore water displaced out from the hydrogels.     

Effect of surface modification on dielectric and magnetic properties of metal powder/polymer nanocomposites

Metal nanopowder (Co and Fe)/polymer composites, both with and without surface modification by behenic acid, were fabricated and their dielectric and magnetic properties were measured at 1 GHz to study the effect of surface modification on the electromagnetic properties. The relative permittivity and the real part of the permeability of the composites with surface modified powders were higher than those with unmodified powders. Related dielectric losses remained at almost the same level, but magnetic losses were somewhat increased. The increase of relative permittivity could result from the increased volume fraction of interphase with a slightly higher relative permittivity at the particle/polymer interface than that of the bulk polymer. The increase in the real part of the permeability may be caused by suppression of the induced demagnetizing field due to suppression of eddy currents by a better particle distribution and a decrease in effective agglomerate size because of the surface modification.