Facile fabrication of superhydrophobic raspberry‐like SIO2/polystyrene composite particles

A facile and novel strategy was reported on the fabrication of raspberry‐like SiO₂/polystyrene (SiO₂/PS) composite particles by emulsion polymerization in the presence of vinyl‐functionalized silica (vinyl‐SiO₂) particles, which were prepared via a one‐step sol–gel process using vinyltriethoxysilane as the precursor. The submicron vinyl‐SiO₂ particles were used as the core, and nanosized PS particles were then adsorbed onto the vinyl‐SiO₂ particles to form raspberry‐like composite particles during the polymerization process. The composition, morphology, and structure of the vinyl‐SiO₂ particles and the SiO₂/PS hybrid particles were characterized by thermogravimetric analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Superhydrophobic surface can be constructed by directly depositing the raspberry‐like SiO₂/PS composite particles on glass substrate, and the water contact angle can be adjusted by the styrene/SiO₂ weight ratio. In addition, the superhydrophobic film possessed a strong adhesive force to pin water droplet on the surface even when the film was turned upside down. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Silica/polystyrene and silica/polystyrene‐b‐polymethacryloxypropyltrimethoxysilane hybrid nanoparticles via surface‐initiated ATRP and comparison of their wettabilities

Both silica/polystyrene (SiO₂/PS) and silica/polystyrene‐b‐polymethacryloxypropyltrimethoxysilane (SiO₂/PS‐b‐PMPTS) hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization (SI‐ATRP) from SiO₂ nanoparticles. The growths of all polymers via ATRP from the SiO₂ surfaces were well controlled as demonstrated by the macromolecular characteristics of the grafted chains. Their wettabilities were measured and compared by water contact angle (WCA) and surface roughness. The results show that the nanoparticles possess hydrophobic surface properties. The static WCA of SiO₂/PS‐b‐PMPTS hybrid nanoparticles is smaller than that of SiO₂/PS hybrid nanoparticles, meanwhile, the surface roughness of SiO₂/PS‐b‐PMPTS hybrid nanoparticles is yet slightly rougher than that of SiO₂/PS hybrid nanoparticles, which shows that the combination and competition of surface chemistry and roughness of a solid material can finally determine its wettability. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Facile preparation of a silica‐sphere–poly(catechol hexamethylenediamine) composite for the competitive removal of cadmium(II), lead(II), and copper(II) ions

A silica‐sphere–poly(catechol hexamethylenediamine) (PCHA–SiO₂) composite was prepared via the one‐step facile polymerization of catechol and hexamethylenediamine; this method uses a silica sphere as a hard template. The chemical structures and morphologies of this composite were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The adsorption experiments indicated that the PCHA–SiO₂ composite served as a very attractive adsorbent for Pb(II)‐, Cu(II)‐, and Cd(II)‐ion removal at lower concentrations and had very good selective adsorption abilities for Pb(II) and Cu(II) ions in a solution contaminated with these three ions at higher concentrations. These interesting results may have been due to the reversible H⁺ adsorption–desorption properties of the characteristic phenol amine structure of the PCHA–SiO₂ composite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45839.     

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L ‐lactide) (PLLA) onto silica nanoparticle surface by ring‐opening polymerization of L‐lactide (LA) was investigated in the presence of an amidine base catalyst. The ring‐opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica‐NH₂) and an amidine base catalyst to give PLLA‐grafted silica, but not in the presence of untreated silica (silica‐OH). In the absence of the amidine base catalyst no ring‐opening polymerization of LA even in the presence of silica‐NH₂ and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring‐opening graft polymerization of LA from the surface of silica‐NH₂. In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA‐grafted silica was smaller than that of silica‐NH₂. Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLA‐grafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improvement of interfacial interaction,dispersion, and properties of chlorosulfonated polyethylene/sio2 nanocomposites using CSPE‐g‐Sio2 nanoparticles synthesized under ultrasonics

Chlorosulfonated polyethylene (CSPE) is a widely used elastomer because of the resistance to gases and aggressive chemicals, fire‐retarding, and electric insulating properties. Silica nanoparticles were usually introduced into the elastomer to improve its critical properties. However, there were some problems of strong aggregation and poor dispersion of nanoparticles in the nanocomposites. In this work, an efficient approach of grafting matrix CSPE onto silica surface was proposed to solve the problems. CPSE‐g‐SiO₂ nanoparticles were prepared via an in situ radical reaction between  Cl in CSPE and Si OH on silica surface under ultrasonics. The successful chemical graft reaction was confirmed using Fourier transform infrared, ultraviolet–visible spectroscopy, ¹H‐NMR, and X‐ray photoelectron spectroscopy. Thermogravimetric analysis indicated that the grafting amount of CSPE was 4.68 wt%. Grafting CSPE onto silica surface significantly improved the dispersion of CSPE‐g‐SiO₂ nanoparticles in CSPE matrix and the interfacial interaction. Therefore, the mechanical, thermal stability, damping capacity, and rheology properties of CSPE/CSPE‐g‐SiO₂ nanocomposites were improved. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation of core–shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres

Core–shell poly(acrylic acid)/polystyrene/SiO₂ (PAA/PS/SiO₂) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO₂ hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO₂ hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO₂ hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO₂ hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006     

Grafting polyisoprene onto surfaces of nanosilica via RAFT polymerization and modification of natural rubber

In this contribution, we reported the investigation of natural rubber (NR) reinforced by silicon dioxide‐graft‐polyisoprene (SiO₂‐g‐PIP) core–shell nanoparticle. First, the hydroxyl on the surface of the SiO₂ nanoparticles was reacted with 2‐methyl‐2‐[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid to produce trithioester‐capped SiO₂ (denoted as SiO₂‐CTA). SiO₂‐CTA was used as a nanoparticle chain transfer agent, and SiO₂‐g‐PIP core–shell nanoparticles were synthesized via reversible addition‐fragmentation chain transfer polymerization (RAFT). The results of FTIR spectroscopy and TGA showed that the grafting weight of the PIP block in SiO₂‐g‐PIP was 2.1 wt%. SiO₂‐g‐PIP and SiO₂ were simultaneously incorporated into NR. The curing properties of the NR compounds showed that the vulcanization rates of the NR/SiO₂‐g‐PIP compounds were much higher than those of NR/silica compounds. The results of scanning electron microscopy showed that SiO₂ microdomains in the NR/SiO₂‐g‐PIP vulcanizate were much better disperse and distribute than SiO₂ microdomains in the NR/SiO₂ composite. The filler–rubber interaction of the NR/SiO₂‐g‐PIP composite endowed the composite with improved mechanical properties. POLYM. ENG. SCI., 59:1167–1174 2019. © 2019 Society of Plastics Engineers     

Solid‐phase preparation method of silica‐supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) and its antioxidative behavior in styrene‐butadiene rubber

A solid‐phase preparation method is applied to the synthesis of a novel supported rubber antioxidant, silica–supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) (SiO₂‐2246), by directly reacting 2,2′‐methylenebis (6‐tert‐butyl‐4‐methyl‐phenol)(antioxidant 2246) with silica. FTIR, Raman spectroscopy and TGA confirm that the antioxidant 2246 is chemically bonded on the surface of the silica particles. The SEM observation shows that the SiO₂‐2246 is homogeneously dispersed in the styrene‐butadiene rubber (SBR) matrix. The results of the apparent activation energy and the attenuated total reflectance infrared spectrometry indicate that the antioxidative efficiency of the SiO₂‐2246 in SBR is superior to the corresponding low‐molecular‐weight 2246. The thermal oxidative stability of the SBR/SiO₂‐2246 composites is much higher than that of the SBR/SiO₂/2246 composites by comparing their mechanical properties retentions and crosslinking densities. Additionally, the advantages of SiO₂‐2246 also include low migration, low volatility, and low pollution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43014.     

Tribological properties of SiO2 nanoparticle filled–phthalazine ether sulfone/phthalazine ether ketone (50/50 mol %) copolymer composites

SiO₂ nanoparticle filled–poly(phthalazine ether sulfone ketone) (PPESK) composites with various filler volume fractions were made by heating compression molding. The tribological behavior of the PPESK composites was investigated using a block‐on‐ring test rig by sliding PPESK‐based composite blocks against a mild carbon steel ring. The morphologies of the worn composite surfaces, wear debris, and the transferred films formed on the counterpart steel surface were examined with a scanning electron microscope, whereas the chemical state of the Fe element in the transfer film was analyzed with X‐ray photoelectron spectroscopy. In addition, IR spectra were taken to characterize the structure of wear debris and PPESK composites. It was found that SiO₂ nanoparticle filled–PPESK composites exhibit good wear resistance and friction‐reduction behavior. The friction and wear behavior of the composites was improved at a volume fraction between 4.2 and 14.5 vol % of the filler SiO₂. The results based on combined SEM, XPS, and IR techniques indicate that SiO₂ nanoparticle filled–PPESK composite is characterized by slight scuffing in dry sliding against steel and polishing action between composite surface and that of the countpart ring, whereas unfilled PPESK is characterized by severe plastic deformation and adhesion wear. In the former case a thin, but not complete, transfer film was formed on the surface of the counterpart steel, whereas in the latter case, a thick and lumpy transfer film was formed on the counterpart steel surface. This accounts for the different friction and wear behavior of unfilled PPESK and SiO₂ nanoparticle filled–PPESK composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2136–2144, 2002     

Advanced antistatic/anticorrosion coatings prepared from polystyrene composites incorporating dodecylbenzenesulfonic acid‐doped SiO2@polyaniline core–shell microspheres

We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)‐doped SiO₂@polyaniline (SP) core–shell microspheres. First, aniline‐anchored SiO₂ (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base‐catalyzed sol–gel process with tetraethyl orthosilicate in the presence of N‐[3‐(trimethoxysilyl)propyl]aniline. SP core–shell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as‐prepared core–shell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as‐synthesized DBSA‐doped SP core–shell microspheres were then blended into PS using N‐methyl‐2‐pyrrolidone as solvent and then cast onto a cold–rolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 µm. The corrosion protection efficiency of the as‐prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as‐synthesized core–shell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP core–shell microspheres showed an electrical resistance of about 3.65 × 10⁹Ω cm^?2, which meets the requirements for antistatic applications. Copyright © 2012 Society of Chemical Industry     

Microencapsulated melamine phosphate via the sol–gel method and its application in halogen‐free and intumescent flame‐retarding acrylonitrile‐butadiene‐styrene copolymer

In this paper, a facile method is introduced to modify melamine phosphate (MP) via the sol–gel process. The aim was simultaneously to increase the water resistance of MP and improve the dispersion and compatibility of MP in acrylonitrile‐butadiene‐styrene copolymer (ABS). In addition, the incorporation of SiO₂ particles into the MP/dipentaerythritol (DPER) system can further ameliorate the char‐forming ability and enhance the flame retardant properties of polymer composites. The chemical structure and surface morphology of SiO₂@MP were confirmed and observed by Fourier transform infrared (FTIR) spectroscopy, SEM and TEM, respectively. The results demonstrate that ABS/SiO₂@MP/DPER (3/1) at a loading of 30 phr reaches 31.2% limiting oxygen index and achieves a UL‐94 V‐0 rating. Moreover, FTIR spectra indicate that the main char‐forming process of the SiO₂@MP/DPER system occurs at 365–420 °C. A potential condensed flame retardant mechanism of SiO₂@MP and DPER in ABS composites is proposed via the systematic analysis of char residue after combustion by FTIR spectroscopy, SEM and X‐ray photoelectron spectroscopy. © 2015 Society of Chemical Industry     

Antibacterial activity and antistatic composites of polyester/Ag‐SiO2 prepared by a sol–gel method

Poly(butylene adipate‐co‐terephthalate) (PBAT) composites containing silver‐silica (Ag‐SiO₂) were prepared using an in‐situ sol–gel process. Maleic anhydride‐grafted PBAT (PBAT‐g‐MA) and multihydroxyl‐functionalized Ag‐SiO₂ were used to improve the compatibility and dispersibility of Ag‐SiO₂ within the PBAT matrix. The composites were characterized morphologically using transmission electron microscopy and chemically using Fourier transform infrared spectrometry. The existence of Ag‐SiO₂ nanoparticles on the substrate was confirmed by the ultraviolet–visible absorption spectra. The antibacterial and antistatic properties of the composites were evaluated whether SiO₂ enhanced the electrical conductivity was tested as well as whether Ag enhanced the antibacterial activity of the PBAT‐g‐MA/SiO₂ or PBAT/SiO₂ composites. The PBAT‐g‐MA/SiO₂ or PBAT/SiO₂ composite that contained Ag had better antibacterial activity (more than 1.3‐fold). The functionalized PBAT‐g‐MA/Ag‐SiO₂ composite can markedly enhanced antibacterial and antistatic properties due to the carboxyl groups of maleic anhydride, which acted as coordination sites for the Ag‐SiO₂ phase, allowing the formation of stronger chemical bonds. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Viscoelastic behavior of poly(butyl methacrylate) densely grafted on silica nanoparticles

A series of poly(butyl methacrylate)s (PBMAs) with various molar masses (33 000–270 000 g mol^?1), which were densely grafted on fumed silica nanoparticles (PBMA–SiO₂), were synthesized by surface‐initiated atom transfer radical polymerization. The dynamic viscoelastic behavior of PBMA–SiO₂ was systematically investigated in the solid and molten states with oscillatory strains, and compared to that of a conventional nanocomposite (PBMA/SiO₂). The storage moduli of PBMA–SiO₂ and PBMA/SiO₂ are equivalent in the solid state, whereas the storage modulus of PBMA–SiO₂ is lower than that of PBMA/SiO₂ in the molten state, especially at high silica loading. This is because the formation of a network structure composed of the silica nanoparticles in PBMA–SiO₂ is strongly suppressed by the polymer brushes on the particles. In contrast, even at low silica loading, the PBMA–SiO₂ system exhibits a gel‐like behavior resulting from a steric repulsion between the composite particles, because all of the tethered polymers behave as bound polymers. Copyright © 2011 Society of Chemical Industry     

Polyimide‐silica nanocomposites exhibiting low thermal expansion coefficient and water absorption from surface‐modified silica

In this study, a commercially available nano‐sized silica (SiO₂) was surface‐modified via esterification with oleic acid (OA), a relatively inexpensive and hydrophobic modifier, and characterized by FTIR, NMR, SEM, EDS, and TGA measurements. Various amounts of the surface‐modified silica nanoparticles (SiO₂‐OA) were dispersed in a poly(amic acid), which were then cyclized at high temperatures to form a series of PI/SiO₂‐OA nanocomposite films (PISA). The effect of the addition of the SiO₂‐OA nanoparticles on the properties of the as‐prepared polyimide nanocomposite was studied. The results indicated that, comparing with pure PI and PI/pristine‐SiO₂ composite film (PISI), the as‐prepared PISA films had enhanced dynamic mechanical properties and thermal stability, as well as reduced water absorption and thermal expansion. The as‐prepared PI/SiO₂‐OA nanocomposites have potential for applications in high performance microelectronic devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4096–4105, 2007     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Facile preparation of superhydrophobic polyester surfaces with fluoropolymer/SiO2 nanocomposites based on vinyl nanosilica hydrosols

A facile method to prepare superhydrophobic fluoropolymer/SiO₂ nanocomposites coating on polyester (PET) fabrics was presented. The vinyl nanosilica (V? SiO₂) hydrosols were prepared via one‐step water‐based sol‐gel reaction with vinyl trimethoxy silane as the precursors in the presence of the base catalyst and composite surfactant. Based on the V? SiO₂ hydrosol, a fluorinated acrylic polymer/silica (FAP/SiO₂) nanocomposite was prepared by emulsion polymerization. The FAP/SiO₂ nanocomposites were coated onto the polyester fabrics by one‐step process to achieve superhydrophobic surfaces. The results showed that silica nanoparticles were successfully incorporated into the FAP/SiO₂ nanocomposites, and a specific surface topography and a low surface free energy were simultaneously introduced onto PET fibers. The prepared PET fabric showed excellent superhydrophobicity with a water contact angle of 151.5° for a 5 μL water droplet and a water shedding angle of 12° for a 15 μL. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40340.     

Synthesis of Polystyrene/Hydrophobic SiO2 Composite Particles via Oil‐in‐Water Pickering Emulsion Polymerization

The aim of this work is to present a facile Pickering emulsion polymerization method for the synthesis of submicron polystyrene/SiO₂ core/shell composite particles. The commercial hydrophobic SiO₂ nanoparticles were used as stabilizing agent for creating a stable oil‐in‐water emulsion. Although the adsorption of hydrophobic SiO₂ nanoparticles in the emulsion system was unfavorable in terms of thermodynamics, by ultrasound treatment, self‐assembly of hydrophobic SiO₂ nanoparticles effectively stabilized oil‐in‐water Pickering emulsions during polymerization. Using 3 wt.% SiO₂ nanoparticles (based on styrene monomer) and 1:10 volume ratio of styrene monomer:water, the composite particles having average size of 790 nm and relatively narrow particles distribution were produced. With decreasing the volume ratio, smaller composite particles were created. Results from scanning electron microscope revealed that SiO₂ nanoparticles were located exclusively at the surface of the polystyrene latex particles. The SiO₂ content, determined by thermogravimetric analysis, was 12.6 wt.% in the composite particles. The route reported here may be used for the preparation of other composite nanostructures. POLYM. ENG. SCI., 59:E195–E199, 2019. © 2018 Society of Plastics Engineers     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrochemical investigations on the corrosion protection effect of poly(vinyl carbazole)‐silica hybrid sol–gel materials

A series of sol–gel derived organic–inorganic hybrid coatings consisting of organic poly (vinyl carbazole) (PVK) and inorganic silica (SiO₂), with 3‐(trimethoxysilyl)propyl methacrylate (MSMA) as coupling agent, were successfully synthesized. First of all, vinyl carbazole (VCz) monomers are copolymerized with MSMA by performing free‐radical polymerization reactions with AIBN as initiator. Subsequently, as‐prepared copolymer (i.e., sol–gel precursor) was further reacted with various feeding content of tetraethyl orthosilicate (TEOS) through organic acid (CSA)‐catalyzed sol–gel reaction to form a series of PVK‐silica hybrid (PSH) sol–gel materials. The as‐synthesized hybrid materials were subsequently characterized by Fourier‐Transformation infrared (FTIR) spectroscopy and solid‐state ²⁹Si NMR. It should be noted that the PVK‐SiO₂ hybrid (PSH) coating on cold‐rolled steel (CRS) electrode with low silica loading (e.g., 10 phr) was found to be superior in anticorrosion property over those of neat PVK based on a series of electrochemical measurements such as corrosion potential, polarization resistance, corrosion current, and electrochemical impedance spectroscopy in 3.5 wt% NaCl electrolyte. The better anticorrosion performance of PSH coatings as compared to that of neat polymer may probably be attributed to the stronger adhesion strength of PSH coatings on CRS electrode, which was further evidenced by Scotch tape test evaluation. Increase of adhesion strength of PSH coatings on CRS electrode may be associated with the formation of Fe–O–Si covalent bonds at the interface of PSH coating and CRS electrode based on the FTIR–RAS (reflection absorption spectroscopy) studies. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Mechanochemical modification of silica with poly(1‐vinyl‐2‐pyrrolidone) by grinding in a stirred media mill

The polymerization of 1‐vinyl‐2‐pyrrolidone (VP) mechanochemically initiated by grinding silica was investigated in a wet stirred media mill. The polymerization itself proceeds from the silica grinding without any additional initiator. We have found that the amount of grafted polymer increases with an increase in total ground silica surface. The suspension of polymer‐modified silica nanoparticles showed high colloidal stability in water because of the appearance of grafted hydrophilic PVP on the surface during the reactive grinding. Because the nanoparticles SiO₂‐graft‐PVP are biocompatible, the developed polymer nanocomposite material can be of particular interest for the performance of membranes and for the fabrication of biocompatible hydrogels with enhanced mechanical properties and porosity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3708–3714, 2007