Development of the scratch resistance on acrylic sheet with basic colloidal silica (SiO2)—methyltrimethoxysilane (MTMS) nanocomposite films by sol–gel technique

The formation of scratch‐resistant coating film prepared from colloidal silica and a polysiloxane matrix was investigated. Methyltrimethoxysilane (MTMS) was hydrolysed and mixed with silica sol (SiO₂) at various compositions to form the hybrid hard‐coating nanocomposite film. The hydrolysed MTMS (polysiloxane) acts as the polymeric binder that is covalently linked to the colloidal silica surface and provides adhesion for the scratch resistant coating film to the substrate. The ratio between the polymeric matrix and the SiO₂ nanoparticles was found to play a major role in controlling the coating film appearance and its resistance to scratching. At a SiO₂ content < 30 wt.%, the agglomeration of the hydrolysed polysiloxane was observed and caused the opacity of the coating film. At a SiO₂ content >70 wt.%, there was not enough polysiloxane to act as a binder for the SiO₂, therefore a shrinkage upon solidification of the coating film caused cracking within the nanocomposite film. The optimum ratio was found to be at 40 wt.% ≤SiO₂ ≤60 wt.%, where the films had a transparent, crack free hard coating, with excellent scratch resistance, good adhesion and very good environmental resistance. The nanoindentation revealed that the nanocomposite film, at the optimum loading, possessed a higher strength with a higher SiO₂ loading. Film properties, including hardness, scratch resistance, adhesion and environmental resistance were also examined. The morphology of nanocomposite films was identified by atomic force microscopy (AFM) and scanning electron microscopy (SEM). © 2011 Canadian Society for Chemical Engineering     

Preparation of Scratch and Abrasion Resistant Polymeric Nanocomposites by Monomer Grafting onto Nanoparticles, 3. Effect of Filler Particles and Grafting Agents

After modification with different trialkoxysilanes, nano‐sized silica and alumina particles were used as fillers in transparent UV/EB curable acrylates for polymer reinforcement, particularly to attain scratch and abrasion resistant coatings. The acid catalyzed condensation of the organosilanes forms a polysiloxane shell which covers the nanoparticle like a nanocapsule. CP MAS NMR spectroscopy and MALDI‐TOF mass spectrometry proved to be useful for the characterization of the polysiloxane structures. Grafted oligomers with more than 20 monomeric units were observed. Nanoparticles modified by methacroyloxy(propyl)trimethoxysilane and vinyltrimethoxysilane can copolymerize with acrylates. Compared with the pure polymers, these crosslinked polyacrylate nanocomposites, containing up to 35 wt.‐% silica, exhibit markedly improved surface mechanical properties. Promising scratch and abrasion resistance of radiation‐cured nanocomposite materials were also obtained by propyltrimethoxysilane grafting which results in an organophilation of pyrogenic silica. Both colloidal and pyrogenic nano‐sized silica nanopowders were used as fillers in polyacrylate films. The concentration of colloidal SiO₂ in commercial acrylate formulations amounts up to 50 wt.‐%, whereas pyrogenic silica, notwithstanding their surface modification by silanes, results in a thickening effect which limits its content to about 35 wt.‐%. Nevertheless, a comparison showed a distinct improvement in the surface mechanical properties such as haze and diamond microscratch hardness for surface‐modified pyrogenic silica.     

On surface deformation of melt‐intercalated polyethylene–clay nanocomposites during scratching

Electron microscopy has been used to examine the mechanically‐induced surface damage introduced during scratching of polyethylene(PE)–clay nanocomposites. The determining role of clay in reducing the susceptibility to surface deformation is predicted from the characteristics of surface morphology and the scratch deformation parameters. The reinforcement of PE with nanoclay reduces the susceptibility to scratch damage and stress whitening. Microcracks and surface deformation features namely wrinkles/ridges are the primary source of light scattering resulting in stress whitening. The scratch deformation behavior is discussed in terms of tensile modulus, percentage crystallinity, elastic recovery, and scratch hardness. Scratch hardness is a relevant parameter that can be appropriately used to determine resistance to scratch deformation. POLYM. ENG. SCI. 46:1625–1634, 2006. © 2006 Society of Plastics Engineers     

Mechanical properties study of micro‐ and nano‐hydroxyapatite reinforced ultrahigh molecular weight polyethylene composites

This is a comparative study between ultrahigh molecular weight polyethylene (UHMWPE) reinforced with micro‐ and nano‐hydroxyapatite (HA) under different filler content. The micro‐ and nano‐HA/UHMWPE composites were prepared by hot‐pressing method, and then compression strength, ball indentation hardness, creep resistance, friction, and wear properties were investigated. To explore mechanisms of these properties, differential scanning calorimetry, infrared spectrum, wettability, and scanning electron microscopy with energy dispersive spectrometry analysis were carried out on the samples. The results demonstrated that UHMWPE reinforced with micro‐ and nano‐HA would improve the ball indentation hardness, compression strength, creep resistance, wettability, and wear behavior. The mechanical properties for both micro‐ and nano‐HA/UHMWPE composites were comparable with pure UHMWPE. The mechanical properties of nano‐HA/UHMWPE composites are better compared with micro‐HA/UHMWPE composites and pure UHMWPE. The optimum filler quantity of micro‐ and nano‐HA/UHMWPE composites is found to be at 15 wt % and 10 wt %, separately. The micro‐ and nano‐HA/UHMWPE composites exhibit a low friction coefficient and good wear resistance at this content. The worn surface of HA/UHMWPE composites shows the wear mechanisms changed from furrow and scratch to surface rupture and delamination when the weight percent of micro‐ and nano‐HA exceed 15 wt % and 10 wt %. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42869.     

丙烯酸酯聚氨酯/SiO2纳米复合涂层结构与形态对其耐刮伤性影响研究

以四乙氧基硅烷(TEOS)作为主要前驱体,通过改变溶胶-凝胶工艺参数制得了结构和形态各异的丙烯酸酯聚氨酯/SiO2纳米复合涂层,利用TEM、SAXS等手段表征涂层的结构与形态,由洗刷前后涂层的失光率来表征耐刮伤性,详细探讨了纳米复合涂层耐刮伤性与SiO2相特征、有机无机相作用力及SiO2质量分数之间的关系。研究表明:丙烯酸酯聚氨酯涂层中引入纳米SiO2相后,耐刮伤性明显提高。有机相与SiO2相之间的作用力是影响涂层耐刮伤性的最重要因素,作用力越强,耐刮伤性越好。网络状纳米SiO2与颗粒状纳米SiO2相比,更有利于耐刮伤性的提高,且网络状纳米SiO2质量分数越大,耐刮伤性越佳,但SiO2相的致密度和尺寸对耐刮伤性影响较小。对于颗粒状胶体SiO2,在15~160 nm范围内,粒径对耐刮伤性没有明显影响;随着胶体SiO2粒子的质量分数增加,耐刮伤性先增大后减小。     

Preparation of an ultraviolet‐curable water‐borne poly(urethane acrylate)/silica dispersion and properties of its hybrid film

An organic–inorganic hybrid material was prepared through the addition of nanometer fumed silica partly modified by dimethyl dichlorosilane into a water‐borne poly(urethane acrylate) (PUA) anionomer. A PUA/silica hybrid film was made via ultraviolet curing. The mechanical properties of the hybrid film were studied. The tensile strength, elongation at break, pendulum hardness and the glass‐transition temperature of the hybrid material increased with increasing content of silica. Scanning electron microscopy showed an asymmetrical distribution of modified silica in PUA. Atomic force microscopy demonstrated that silica particles could make the surface of the film smooth. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1347–1352, 2004     

A macroscopically nondestructive method for characterizing surface mechanical properties of polymeric coatings under accelerated weathering

The surface of coatings and plastics is the first target in any degradation process initiated by ultraviolet (UV) radiation or mechanical stress (via scratch and abrasion). Surface damage can lead to changes in optical, morphological, and mechanical properties and can result in pathways for ingress of moisture and corrosive agents. Current test methods for monitoring performance of protective coatings focus on chemical properties and optical properties, such as color and gloss measurements, or invasive tests such as abrasion and cross-cut adhesion. In this study, a macroscopically nondestructive performance protocol using nanoindentation metrology via a well-controlled scratch test was applied to evaluate the scratch resistance and monitor the surface mechanical property changes in a protective coating under accelerated weathering. Polyurethane (PU) coatings with different polyol compositions were chosen for this study. Coating specimens were exposed to high-intensity UV radiation at 55°C and 75% RH conditions. Exposed specimens were removed at specified UV exposure times for surface modulus/hardness and scratch resistance characterization via nanoindentation and scratch test. The effect of polyol type and UV radiation dose on the scratch damage (scratch morphology) was investigated and correlated with the surface hardness and modulus of the materials.     

Film‐forming behavior and mechanical properties of colloidal silica/polymer latex blends with high silica load

In this article, silica sol (diameter: 8–100 nm) and polymer latex (T_g < 25°C) were mixed and dried at room temperature to prepare nanocomposite films with high silica load (≥50 wt %). Effects of silica size, silica load, and the T_g of the polymer on the film‐forming behavior of the silica/polymer latex blend were investigated. The transparency, morphology, and mechanical properties of the nanocomposite films were examined by UV–Vis spectroscopy, SEM, and nanoindentation tests, respectively. Transparent and crack‐free films were produced with silica loads as high as 70 wt %. Thirty nanometers was found to be the critical silica size for the evolution of film‐forming behavior, surface morphology, and mechanical properties. Colloidal silica particles smaller than this critical size act as binders to form strong silica skeleton. This gives the final silica/polymer nanocomposite film its porous surface and high mechanical strength. However, silica particles with sizes of 30 nm or larger tend to work as nanofillers rather than binders, causing poor mechanical strength. We also determined the critical silica load appeared for the mechanical strength of silica/polymer film at high silica load. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology of hybrid coatings based on polyester, melamine resin, and silica and the relation with hardness and scratch resistance

The morphology of hybrid coatings based on polyester, melamine resin, and various amounts of silica has been investigated, and the hardness and scratch resistance were determined. By increasing silica content, an increase of silica particles in size and number was observed. Small silica particles were preferentially present at the surface. The influence of the silica content on the K?nig hardness, indentation hardness, and elastic modulus was minor. The improved scratch resistance determined for a hybrid coating with 11.4 wt% silica, compared to a similar organic coating without silica, was attributed to small silica particles preferentially present at the surface. Presented at the 26th International Waterborne, High-Solids, and Powder Coatings Symposium, February 10–12, 1999, New Orleans, LA. Dept. of Polymer Chemistry and Coatings Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands. Materials Division, Dept. of Materials Chemistry and Coatings, P.O. Box 595, 5600 AN Eindhoven, The Netherlands.     

Enhancement of the surface and bulk mechanical properties of polystyrene through the incorporation of raw multiwalled nanotubes with the twin‐screw mixing technique

In this article, we present the effects of incorporated multiwalled nanotubes (MWNTs) on a metal surface and the bulk mechanical properties of as‐synthesized polystyrene (PS)–MWNT composites prepared with the twin‐screw mixing technique. The MWNTs used for preparing the composites were raw compounds that were not treated with any surface modifications. The morphology for the dispersion capability of the MWNTs in the PS matrix was subsequently characterized with transmission electron microscopy. Surface mechanical property studies (i.e., wear resistance and hardness) showed that the integration of MWNTs led to a distinct increase in the wear resistance and also the micro/nanohardness with up to a 5 wt % MWNT loading in the composites. Moreover, the enhancement of the wear resistance of the as‐prepared composites, in comparison with pure PS, was further identified with scanning electron microscopy observations of the surface morphology after testing. On the other hand, for bulk mechanical property studies (i.e., the tensile strength and flexural strength), the composites containing a 3 wt % concentration of MWNTs in the PS matrix exhibited the best performance with respect to the tensile strength and flexural strength. This means that this composition of MWNTs exhibited good compatibility with the PS matrix, and this can be attributed to the π–π interacting forces existing between the aromaticity of the MWNTs and PS matrix. Furthermore, at higher MWNT loadings (e.g., 5 wt %), raw MWNTs were aggregated in the polymer matrix, as observed by transmission electron microscopy. Also, this led to an obvious decrease in the tensile strength and flexural strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of scratch and mar resistant waterborne epoxy/silica nanocomposite clearcoat

Colloidal nano‐silica particles were used to improve the scratch and mar resistance of waterborne epoxy coatings by directly blending. To enhance the compatibility of nano‐silica particles within polymer matrix, nano‐silica particles were first modified with 3‐glycidoxypropyl‐trimethoxysilane (GPTMS) and characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The modified nano‐silica particles were found to have a better dispersion and compatibility in the polymer matrix than the unmodified nano‐silica particles. Macro‐scratch and nano‐scratch testers were employed to characterize the scratch and mar resistances of the nanosilica‐reinforced epoxy coatings. Relative to unmodified nano‐silica, GPTMS‐modified nano‐silica particles can improve the scratch and mar resistance more significantly and reduce the transparency and gloss of waterborne epoxy coatings less seriously. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nylon 11/silica nanocomposite coatings applied by the HVOF process. II. Mechanical and barrier properties

Nylon 11 coatings filled with nominal 0–15 vol % of nanosized silica or carbon black were produced using the high velocity oxy‐fuel combustion spray process. The scratch and sliding wear resistance, mechanical, and barrier properties of nanocomposite coatings were measured. The effect of powder initial size, filler content, filler chemistry, coating microstructure, and morphology were evaluated. Improvements of up to 35% in scratch and 67% in wear resistance were obtained for coatings with nominal 15 vol % contents of hydrophobic silica or carbon black, respectively, relative to unfilled coatings. This increase appeared to be primarily attributable to filler addition and increased matrix crystallinity. Particle surface chemistry, distribution, and dispersion also contributed to the differences in coating scratch and wear performance. Reinforcement of the polymer matrix resulted in increases of up to 205% in the glass storage modulus of nanocomposite coatings. This increase was shown to be a function of both the surface chemistry and amount of reinforcement. The storage modulus of nanocomposite coatings at temperatures above the glass transition temperature was higher than that of unfilled coatings by up to 195%, depending primarily on the particle size of the starting polymer powder. Results also showed that the water vapor transmission rate through nanoreinforced coatings decreased by up to 50% compared with pure polymer coatings. The aqueous permeability of coatings produced from smaller particle size polymers (D‐30) was lower than the permeability of coatings produced from larger particles because of the lower porosities and higher densities achieved in D‐30 coatings. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2272–2289, 2000     

Radiation–chemical modification of PTFE in the presence of graphite

PTFE with a 15% addition of graphite was subjected to irradiation using an electron beam of 10 MeV energy with absorbed doses of 26, 52, 78, 104, and 156 kGy. The effect of electron‐beam irradiation on the mechanical, sclerometic, and tribological properties, the crystallinity degree, and the morphology of the polymer surface was examined. It was found that the modification through irradiation entailed a gradual increase in the degree of crystallinity, which had a direct influence on the mechanical properties. An increase in the hardness, Young's modulus, and compressive strength of the polymer irradiated with an electron beam was also demonstrated. The electron‐beam irradiation reduced the value of components of the work‐of‐indentation, showing the growing resistance to deformation. An analysis of the scratch test parameters showed a reduced depth of penetration of the indenter into the material, proportionally to the irradiation value, at relatively constant values of the scratch depth after scratching load removal. A stereometric analysis of the scratch traces on the material allowed to determine coefficients of the wear micromechanism, β, and resistance to wear, W_β. It was found that after irradiation (especially with a dose of 4 × 26 kGy), a significant quantity of the material showed traces of ploughing, which meant a positive effect on the wear mechanism. The value of the wear resistance coefficient W_β for PTFE subjected to the absorbed irradiation dose increased intensively, which portended a significant reduction of the tribological wear compared to the nonirradiated material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42348.     

Preparation and property of raspberry‐like AS/SiO2 nanocomposite particles

Surfactant‐free poly(acrylonitrile‐co‐styrene)/silica (AS/SiO₂) nanocomposite particles was synthesized in the presence of cheap, commercially amorphous aqueous silica sol at ambient temperature. Thermogravimetric analysis (TGA) indicated silica contents ranging from 5 wt % to 29 wt %, depending on reaction conditions. Particle size distributions and morphologies were studied using dynamic light scattering (DLS) and transmission electron microscopy (TEM), which clearly showed that most of the colloidal nanocomposites comprised approximately spherical particle with raspberry‐like morphology and relatively narrow size distributions. The optical clarity of solution‐cast nanocomposite films was assessed using UV–vis spectrometer, with high transmission being obtained over the whole visible spectrum. Differential scanning calorimetry (DSC) studies showed that the glass transition temperature of AS/SiO₂ nanocomposites can be higher than the corresponding pure AS, resulting from the hydrophilicity of the nanometer silica. The robustness and simplicity of this method may make large‐scale manufacture of this nanocomposite possible. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 415–421, 2007     

Effect of addition of surface modified nanosilica into silica–zirconia hybrid sol–gel matrix

An organic–inorganic hybrid sol (MZ) comprising a methacrylate functionalized silane matrix (M) and zirconium-n-propoxide (Z) was prepared using sol–gel technique. Two methodologies were adopted to modify the hybrid sol for generating nanocomposite coatings viz., (a) addition of acrylic surface modified silica nanoparticles (N) of diameter ～20 nm to the sol to enhance their compatibility with the hybrid sol–gel matrix and (b) in-situ formation of a three dimensional silica network by addition of tetraethoxy silane (T) to the sol MZ. In the first methodology, the sols were prepared with six different weight ratios of the nanoparticles to the sol, i.e. 0, 0.01, 0.05, 0.1, 0.25 and 1 which were labelled as MZ+Nx where x=0, 1, 2, 3, 4 and 5 respectively. The prepared sols were dip coated on 100 mm×100 mm polycarbonate substrates followed by thermal curing at 130 °C. The coatings were characterized for their mechanical properties like pencil scratch hardness, scratch resistance using scratch tester, nanoindentation hardness, and abrasion resistance as well as visible light transmittance. FT-IR studies were also carried out on heat-treated gels derived from the sols. A maximum pencil scratch hardness of 3H was obtained for the MZ+T coatings and these coatings withstood a critical load of 4.3±0.7 N before failure during scratch test. The maximum nanoindentation hardness of 3.8±0.01 GPa was obtained for the MZ+N5 coatings. The abrasion resistance of MZ+T coatings was higher when compared to MZ+N0 and MZ+N5 coatings. The scratch and nanoindentation hardness were seen to be better for an in-situ formed –Si–O–Si– network in the hybrid sol when compared to those obtained from coatings generated by external addition of acrylic surface modified silica nanoparticles. The difference in properties was attributed to the level of interaction between the nanoparticles and hybrid sol–gel matrix.     

Scratch deformation characteristics of micrometric wollastonite‐reinforced ethylene‐propylene copolymer composites

The scratch deformation behavior of neat and wollastonite‐containing ethylene‐propylene copolymer composites has been studied by electron microscopy and atomic force microscopy techniques. The study indicates that the severity of plastic deformation during scratch testing in reinforced ethylene‐propylene copolymers is a function of debonding/detachment of wollastonite mineral particles from the ethylene‐propylene matrix. The resistance to scratch deformation was evaluated in terms of scratch hardness, scratch depth, average scratch roughness, and change in gray level before and subsequent to scratching. The data suggests that resistance to scratch deformation follows the sequence: coated + coupled wollastonite‐containing EP copolymer > fine wollastonite‐containing EP copolymer > coated wollastonite‐containing EP copolymer > coarse wollastonite‐containing EP copolymer > neat EP copolymer. EP copolymer containing coated wollastonite and coupling agent is characterized by highest scratch hardness and minimum scratch depth and scratch roughness. The visibility of scratch, quantified in terms of gray level, suggests that coated + coupled wollastonite‐containing copolymer exhibits significantly reduced susceptibility to stress whitening, and is characterized by a lower gray level in the scratch‐deformed regions. In the present case of wollastonite‐containing copolymer composites, the resistance to scratch deformation follows a trend similar to that of gray level or scratch visibility. Polym. Eng. Sci. 44:1738–1748, 2004. © 2004 Society of Plastics Engineers.     

Morphology,thermal, and mechanical properties of flame‐retardant silicone rubber/montmorillonite nanocomposites

Flame‐retardant methyl vinyl silicone rubber (MVMQ)/montmorillonite nanocomposites were prepared by solution intercalation method, using magnesium hydroxide (MH) and red phosphorus (RP) as synergistic flame‐retardant additives, and aero silica (SiO₂) as synergistic reinforcement filler. The morphologies of the flame‐retardant MVMQ/montmorillonite nanocomposites were characterized by environmental scanning electron microscopy (ESEM), and the interlayer spacings were determined by small‐angle X‐ray scattering (SAXS). In addition to mechanical measurements and limited oxygen index (LOI) test, thermal properties were tested by thermogravimetric analysis (TGA). The decomposition temperature of the nanocomposite that contained 1 wt % montmorillonite can be higher (129°C) than that of MVMQ as basal polymer matrix when 5% weight loss was selected as measuring point. This kind of silicone rubber nanocomposite is a promising flame‐retardant polymeric material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3275–3280, 2006     

Surface properties and surface patterning of UV-curable coating using perfluorosilane-treated nanosilica

In this work, a one-step film formation method is demonstrated to obtain the patterned surface of an acrylate photocuring coating using nano-silica particles treated with a perfluoroalkoxysilane ((heptadecafluoro-1,1,2,2-tetra hydrodecyl) triethoxysilane) as a nanoadditive. Nanosilica particles were treated with perfluoroalkoxysilane and used in a UV-curable matrix. The typical patterns on the surface of the UV-cured films are revealed in AFM images. The surface properties of the cured films were investigated by measuring water contact angle and surface energy. The degree of conversion of the samples was obtained by FTIR analysis and pendulum hardness was measured using a Konig hardness meter. Scratch resistance of cured films was measured by standard scratch measuring pens. The characteristics obtained from AFM analysis showed that rough surface patterns in this system are controlled linearly by changes in the treated nano-particle concentration. The subtraction of surface energy of the cured film was clear and the water contact angle showed a 60% increase with the addition of a fluorinated nano-particle concentration. Surface hardness decreased and scratch resistance increased as the concentration of treated nanoparticles increased, while the final degree of conversion of the film remained unchanged.     

Fabrication and properties of chemically bonded polysilsesquioxane‐polyacrylate/silica hybrid latex films with high silicon content

Polysilsesquioxane‐polyacrylate/silica hybrid latexes (PSQ‐PAS) with high silicon content were prepared by directly mixing colloidal silica with polysilsesquioxane‐polyacrylate emulsion (PSQ‐PA), which was prepared through seeded emulsion polymerization using polymethacryloxypropylsilsesquioxanes as the core and polyacrylate (PA) as the shell respectively. The chemically bonded PSQ‐PAS thin films were obtained via sol‐gel process after addition of hydrophilic cosolvent to PSQ‐PAS emulsion and subsequent drying at room temperature. The effects of silica/PSQ‐PA ratio (w/w) on the film properties of hardness, optical property and thermal stability were investigated. Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to characterize the chemical composition and morphology of the resultant hybrid particles. DLS and TEM results indicated that both PSQ and PSQ‐PA particles had narrow size distribution and their average diameters were about 200 and 350 nm, respectively. Pendulum durometer, UV–vis spectroscopy, and thermogravimetric analysis (TGA) were used to characterize the hardness, optical property and thermal stability of PSQ‐PAS latex films. The results showed that the PSQ‐PAS films hardness increased with the increasing ratio of silica/PSQ‐PA, whereas the transmittance decreased slightly. TGA curves demonstrated PSQ‐PAS films displayed excellent thermal stability, and the residual silicon weight exceeded 30%. POLYM. COMPOS., 36:389–396, 2015. © 2014 Society of Plastics Engineers     

Synthesis and characterization of novel polyimide/SiO2 nanocomposite materials containing phenylphosphine oxide via sol‐gel technique

In this article, a series of novel polyimide/silica (PI/SiO₂) nanocomposite coating materials were prepared from tetraethoxysilane (TEOS), γ‐glycidyloxypropyltrimethoxysilane (GOTMS), and polyamic acid (PAA) via sol‐gel technique. PAA was prepared by the reaction of 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and bis (3‐aminophenyl) phenyphosphine oxide (BAPPO) in N‐methyl‐2‐ pyrrolidone (NMP). BAPPO was synthesized hydrogenation of bis (3‐nitrophenyl) phenyphosphine oxide (BNPPO) in the presence of Pd/C. The silica content in the hybrid coating materials was varied from 0 to 20 wt %. The molecular structures of the composite materials were analyzed by means of FT‐IR and ²⁹Si‐NMR spectroscopy techniques. The physical and mechanical properties of the nanocomposites were evaluated by various techniques such as, hardness, contact angle, and optical transmission and tensile tests. These measurements revealed that all the properties of the nanocomposite coatings were improved noticeable, by the addition of sol‐gel precursor into the coating formulation. Thermogravimetric analysis showed that the incorporation of sol‐gel precursor into the polyimide matrix leads to an enhancement in the thermal stability and also flame resistance properties of the coating material. The surface morphology of the hybrid coating was characterized by scanning electron microscopy (SEM). SEM studies indicated that nanometer‐scaled inorganic particles were homogenously dispersed throughout the polyimide matrix © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010