Preparation of titanium dioxide/polyacrylate nanocomposites by sol–gel process in reverse micelles and in situ photopolymerization

UV‐curable, transparent acrylic resin/titania organic–inorganic hybrid films were prepared by controlled hydrolysis of titanium tetrabutoxide in Span‐85/Tween 80 reverse micelles and the subsequent in situ photopolymerization of the acrylic monomers. UV–vis spectra and atomic force microscopy (AFM) indicated the presence of a nanoscale hybrid composition. The onset of absorption (λ_onset) of titania in the hybrids appeared between 363.4 and 383.5 nm, which exhibited blue shifts relative to that of bulk anatase (λ_onset = 385 nm). The titania content increased rapidly at higher temperature and higher TTB content, whereas it increased slowly with longer post‐thermal treatment times. The refractive index and UV shielding properties of the organic polymer were obviously improved with increasing titania content. AFM images showed the inorganic domains (mean size 25.3–28.8 nm) were uniformly dispersed in the polymeric networks. The roughness parameters of the hybrid material were: toughness, 1.5–2.3 nm; root mean square roughness, 4.5–4.6 nm; and peak and valley distance, 9.7–19.4 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5105–5112, 2006     

Preparation and Characterization of Nanostructured TiO2/Epoxy Polymeric Films

Summary: Titania‐containing coatings were prepared by cationic photopolymerization of an epoxy resin either by dispersion of preformed TiO₂ nanoparticles or by their in‐situ generation through a sol‐gel dual‐cure process. The kinetics of photopolymerization was evaluated by real‐time FT‐IR, studying the effect of the TiO₂ concentration. The properties of cured films were investigated, showing an increase of hydrophilicity on the surface of the coatings with increasing TiO₂ content. TEM analysis demonstrated that it is possible to achieve a significantly better control of the dispersion of the inorganic particles within the organic matrix by in‐situ generation of TiO₂, thus completely avoiding macroscopic phase separation and obtaining homogeneous, transparent coatings.

Bright‐field TEM micrograph for TIP20 dual‐cured film.     

Kinetic study on the UV‐induced photopolymerization of epoxy acrylate/TiO2 nanocomposites by FTIR spectroscopy

The kinetics of the photopolymerization of epoxy acrylate/TiO₂ nanocomposites, with 2′2‐dimethoxy‐1,2‐diphenylethan‐1‐one (Irgacure 651) or benzophenone/N‐methyl diethanolamine as photoinitiators, were studied by FTIR spectroscopy. It was found that nanocomposites had a decreasing photopolymerization rates in comparison with pure epoxy acrylate. The photopolymerization rate of the nanocomposite could also be influenced by initiator types, oxygen, film thickness, irradiation intensity, dispersing media of TiO₂ slurry, and so forth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3281–3287, 2006     

Preparation and characterization of hybrid nanocomposite coatings by photopolymerization and sol-gel process

Organic-inorganic nanocomposite hybrid coatings were prepared through a dual-cure process involving cationic photopolymerization of epoxy groups and subsequent condensation of alkoxysilane groups. The kinetics of the photopolymerization and condensation reactions were investigated; suitable conditions for obtaining a complete conversion of both reactive groups were found. The obtained films are transparent to visible light. The T_g values of the hybrids increase by increasing the TEOS content in the photocurable formulation. Also, a significant increase in surface hardness could be obtained for the hybrid systems. AFM analysis gave evidence of a strong interaction between the organic and inorganic phase with the formation of silica domains in the nanoscale range.     

Structure and thermal properties of titanium dioxide-polyacrylate nanocomposites

Summary UV curable, transparent acrylic resin/titania organic–inorganic hybrid films were prepared by controlled hydrolysis of titanium tetrabutoxide (TTB) in Span85/Tweeen80 reverse micelles and subsequent in situ photopolymerization of acrylic monomers. The qualitative content of TiOTi group and TiOH was monitored by FTIR spectrum, and the thermal stability and film surface were characterized by TGA, DSC and AFM, respectively. TGA data show that TiO₂-hybrid films can upgrade the decomposition onset temperature and the temperature at which there is a maximum mass loss rate (T_max). DSC data show that prolonged exposure to UV light and post-thermal treatment can decrease the T_onset and T_peak of the exothermal peak and the condensation temperature between TiOH, and increase ΔH of the exothermal peak. FTIR spectra show the presence of two νs(COO^-) modes with the νa-νs splitting magnitude (Δν∼87 cm^-1 and 148 cm^-1, respectively), suggesting that acrylic acid acts as a bidentate coordination mode and therefore chemical linkages exist between inorganic and organic phases. AFM phase images showed the presence of inorganic domains, with mean size of 21.6 nm–28.8 nm, were uniformly dispersed in the polymeric networks.     

Synthesis and properties of PMMA‐ZrO2 organic–inorganic hybrid films

In this work we report the synthesis process and properties of PMMA‐ZrO₂ organic–inorganic hybrid films. The hybrid films were deposited by a modified sol‐gel process using zirconium propoxide (ZP) as the inorganic (zirconia) source, methyl methacrylate (MMA) as the organic source, and 3‐trimetoxy‐silyl‐propyl‐methacrylate (TMSPM) as the coupling agent between organic and inorganic phases. The films were deposited by dip coating on glass slide substrates from a hybrid precursor solution containing the three precursors with molar ratio 1 : 0.25 : 0.25 for ZP, TMSPM, and MMA, respectively. After deposition, the hybrid thin films were heat‐treated at 100°C for 24 h. The macroscopic characteristics of the hybrid films such as high homogeneity and high optical transparence evidenced the formation of a cross‐linked, interpenetrated organic–inorganic network. The deposited PMMA‐ZrO₂ hybrid films were homogeneous, highly transparent and very well adhered to substrates. Fourier Transform Infra‐Red measurements of the hybrid films display absorption bands of chemical groups associated with both PMMA and ZrO₂ phases. The amounts of organic and inorganic phases in the hybrid films were determined from thermogravimetric measurements. The surface morphology and homogeneity of the hybrid films at microscopic level were analyzed by scanning electron microscopy and atomic force microscopy images. From the analysis of optical transmission and reflection spectra, the optical constants (refraction index and extinction coefficient) of the hybrid films were determined, employing a physical model to simulate the hybrid optical layers. The refraction index of the hybrid films at 532 nm was 1.56. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42738.     

Preparation of transparent PMMA/Fe(IO3)3 nanocomposite films from microemulsion polymerization

Polymethyl methacrylate (PMMA)/Fe(IO₃)₃ nanocomposite thin films are obtained by in situ particle generation in microemulsions and subsequent photopolymerization of a mixture containing methyl methacrylate, trimethylolpropane triacrylate, and crystallized iron iodate (Fe(IO₃)₃) nanorods. Hyper‐Rayleigh scattering measurements combined with X‐ray diffraction, transmission electron microscopy, and dynamic light scattering are first used to probe in situ the crystallization kinetics of iron iodate nanorods in water‐in‐oil microemulsions prepared with methyl methacrylate as the oil phase and marlophen NP12 as a surfactant. Trimethylolpropane triacrylate is then added as a crosslinker before spin‐coating. Films are deposited on glass substrates for the nonlinear optical characterizations and on silicon wafers for the piezoelectric and mechanical measurements. Nanocomposite films treated by corona discharge are finally characterized through optical microscopy, laser Doppler vibrometry, and Brillouin spectroscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1203‐1211, 2013     

Compatibilization and property characterization of polycarbonate/polyurethane polymeric alloys

Semi‐crystalline dendritic poly(ether‐amide)s were synthesized by modifying hydroxyl end‐groups of dendritic poly(ether‐amide) with aromatic urethane acrylate and octadetyl isocyanate. The ratio of these modifiers can adjust the final properties of products to fulfill the requirements of UV‐curable powder coatings. These UV‐curable semi‐crystalline dendritic poly(ether‐amide)s have a T_g in the range of 41–45°C and a T_m of around 120°C. Their thermal behavior and semi‐crystalline properties were studied by DSC and XRD. The photopolymerization kinetics was investigated by Photo‐DSC. The residual unsaturation, thermal stability, and hardness of the UV‐cured films were also studied. The obtained results show that these semi‐crystalline dentritic poly(ether‐amide)s may be used as prepolymers in UV‐curable powder coating systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 287–291, 2003     

A (Triphenylphosphine)Silver (I) Complex as a New Performance Additive in Free‐Radical Photopolymerization under Air

Unusual photochemical properties of an Ag(I)‐derived complex, i.e., bis[(µ‐chloro)bis(triphenylphosphine)silver (I)] ([Ag](PPh₃)) are demonstrated when used in free‐radical photopolymerization reactions: i) [Ag](PPh₃) can act as an innovative photoinitiating system when associated with a commercial type I photoinitiator 2,2‐dimethoxy‐2‐phenylacetophenone to overcome the oxygen inhibition effect during the free‐radical photopolymerization of acrylate monomers, thus accelerating the kinetics of polymerization under air; ii) silver‐based nanoparticles can be in situ generated under air, thus leading to new antibacterial coatings which prevent the growth of Escherichia coli and Staphylococcus aureus after few hours of incubation.     

Preparation of siloxane–silsesquioxane hybrid thin films for large‐scale‐integration interlayer dielectrics with excellent mechanical properties and low dielectric constants

Several kinds of homogeneous organic–inorganic hybrid polymer thin films were designed with improved mechanical properties and low dielectric constants (<3.0). Novel soluble siloxane–silsesquioxane hybrid polymers were synthesized with cyclic and/or cage silane monomers, which had triorganosiloxy (R₃Si_1/2), diorganosiloxane (R₂SiO_2/2), and organosilsesquioxane (RSiO_3/2) moieties with ethylene bridges at the molecular level, by the hydrolysis and condensation of 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane (a cyclic monomer). The electrical properties of these films, including the dielectric constant (～2.51), leakage current (6.4 × 10^?11 A/cm² at 0.5 MV/cm), and breakdown voltage (～5.4 MV/cm) were fairly good. Moreover, the mechanical properties of the hybrid films, including the hardness (～7 GPa), modulus (～1.2 GPa), and crack‐free thickness (<2 μm), were excellent in comparison with those of previous spin‐on‐glass materials with low dielectric constants. The excellent mechanical properties were proposed to be due to the high contents of Si? OH groups (>30%) and the existence of ethylene bridge and siloxane moieties in the hybrid polymer precursors. In addition, the mechanical properties of the hybrid films were affected by the contents of the cagelike structures. The more cagelike structures a hybrid film contained, the worse its mechanical properties were. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 626–634, 2003     

Morphology,dynamic mechanical properties,and gas separation of crosslinking silica‐containing polyimide nanocomposite thin film

Silica‐containing polyimide (PI‐Si) crosslinked hybrid films are synthesized and applied to gas separation application. The PI‐Si hybrid films are prepared from 4,4′‐diaminodiphenyl ether (ODA), 3, 3′‐oxydiphthalic anhydride (ODPA), p‐aminophenyltrimethoxysilane (APTS), and phenyltrimetoxysilane (PTS). The monomer of monoamide APTS is used to modulate the block chain length of ODA–ODPA and then form bonding between PTS and ODA–ODPA phases. In the series of xASPI (where x indicates the molecular weight (in kg/mol) of PI block chain length of ODA–ODPA and ASPI denotes PI modified with APTS) hybrid films, the glass transition temperature (T_g) increases and α‐relaxation damping peak intensity decreases with the increase of APTS content. Meanwhile, the gas permeabilities of O₂ and N₂ of xASPI films are slightly higher as compared with pure PI. The other series of (5AS–y‐S)PI (5ASPI incorporates with PTS and y is the weight of PTS) hybrid films, the properties of T_g, density, and α‐relaxation damping peak intensity are decreased with increasing the PTS content. However, higher O₂ and N₂ gas permeabilities and O₂/N₂ selectivity are achieved by increasing the PTS content in (5AS–y‐S)PI hybrid films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Atomic oxygen erosion resistance of titania–polyimide hybrid films derived from titanium tetrabutoxide and polyamic acid

A series of polyimide/titania (PI/TiO₂) hybrid films have been successfully synthesized based on titanium tetrabutoxide (Ti(OEt)₄), 3,3′,4,4′‐bezonphenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydianiline (ODA), and 1,3‐bis(aminopropyl) tetramethyldisiloxane (APrTMOS) by a sol–gel process. The atomic oxygen (AO) exposure tests were carried out using a ground‐based AO effects simulation facility. The chemical structure of PI/TiO₂ films was characterized by Fourier transform‐infrared (FT‐IR) spectroscope before and after AO exposure. The glass transition temperature (T_g) and mechanical properties were examined by dynamic mechanical analysis (DMA) and universal mechanical testing machine, respectively. The tensile strength and elongation of the hybrid film decreased with the increase of TiO₂ content, whereas the T_g increased with the increase of TiO₂ content. The effects of TiO₂ content on the morphology and structure evolvement of PI/TiO₂ hybrid films were also investigated using field emission scanning electron microscopy (FE‐SEM) and X‐ray photoelectron spectroscope (XPS), respectively. The results indicated that a TiO₂‐rich layer resulting from the Ti(OEt)₄ formed on the PI film after AO exposure, which decreased the mass loss rate and obviously improved the AO resistance of PI films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of sol maturation on the preparation of luminescent ormosils

An UV‐polymerization approach was proposed to construct luminescence organic‐inorganic hybrid. Methacryloxypropyltrimethoxysilane (MAPTMS) was chosen as sol–gel precursor to prepare the host matrix and acrylic europium Eu(AA)₃ was used as guest dopants. Structural modifications during irradiation were evident in both the inorganic and organic domains of the hybrid material. The influence of condensation degree of the silicate network on the photopolymerization kinetics of organic moieties was investigated. It appeared that the sol maturation time was of vital importance to the phase homogeneity and optical transparency of materials. To get more efficient copolymerization and higher luminescence intensity of the target ormosils, two key processing factors including incorporation time and entrapping concentration are reported. Incorporation time when acrylic europium was introduced into the matrix during sol maturation is found to be helpful to overcome phase separation. The effect of entrapping concentration of europium(III) compound on the luminescence performance was further studied. Material synthesized by this approach has three advantages: optical transparency with little phase separation, organic and inorganic composite with interpenetrating network, covalent grafting of acrylic europium without luminescent species leakage. This “photopolymerization of molecular grafting” strategy is hopeful to offer a promising development for luminescent ormosil glasses. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45146.     

Highly branched polyurethane acrylates and their waterborne UV curing coating

A series of UV curable highly branched waterborne polyurethane acrylates (BWPUAs) were synthesized using an “oligomeric A₂ + B₃” approach. The thiol-endcapped difunctional oligomeric A₂ was synthesized first by the addition reaction of isophorone diisocyanate, α,α-dimethylol propionic acid and 2-hydroxyethyl acrylate, then further underwent thiol-Michael reaction with 1,6-hexamethylene bis(thioglycolic acetate). Trimethylolpropane triacrylate was used as a B₃ monomer. The molecular structures were characterized with FT-IR and ¹H NMR spectroscopy. 1,6-Hexanediol diacrylate (HDDA) was incorporated into the polymeric chain for preparing the HDDA-modified BWPUAs (BWPUA-Hs). For the comparison, the linear waterborne polyurethane acrylate (LWPUA) was synthesized. The UV curing kinetics study results by using the photo-DSC approach showed that the BWPUAs possessed higher photopolymerization rate and final unsaturation conversion in the UV cured films compared with the LWPUA, which increased with the increase of unsaturation concentration in BWPUA. Moreover, the photopolymerization performance, and water and solvent resistance properties were greatly enhanced by the incorporation of HDDA segment into the BWPUA chain. The dynamic mechanical thermal analysis results showed that the elastic modulus in the rubbery plateau, and the glass transition temperature of UV cured film increased with increasing unsaturation concentration in BWPUA, whereas decreased with the introduction of HDDA flexible segment. The thermogravimetric analysis confirmed the high thermal stability of UV cured BWPUA films. All UV cured BWPUA and BWPUA-H films showed better flexibility and middle refractive indices due to the thioether linkage in the polymer network.     

Controlling the surface wettability of poly(sulfone) films by UV‐assisted treatment: benefits in relation to plasma treatment

Hydrophilic and superhydrophilic surfaces of poly(sulfone) (PSU) thin films were prepared by UV irradiation in the presence of O₂ or acrylic acid (AA) vapor. Treated surfaces were then investigated by water contact angle measurements, Fourier transformed IR spectroscopy in attenuated total reflectance mode (FTIR‐ATR), X‐ray photoelectron spectroscopy (XPS), near‐edge X‐ray absorption fine structure (NEXAFS) and AFM. Water contact angle values of treated PSU films using either O₂ or AA vapor as the reactive atmosphere reached about 6° after more than 120 min of irradiation. FTIR‐ATR, XPS and NEXAFS analysis showed incorporation of oxygenated groups onto the surface that led to its hydrophilic characteristics. In addition, when AA vapor was used as the reactive atmosphere, a photopolymerization process of poly(acrylic acid) onto the surface of the PSU was observed. AFM analysis showed a very low level of roughness after the treatments. A comparison of UV‐assisted surface modifications of PSU films with traditional plasma treatments showed excellent qualitative agreement between the two techniques. Our results show that UV‐assisted treatments in the presence of AA vapor or O₂ are efficient ways of controlling the surface wettability and functionalities grafted on the surface of PSU films. This treatment can be considered as a permanent dry grafting method that resists aging and uses a simple experimental setup. © 2012 Society of Chemical Industry     

Preparation and characterization of acrylic resin/titania hybrid nanocomposite coatings by photopolymerization and sol–gel process

Titania‐containing coatings were prepared through a dual‐cure process involving radical photopolymerization of a polysiloxane diacrylate and subsequent condensation of alkyltitanate groups. The kinetics of photopolymerization and condensation reaction was investigated as a function of the inorganic phase precursor (titanium tetraisopropoxide) content. AFM analysis gave evidence of a strong interaction between the organic and inorganic phase with the formation of titania domains in the nanoscale region. An increase of hydrophilicity in the coatings surface with increasing TiO₂ content was evidenced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4659–4664, 2006     

Polymeric hybrid films with photocatalytic activity under visible light

The immobilization of photocatalysts on several kinds of substrates has been widely studied over the past few years, focusing mainly on improving its industrial application. In this work, novel hybrid films were prepared, employing TiO₂ P25, commercial ZnO or BiOI, synthetized through hydrothermal method and immobilized on poly(vinylidene fluoride) by the non‐solvent‐induced phase inversion technique. Subsequently, the prepared composites were evaluated by photodegradation of methylene blue (MB) under ultraviolet or visible light. The samples were also characterized by scanning electron microscope, thermo‐gravimetric analysis, attenuated total reflection–Fourier transform infrared spectroscopy, and X‐ray diffractometer analysis to improve comprehension of the composites' photocatalytic behavior. The degradation reaction of the contaminants exhibited pseudo‐first order kinetics in all samples, and achieved better performance when compared to simple photolysis. The recyclability of the hybrid films was also evaluated and proved that polymeric matrix is a promising material for the preparation of composites for photocatalysis applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46367.     

Barrier,Biodegradation, and mechanical properties of (Rice husk)/(Montmorillonite) hybrid filler‐filled low‐density polyethylene nanocomposite films

Rice husk (RH)/montmorillonite (MMT) hybrid filler‐filled low‐density polyethylene nanocomposite films were prepared by extrusion blown film. RH was used as a biodegradable filler in various concentrations (2, 5, and 7 parts per hundred composite), while the amount of MMT was held constant at 2 wt%. Delamination of MMT platelets and distribution of RH were investigated by X‐ray diffraction and scanning electron microscopy. Diffractograms revealed the formation of intercalated structures, regardless of the RH content. Barrier properties revealed that MMT platelets have the potential to retard the diffusion of permeating molecules while, on the other hand, barrier efficiency of MMT is balanced by the subsequent incorporation of RH in RH/MMT hybrid filler‐filled composite films. Despite an increase in permeability, the selectivity ratio (CO₂/O₂ permeability) increased with increasing RH contents in the hybrid filler‐filled composite films showing the potential of these films in the development of modified atmosphere for fresh fruits and vegetables. The colonization of fungus and formation of holes as observed in micrographs of the test samples subjected to soil burial revealed that the biodegradation rate increased with the incorporation of RH in the hybrid composites. The composite films with higher contents of RH in hybrid filler are also more biodegradable than those having lower contents. Addition of RH contents in the hybrid filler increased the tensile modulus, while decreasing the tensile and tear strength. Addition of RH in the hybrid filler increased the melting and crystallization temperatures of the resulting nanocomposite films as well. J. VINYL ADDIT. TECHNOL., 23:162–171, 2017. © 2015 Society of Plastics Engineers     

Effective photopolymerization of C60 films under simultaneous deposition and UV light irradiation: Spectroscopy and morphology study

An effective method for uniform photopolymerization of C₆₀ films using simultaneous deposition and irradiation with ultraviolet (UV) light is described. The photopolymerization process was monitored as a function of irradiation time using Raman and infrared (IR) spectroscopy. New features appeared in the Raman (near the pentagonal pinch A_g(2) mode) and IR spectra (400-1500 cm⁻¹) after more than 20 h of UV irradiation testifying to the transformation of pristine C₆₀ to polymerized C₆₀ phases. Band shape analysis of the vibrational data revealed: (i) the degree of photopolymerization to be ∼90% after 20 h of irradiation, and (ii) the presence of orthorhombic, tetragonal, and rhombohedral phases in the photopolymerized films. Electron microscopy and diffraction studies revealed the amorphous nature of the photopolymerized films which comprised of crystals with a linear dimension of ∼40-60 nm. No evidence for cracks in the surface of the polymerized film was found. The proposed route for photopolymerization provides an opportunity to prepare extended polymeric C₆₀ films suitable for technological applications.     

Preparation and characterization of polyimide/Al2O3 hybrid films by sol–gel process

A sol–gel process has been developed to prepare polyimide (PI)/Al₂O₃ hybrid films with different contents of Al₂O₃ based on pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA) as monomers. FESEM and TEM images indicated that Al₂O₃ particles are relatively well dispersed in the polyimide matrix after ultrasonic treatment of the sol from aluminum isopropoxide and thermal imidization of the gel film. The dimensional stability, thermal stability, mechanical properties of hybrid PI films were improved obviously by an addition of adequate Al₂O₃ content, whereas, dielectric property and the elongation at break decreased with the increase of Al₂O₃ content. Surprisingly, the corona‐resistance property of hybrid film was improved greatly with increasing Al₂O₃ content within certain range as compared with pure PI film. Especially, the hybrid film with 15 wt % of Al₂O₃ content exhibited obviously enhanced corona‐resistance property, which was explained by the formation of compact Al₂O₃ network in hybrid film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008