Structural characteristics and properties of silica/poly(2-hydroxyethyl methacrylate) (PHEMA) nanocomposites prepared by mixing colloidal silica or tetraethyloxysilane (TEOS) with PHEMA

Two methods were used to prepare the silica/poly(2-hydroxyethyl methacrylate) (PHEMA) nanocomposites: one was the direct mixing of colloidal silica with PHEMA using methanol as a co-solvent (colloidal silica/PHEMA) and the other was the adding of the inorganic precursor, tetraethyloxysilane (TEOS), to the PHEMA/methanol solution, followed by the sol-gel process with an acid-catalyst (TEOS/PHEMA). The structure of the colloidal silica/PHEMA hybrid consisted of nano-silica uniformly dispersed in the PHEMA phase with slight inter-molecular hydrogen bonding. The structure of TEOS/PHEMA hybrid was similar to a semi-interpenetrated network with PHEMA chains tethered into the nano-silica network by inter- and intra-molecular hydrogen bonding. Consequently, the TEOS/PHEMA hybrid gels exhibited a smoother surface, higher transparency, and better thermal stability than the colloidal silica/PHEMA hybrid gels.     

Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2'-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles, and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites, followed by HF etching. Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated. N₂ adsorption-desorption, scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials. Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles. The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm. The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%. The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

Enhance photocatalysis of TiO2 and ZnO ceramics by addition of fused silica as a UV guiding medium

We report a facile method to prepare porous TiO₂ and ZnO photo-catalytic ceramics in which colloidal silica was added to yield nano fused silica (FS). The colloidal silica forms continuous media within the porous ceramic structure, and when calcined at 550 °C, it converted to fused silica phase which is an excellent UV wave-guiding material. With light wave guiding effect of FS and capillary effect of reaction solution in the porous channels, the photo-catalytic reactions could occur at the vast active sites at interface inside the porous bulks, as well as at the external surfaces. Photo-catalysis experiments and kinetics were investigated and analyzed. The photo-catalytic efficiencies tested for methylene blue were enhanced by a factor of 4.1 for TiO₂/FS system and, astonishingly, by a factor of 34.6 for ZnO/FS system, when compared with pure TiO₂ and ZnO under identical testing conditions. A model of UV-waveguide ceramic systems was proposed and discussed. This study proposes a practical approach to construct UV-waveguide porous structures, of which the principle is also potentially applicable to other types of photo-catalytic materials, including visible light active photo-catalysts.     

Experimental determination and mathematical modeling of the drying kinetics of a single droplet of colloidal silica

ABSTRACT

Colloidal silica has been used frequently as a model material of drying in the past two decades. Several models of single droplet drying have been validated against the sole experimental evidence by Ne?i? and Vodnik (Kinetics of droplet evaporation. Chemical Engineering Science 1991, 46(2), 527–537), in which relatively scattered experimental data on drying of single droplet of colloidal silica were provided. Due to the importance of this sort of data, the drying of single droplet of colloidal silica was determined more accurately under more extensive conditions in this work. The effect of air temperature on the drying of single droplet of colloidal silica was probed as well as the evolution of particle morphology. The droplet of colloidal silica was found to shrink irregularly during drying due to uneven exposure of droplet surface to air stream. The moisture within the droplet appears to transfer freely to the surface, keeping the surface highly moist. For a large part of drying process, drying of single droplet of colloidal silica is similar to the evaporation of water droplet, which can be predicted well using a simple mathematical model.     

Effects of addition of colloidal silica particles on TEOS-based stone protection using n-octylamine as a catalyst

Protective agents based on tetraethoxysilane (TEOS) have been widely used for the protection of stone heritages. However, TEOS-based protective agents suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developed capillary force, which is typical for TEOS-based protective agents. In this paper, we have prepared new TEOS-based protective agent containing flexible hydroxyl-terminated polydimethylsiloxane (PDMS-OH) and colloidal silica particles (167 nm) using n-octylamine as a catalyst in order to reduce capillary force development and increase hydrophobicity, and have characterized them for the application of stone protective agent. The extent of surface hydrophobization depends on concentration of colloidal silica particles and reaches a maximum value of 123° at 0.2% (w/v) of colloidal silica particles for the case of treated with the modified composition. The presence of n-octylamine is a key factor which promotes the increase of the gel pore size. The protective performances were also evaluated by its ability to resist acid corrosion. The results reveal that the protective effects are satisfying.     

Multifunctional PP-Based Nanocomposites Incorporated with Organoclays,Poly(MA-alt-1-Dodecene)-g-SiO2 Nanoparticles and Bioengineering Polyesters in Melt by Reactive Extrusion

Polypropylene-based multifunctional nanocomposites were fabricated in melt by a one-step reactive extrusion using a twin-screw extruder. The in situ chemical and physical processes during the extrusion of polymer blend composites consisting (1) polypropylene as a matrix polymer, (2) polypropylene–g-maleic anhydride graft copolymer compatibilizer, (3) copolymer–g-SiO₂ encapsulated nanoparticles, (4) biodegradable polyesters, and (5) reactive and nonreactive organoclay nanofillers were investigated. The crystallinity, thermal stability, rheological, mechanical parameters, and surface and internal morphologies of the nanocomposites have been improved compared to polypropylene and its composites. Moreover, the colloidal copolymer–silica nanoparticles play an important role in the formation of nanocomposites with well dispersion in morphology.     

Nanocomposites of silica reinforced polypropylene: Correlation between morphology and properties

Polypropylene/fumed hydrophilic silica nanocomposites were prepared via melt mixing method using a single‐screw extruder. Comparative study with and without compatibilizing copolymer agent (maleic anhydride grafted polypropylene: PP‐g‐AM) was conducted. The obtained results were interpreted in terms of silica nanoparticle–silica nanoparticle and silica nanoparticle‐polymer interactions. These results have shown that the addition of nanofillers improves the properties of the nanocomposites. From transmission electron microscopy, it was found that agglomerations of silica particles into the PP matrix increased in average size with increasing silica contents, except in presence of the copolymer. Storage modulus values of the nanocomposites measured by dynamic mechanical thermal analysis were sensitive to the microstructure of the nanocomposites. Higher silica contents resulted in higher storage modulus, revealing that the material became stiffer. By adding the compatibilizer, a further increase of storage modulus was observed due to the finer dispersion of the filler in the matrix and the increased interfacial adhesion. Crystallization rates were found to increase with the increase of silica nanoparticles as well as PP‐g‐MA content. In addition, silica nanoparticles and the compatibilizing agent present centers of germination and nucleation of crystallites. Thus, the use of the coupling agent resulted in a further enhancement of mechanical properties of the nanocomposites due to the reduction of silica agglomeration. POLYM. ENG. SCI., 54:2187–2196, 2014. © 2013 Society of Plastics Engineers     

纳米二氧化硅对卡波姆凝胶流变行为的影响

采用红外光谱(FTIR)和扫描电子显微镜(SEM)分析了气相法二氧化硅(FS)和沉淀法二氧化硅(PS)的表面性质,结果表明,FS表面比PS含有更多的羟基,在水中分散性更好。利用流变仪对比研究了FS和PS对卡波姆956凝胶流变行为的影响规律,结果表明,FS和PS的加入均能明显提高卡波姆凝胶的弹性模量、屈服应力、触变性等流变学性质;在纳米二氧化硅质量百分数≤4%,FS在卡波姆凝胶中分散粒径较小且更均匀,其对上述流变学性质的增强作用大于PS;纳米二氧化硅质量分数从4%增大到8%时,PS形成大团聚体,能更好地提高上述流变学性质。结合SEM的测试结果阐明了FS与PS同卡波姆之间不同的相互作用方式。     

Fabrication of chemically bonded polyacrylate/silica hybrid films with high silicon contents by the sol–gel method

Polyacrylate/silica hybrid latexes (PAES) with high silicon contents (up to 21%) were prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a silane coupling agent. Sol–gel-derived organic/inorganic thin films were obtained by addition of hydrophilic co-solvents to PAES and subsequent drying at room temperature. The effects of co-solvents and γ-methacryloxypropyltrimethoxysilane (KH570) content on the properties of PAES films were investigated. Dynamic light scattering (DLS) data indicated that the average diameter of PAES (96 nm) was slightly larger than that of PAE (89 nm). TEM photo revealed that colloidal silica particles were dispersed uniformly around polyacrylate particles and that some of the colloidal silica particles were adsorbed on the surface of PAE particles. The data of crosslinking degree and FT-IR spectra confirmed that the chemical structure of the PAES changed to form Si–O–Si-polymer crosslinking networks during the film formation. AFM photos, contact angle for water, and XPS analysis showed that the polyacrylate/inorganic hybrid films with high silicon contents were formed by the co-solvent-mediated, sol–gel method and that the Si-based polymers were uniformly distributed on the surface of the dried films. TGA data demonstrated that the PAES films display much better thermal stability than the PAE counterpart.     

Homogeneous dispersion of SiO2 nanoparticles in an hydrosoluble polymeric network

The main difficulty still encountered in the elaboration of polymer/silica nanocomposites is the control of the nanoparticles dispersion homogeneity and the stability of the nanoparticle dispersion in the surrounding substance. The innovative point of this work is the elaboration of hybrid networks in aqueous solution performed with ASE (alkali swellable emulsion) thickeners grafted with silica nanoparticles. The thickening ability of the polymer should favour silica nanoparticles dispersion in fluid matrices. Two ASE copolymers were realised by copolymerisation in emulsion of MA (methacrylic acid) and EA (ethyl acrylate) and/or TFEM (trifluoroethyl methacrylate). The substitution of a part of EA by TFEM gave fluorinated ASE copolymers. Their free acid functions were then coupled with different ratio of amine functionalized silica nanoparticles to afford nanocomposites. The amounts of silica nanoparticles in the copolymers were determined by thermogravimetric experiments. Depending on the silica nanoparticles/copolymer ratio in basic aqueous solutions we achieved stable translucent gel like aqueous suspensions of silica nanoparticles containing 1 wt.% of the polymer/SiO₂ nanocomposite.     

Production and characterization of UHMWPE/fumed silica nanocomposites

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/fumed silica nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler‐Natta catalytic system. Nanocomposites with different nanoparticle weight fractions were produced in order to investigate the effect of fumed silica on thermal and mechanical properties of UHMWPE/fumed silica nanocomposites. The viscosity average molecular weight (M ) of all samples including pure UHMWPE as the reference sample and nanocomposites were measured. Scanning electron microscope (SEM) images showed the homogenous dispersion of nanoparticles throughout the UHMWPE matrix while no nanoparticle cluster has been formed. Crystallization behavior of nanocomposites was investigated by differential scanning calorimetry (DSC), which showed a slight increase in melting temperature by enhancing the nanoparticle concentration while no significant change was observed in the crystallization temperature as the fumed silica concentration enhanced. The improvement in all thermal stability parameters was recorded by thermogravimetric analysis (TGA). Besides, via tensile testing, it was confirmed that addition of nanoparticles caused considerable improvement in such mechanical properties as Young's modulus, yield stress, and tensile strength of samples while the elongation at break declined by addition of more nanoparticles. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Properties of Colloidal Silica‐Fixed and Propionylated Wood Composite (II): Flame Resistance and Other Properties of the Composites

Abstract

The flame resistance, color change, strength, and decay resistance of colloidal silica‐fixed (CSW), propionylated only, and propionylated dual‐treated wood (CSPW) composites were evaluated. The oxygen indexes of the CSPW composites were similar to the CSW composites but much higher than those of untreated woods and the propionylated woods. The oxygen indexes increased with an increase in the weight percent gain of the colloidal silica (WPG_csi) in the composites, showing an effective reduction in the flammability by the fixation of colloidal silica. The CSPW composites showed little or no difference in the modulus of elasticity and modulus of rupture compared with the untreated woods, indicating little or no significant reduction in strength properties of the wood specimens. The color difference of the wood specimens before and after treatment changed slightly. Minimal weight losses of the CSPW composites occurred upon fungal attack by T. versicolor and F. palustris, showing good decay resistance by propionylation of the composites.     

Microstructure and reactivity evolution of colloidal silica binder in different systems at elevated temperatures

Colloidal silica as nanostructured binder for refractory castables has attracted many attentions in recent years. In the present study, phase composition, microstructure and reactivity evolution of silica gel at different heating conditions were investigated to find suitable system for colloidal silica application. The results showed that atmosphere and carbon slightly affected phase composition of the silica gel at elevated temperatures, and the crystalline phases were composed of major α-cristobalite and minor α-tridymite. The morphology and particle size of the silica gel were greatly affected by atmosphere and carbon during heating. The spherical nano-silica particles with sizes of 40–50 nm rapidly grew into macroscale rod-like particles with temperature increasing from 800-1000 °C to above 1200 °C in air, and sintering of silica particles was observed. However, the size and morphology of the spherical nano-silica particles retained at high temperature in a reducing atmosphere, and many well developed columnar mullite crystals and some SiC whiskers formed on heating silica gel, alumina fines and carbon at 1500 °C, which was due to carbon inclusions retarding the growth of nano-silica particles and the nano silica remained high reactivity at high temperature. Thus, colloidal silica was suitable for application in carbon-containing refractory castables.     

Polypropylene/silica nanocomposites prepared by in-situ melt ultrasonication

A novel process using ultrasonic irradiation to enhance nanosilica dispersion in polypropylene-based nanocomposites has been proposed and investigated. The nanocomposites were isotactic polypropylene reinforced with silica nanoparticles at 3 wt% loading level. Ultrasonic processing in the melt state is an effective method for improving nanosilica dispersion. The effectiveness of the proposed ultrasonic processing technique on polypropylene nanocomposites was evaluated by XRD and transmission electron microscopy (TEM). Poly(propylene-g-maleic anhydride) copolymer (PP-g-MAH) containing 5 wt% maleic anhydride content was added to nanocomposites at 0.5 wt% concentration based on silica content. PP-g-MAH plays an important role in nanosilica dispersion in polymer matrix and interface interaction. The reaction of maleic anhydride groups with the hydroxyl groups on the surface of nanosilica was characterized by FTIR spectrum. The final nanocomposites result in a further enhancement of mechanical properties because of silica agglomerate reduction and improving interface combination, even loading level being much lower than that of ordinary fillers in conventional composites. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

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

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

In situ preparation and property investigation of polypropylene/fumed silica nanocomposites

We present the preparation of polypropylene (PP)/fumed silica (FS) nanocomposites via in situ polymerization in this article. The approach includes preparation and utilization of a bisupported Ziegler–Natta catalytic system in which magnesium ethoxide and FS are used as conjugate supports of the catalyst. Catalyst preparation and polymerization processes are carried out in the slurry phase and under argon atmosphere. Scanning electron microscopy images show a good dispersion of the FS throughout the PP matrix. Results from differential scanning calorimetry reveal that the crystallization temperature of prepared nanocomposites increases by increasing FS loading. Also, crystal content of nanocomposites increases as the FS concentration increases up to 3.48 wt%. Nanocomposites containing <3.14 wt% of nanoparticles do not show considerable change in their melting point where with more increment in filler concentration, melting temperature slightly increases. Thermogravimetric analysis shows a considerable improvement in the thermal stability of PP/FS nanocomposites compared to pure PP. Rheological studies indicate that the incorporation of FS into PP matrix results in increment in storage modulus, loss modulus, and complex viscosity of polymeric matrix, particularly in low frequency region. By increasing FS loading, the PP/FS nanocomposites show a transition from liquid‐like to solid‐like viscoelasticity behavior depicting microstructural changes in their structures. POLYM. COMPOS., 35:37–44, 2014. © 2013 Society of Plastics Engineers     

Effect of isocyanate‐modified fumed silica on the properties of poly(butylene succinate) nanocomposites

Using the grafting method on a silica surface with PBS molecules, we prepared novel poly(butylene succinate) (PBS)/silica nanocomposites to enhance dispersibility and interfacial adhesion between silica particles and the PBS matrix, and also investigated the effects of silica‐g‐PBS on the PBS matrix using differential scanning calorimetry, thermogravimetric analysis, transmission electron microscopy, a tensile testing machine, and rheometry. The thermal stability, mechanical properties, and rheological properties of PBS nanocomposites containing silica‐g‐PBS was remarkably improved because of the surface characteristics of the silica grafted with PBS molecules, which provided good compatibility and dispersion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(ethylene-oxide)/clay/silica nanocomposites: Morphology and thermomechanical properties

Poly(ethylene-oxide) PEO/clay/silica nanocomposites were prepared via solution intercalation by exploiting phase separation based on the bridging of particles by polymer chains. The intercalated morphology of nanocomposites was confirmed by XRD. Vibrational modes of the ether oxygen of PEO in the hybrids are shifted due to the coordination of the ether oxygen with the sodium cations of clay and the H-bonding interactions of the ether oxygen with the surface silanols of hydrophilic fumed silica. Based on SEM, the overall density of nanoparticle aggregates in the interspherulitic region was observed to be higher compared to that inside spherulites. PEO/clay/silica hybrids show significant property improvements compared to PEO/clay hybrids and pure PEO. The system containing 10 wt.% clay and 5 wt.% silica has substantially higher modulus and much lower crystallinity compared to the 15 wt.% clay system. The physics behind the reinforcement effect and the reduction of crystallinity as a function of fumed silica loading is discussed based on the morphological characterization of the hybrids. Lastly, PEO/clay/silica hybrids display good thermal stability and are much stiffer compared to pure PEO and PEO/clay nanocomposites.     

Flame retardancy of polycarbonate–polydimethylsiloxane block copolymer/silica nanocomposites

This report describes the flame retardancy and the thermal degradation behavior of polycarbonate–polydimethylsiloxane (PC–PDMS) block copolymer/silica nanocomposites. PC–PDMS block copolymer with dimethylsiloxane (DMS) block size 40 units increased the dispersibility of nanosized amorphous silica. Addition of the slight nanosized silica caused the increment of flame retardancy of PC–PDMS block copolymer, and the PC–PDMS block copolymer with 1.0 wt % PDMS had the highest limiting oxygen index value when the nanosized silica was added 0.5 wt %. The maximum rate temperature of the PC–PDMS block copolymer increased with the addition of silica and the maximum loss rate was the lowest when silica content is 0.5 wt %. The monodisperse nanosized silica had an effect that enhances the flame retardant mechanism of PDMS for PC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3862–3868, 2006