Topographical observation of silane-treated inorganic surface using atomic force microscopy

The topography of the silane-treated layer on an inorganic surface was observed using an atomic force microscope. For this purpose, the cleaved mica plate was treated with some silane coupling agent at varying conditions. The silanes having aminopropyl or methacryloxypropyl group as organofunctional groups with di- or trialkoxyl structures were used. Three different solvents for silane solution — 2-propanol, 2-propanol/water mixture and water — were used. The pH of the aqueous solution was controlled. As a result, the most suitable solvent and pH in order to obtain smooth silane layer was clarified. The solubility of silane molecules in the solution, the wettability of silane molecule onto inorganic surface, and prevention of the mutual condensation of silane molecules in the solution were found to be important parameters for this purpose.     

1H pulse NMR analysis of silane-treated layers on glass fiber surfaces

The surface treatment of a glass fiber using mercapto-functional silane coupling agent having a di- or trialkoxy group has been studied. The surface of silane-treated fiber is observed by scanning electron microscopy. The treated layer looks hard like glass for the trialkoxy silane-treated, whereas it looks soft for the dialkoxy silane-treated. Molecular mobility of the treated layer is analyzed by ¹H pulse nuclear magnetic resonance spectroscopy. The amount of silane loading increases with increased silane concentration in the treatment solution. The relaxation time for the surface layer is longer for the dialkoxy structure than for the trialkoxy structure. The silane chain is flexible in the dialkoxy structure, but is rigid for the trialkoxy structure, independent of the loading amount of silane. The relaxation behavior for the mixture of the di- and trialkoxy structures is between those of the pure dialkoxy and trialkoxy structures and depends on the mixing ratio. The network density of silane chains on the glass fiber can be controlled by varying the mixing ratio of the di- and trialkoxy compounds.     

Surface treatment of CaCO3 with a mixture of amino- and mercapto-functional silane coupling agents and tensile properties of the rubber composites

In order to reinforce the composite consisting of isoprene rubber (IR) and calcium carbonate (CaCO₃) particles, the surface treatment of CaCO₃ particles with a mixture of amino- and mercapto-functional silane coupling agents was investigated. The quantity of chemisorbed silanes in treated CaCO₃ measured using thermogravimetry was greater for amino- than for mercapto-silane and for the tri- than for the dialkoxy structure. Second, the molecular mobility of polycondensate of the mixtures with the trialkoxy structure measured using ¹H pulse nuclear magnetic resonance had the least molecular mobility, i.e., formed the highest density network. The greater values of stress at 500% strain, fracture stress, and elongation at break were determined for the treatment with amino- and mercapto-functional silanes having a trialkoxy structure from the stress-strain curves of composite. The mixture treatment with dialkoxy structure and with amino- or mercapto-functional silane only did not improve the mechanical properties sufficiently. Interactions between the amino group and the CaCO₃ surface, covalent bonding between the mercapto group and the IR, and high density network formation of trialkoxy silane were important for improving the mechanical properties of the composite.     

Modification of bonding properties and microstructure of resin-cement interface by coupling agents

To solve the problem of organic-inorganic light conductive composite interface features, transparent resin and cement matrix were used as carriers to further study features of the organic-inorganic interface formed by transparent resin and cement matrix and the interface modification of the coupling agent. The bond strength, micro-hardness, microstructure and surface morphology of a resin light conductive cementitious materials (RLCCM) interface were evaluated by tests of tensile and oblique shear, micro-hardness, environmental scanning electron microscopy, and atomic force microscope. The results show that the silane A-151 and aluminate coupling agent could significantly improve interface bond properties of RLCCM. At 7 d, the interface tensile bond strength of the silane A-151 and aluminate coupling agent increased by 117 and 105%, respectively. At 28 d, strength on average increased by 73%. At 7 d, interface shear strength the silane A-151 and aluminate coupling agent of 45° increased by 43 and 53%, respectively, At 28 d, strength on average increased by 40%. The transparent resin performance weakened region thickness up to 100 μm; the hardness of the transparent resin in the transition region was increased by 19.6 and 39.9%, respectively. Silane coupling agent A-151 and cement hydration products formed flat spherical particles with diameter of approximately 78 nm, and these particles mosaicked and fused in the surface of the hydrate; therefore, the surface became denser and smoother.     

An IETS study of a silane coupling agent; the interaction of 3-(trimethoxysilyl)propanethiol with aluminium oxide and silver surfaces

The inelastic electron tunnelling spectrum of a silane coupling agent, 3-(trimethoxysilyl)propanethiol, is presented. Approximately monolayer quantities of this silane are present on the barrier oxide of an aluminium-aluminium oxide-metal tunnelling junction, in which the counter electrode is either lead or silver. It is deduced from the IETS spectra that the alkoxy groups of this silane condense with the surface hydroxyl groups. No interaction with the lead is observed but the silver layer clearly reacts with the thiol group of the silane molecule, since the thiol stretching vibration is absent in the spectra, and probably forms the corresponding silver thiolate. The influence of this reaction on the conformation of the bound silane is discussed.     

Fixation of silane coupling agents to glass fiber in silane treatment process

Fixation of silane coupling agents to glass fiber was quantitatively determined using pyrolysis-GC/FT-IR to explore the formation of chemical-bonded and physisorbed silanes. The silane coupling agent used was N-phenyl-1-aminopropyltrimethoxysilane (AnPS). In silane treatment, E-glass fiber was dipped into acetic acid solution containing AnPS and was cured under different temperature and time. The fixation of silane was obtained by determining the amount of AnPS at the glass surface after and before washing the treated fiber with methanol. The silane fixation increased with decrease in the silane concentration, but it fell significantly below a lower silane concentration. The change of fixation in curing temperature gave an optimum temperature for the fixing. The dependence of curing time on the fixing ratio showed that the fixation was depressed below the curing temperature of 100°C. These results suggested that more than a specific amount of AnPS deposit on glass fiber was necessary to form silane networks fixed to glass fiber through siloxane bonds. The networks formation was interpreted in terms of the competitive reaction of the silanol group of silane to hydroxyl of glass fiber and to other silane molecules.     

Effect of surface treatment condition on interfacial degradation behavior in GFRP under acidic conditions

Interfacial degradation behavior of E-glass cloth reinforced vinyl ester resin under acidic conditions has been investigated. Specimens with different surface treatment conditions were prepared. Mode I fracture toughness tests were performed using DCB specimen, and the effect of surface treatment condition and immersion time on the crack propagation behavior is discussed. The crack propagation behavior changes as a function of the condition of the silane coupling agent and the immersion time due to the degradation of the interphase. A technique is proposed to evaluate the interfacial property. The change of fracture toughness of interphase and resin as a function of immersion time is studied by the crack propagation behavior and the fracture toughness of interphase and resin evaluated by this technique. The fracture toughness of interphase decreases rapidly with immersion in acidic solution.     

Supercritical fluid-assisted synthesis of a carbon nanotubes-grafted biocompatible polymer composite

A nanocomposite consisting of multi-wall nanotubes (MWNTs) grafted with a biocompatible polymer poly(2-hydroxyethyl methacrylate) was prepared by in situ polymerization in supercritical carbon dioxide. The surface of the MWNTs was first surface modified with hydroxyl groups in the solution of KMnO₄ and a phase-transfer catalyst. MWNT-OH was then functionalized with vinyl groups using a silane coupling agent, γ-methacryloxypropyltrimethoxysilane. The silane groups can improve the dipersion of MWNTs in supercritical carbon dioxide, while the terminal vinyl groups help fabricate polymer chains on the MWNT surface. The as-synthesized products were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermo-gravimetric analysis. The SEM and TEM images showed that the nanotubes were well coated with the polymer shell. The composite had higher thermal stability than the pure polymer and dispersed well in methanol. This biocompatible polymer composite was prepared using a green method and is expected to be useful as a biomaterial composite with potential applications in the biological field.     

Mechanical properties of poly(vinyl chloride)/silane-treated glass beads composite: effects of organofunctional group and alkoxy group numbers of silane coupling agent

The surface treatment of glass beads, chosen as model filler, is carried out using four kinds of silane coupling agents with multilayer coverage. For this purpose, the silanes having aminopropyl or methacryloxypropyl group as an organofunctional group with two or three alkoxy group numbers are used. The amount of silane detected on the bead surface is 4–6 times that required for monolayer coverage. Using these treated beads, the effects of the organofunctional group and the alkoxy group numbers of silanes on the mechanical properties of the bead-filled poly(vinyl chloride), chosen as a typical ductile polymer, were investigated. Higher yield stress was observed in the silane with aminopropyl group than with methacryloxypropyl group. The effect of alkoxy group numbers was more effective in the dialkoxy than trialkoxy silanes. Scanning electron microscopy shows improvement in the interfacial adhesion by the silane treatment in the above order. The interfacial debonding at the yield point is depressed.     

Experimental and computational study on hydrolysis and condensation kinetics of γ-glycidoxypropyltrimethoxysilane (γ-GPS)

Since the amount of silanol units in the hydrolysis solution directly determines the interfacial adhesive strength and corrosion resisting property of self-assembled silane films, therefore, it is very essential to have a deep understanding of hydrolysis behaviors of SCAs (silane coupling agents). Conductivity measurement, RA-IR measurement and density functional theory (DFT) calculation was applied to the study of the hydrolysis and condensation kinetics of γ-glycidoxypropyltrimethoxysilane (γ-GPS) under near-neutral and acidic conditions. The results indicated that a critical point existed at about 50 h, dividing the entire hydrolysis period into two stages: Stage 1 (S1) and Stage 2 (S2). In S1, the first step hydrolysis reaction prevailed, while the second and third step hydrolysis reactions only played minor roles. The pH value of the hydrolysis solution imposed little influence on the reactions occurring in the solution. However, in S2, pH value exerted a significant influence on the hydrolysis and condensation reactions, based on which there was an optimum pH value range. The results of DFT calculation were consistent with the experimental measurements. Hitherto, a validate method was proposed to simulate the reactions occurring in the hydrolysis solution.     

Lysine adsorption on the silanized SiO2-surface for immobilization of the estrogen receptor hERα

We investigated the adsorption of the l-lysine (200 mmol) molecule to a silanized SiO₂ surface as a function of the pH value. The SSC (Spraying Spin Coating) method [Cherkouk et al., J. Colloid Interf. Sci. 337 (2009) 375-380] was applied to functionalize the SiO₂ surface by using the (3-aminopropyl)trimethoxysilane (APMS) as coupling agent with a NH₂ functional group. We adsorbed lysine molecules to the silane film for pH-values of 2.5, 7.5, 8.7, 9.5 and 13, which correspond to the di-cationic, cationic, zwitterinonic (pH 8.7 and 9.5) and the anionic charge state of lysine, respectively. The infrared spectroscopy is not suitable to investigate the system because the NH³⁺ signal at 1600 cm⁻¹ originating from the silane film overlaps with the infrared signal of the deprotonated carboxyl group of the lysine molecule. X-ray photoelectron spectroscopy (XPS) was used to measure the binding energies C 1s and N 1s as function of the pH value. This pH change affects the charge state which was fitted in the XPS spectra to obtain the optimal adsorption conditions at pH 7.5 of the lysine to the functionalized SiO₂ surface.     

可循环表面增强拉曼光谱基底的制备及其应用

以氨基硅烷为偶联剂,硅酸钠为硅源,合成了一种以金为核,二氧化硅为壳的核壳纳米粒子。通过调节硅酸钠的量,反应温度和反应时间控制二氧化硅壳层厚度,获得理想的表面增强效应。通过研究表面增强拉曼光谱(SERS)信号强度和二氧化硅层厚度之间的关系优化基底的制备条件。采用对巯基苯和联吡啶作为探针分子进行SERS实验,在一定浓度范围内得到SERS信号强度和浓度的对数之间的线性关系,实验结果表明此组装有Au@SiO2的ITO基底作为可循环利用基底可定量分析吸附物种的浓度。     

Surface Modification of Ultrahigh-molecular-weight Polyethylene Fibers with Coupling Agent during Extraction Process

Ultrahigh molecular weight polyethylene (UHMWPE) fibers were treated with a coupling agent following the extraction of gel fibers, resulting in modified fibers after subsequent ultra-drawing. The structure and morphology of the modified UHMWPE fibers were characterized and their surface wetting, interfacial adhesion, and mechanical properties were investigated. It was found that the coupling agent was absorbed into the UHMWPE fiber and trapped on the fiber surface. Compared with unmodified UHMWPE fibers, the modified fibers had smaller contact angle, higher crystallinity, and smaller crystal size. The interfacial adhesion and mechanical properties of UHMWPE fibers were significantly improved with increasing coupling agent concentration and gradually reached a plateau value. After treatment with 1.5 wt% solution of a silane coupling agent (γ -aminopropyl triethoxysilane, SCA-KH-550), the interfacial shear strength of the UHMWPE-fiber/epoxy composites was increased by 108% and the tensile strength and modulus of modified UHMWPE fibers were increased by 11% and 37% respectively.     

Enhancing indium tin oxide (ITO) thin film adhesiveness using the coupling agent silane

The coupling agent γ-mercapto propyl trimethoxy silane (WD-80) was used to enhance the adhesiveness of the indium tin oxide (ITO) thin film, which was prepared on a glass substrate using the sol-gel method. The nano-scratching test, XRD, TEM, SEM, and UV-vis spectrophotometer were employed to examine film adhesion, crystal structure, surface morphology, and transmittance. The results indicated that silane coupling agent, used in low concentration, did not change the film structure but increased the critical load of the film by 49%, from 4.16 mN to 6.20 mN, when the film was peeled off from the substrate. The principle by which the coupling agent works is discussed. In addition to increasing with the light wavelength, the average transmittance of the film in the visible range varied from 78.9% to 83.6%. Moreover, as a function of the WD-80 silane coupling agent, the film exhibited a high smoothness and density due to the orderly arrangement of particles.     

An original route to stabilize and functionalize magnetite nanoparticles for theranosis applications

A versatile method for the introduction of cyano groups onto the surface of iron oxide nanoparticles has been developed. This protocol is based on the hydrolysis and the condensation of cyanoethyltrimethoxysilane (CES) on the magnetite surface. The optimal concentration of silane coupling agent was determined ([Fe]/[CN] ratio=0.4) in order to obtain an appropriate surface density of activating groups on the nanoparticles. The size distribution of the particles was also optimized by a magnetic size sorting procedure. An adequate surface with cyano groups could facilitates their use in biomedical applications by improving the cellular labeling and the cell targeting.     

Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent

A superhydrophobic complex coating for cotton fabrics based on silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent (PFSC) was reported in this article. The complex thin film was prepared through a sol-gel process using cotton fabrics as a substrate. Silica nanoparticles in the coating made the textile surface much rougher, and perfluorooctylated quaternary ammonium silane coupling agent on the top layer of the surface lowered the surface free energy. Textiles coated with this coating showed excellent water repellent property, and water contact angle (CA) increased from 133° on cotton fabrics treated with pure PFSC without silica sol pretreatment up to 145°. The oil repellency was also improved and the contact angle of CH₂I₂ droplet on the fabric surface reached to 131°. In contrast, the contact angle of CH₂I₂ on the fabric surface treated with pure PFSC was only 125°.     

Effect of surface treatment on sand erosion behavior of glass beads-filled epoxy resin

Effects of the adhesion between filler particle and matrix on the erosion rate were studied in cured epoxy resin filled with glass beads having mean diameter 17 um. In order to observe the effect of adhesion on erosion rate. the filler particles were treated with silane coupling agent, silicone oil and washed by acetone as well. The filler content of the specimen was varied and also the specimens were attacked by different size angular particles. The comparison of each type of specimen shows that by using acetone and silicone oil for surface treatment, the erosion rate is relatively high. Whereas the specimen in which the filler was treated by silane have low erosion rate. The difference of erosion behavior is influenced by impacting particle size and filler content. Using small impacting particles and also low filler content, the erosion behavior between silane and acetone treated was quite different. On the other hand, using large impacting particles and high filler content, the erosion behavior between them was similar.     

硅烷偶联剂改性的芪3掺杂铅-锡-氟磷酸盐玻璃发光性能的研究

采用硅烷偶联剂KBM403对SnF2粉末进行表面改性,改性粉末的IR透射谱显示KBM403已经吸附在SnF2粉末表面,这种改性除了物理吸附外还存在微弱的化学吸附。采用溶有芪3的硅烷偶联剂KBM403对SnF2粉末进行改性,经改性的SnF2粉末有利于提高有机染料芪3掺杂的分散性。将含有芪3的改性SnF2粉末掺入低熔点铅-锡-氟磷酸盐玻璃,获得了芪3掺杂的有机/无机杂化玻璃。对玻璃的吸收、透射谱和激发发射谱进行分析,表明KBM403的介入改善了芪3在玻璃中的溶解性和分散性,减少了芪3二聚物的产生,提高了玻璃的透射率和均匀性。由于KBM403的改性减少了芪3二聚物所带来的荧光猝灭,同时KBM403与染料分子的相互作用增加了染料分子的刚性,玻璃的发光强度显著提高。     

基于FTIR与XRD的改性脱硫灰取代部分炭黑 制备复合橡胶的补强机理研究

脱硫灰是半干法脱硫的主要副产品,其利用难度大且成本高,导致大量脱硫灰以直接堆放和填埋的方式处理,不但造成环境污染,而且浪费潜在资源。炭黑(8 000 元·t-1)与白炭黑(6 000 元·t-1)是常用的橡胶补强填料,生产工艺繁杂,消耗大量能源和资源,导致成本较高。面对上述问题,如何利用脱硫灰开发一种价格低廉的无机橡胶补强填料,既是固体废弃物高附加值利用的重要途径之一,也是橡胶企业大幅降低填料成本提高经济效益的重要途径之一。由于脱硫灰属于无机材料,橡胶属于有机材料,为了更好的降低脱硫灰界面与橡胶界面(无机界面/有机界面)的不相容性,需要对脱硫灰进行化学改性处理,以提高脱硫灰代替部分炭黑制备橡胶的力学性能。该研究创新性以硅烷偶联剂Si69、硅烷偶联剂KH550与脱硫灰制备改性脱硫灰,然后以改性脱硫灰取代部分炭黑制备复合橡胶。根据国家与行业标准测试复合橡胶的力学性能,如拉伸强度、撕裂强度和硬度。利用扫描电子显微镜(SEM)对复合橡胶的微观形貌进行测试与分析,傅里叶变换红外光谱仪(FTIR)对改性脱硫灰的组成结构进行测试与分析,X射线衍射仪(XRD)对改性脱硫灰的矿物组成进行测试与分析,以揭示硅烷偶联剂Si69与硅烷偶联剂KH550协同对脱硫灰的改性机理,以及改性脱硫灰对复合橡胶的补强机理。结果表明：采用硅烷偶联剂KH550与硅烷偶联剂Si69协同改性脱硫灰,其取代炭黑的增强效果最佳,即复合橡胶的拉伸强度为20.36 MPa、撕裂强度为45.71 kN·m-1和邵尔A硬度为66;硅烷偶联剂KH550与硅烷偶联剂Si69协同改性脱硫灰,不仅保持脱硫灰依然良好的碱性,有利于对复合橡胶起到增强效果;而且可以改善脱硫灰的表面特性与结构,提高改性脱硫灰与丁苯橡胶的无机界面/有机界面相容性。     

Ultrasound-assisted synthesis of nanocomposites based on aromatic polyamide and modified ZnO nanoparticle for removal of toxic Cr(VI) from water

In this study, novel nanocomposites (NCs) of aromatic polyamide (PA) and surface modified ZnO nanoparticle with s-triazine heterocyclic ring was introduced for efficient removal of toxic hexavalent chromium (VI) from aqueous solution. The surface of ZnO nanoparticle was modified by s-triazine core silane coupling agent (ZnO-TSC) and PA/ZnO-TSC NCs with different amount of ZnO-TSC nanoparticles (0, 5, 10 and 15 wt%) were prepared by ultrasonic irradiation. The synthesized PA/ZnO-TSC NCs were characterized by FT-IR, XRD, FE-SEM, TEM and TGA methods. TEM images showed that ZnO nanoparticles were dispersed homogeneously in the polymer matrix. The adsorption experiments were carried out in batch mode to optimize various parameters like contact time, pH and concentration of metal ion that influence the adsorption rate. The maximum uptakes of Cr(VI) at pH 4.0 was 72%, 81%, 89% and 91% for pure PA, NC5%, NC10% and NC15%, respectively. The kinetic of adsorption was investigated and the pseudo second-order model is an appropriate model for interpretation of adsorption mechanism of Cr(VI) ions.