Sol‐Gel‐Derived Sb‐Doped SnO2 Nanoparticles Controlled in Size by Nb2O5

Nanocrystalline Sb‐doped SnO₂ particles were prepared by sol‐gel and their particle growth was controlled by niobium oxide. In the present synthesis, SnCl₄ and SbCl₃, as precursors, were dissolved and hydrolyzed in ethylene glycol at 80–120 °C, and further 0.1 mol.‐% Nb₂O₅ through its precursor NbCl₅ was mixed to the above solution. The mixture was then dried at 120–150 °C and calcinated at 600 °C for 2 hours. By XRD and TEM, Sb‐doped SnO₂ nanoparticles were highly crystalline and their mean crystal size was ca.10–20 nm with narrow particle size distribution. As the addition of antimony increased, the crystallinity and particle size distribution of SnO₂ particles had the trend to decrease.     

Radiation processing and characterization of poly(vinyl alcohol) nano‐composites,Part 1: Nano‐particulate filler tuned crosslinking behavior

Nano‐composites of poly vinyl alcohol containing different nano‐fillers namely multiple walled carbon nanotubes (MWNT), single walled carbon nanotubes (SWNT), silica nanoparticles, and silver nanoparticles were prepared by sonication‐assisted solution mixing and subjected to different doses of gamma radiation. The efficacy of radiation crosslinking was analyzed by sol–gel analysis, Charlesby‐Pinner parameter estimation and crosslinking density measurements. Crosslinking of nano‐composites was found to increase with radiation dose and markedly affected with the type of nano‐particulate filler in the matrix (p_o/q_o in the range: 0.40–0.83). The results have been explained on the basis of Raman spectroscopy, hydrodynamic volume measurements, contact angle measurements, and scanning electron microscopy (SEM). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

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     

Thermomechanical properties of styrene‐butyl acrylate/organo‐silica nanocomposite films prepared by seed emulsion polymerization

Organo‐silica nanoparticles were prepared by sol–gel technique of triethoxyvinylsilane (VTES) in aqueous solution. The vinyl groups located on the surface of organo‐silica were used to induce the polymerization process and the encapsulation into styrene‐butyl acrylate copolymer emulsion. The prepared latex samples were characterized using FTIR, ¹HNMR, UV–visible, thermal analysis, field emission‐SEM and TEM. Results of TGA revealed that nanosilica has retarded the decomposition of nanocomposite polymers with at least 10°C higher than that of pure emulsions. DSC has shown an increase in the nanosilica ratio up to 5% which leads to a dramatic decrease in the glass transition (T _g) of nanocomposite polymer due to the formation of silica nanoparticles homopolymer. DMTA results indicated that the storage modulus of pure polymer is less than nanocomposite, which proves the reinforcing role of nanosilica in the matrix of polymer. Water resistance and UV‐blocking ability have improved by introducing the nanosilica into the matrix of prepared polymer. POLYM. COMPOS., 38:61–67, 2017. © 2015 Society of Plastics Engineers     

The Assembly of TiO2 Nanoparticles into Micrometer‐Sized Structures,Photocatalytically Active Under UV and Vis Light

Micrometer‐sized structures consisting of TiO₂ nanoparticles were prepared using the sol–gel technique in combination with the structure‐directing agent triethanolamine (TEA). The interaction of the TEA with the hydrolyzed sol–gel products led to the formation of TEA titanate complexes, which then enabled the assembly of sol–gel‐precipitated nanosized powders. A subsequent thermal treatment of these powders resulted in the formation of micrometer‐sized structures consisting of TiO₂ anatase and rutile nanoparticles. To characterize the prepared powders, FTIR spectroscopy, XRD analysis, the Brunauer‐Emmett‐Teller method (s_BET), UV–Vis spectrometry and electron microscopy (FE‐SEM, and TEM) were employed. The photocatalytic degradation of the azo dye known as methylene blue was monitored under UV and Vis irradiation and showed that the micrometer‐sized structures consisting of TiO₂ nanoparticles exhibited a similar photocatalytic activity to submicrometer‐sized structures consisting of TiO₂ nanoparticles prepared without TEA.     

Preparation of Nano‐Structured RDX in a Silica Xerogel Matrix

RDX is preferred as explosive in munitions due to its balance of power and sensitivity that is known to be dependent on its particle size and size distribution. In this study, we prepared nano‐sized RDX in a silica xerogel matrix using a sol‐gel method and investigated its sensitivity for explosive properties. The presence of RDX in composite xerogel was confirmed by TG‐DSC and FTIR techniques. Microstructure and porosity were characterized by transmission electron microscopy (TEM), small angle X‐ray scattering, and N₂‐physisorption techniques. TEM results showed that the size of RDX particles in the RDX‐silica composites is in the range of 10–30 nm. The sensitivity to impact and friction was found to be higher for the composites compared to raw RDX. It was also found to be significantly dependent on the acetone/TMOS ratio used in the preparation.     

Activation of lipase by sol–gel coating with hydrophobic alkyl‐substituted silicates in supercritical carbon dioxide

BACKGROUND: Sol–gel entrapment of lipases is usually performed in an aqueous solution. A novel method of sol–gel coating of lipase in supercritical carbon dioxide (SC‐CO₂) is proposed. RESULTS: Crude lipase powder (Rhizopus oryzae) coated with hydrophobic silicates, derived from dimethyldimethoxysilane and tetramethoxysilane in SC‐CO₂ at 35 °C and 15 MPa, exhibited 5–7 times higher esterification activity than that prepared via an aqueous sol–gel route. Lipase immobilized in a methyl‐substituted silica monolith was also highly activated by sol–gel coating using the same silica precursors in SC‐CO₂. CONCLUSION: Sol– gel coating in SC‐CO₂, of lipases in powder and immobilized forms with hydrophobic alkyl‐substituted silicates provides an efficient tool for the enhancement of enzymatic activities in non‐aqueous media. Copyright © 2009 Society of Chemical Industry     

Epoxy‐silica nanocomposites: Preparation,experimental characterization,and modeling

Silica nanoparticles having different sizes were obtained by the sol‐gel process and characterized. The prepared nanoparticles were subsequently used as reinforcing fillers to prepare epoxy‐based composites with a silica content ranging from 1 to 5 wt %. SEM analysis and tensile tests carried out on the silica‐epoxy nanocomposites indicated the absence of particle aggregation and a reinforcing effect in terms of increased elastic modulus. Mechanical properties were also modeled by using a finite element code able to construct a numerical model from a microstructural image of the material. A more reliable model was prepared by considering the presence of an interphase layer surrounding the particles with intermediate elastic properties between the epoxy and the inclusions and a characteristic size proportional to the particle radius. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2382–2386, 2005     

Polyamide–silica nanocomposites: mechanical,morphological and thermomechanical investigations

BACKGROUND: The physical properties of polyamides can be enhanced through incorporation of inorganic micro‐ and nanofillers such as silica nanoparticles. Transparent sol‐gel‐derived organic‐inorganic nanocomposites were successfully prepared by in situ incorporation of a silica network into poly(trimethylhexamethylene terephthalamide) using diethylamine as catalyst. Thin films containing various proportions of inorganic network obtained by evaporating the solvent were characterized using mechanical, dynamic mechanical thermal and morphological analyses. RESULTS: Tensile measurements indicate that modulus as well as stress at yield and at break point improved while elongation at break and toughness decreased for the hybrid materials. The maximum value of stress at yield point (72 MPa) was observed with 10 wt% silica while the maximum stress at break point increased up to 66 MPa with 20 wt% silica relative to that of pure polyamide (44 MPa). Tensile modulus was found to increase up to 2.59 GPa with 10 wt% silica in the matrix. The glass transition temperature and the storage moduli increased with increasing silica content. The maximum increase in the T_g value (144 °C) was observed with 20 wt% silica. Scanning electron microscopy investigation gave the distribution of silica, with an average particle size ranging from 3 to 24 nm. CONCLUSION: These results demonstrate that nanocomposites with high mechanical strength can be prepared through a sol‐gel process. The increase in the T_g values suggests better cohesion between the two phases, and the morphological results describe a uniform dispersion of silica particles in the polymer matrix at the nanoscale. Copyright © 2007 Society of Chemical Industry     

Electrochemical Deposition of 58SiO2‐33CaO‐9P2O5 Nanobioactive Glass Particles on Ti‐6Al‐4V Alloy for Biomedical Applications

The nanobioactive glass (58SiO₂‐33CaO‐9P₂O₅) powders were synthesized by simple sol–gel method. The prepared samples reveal amorphous nature, agglomerated spherical morphology with particle size of 100–150 nm. The specific surface area of nanobioactive glass (NBG) particle is 147 m²/g. The NBG samples were coated on titanium (Ti‐6Al‐4V) alloy through electrochemical deposition method. The particle size of the NBG‐coated surface was in the order of 200–300 nm, and it was confirmed by atomic force microscopy (AFM) analysis. In vitro and AFM studies reveal the existence of higher bioactivity and uniform coating of NBG on implants at 80 V for 1 h.     

Structure and dielectric properties of polyimide/silica nanocomposite nanofoam prepared by solid‐state foaming

In this article, polyimide (PI)/silica nanocomposite nanofoams were prepared by solid‐state foaming using supercritical CO₂ as foaming agent. To control the cell size and morphology of the PI/silica foam, the silica nanoparticles as nucleating agent were in situ formation from TEOS via sol‐gel process, which make the silica nanoparticles homogeneously dispersed in PI matrix. The resulting PI/silica nanocomposite nanofoams were characterized by scanning electron microscopy (SEM), the image analysis system attached to the SEM and dielectric properties measurements. In PI/silica nanocomposite nanofoams, one type of novel morphology was shown that each cell contained one silica nanoparticle and many smaller holes about 20–50 nm uniformly located in the cell wall. This special structure could visually prove that the nucleation sites during foaming were formed on the surface of nucleating agents. Compared with those of neat PI foam, the cell size of PI/silica nanocomposite nanofoams was smaller and its distribution was narrower. The dielectric constant of PI/silica nanocomposite nanofoams was decreased because of the incorporation of the air voids into the PI/silica nanofoams. While the porosity of PI/silica nanocomposite nanofoam film was 0.45, the dielectric constant of the film (at 1 MHz) was reduced from 3.8 to about 2.6. Furthermore, the dielectric constant of PI/silica nanofoam films remained stable across the frequency range of 1×10²～1×10⁷ H_Z. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42355.     

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.     

Study on Ultrasound‐ and Spray‐Assisted Precipitation of CL‐20

Ultrafine hexanitrohexaazaisowurtzitane (CL‐20) samples were prepared by a ultrasound‐ and spray‐assisted precipitation method. Raw CL‐20 and ultrafine CL‐20 samples were characterized by SEM, FT‐IR spectroscopy, XRD, and particle size analysis. The impact sensitivity and thermal stability of two CL‐20 samples were also tested and compared. The results indicate that by this recrystallization process, the mean particle size of CL‐20 is 470 nm, and the particle size distribution was in the range from 400–700 nm. The particle morphology is nearly spheric with a smooth surface. Compared with raw CL‐20, the impact sensitivity of the ultrafine sample is significantely reduced and the drop height (H₅₀) is increased from 12.8 to 37.9 cm. The critical explosion temperature of ultrafine CL‐20 decreased from 235.6 to 229.0 °C, which suggests that the thermal stability of ultrafine CL‐20 is lower than that of raw CL‐20.     

Preparation of poly(methyl methacrylate)‐Silica nanoparticles via differential microemulsion polymerization and physical properties of NR/PMMA‐SiO2 hybrid membranes

Poly(methy methacrylate) (PMMA)‐SiO₂ nanoparticles were prepared via differential microemulsion polymerization. The effects of silica loading, surfactant concentration, and initiator concentration on monomer conversion, particle size, particle size distribution, grafting efficiency, and silica encapsulation efficiency were investigated. A high monomer conversion of 99.9% and PMMA‐SiO₂ nanoparticles with a size range of 30 to 50 nm were obtained at a low surfactant concentration of 5.34 wt% based on monomer. PMMA‐SiO₂ nanoparticles showed spherical particles with a core‐shell morphology by TEM micrographs. A nanocomposite membrane from natural rubber (NR) and PMMA‐SiO₂ emulsion was studied for mechanical and thermal properties and pervaporation of water‐ethanol mixtures. PMMA‐SiO₂ nanoparticles which were uniformly dispersed in NR matrix, significantly enhanced mechanical properties and showed high water selectivity in permeate flux. Thus, the NR/PMMA‐SiO₂ hybrid membranes have great potential for pervaporation process in membrane applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Preparation and high oxygen‐enriching properties of cross‐linking polydimethylsiloxane/SiO2 nanocomposite membranes for air purification

Nanocomposite membrane based on polydimethylsiloxane (PDMS) and nanoscale SiO₂ particles were prepared by a convenient and mild sol–gel copolymerization of tetraethoxysilane as well as cross‐linking reaction. The oxygen‐enriching properties of cross‐linking PDMS/SiO₂ nanocomposite membranes containing different silica conversion and SiO₂ contents were investigated. The results showed that the nanocomposite membranes exhibited good membrane‐forming ability, superior mechanical properties, and high solvent resistance as well as excellent oxygen‐enriching properties for air purification. The oxygen‐enriching performance was regulated by the organic/inorganic ratio and silica conversion in the sol–gel synthesis process. Permeability and selectivity could increase simultaneously with the addition of nanoscale SiO₂. The oxygen permeation coefficient of the nanocomposite membrane increased to 680 Barrer and oxygen/nitrogen separation factor kept 3.0 or so, both higher than those of the corresponding pure PDMS membrane. The high oxygen‐enriching properties of the nanocomposite membranes arose from the introduction of SiO₂ particles, the sol–gel copolymerization, and cross‐linking method. © 2012 American Institute of Chemical Engineers AIChE J, 59: 650–655, 2013     

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 meta and para diamines on the properties of polyetherimide nanocomposite films prepared by the sol‐gel process

The effects of chemical structure of diamines on the properties of polyetherimide (PEI) nanocomposite films prepared by the sol‐gel process were investigated. For meta diamine, nanocomposites with improved thermal, mechanical, and dielectric properties can be prepared by a sol‐gel process from soluble PEI via chemical imidization, with silica content up to 10%. However, for the PEI with pPDA as diamine and bisphenol A dianhydride, a two‐stage sol‐gel process via thermal imidization was necessary to prepare the nanocomposites. The thermal stability and mechanical properties were improved with the addition of up to 5 wt % of silica content. The variation could be attributed to the fact that differences in the compatibility between PEI and SiO₂ for two kinds of PEI with the different meta and para structure of the diamine monomer. The morphology of the fracture surfaces investigated by SEM showed a finely interconnected or cocontinuous phase for PEI nanocomposites with the silica content of up to 10% and 5 wt % for mPDA and pPDA as diamine, respectively. At higher silica contents, thermal and mechanical properties were reduced due to the aggregation of SiO₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Development of ZrO2‐MgO nanocomposite powders by the modified sol‐gel method

The ZrO₂‐MgO nanocomposites were synthesized using a new sol‐gel method with sucrose and tartaric acid as a gel agent. The samples were characterized by thermal analysis (TG/DTA), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), energy‐dispersive X‐ray mapping (EDX mapping), and Ultraviolet‐visible spectroscopy (UV‐vis). The results showed that the cubic phase of ZrO₂‐MgO was formed in the presence of both gel agents. The average particle size of the samples synthesized with sucrose was lower (30 nm) than that of tartaric acid (50 nm). Finally, the formation mechanism and the optical properties of zirconia‐magnesia have been discussed.     

Crystalline BaTiO3 synthesis by ultrasound and microwave‐assisted sol–gel process

Highly crystalline BaTiO₃ particles were prepared by sol–gel process. Ultrasound and microwave techniques were used to facilitate the synthesis of BaTiO₃. BaTiO₃ samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), particle size analyser, and high temperature differential scanning calorimetry/thermogravimetric analysis (DSC/TGA). The results indicate that both barium and titanium sources and preparation techniques affected BaTiO₃ purity and crystallite size. The smallest particle and crystallite sizes were obtained by using BaCl₂ and (C₄H₉O)₄Ti and the crystallite size of BaTiO₃ was 8 ± 1 nm via MW technique.