Phase‐separation prevention and performance improvement of poly(vinyl acetate)/TEOS hybrid using modified sol‐gel process

The formation of covalent bonds between silanols in copolymer and those in silica prevents organic–inorganic phase separation. Two series of hybrid composite materials, poly(vinyl acetate‐co‐vinyl trimethoxysilane)/TEOS and poly[vinyl acetate‐co‐3‐(trimethoxysilyl)propyl methacrylate]/TEOS, were fabricated using a modified sol‐gel process. The hybrids were transparent. Two kinds of silane coupling agents, vinyl trimethoxysilane (VTS) and 3‐(trimethoxysilyl)propyl methacrylate (γ‐MPS), were used to prevent macrophase separation through formation of covalent bonds. Thermal analysis showed that γ‐MPS was more effective than VTS for the formation of covalent bonds. Enhancement of thermal stability of the hybrids was investigated by thermogravimetric analysis. Photomicrographs of scanning electron microscopy and images of atomic force microscopy indicated that inorganic silica particles were homogeneously dispersed in less than 50 nm in organic matrix. The morphological properties of hybrids were strongly dependent on the organic–inorganic composition. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2310–2318, 2001     

Effect of 3‐aminopropyltriethoxysilane on properties of poly(butyl acrylate‐co‐maleic anhydride)/silica hybrid materials

The transparent poly(butyl acrylate‐co‐maleic anhydride)/silica [P(BA‐co‐MAn)/SiO₂] has been successfully prepared from butyl acrylate‐maleic anhydride copolymer P(BA‐co‐MAn) and tetraethoxysilane (TEOS) in the presence of 3‐aminopropyltriethoxysilane (APTES) by an in situ sol–gel process. Triethoxysilyl group can be readily incorporated into P(BA‐co‐MAn) as pendant side chains by the aminolysis of maleic anhydride unit of copolymer with APTES, and then organic polymer/silica hybrid materials with covalent bonds between two phases can be formed via the hydrolytic polycondensation of triethoxysilyl group‐functionalized polymer with TEOS. It was found that the amount of APTES could dramatically affect the gel time of sol–gel system, the sol fraction of resultant hybrid materials, and the thermal properties of hybrid materials obtained. The decomposition temperature of hybrid materials and the final residual weight of thermogravimetry of hybrid both increase with the increasing of APTES. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed that the morphology of hybrid materials prepared in the presence of APTES was a co‐continual phase structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 419–424, 1999     

Preparation and properties of thermosensitive organic‐inorganic hybrid gels containing modified nanosilica

A series of thermosensitive organic–inorganic hybrid gels containing nanosilica or modified nanosilica were prepared from N‐isopropylacrylamide (NIPAAm), and N,N′‐methylene‐bis‐acrylamide (NMBA) and nanosilica (AE200) or modified AE200 (mAE200); and NIPAAm, NMBA, 3‐(trimethoxysilyl) propyl methacrylate (TMSPMA) as coupling agent and AE200 or mAE200 in this study. The effect of inorganic nanosilica on the swelling behaviors and mechanical properties were investigated by adding different amount of nanosilica and modified nanosilica. Results showed that the swelling ratios of the hybrid gels decrease with increasing nanosilica content. Existence of silane coupling agent would also reduce the swelling ratios of the hybrid gels. Adding coupling agent or nanosilica would improve the gel strength. Modification of nanosilica by grafting amino‐silane via sol–gel process was carried out and the effect of addition of modified silica on gel properties was also investigated. Results showed that the hybrid gels containing modified silica would have higher swelling ratios and moduli than those containing unmodified silica. Gels containing both silane coupling agent and silica would have higher crosslinking density because the silica would be better crosslinked with coupling agent. POLYM. COMPOS., 31:1712–1721, 2010. © 2010 Society of Plastics Engineers.     

Thermally and mechanically enhanced epoxy resin‐silica hybrid materials containing primary amine‐modified silica nanoparticles

In this article, a series of hybrid materials consisted of epoxy resin matrix and well‐dispersed amino‐modified silica (denoted by AMS) nanoparticles were successfully prepared. First of all, the AMS nanoparticles were synthesized by performing the conventional acid‐catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS), which acts as acceded sol–gel precursor in the presence of 3‐aminopropyl trimethoxysilane (APTES), a silane coupling agent molecules. The as‐prepared AMS nanoparticles were then characterized by FTIR, ¹³C‐NMR, and ²⁹Si‐NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in situ thermal ring‐opening polymerization reactions of epoxy resin in the presence of as‐prepared AMS nanoparticles and raw silica (RS) particles (i.e., pristine silica). AMS nanoparticles were found to show better dispersion capability in the polymer matrices than that of RS particles based on the morphological observation of transmission electron microscopy (TEM) study. The better dispersion capability of AMS nanoparticles in hybrid materials was found to lead enhanced thermal, mechanical properties, reduced moisture absorption, and gas permeability based on the measurements of thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and gas permeability analysis (GPA), respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and anticorrosive properties of hybrid coatings based on epoxy‐silica hybrid materials

A series of sol‐gel derived organic–inorganic hybrid coatings consisting of organic epoxy resin and inorganic silica were successfully synthesized through sol‐gel approach by using 3‐glycidoxypropyl‐trimethoxysilane as coupling agent. Transparent organic–inorganic hybrid sol‐gel coatings with different contents of silica were always achieved. The hybrid sol‐gel coatings with low silica loading on cold‐rolled steel coupons were found much superior improvement in anticorrosion efficiently. The as‐synthesized hybrid sol‐gel materials were characterized by Fourier‐transformation infrared spectroscopy, ²⁹Si‐nuclear magnetic resonance spectroscopy and transmission electron microscopy. Effects of the material composition of epoxy resins along with hybrid materials on the thermal stability, Viscoelasticity properties and surface morphology were also studied, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ethylene–propylene copolymer/ordered polysilsesquioxane nanocomposites prepared via organic acid‐ or base‐catalyzed binary silica water‐crosslinking reactions

In situ silica sol–gel‐derived organic–inorganic hybrid materials, which comprise a vinyltrimethoxysilane‐grafted ethylene–propylene copolymer (EPR‐g‐VTMS) and n‐hexyltrimethoxysilane (HTMS), were successfully prepared in the presence of an organic acid and base catalyst. Benzenesulfonic acid and aniline were selected as the organic acid and base catalyst, respectively, to examine the progress and effect of progressive changes in the silane water‐crosslinking reaction of EPR‐g‐VTMS/HTMS composites. The water‐crosslinked EPR‐g‐VTMS/HTMS composites were characterized by means of attenuated total reflectance Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si cross‐polarization/magic‐angle spinning NMR, wide‐angle X‐ray scattering, tensile strength and field‐emission scanning electron microscopy measurements. These results revealed that the type of catalyst has a substantial influence on the nature of siloxane bonds and eventually the physical tensile properties of the water‐crosslinked EPR‐g‐VTMS/HTMS composites, which can be explained mainly from knowledge of the traditional acid‐ and base‐catalyzed silica sol–gel reaction. Moreover, an in‐depth analysis of the aniline‐catalyzed composites indicated the formation of ladder‐type poly(n‐hexylsilsesquioxane)s and the presence of a highly ordered structure with a thickness equal to the length of two n‐hexyl groups in all‐trans conformation. We demonstrate potential for the future design of highly ordered silicate‐based organic–inorganic hybrid nanocomposites. Copyright © 2009 Society of Chemical Industry     

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.     

Effects of surface chemistry of silica particles on secondary structure and tensile properties of silica‐filled rubber systems

Silica particles were treated by silane coupling agents to study the effects of surface chemistry of silica particles on the secondary structure formed by silica particles in styrene–butadiene rubber (SBR). The relation between the size of secondary structure and tensile properties of silica‐filled SBR vulcanizates was also investigated. The water molecules adsorbed on the silica surface enhanced both the reactivity of the coupling agents with silanol groups on the silica surface and the condensation reaction between coupling agents. The averaged size of one agglomerate in the filled vulcanizate (S_agg ) decreased with the increase of the hydrophobic character of silica particles, which were obtained by the introduction of coupling agents with alkyl groups. The initial slope of stress–strain curves for silica‐filled vulcanizates decreased with the decrease of S_agg . Further, a clear Payne effect was observed in all silica‐filled vulcanizates, with this tendency more prominent in the larger S_agg . © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1622–1629, 2002     

Polymerization and characterization of acrylonitrile with γ‐methacryloxypropyltrimethoxy‐silane grafted bentonite clay

Novel natural clay–polymer hybrid materials are prepared from natural bentonite that was modified with silane‐coupling agent, γ‐methacryloxypropyltrimethoxysilane (A‐174), and acrylonitrile. By changing the molar ratio of acrylonitrile in the initial monomer feed, several clay–hybrid materials were prepared. The structure and thermal stability of hybrid materials were investigated by various methods. The A‐174‐modified bentonite was dispersed in a solution of acrylonitrile in toluene. In this system, radical polymerization in the presence of AIBN was carried out. Product formed at the particle surface was either physically bound by entanglement or chemically bound by covalent bonding to the silane. In this way, core–shell morphology was obtained with an inorganic core and a polymer shell. The results showed that bonding at the surface of bentonite took place by hydrolytic cleavage of methoxy groups of A‐174 with hydroxy groups of bentonite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 164–171, 2002; DOI 10.1002/app.10289     

Role of silane coupling agents for performance improvement of poly(vinyl acetate)/tetraethyl orthosilicate hybrid composites prepared by a sol–gel process

Silica based poly(vinyl acetate)/inorganic hybrid composites were prepared via a sol–gel process under acidic conditions. Because the phase behaviour of the hybrids is greatly affected by weak interactions such as hydrogen bonding between organic polymer and inorganic network, two types of silane coupling agent (vinyl trimethoxysilane and 3‐(trimethoxysilyl)propyl methacrylate) were used to introduce specific interactions and to control phase behaviour in the interface between polymer and silica. The interfacial interactions between polymer and inorganic segment in the presence of silane have been investigated by Fourier transform infrared spectroscopy. Thermogravimetric analysis shows that the thermal stability of organic components in the hybrids is enhanced by addition of silane coupling agents. Scanning electron micrographs reveal that silica particles are homogeneously dispersed in the organic matrix as a result of the specific interactions. © 2001 Society of Chemical Industry     

New anion exchanger organic–inorganic hybrid materials and membranes from a copolymerof glycidylmethacrylate and γ‐methacryloxypropyl trimethoxy silane

Organic–inorganic hybrid materials and mem branes were prepared through coating on Teflon plate or dip‐coating on microporous alumina substrates with the solution of glycidylmethacrylate (GMA) and γ‐methacryloxypropyl trimethoxy silane (γ‐MPS) copolymer, followed by ring‐opening of the GMA moiety with trimethylamine hydrochloric and sol–gel reaction of the γ‐MPS moiety. Composition of the GMA and γ‐MPS copolymer was varied by changing the feed ratio of GMA to γ‐MPS during the copolymerization. So the thermal stability, hydrophilicity, electrical properties, etc. of the hybrid materials and membranes were varied. Results showed that as the γ‐MPS amount increased in the copolymer, T_d (the temperature on thermogram at 5% weight loss) value of the hybrid materials and water contact angle of the hybrid membrane generally increased, while the anion exchange capacity, water uptake (W_R) and pure water flux decreased. The charge transition point of the hybrid membranes deduced from their streaming potential behavior decreased from pH > 12 to pH = 7–8 as the γ‐MPS amount increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3580–3589, 2006     

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     

Synthesis of modified silica spheres used for the preparation of dual ultraviolet‐ and thermo‐cured epoxyacrylate/silica composites

To investigate the interfacial effect on properties of epoxyacrylate–silica composites, submicron‐sized silica spheres were synthesized by sol–gel reaction under a basic environment and their surfaces were endowed with vinyl functional groups by further modification with 3‐methacryloxypropyl trimethoxy silane. The pure silica (PS) and the modified silica (MPS) spheres were characterized by Fourier transform infrared, ²⁹Si‐ and ¹³C‐nuclear magnetic resonance (NMR), scanning electron microscope (SEM), and particle size analyzer. The silica spheres were then added to the presynthesized difunctional epoxyacrylate resin with one vinyl group and one epoxide group at each end, in addition to the photo‐ and thermo‐curing agents. After cure, thermal and mechanical properties of the obtained epoxyacrylate–silica composites were measured and compared. Tensile mechanical properties including initial modulus, ultimate tensile strength, and elongation at break, as well as the fracture energy of the epoxyacrylate–silica composite were all increased by increasing the content of silica spheres. Moreover, the composites filled with MPS had stronger interfacial strength between silica sphere and matrix than those with PS and thus exhibited an additional increase of tensile mechanical properties and fracture toughness. The increase of fracture toughness was owing to the crack deflection and particle–matrix debonding as evidenced by SEM pictures on the fracture surface. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Hybrid of bamboo charcoal and silica by tetraethoxysilane hydrolysis over acid catalyst reinforced styrene‐butadiene rubber

The hybrid of bamboo charcoal (BCC) and silica‐reinforced styrene‐butadiene rubber was prepared by a modified sol–gel method of hydrolyzing tetraethoxysilane over an acid catalyst. The fracture surface of the samples after tensile test was characterized by field emission‐scanning electron microscopy. The tensile strength, storage modulus, hardness, friction coefficient, and swelling test were discussed based on the samples with or without 3‐(methacryloxy) propyl trimethoxy silane modification. The results showed that the storage modulus clearly increased with the increasing of silica contents among the hybrid of BCC and silica‐reinforced samples. The storage modulus of the sample decreased after modification by 3‐(methacryloxy) propyl trimethoxy silane, indicating the improvement of the filler in SBR matrix. The tensile stress and the hardness both increased with the increasing of silica contents in the SBR matrix. Besides, the friction coefficient and the swelling ratio for the hybrid of BCC and silica‐reinforced SBR decreased with the decreasing of BCC contents in SBR matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46219.     

Reinforcing effect of silica on the properties of styrene butadiene rubber–reclaim rubber blend system

Incorporation of silica into styrene butadiene rubber (SBR)–reclaim rubber (RR) blend system was carried out by sol–gel technique and conventional method. A well known silica coupling agent bis(3‐triethoxysilyl propyl) tetrasulfide was found to affect the curing characteristics and mechanical properties of SBR/RR vulcanizate. Here, the effect of RR on silica reinforcement was studied for different SBR/RR blend system. Silica incorporation by conventional mechanical mixing in absence of TESPT showed a much higher tensile properties than that of silica incorporated by the in situ sol–gel reaction of tetraethoxy silane both in presence and absence of TESPT. Studies of equilibrium swelling in a hydrocarbon solvent were also carried out. ATR study indicates that RR forms bond with silica particles due to the presence of active functional site on RR. The amount of silica incorporated by sol–gel reaction was determined through thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) studies further indicate the coherency and homogeneity in the silica filled SBR/RR vulcanizate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 957–968, 2006     

A statistical study of poly(ε‐caprolactone) crystallinity in poly(ε‐caprolactone)–silica sol–gel materials and their in vitro calcium phosphate‐forming ability

Composite poly(ε‐caprolactone) (PCL)–silica materials for potential use in orthopaedic applications have been prepared by a sol–gel method using an experimental design approach to investigate the effect of synthesis variables, separately and together, on the physical form of the organic polymer. A combination of differential scanning calorimetry, X‐ray diffraction and Fourier‐transform infrared methods were used to obtain information on the arrangement of the organic polymer in the hybrid material. As our studies investigated the effect of synthesis variables simultaneously, it was possible to establish that the increase of tetraethyl orthosilicate (TEOS)/PCL and HCl/TEOS molar ratios decreased the poly(ε‐caprolactone) crystallinity and provided for a better mixing of the two phases. At a mechanistic level it was possible to show that increase in catalyst content affected the condensation of silicon containing species. In vitro calcium phosphate‐forming ability tests using the static biomimetic method have been carried out on selected PCL–silica sol–gels. In vitro bioactivity was only observed for PCL–silica sol–gel composites with high silica content (30% weight). Changes in catalyst levels had a smaller but still significant effect. Calcium phosphate formation on largely non‐porous surfaces is proposed to occur via the formation of a silica sol–gel layer, and is influenced by the topography and the chemistry of the materials surface. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of poly(methyl acrylate‐co‐itaconic anhydride)/TiO2 hybrid materials via sol–gel process

In the presence of 3‐aminopropyltriethoxysilane (APTES), the transparent and yellowish poly(methyl acrylate‐co‐itaconic anhydride)/TiO₂ [P(MA‐co‐Itn)/TiO₂] hybrid materials were prepared from the copolymer of methyl acrylate and itaconic anhydride [P(MA‐co‐Itn)] and tetrabutyl titanate (TBT) via a sol–gel process. At first, the triethoxysilane groups were incorporated into the copolymer P(MA‐co‐Itn) as pendant side chains by the aminolytic reaction between the itaconic anhydride units of the copolymer and the amino group of 3‐aminopropyltriethoxysilane (APTES), and then the covalent bonds between the organic and inorganic phases were introduced by the hydrolysis and polycondensation of the triethoxysilane groups on the copolymer with TBT. FTIR analysis proved the existence of the covalent bonds. The influences of APTES on glass transition and morphology of the hybrid materials was studied by differential scanning calorimetry, scanning electron microscope, and atomic force microscope. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1763–1768, 2000     

Recoverable Palladium Catalysts for Suzuki–Miyaura Cross‐ Coupling Reactions Based on Organic‐Inorganic Hybrid Silica Materials Containing Imidazolium and Dihydroimidazolium Salts

The systems formed by palladium acetate [Pd(OAc)₂] and hybrid silica materials prepared by sol‐gel from monosilylated imidazolium and disilylated dihydroimidazolium salts show catalytic activity in Suzuki–Miyaura cross‐couplings with challenging aryl bromides and chlorides. They are very efficient as recoverable catalysts with aryl bromides. Recycling is also possible with aryl chlorides, although with lower conversions. In situ formation of palladium nanoparticles has been observed in recycling experiments.     

Synthesis of silica hybrid nanoparticles modified with photofunctional polymers and construction of colloidal crystals

Photofunctional polymer as silane coupling agent (PFD) was prepared by free radical copolymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC) and methyl methacrylate (MMA) in the presence of (3‐mercaptopropyl)trimethoxysilane (MPMS) as chain transfer agent. Next, silane (SiO₂; the average diameter D_n = 192 nm) nanoparticles was surface‐modified with PFD and 3‐(trimethoxysilyl)propyl methacrylate (γ‐MPS) by covalent bond formed between silanol groups and silane coupling agents. The PFD and γ‐MPS functionalizations changed the silica surface into hydrophobic nature and provided grafting initiation sites and methacrylate terminal groups respectively. We performed the construction of hybrid nanocomposites by using these modified SiO₂ nanoparticles. It was found from electron microscopy observations that SiO₂ particles were packed into repeating cubic arrangements in a poly(methyl methacrylate) (PMMA) matrix such as colloidal crystals. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of baking treatment and materials composition on the properties of bulky PMMA–silica hybrid sol–gel materials with low volume shrinkage

A series of bulky PMMA–silica hybrid sol–gel materials had been successfully prepared through the conventional HCl‐catalyzed sol–gel approach with 2‐hydroxyethyl methyl methacrylate (HEMA) as coupling agent under pumping pretreatment (i.e., exhaustive vacuum evacuation). In this work, the hydroxyl groups of HEMA monomers were first cohydrolyzed with various contents of tetraethyl orthosilicate (TEOS) to afford chemical bonding for the forming silica networks by removal of solvent and byproduct of sol–gel reactions through pumping pretreatment before gelation reactions. Subsequently, the resultant viscous solution was then copolymerized with methyl methacrylate (MMA) monomers at specific feeding ratios by using benzoyl peroxide (BPO) as free‐radical initiator. Eventually, transparent bulky organic–inorganic hybrid sol–gel materials loaded with different silica content were always achieved. The obtained bulky hybrid sol–gel materials were found to be transparent, crack‐free, and of relatively low volume shrinkages even in high silica content. The as‐prepared bulky hybrid sol–gel materials were then characterized through silicon element mapping studies of energy‐dispersive X‐ray (EDX) and transmission electron microscopy (TEM). Effect of heating process at 150°C for 5 h after polymerization and material composition on the thermal properties, mechanical strength, and optical clarity of a series of bulky PMMA–silica hybrid sol–gel materials was investigated and compared by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), hardness test, dynamic mechanical analysis (DMA), and UV–vis transmission spectroscopy, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1151–1159, 2006