Preparation and characteristics of a waterborne preventive stain coating material with organic-inorganic composites

With the goal of developing a waterborne coating material that prevents staining, organic-inorganic composites prepared from colloidal silica and two types of acrylic resin emulsions were investigated as exterior coatings. conventional acrylic resin emulsion and organic silane hybridized acrylic resin emulsion prepared by emulsion polymerization were mixed with colloidal silica to form organic-inorganic comiposite films. The addition of colloidal silica to emulsions yielded films with higher hydrophilicities, as indicated by lower water contact angles for these films in comparison to films without colloidal silica. The water contact angles of organic silane hybridized acrylic resin emulsion/colloidal silica films were lower than those of acrylic resin emulsion/colloidal silica films. Composite films containing colloidal silica particles smaller than 100 nm in diameter showed high hydrophilicities. Observations of the dispersed state of colloidal silicaparticles in organic-inorganic composite films by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) demonstrated that colloidal silica particles were densely aggregated on the film surface. Outdoor exposure tests of the coating materials prepared from organic silane hybridized acrylic resin and colloidal silica particles with diameters of 7.5 nm showed excellent stain resistance.     

Synthesis and characterization of nanosilica/polyacrylate composite latex

The nanosilica/polyacrylate organic–inorganic composite latex was synthesized by in‐situ emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of silica nanoparticles, which were modified by silane coupling agent. The surface properties and dispersibility of silica nanoparticles modification, chemical structure, Zeta potential, diameter distribution of the composite latex prepared, surface roughness, and thermal stability of the hybrid film formed by the composite latex were investigated by fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), Zeta meter, ZetaPlus apparatus (dynamic light scattering method), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. After modification with silane coupling agent, silane was grafted onto the surface of silica nanoparticles to form the organic layers, which was able to efficiently prevent the silica nanoparticles from aggregating to individually homogeneous disperse in the in‐situ emulsion polymerization system and improve the compatibility of silica nanoparticles with the acrylate monomers. The nanosilica/polyacrylate organic–inorganic composite latex prepared had the properties of silica nanoparticles and pure polyacrylate latex but was not simply a combination. Strong chemical bonding tethered the silica and acrylate chains to form the core/shell structural composite latex. Consequently, the hybrid film formed by nanosilica/polyacrylate composite latex exhibited a smooth surface and better thermal properties than the pure polyacrylate film. POLYM. COMPOS. 27:282–288, 2006. © 2006 Society of Plastics Engineers     

Fabrication of chemically bonded polyacrylate/silica hybrid films with high silicon contents by the sol–gel method

Polyacrylate/silica hybrid latexes (PAES) with high silicon contents (up to 21%) were prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a silane coupling agent. Sol–gel-derived organic/inorganic thin films were obtained by addition of hydrophilic co-solvents to PAES and subsequent drying at room temperature. The effects of co-solvents and γ-methacryloxypropyltrimethoxysilane (KH570) content on the properties of PAES films were investigated. Dynamic light scattering (DLS) data indicated that the average diameter of PAES (96 nm) was slightly larger than that of PAE (89 nm). TEM photo revealed that colloidal silica particles were dispersed uniformly around polyacrylate particles and that some of the colloidal silica particles were adsorbed on the surface of PAE particles. The data of crosslinking degree and FT-IR spectra confirmed that the chemical structure of the PAES changed to form Si–O–Si-polymer crosslinking networks during the film formation. AFM photos, contact angle for water, and XPS analysis showed that the polyacrylate/inorganic hybrid films with high silicon contents were formed by the co-solvent-mediated, sol–gel method and that the Si-based polymers were uniformly distributed on the surface of the dried films. TGA data demonstrated that the PAES films display much better thermal stability than the PAE counterpart.     

PDMS乳液/硅溶胶杂化水分散体系及其复合膜的制备与表征

以聚硅氧烷(PDMS)乳液/硅溶胶杂化水分散液为成膜基质,硅烷偶联剂KH 550为固化剂,制备了双组分水基有机硅涂料;将其固化后得到PDMS/硅溶胶复合膜。通过水分散液的粒径分布及红外光谱分析,研究了水分散液的脱水成膜过程;采用扫描电镜(SEM)和原子力显微镜(AFM)对复合膜的断面和表面形态进行了表征。结果表明:PDMS乳液加入硅溶胶后,粒径分布变宽,粒径略有增加;成膜后,硅溶胶粒子与PDMS长链发生了相互作用,并作为分散相被包埋在PDMS中;复合膜表面形成簇状结构,表面粗糙度随着硅溶胶含量的增加而增加。当硅溶胶与PDMS乳液的固体质量比由10%增加到30%时,复合膜的拉伸强度由0.76MPa升高到3.10MPa,而拉断伸长率从680%下降到470%。     

Preparation of spherical nanocomposites consisting of silica core and polyacrylate shell by emulsion polymerization

Nanocomposite particles consisting of silica (inorganic core) and polyacrylate (organic shell) were prepared in a form of emulsion by a new and simple method—the emulsion polymerization of acrylic monomers in the presence of silica sol. The key technique of the present emulsion polymerization, which made the formation of the nanocomposites successful, is the usage of nonionic surfactant above its cloud point. The morphology of the composite was investigated by DLS, AFM, and TEM, which clearly showed formation of the core‐shell‐type particles. A transparent film was prepared by casting the emulsion, which showed high resistibility against organic solvents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 659–669, 2006     

Film‐formation of polyacrylate/silica composite latexes by sol‐gel process

The polyacrylate/silica composite latexes were prepared by directly mixing silica particles with polyacrylate modified by γ‐methacryloxypropyltrimethoxysilane (MPS). Fourier transform infrared (FTIR) spectra and X‐ray photoelectron spectroscopy (XPS) analysis of polyacrylate/silica composite films confirmed the sol‐gel processes occurred to form Si–O–Si crosslinking bonds during the process of film‐formation. Transmission electron microscope (TEM) images revealed that the polyacrylate latexes were in contact with silica particles while some silica particles stayed together. Atomic force microscope (AFM) photos showed that organic and inorganic phases were strictly connected with each other and silica particles were embedded in the polymeric matrix with a size range of 20–50 nm. Differential scanning calorimetry (DSC) curves demonstrated that the composite film with 3% MPS has higher T_g than those of pure polyacrylate films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42417.     

Mechanical and surface hardness properties of ultraviolet‐cured polyurethane acrylate anionomer/silica composite film

An organic‐inorganic composite was prepared by mixing silica emulsion with urethane acrylate anionomer (UAA) emulsion. The silica emulsion was prepared by sol‐gel process, and stabilized by a steric stabilizer, polyvinyl pyrrolidone. UAA/silica composite film was made by an ultraviolet curing method. The mechanical and rheological properties of the UAA/silica composite were greatly improved. This composite also showed thermal stability during increase of temperature. Surface hardness was improved with increasing silica content up to proper amount of silica. However, in abrasive test, because UAA/silica composite film has a more abrasive contact area than UAA film, the former was abraded much more than the latter. In comparison to UAA film, the UAA/silica composite showed much smoother abrasive surface and less roughness. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 968–975, 2000     

水性聚氨酯/硅溶胶复合涂层的制备与性能

将水性聚氨酯乳液与硅溶胶共混,制备了水性聚氨酯/硅溶胶复合乳液。采用TEM、激光粒度分析仪、流变仪、ATR-FTIR、TG对复合乳液及其涂膜进行表征,探讨了硅溶胶用量对复合涂膜性能的影响。ATR-FTIR分析表明,聚氨酯分子和硅溶胶之间可以形成氢键,但不存在化学键结合;TEM、激光粒度分析测试表明,硅溶胶质量分数的增加,使复合乳液粒子粒径增大,粒度分布变宽,当硅溶胶质量分数20%后,乳胶粒子间易发生团聚;流变分析发现,加入硅溶胶后,乳液的表观黏度(ηa)增大,假塑性增强。性能测试结果表明,硅溶胶质量分数20%时,复合乳液具有好的储存稳定性,复合涂膜表现出很好的热稳定性,48 h吸水率仅为18.94%,同时表现出很好的耐溶剂性能,拉伸强度达到28.98 MPa,铅笔硬度达2H,附着力0级。     

Synthesis and characterization of organic-inorganic hybrid thin films from poly(acrylic) and monodispersed colloidal silica

Hybrid thin films containing nano-sized inorganic domain were synthesized from poly(acrylic) and monodispersed colloidal silica with coupling agent. The 3-(trimethoxysilyl)propyl methacrylate (MSMA) was bonded with colloidal silica first, and then polymerized with acrylic monomer to form a precursor solution. Then, the precursor was spin coated and cured to form the hybrid films. The silica content in the hybrid thin films was varied from 0 to 50 wt%. The experimental results showed that the coverage area of silica particle by the MSMA decreased with increasing silica content and resulted in the aggregation of silica particle in the hybrid films. Thus, the silica domain in the hybrid films was varied from 20 to 35 nm by the different mole ratios of MSMA to silica. The results of scanning electron microscope, transmission electron microscope, and elemental analysis support the above results. The prepared hybrid films from the crosslinked acrylic polymer moiety showed much better film uniformity, thermal stability and mechanical properties than the poly(methyl methacrylate) (PMMA) based hybrid materials. Large pin-holes were found in the PMMA-silica hybrid films probably due to the significant difference on thermal properties between the two moieties or the evaporation of solvent. The refractive index decreased linearly with increasing the silica fraction in the hybrid films. Excellent optical transparence was obtained in the prepared hybrid films. These results show that the hybrid thin films have potential applications as passive films for optical devices.     

Grafting of Epoxy Resin on Surface-modified Poly(tetrafluoroethylene) Films

An epoxy/PTFE composite was prepared by curing the epoxy resin on the surface-modified PTFE film. Surface modification of PTFE films was carried out via argon plasma pretreatment, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The film composite achieved a 90°-peel adhesion strength above 15 N/cm. The strong adhesion of the epoxy resin to PTFE arose from the fact that the epoxide groups of the grafted GMA chains were cured into the epoxy resin matrix to give rise to a highly crosslinked interphase, as well as the fact that the GMA chains were covalently tethered on the PTFE film surface. Delamination of the composite resulted in cohesive failure inside the PTFE film and gave rise to an epoxy resin surface with a covalently-adhered fluoropolymer layer. The surface composition and microstructures of the GMA graft-copolymerized PTFE (GMA-g-PTFE) films and those of the delaminated epoxy resin and PTFE film surfaces were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and scanning electron microscope (SEM) measurements. The delaminated epoxy resin surfaces were highly hydrophobic, having water contact angles of about 140°C. The value is higher than that of the pristine PTFE film surface of about 110°. The epoxy resin samples obtained from delamination of the epoxy/GMA-g-PTFE composites showed a lower rate of moisture sorption. All the fluorinated epoxy resin surfaces exhibited rather good stability when subjected to the Level 1 hydrothermal reliability tests.     

Grafting of Epoxy Resin on Surface-modified Poly(tetrafluoroethylene) Films

An epoxy/PTFE composite was prepared by curing the epoxy resin on the surface-modified PTFE film. Surface modification of PTFE films was carried out via argon plasma pretreatment, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The film composite achieved a 90°-peel adhesion strength above 15 N/cm. The strong adhesion of the epoxy resin to PTFE arose from the fact that the epoxide groups of the grafted GMA chains were cured into the epoxy resin matrix to give rise to a highly crosslinked interphase, as well as the fact that the GMA chains were covalently tethered on the PTFE film surface. Delamination of the composite resulted in cohesive failure inside the PTFE film and gave rise to an epoxy resin surface with a covalently-adhered fluoropolymer layer. The surface composition and microstructures of the GMA graft-copolymerized PTFE (GMA-g-PTFE) films and those of the delaminated epoxy resin and PTFE film surfaces were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and scanning electron microscope (SEM) measurements. The delaminated epoxy resin surfaces were highly hydrophobic, having water contact angles of about 140°C. The value is higher than that of the pristine PTFE film surface of about 110°. The epoxy resin samples obtained from delamination of the epoxy/GMA-g-PTFE composites showed a lower rate of moisture sorption. All the fluorinated epoxy resin surfaces exhibited rather good stability when subjected to the Level 1 hydrothermal reliability tests.     

Flexural and Charpy impact behaviour of epoxy/glass fabric treated by nano-SiO2 and silane blend

A sizing formulation, containing compatible and incompatible silane coupling agents with epoxy resin in conjunction with nanoscale colloidal silica, was used to modify the surface of glass fabric. The modified glass fabric/epoxy resin composite panels were fabricated and characterised by flexural test, Charpy impact test and scanning electron microscope (SEM). By combining nano silica with silane blend in the fabric sizing, more energy was consumed under bending and impacting, which resulted in an improvement of the toughness in composites. The flexural strength, bending stain and Charpy impact strength of the epoxy composite/glass fabric treated with 1?wt-% nano silica and silane blend were ～42, ～22 and 35%, respectively, higher than those of silane blend coated glass fabric-reinforced composites (without nano silica). Furthermore, the change of the brittle fracture of the composite into ductile fracture was investigated by SEM micrographs. A possible toughening mechanism was also proposed.     

高硅含量有机无机杂化乳液的制备和溶胶-凝胶驱使成膜

A novel polymer/SiO2 hybrid emulsion (PAES) was prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a saline coupling agent. The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES. The effects of γ-methacryloxypropyltrimethoxysilane (KH-570) content and co-solvent on the properties of PAES films were investigated. Dynamic laser scattering (DLS) data indicate that the average diameter of PAES (96 nm) is slightly larger than that of PAE (89 nm). Transmission electron microscopy (TEM) photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles. The crosslinking degree data and Fourier transform infrared (FT-IR) spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation. Atomic force microscope (AFM) photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES. Thermogravimetric analysis (TGA) curves demonstrate that the PAES films display much better thermal stability than PAE.     

高疏水性硅橡胶防污闪涂料的制备及其性能研究

以端羟基聚二甲基硅氧烷、不同粒径的改性二氧化硅粒子、硅烷偶联剂及助剂为原料,采用有机-无机杂化纳米技术,制得具有高疏水性能的室温硫化(RTV)硅橡胶防污闪涂料。采用扫描电镜表征了涂层的表面形貌,用静态接触角测试仪测定了二氧化硅用量对涂层的憎水性及憎水迁移性变化。结果表明,固定纳米级二氧化硅的用量,当微米级二氧化硅用量为10份时,涂层表面形成一定的微米二级粗糙结构,涂层表面接触角为131.50,具有较高的疏水性能;同时,涂层也具有优良的憎水迁移性。此时,硅橡胶的拉伸强度为2.08 MPa,伸长率581%,撕裂强度5.65 kN/m,体积电阻率1.38×1015Ω·m,污秽湿工频闪络电压3 kV,阻燃性FV-0级。     

Characterization of UV curable hybrid hard coating materials prepared by sol-gel method

Using sol-gel method, UV-curable urethane acrylate resin system was hybridized with inorganic silicate network to produce hybrid coating materials with high anti-abrasive property. In preparation of acrylate/SiO₂ hybrid materials, various acrylic reactants with multi-functional groups in addition to urethane acrylate oligomer as the main network former were employed to obtain more densified organic network structure with a high degree of cross-linking. As a silane coupling agent, 3-methacryloxypropyl-trimethoxysilane (MPTMS) was used to promote interfacial attraction between UV-cured organic acrylate resin and inorganic silicate component in the hybrid. The addition of MPTMS offered significant effect on the improvement of phase compatibility between organic and inorganic phases, which resulted in stable and homogeneous morphology with a dispersion of nano-sized fine silica particles. The results of morphological observation, glass transition behavior, and optical transparency for the hybrid gels provided an evidence for the increased interfacial attraction between two phases. From the Taber abrasion test for the hybrid coating films, it was revealed that there existed optimal ranges of inorganic silicate precursor TEOS and silane coupling agent MPTMS contents for the preparation of UV cured acrylate/SiO₂ hybrid with high abrasion resistant property.     

Thermally and mechanically superior hybrid epoxy–silica polymer films via sol–gel method

Hybrid organic–inorganic polymer films composed of an epoxy resin crosslinked with a flexible diamine hardener, and a silica reinforcing phase were produced and their thermo-mechanical properties were determined. Two types of hybrid epoxy–silica polymer films, named EAS-1 and EAS-2, were obtained by hydrolysis and condensation of various amounts of tetraethoxysilane within epoxy network matrix. In EAS-2 hybrids, minor amounts of an amine silane coupling agent were added to enhance interfacial compatibility. FTIR spectroscopy confirmed the formation of organic and inorganic networks. The grafting of amine silane on to the epoxy resin influenced the size and distribution of hyper-branched clusters of silica as indicated by transmission electron microscopy (TEM). The dynamic mechanical and thermal analysis (DMTA) and thermo-gravimetric analysis (TGA) results showed an increase in the storage modulus, the glass-transition temperature, and the thermal stability of hybrid polymer films as compared to the neat matrix. The integration of amine silane coupling agent produced smaller, effectively dispersed silica nanoparticles and consequently improved the ultimate properties of polymer films.     

Transparent polysilicone coatings as protecting films for gold commemorative coins

Novel transparent organic silicone resin coatings were successfully prepared through the reaction between the alkoxy groups of methyltrimethoxy‐silane (MTMS) and γ‐aminopropyltriethoxysilane (APTES) and hydroxyl groups of hydroxyl terminated silicone oil (HTSO). The influences of different monomer feed mass ratio on the coating properties were investigated via measuring the hydrophobicity and hardness of coating films. The coating films were characterized with IR, UV, TG, scanning electron microscope (SEM), and automatic contact angle meter. Some properties of coating films, such as adhesion, impact resistance, and wear‐resistance, were also evaluated. The results indicated that these coating films formed on the surfaces of gold commemorative coins possessed some good properties including high hydrophobicity, high water contact angles, high light transmittance, good heat‐resistance, adhesion, hardness, and weatherability, etc. Moreover, the uniform, clear, transparent, and dense coating films did not cover the symphony surface patterns or affect the metallic luster. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and surface properties of a novel bulk-matte waterborne polyurethane coating composite

This paper reports on a novel self-matte or bulk-matte waterborne polyurethane coating composite with inherently extremely low gloss. The coating composite was comprised of a siloxane-containing waterborne polyurethane (SPU) resin and a crosslinked waterborne polyurethane (CPU) resin. The CPU resin was mainly responsible for fabricating the micro-rough surface of the film, which was achieved by a crosslinking reaction between the waterborne polyurethane and bisphenol A-type epoxy E-44 resin. The SPU resin was used to improve the comprehensive properties of the film, which was ascribed to the addition of silane coupling agent KH792. Compared with traditional matte coatings, this coating composite made it possible to avoid high loadings of matting agent and to arrive at highly flexible low-gloss finishes. Gloss levels of as low as a few tenths of a percent, even at high incidence angles, have been achieved with zero loading of extraneous dulling agent. The chemical structures of the SPU and CPU resins were characterized by FTIR-ATR and NMR spectra. The micro-rough topographies and surface rough degrees of the SPU, CPU and their 50%/50% composite films were measured by SEM and MSP, respectively. The particle sizes and particle morphologies of the SPU and CPU resins were imaged by TEM. Finally, the comprehensive properties of the SPU, CPU and their 50%/50% composite resins were evaluated, including the water contact angle, film transparency, tensile strength and storage stability.     

Nanocomposite acrylic paint with self-cleaning action

A nanodispersion of surface-functionalized fumed silica was incorporated into an acrylic paint formulation. SEM imaging indicated good dispersion of silica within the polymer matrix. This hybrid coating showed significantly lower dirt pick-up than the equivalent paint formulation without nanosilica additive, towards both organic and inorganic ashes. Washing with running water further decreases dirt retention. This self-cleaning performance remained unchanged after several dirt/washing cycles, during a 1-month period. Surface hardness measurements indicated no significant differences between the original and composite paint films. The lower dirt pick-up was attributed to nanoroughness created by the nanosilica particles present in the film.     

Role of additives on UV curable coatings on wood

An epoxy resin-coating formulation was prepared from diacrylated epoxy bisphenol-A-epichlorohydrin and a reactive monomer, tripropyleneglycol diacrylate. The additives, silane and fluorochemicals, were included in the formulation to evaluate their effects on the UV curing of the epoxy resin onto timber. Thin films coated on wood substrates were cured under UV radiation in the presence of the photoinitiator, benzoin ethyl ether. Adhesion of the cured films onto wood substrates was evaluated using the cross-cut and the pull-off tests. Film hardness was evaluated using the pencil hardness and the pendulum hardness tests. Water repellency of the films were measured from contact angles using a telegoniometer. Scanning electron microscopy (SEM) was used to investigate the interface between the films and the wood substrates. These studies showed that silane only enhanced the adhesion of the film onto the wood substrates but had no effect on the hardness of the films. The additives improved the water repellency of the films with the fluorochemicals, exhibiting dramatic improvement. SEM revealed that only the fluorochemical aided the penetration of the resin into the wood. © 1996 John Wiley & Sons, Inc.