Synthesis of Kenyaite, Magadiite and Octosilicate Using Poly(ethylene glycol) as a Template

Three types of layered silicates, namely octosilicate, magadiite and kenyaite, were synthesized using poly(ethylene glycol) (PEG). The influence of reaction parameters, including alkali source, silica source, PEG molecular weight, reaction time and temperature, on the formation of these three phases was investigated. The results indicate that magadiite is preferred when (i) using NaOH as the alkali source and at a lower temperature (150°C), with fumed silica, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), Ludox-AS 40 or colloidal sol acting as the silica source in the presence of PEG 200; (ii) using fumed silica as the silica source and PEG 300 as the template at 150°C; (iii) at a higher temperature (180°C), using PEG 200 as template and TEOS as the silica source; and (iv) at 180°C with a combination of PEG 300 and fumed silica. Compared to magadiite, kenyaite was favored at a higher temperature (180°C) with PEG 200 and NaOH, KOH or RbOH, while using fumed silica, silica gel, or colloidal sol as silica source; or at the lower temperature (150°C) using NaOH as alkali source, PEG 200 as template, and silica gel or silicic acid as the silica source. Octosilicate was obtained at 90°C with the combination of NaOH, PEG 200 and fumed silica.     

Preparation of nanosilica reinforced waterborne silylated polyether adhesive with high shear strength

Waterborne adhesives are extremely environment‐friendly but unfortunately deficient in mechanical properties. In this article, nanosilica, stemming from tetraethyl orthosilicate (TEOS), silica sol, and/or fumed silica powder, was employed to reinforce the waterborne silylated polyether adhesives. Effects of TEOS content, silica sol content, and the type and content of fumed silica on the shear strength of the adhesive were investigated using a scanning electronic microscope and an electronic instron tester and the strengthening mechanisms of different silica source were discussed. All the shear strengths of silylated polyether adhesives first increased and then decreased as TEOS content, silica sol content or fumed silica content increased. Colloidal silica particles was less efficient than fumed silica particles for reinforcing the polyether adhesive but can increase the shear strength of hydrophobic fumed silica embedded adhesive. Comparing the adhesives with the hydrophilic fumed silica (HS‐5) or the extremely hydrophobic fumed silica (TS‐720), the adhesive with moderate hydrophobic fumed silica (TS‐610) had the highest shear strength. The maximal shear strength of 2.5 MPa was achieved when TEOS, silica sol, and fumed silica were combined. It seemed that TEOS, silica sol, and fumed silica played crosslinking (with polyether chain), dispersing (for fumed silica), and reinforcing roles on waterborne adhesive, respectively. This reinforcing mechanism opened a new way to fabricate waterborne adhesives (or coatings) with high performances. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Size-controlled synthesis of mesoporous silica nanoparticles using rice husk by microwave-assisted sol–gel method

Mesoporous silica nanoparticles with distinct characteristics like particle size, tunable pores, and high surface area have received much interest for environmental remediation, energy conversion, and biological applications. In this work, we synthesized spherical silica nanoparticles with tunable particle size and mesoporous properties using a low-cost silica source (rice husk) and polyethylene glycol (PEG) via microwave-assisted sol–gel synthesis. The formation of an amorphous silica structure was found using XRD and FTIR analysis. FESEM analysis showed that altering the PEG concentration from .01 to .005 M produced spherical silica nanoparticles with 100–500 nm in size. Nitrogen adsorption–desorption demonstrated that silica nanoparticles obtained with .005, .007, and .01 M of PEG had unique pore sizes and distributions, with specific surface areas of 51.475, 62.367, and 84.251 m²/g, respectively. These results might be due to PEG molecules’ capping effect, which acts as a soft template to regulate particle size, pore size, and dispersion by interacting with sodium silicate precursor. Hence, this approach can be a facile and cost-effective method to prepare mesoporous silica nanoparticles with controllable nanoscale characteristics for suitable applications.     

Dispersion,crystallization behavior,and mechanical properties of poly(3-hydroxybutyrate) nanocomposites with various silica nanoparticles: effect of surface modifiers

Silica nanoparticles (NPs) with various surface properties were introduced in poly(3-hydroxybutyrate) (PHB) matrix and the their effect on the dispersion, crystallization behavior, and reinforcement in the nanocomposites was discussed in this article. Two kinds of commercial fumed silica NPs and two kinds of self-prepared sol-gel silica (bare and PEGylated) NPs were used. The cross-sectional SEM (scanning electron microscopy) images, provided the micrometer scale view (observation area: 12.6×8.2 μm²), showed that commercial fumed silica and PEG–silica NPs were aggregated and well-dispersed in PHB matrix, respectively. Similarly, Morisita’s analysis of TEM (transmission electron microscopy) images (observation area: 2.4×1.6 μm²) indicated that PEG-silica NPs were Poisson dispersed and commercial fumed silica NPs were serious aggregated in PHB matrix. However, SEM-EDX (energy dispersive X-ray analysis) Si-mapping micrographs, provided the millimeter scale view (observation area: 0.79×0.61 mm²), showed that four kinds of silica NPs were well-dispersed in PHB matrix. PLM (polarized light microscopy) images indicated that spherulite growth rate and morphology of PHB did not change obviously upon the addition of various silica NPs, except the PHB/PEG–silica system. PHB/PEG–silica showed a decreased spherulite growth rate, which was consistent with the DSC (differential scanning calorimetry) results, because the good miscibility between PHB and the grafted PEG chains on PEG–silica could decrease the polymer chain mobility during crystallization. The Young’s modulus and tensile strength of the PHB were enhanced by up to 34% and 63% by adding a small amount of PEG–silica. Fully well-dispersed PEG–silica NPs functioned as physical cross-linking centers for enhancing the mechanical properties of PHB but as retarding agents for reducing the crystallization rate.     

Rheological study of aqueous dispersions of in situ gelable thermosensitive polymer nanogels

Thermosensitive poly(N‐isopropylacrylamide‐co‐acrylamide) nanogels with varied monomer compositions were prepared by precipitation polymerization. The aqueous dispersions of these thermosensitive nanogels (9 wt% of nanogel particles in phosphate‐buffered saline solution) exhibited in situ gelable characteristics. A steady‐state and dynamic rheological analysis demonstrated that the nanogel dispersions were typical pseudoplastic liquids at room temperature. The viscosity of the nanogel dispersions at a constant shear rate increased with an increase of the acrylamide content. When the temperature was increased to 37°C, the pseudoplastic liquid turned into an elastic solid, as the result of a sol–gel phase transition of the nanogel aqueous dispersion during the raise of the temperature. Dynamic temperature ramp circle curves suggest that the sol–gel transition was reversible but with a clear hysteresis. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Role of fumed silica on ion conduction and rheology in nanocomposite polymeric electrolytes

The electrochemical, rheological, calorimetric, spectroscopic and morphological investigations have been used to examine poly(methyl methacrylate), PMMA based electrolytes dispersed with nano-sized fumed silica (SiO₂). The observed ionic conductivity was one of the highest and is of the order ∼mS/cm at ambient temperature which was studied as a function of concentration of fumed silica nano-particles. It was further found that the fumed silica acted as a passive filler and played a predominant role in controlling the rheological properties while ion transport properties were least effected. The differential calorimetry studies revealed single glass transition temperature pointing towards homogeneous nature of the composite polymeric electrolytes (CPEs). At an optimum concentration of fumed silica (2 wt%) the observed maximum conductivity and morphology was attributed to the presence of a strong network structure, while at a higher concentration the elastic behavior was more pronounced which impeded ion transport. This contention was supported by spectroscopic data.     

Mechanical and dynamic mechanical properties of natural rubber blended with waste rubber powder modified by both microwave and sol–gel method

Waste rubber powder (WRP) was modified by microwave, sol–gel method, and both microwave and sol–gel method, respectively. The mechanical and dynamic mechanical properties of natural rubber (NR)/modified WRP composite were investigated. The influence of bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) content on curing characteristics and mechanical properties of vulcanizate was also studied. The results showed that NR/WRP modified by both microwave and sol–gel method composite owned the best mechanical properties. Rubber processing analyzer was used to characterize the interaction between silica and rubber chains and the dispersion of silica. With increase of TESPT content, the Payne effect decreased. Scanning electron microscopy indicated the coherency and homogeneity of in situ generated silica filled vulcanizate. Dynamic mechanical analyzer showed that NR/WRP modified by both microwave and sol–gel method composite with 5 phr TESPT exhibited the lower tan δ at temperature range of 50–80°C, compared with composite without TESPT and the higher tan δ at temperature of 0°C, compared with the conventional modification of WRP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of the tetraethoxysilane-derived sol–gel process by rheological oscillation test and the effect of different synthetic parameters

The tetraethoxysilane (TEOS)-derived sol–gel process was systematically investigated by the rheological oscillation test and the effect of different synthetic parameters, including TEOS concentration, water content, base catalyst concentration and temperature, on the viscoelastic properties of the formed gel was analyzed. It is found that the rheological oscillation test provides an efficient and accurate way to determine the gelation time in the sol–gel process. The time at which the storage modulus and loss modulus intersect can be regarded as the gelation time in the sol–gel process and it matches well with the time observed with the naked eyes. Furthermore, both the increased TEOS and base catalyst concentration can be beneficial to the improvement of the gel elasticity, which could be related to the increased concentration of silica primary particles and its condensation reaction rate. However, the increased water content and temperature lead to a first increase and then a decrease in the elasticity of the gel. The proper molar ratio of TEOS to water is 0.67:4.01 and the suitable reaction temperature is 318 K in this study.     

Rheological behavior of concentrated silica suspension and its application to soft armor

The objective of this study is to develop an advanced stab and/or ballistic proof material composed of shear thickening fluid (STF) and Kevlar composite fabric. In this study, we prepared STF using sphere silica and fumed silica as silica particles and ethylene glycol and polyethylene glycol (PEG 200) as medium fluid, respectively. And the rheological properties of the STF were investigated under different conditions. Also, we impregnated Kevlar fabrics with the STF, and investigated the stab and ballistic resistances of the targets layered by the STF impregnated Kevlar fabrics. From the results, we observed that the STF significantly showed the reversible liquid–solid transition at a certain shear rate, and the STF treatment significantly improved the stab and ballistic resistance of Kevlar fabric. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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。     

Thermo‐mechanical behavior of poly(butylene terephthalate)/silica nanocomposites

In this work, experimental results about poly(butylene terephthalate) (PBT) based nanocomposites filled with various amounts of silica nanoparticles (NPs) are reported. Two different types of filler are used: silica gel NPs, produced through the Stöber method, and a commercial fumed silica, both coated by a PBT shell. Melt‐mixed samples have been thoroughly investigated by scanning and transmission electron microscopy, infrared Fourier transform spectroscopy (FTIR), thermal gravimetric analysis, differential scanning calorimetry, wide and small angle X‐ray diffraction, and dynamic mechanical analysis. A fine and very good dispersion of NPs into the polymeric matrix is revealed through the morphological analysis when Stöber NPs were used as filler with respect to systems including commercial fumed silica particles. This evidence, combined with matrix–filler interactions revealed by FTIR spectroscopy, justifies the enhancement of both storage modulus and glass transition temperature of the former samples in comparison with reference pristine PBT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46006.     

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     

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     

The effect of particle concentration on the rheology of polydimethylsiloxane filled with fumed silica

The effects of particle concentration on the shear-rate-dependent viscosity, stress relaxation, and stress growth function were investigated for various molecular weight polydimethylsiloxane (PDMS) fluids filled with colloidal fumed silica. Shear-rate-dependent stress relaxation was observed for all dispersions, and a significant stress growth overshoot was observed when the PDMS molecular weight was just greater than the entanglement molecular weight. The rate of stress—relaxation and the type of stress growth are primarily determined by the previous shear rate history and the PDMS molecular weight, while particle concentration only affects the quantitative details of the filled fluid's rheology. The observed effects of particle concentration are consistent with a molecular deformation process, where the silica particles interact via the entanglements of the polymer adsorbed on the surface of the fumed silica.     

二氧化硅表面处理及其对聚二甲基硅氧烷体系凝胶时间的影响

以六甲基二硅胺烷及六甲基环三硅氧烷(})为原料,通过干法对二氧化硅进行了表面处理,并研究了二氧化硅预处理温度对改性二氧化硅填充聚硅氧烷体系凝胶时间及力学性能的影响。利用红外光谱(F工IR)及X射线光电子能谱( XPS)研究了二氧化硅的组成,利用二氧化硅在溶剂中的分散情况研究了处理效果。结果表明:二氧化硅表面接枝上Me3Si一及一MezSi-,在有机溶剂中的溶解性变好;随着二氧化硅预处理温度的提高,二氧化硅填充聚硅氧烷体系凝胶时间缩短,力学性能呈下降趋势。随二氧化硅含量的增加,力学性能呈明显上升趋势。     

Fine-tuning of phase behavior of oxazoline copolymer-based organic–inorganic hybrids as solid-supported sol–gel materials

Silica-supported organic–inorganic polymer hybrids were synthesized via in situ sol–gel condensation of silica monomer in the presence of oxazoline copolymer. A stable copolymer of 2-ethyl-2-oxaoline and 2-isopropyl-2-oxazoline was prepared using methyl p-tosylate as the living polymerization initiator with molecular mass of 4200 g mol⁻¹. Lower critical solution temperature (LCST) of this copolymer was thermally found to be at 77 °C. The copolymer was mixed with tetramethoxysilane (TMOS) in different amounts (0.039:1 to 0.158:1 weight ratios) via in situ sol–gel condensation to produce organic–inorganic hybrids including thermosensitive copolymer. Tuning of these solid-supported materials showed sharp phase transitions changes in a temperature range from 42 to 58 °C, which was confirmed using differential scanning calorimetry. Enthalpy of the phase transition was also calculated using the area above the endothermic peak. A typical concave curve was obtained for LCST-type phase diagram suggesting the dependence of phase transition temperature on the concentration of the copolymer in the hybrid. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48163.     

Isoprene rubber filled with silica generated in situ

We modified synthetic isoprene rubber by means of the in situ generation of silica particles through the sol–gel process starting from tetraethoxysilane (TEOS) as an inorganic oxide precursor. Different reaction conditions were investigated with variations in the initial TEOS content, the reaction time of the sol–gel process, and the presence of a coupling/surfactant agent (octyltriethoxysilane). Organic–inorganic hybrid materials with a silica content up to 70 phr were obtained with the complete conversion of TEOS to silica for a long enough sol–gel reaction time. A very homogeneous dispersion of silica particles was observed in all cases together with a very good adhesion between the filler and matrix. The size of the in situ generated silica was controlled by the appropriate addition of octyltriethoxysilane. Swelling and extraction tests and dynamic mechanical analysis indicated that the vulcanization process of isoprene rubber was perturbed by the sol–gel process; this led to a slight decrease in the crosslinking degree. However, a significant reinforcing effect due to the presence of silica particles was observed for all of the investigated samples. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Interaction Between Fumed-Silica and Epoxidized Natural Rubber

Epoxidized natural rubber (ENR)/fumed silica vulcanizates were prepared by mechanical mixing method. Fumed silica content can affect mechanical properties of the composites, and ten parts per hundreds of rubber (phr) fumed silica lead to the best tensile strength. The interaction between ENR and fumed silica was characterized by Kraus equation, crosslink density (tested by NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and scanning electron microscope (SEM). The results showed that the dispersion of silica in ENR was better than in natural rubber (NR), hydrogen bond was produced between ENR and fumed-silica in ENR/silica blends, and glass transition temperature of ENR/silica vulcanizate was higher than pure ENR vulcanizate. TGA and DMA confirmed that there was intense interaction between ENR and silica.     

Effect of reaction parameters on the structure and properties of acrylic rubber/silica hybrid nanocomposites prepared by sol‐gel technique

The effects of a few reaction parameters, namely, type of solvents, tetraethoxysilane (TEOS)‐to‐water mole ratio, and temperature of gelation at constant concentration of TEOS (45 wt %) and pH of 1.5 were investigated for acrylic rubber/silica hybrid nanocomposites prepared by sol‐gel technique. Infrared spectroscopic studies indicated the maximum silica generation within the system when tetrahydrofuran was used as the solvent for the sol‐gel reaction. The distribution of the silica particles (average dimension 100 nm) forming a network type of structure within the composite was confirmed by scanning electron microscopic studies (SEM). The other solvents studied here produced a lower amount of silica because of either high polarity of the solvents (methyl ethyl ketone and dimethyl formamide) or their limited miscibility with water (for ethyl acetate). An increase in the proportion of water caused silica agglomeration. Energy dispersive X‐ray analysis (EDAX) silicon mapping also demonstrated the existence of agglomerated silica structures at high TEOS‐to‐water mole ratio (>2). Higher temperature for gelation of the composites caused the aggregation of silica particles. The uncured composites containing nanolevel (<90 nm) dispersion of silica particles demonstrated slightly higher storage modulus, lower value of tan δ_max, and higher glass transition temperature compared to the composites with silica particles of a larger dimension (>2 μm). Improvement in tensile strength and modulus was observed in the uncrosslinked as well as in the crosslinked state (cured by a mixed crosslinking system of hexamethylenediamine carbamate and ammonium benzoate). However, the extent of improvement in strength and modulus for the nanocomposites was higher (247 and 57%, respectively) compared to the microcomposite (150 and 27%, respectively) in the cured state. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1418–1429, 2005     

Thermoresponsive hydrogels from BSA esterified with low molecular weight PEG

Bovine serum albumin (BSA) and low molecular weight polyethylene glycol (PEG) were reacted in a single‐step reaction to synthesize translucent hydrogels with a sol–gel transition at temperatures between 37 and 40°C. Gelation occurred by aggregation of smaller assemblies of BSA–PEG precursors within minutes. The sol–gel transition concentration depended on the molecular weight of PEG only at temperatures below 35°C; above 45°C phase separation occurred and a precipitate formed. Microscopic examination showed the porous structure of the gels. At a fairly low grafting ratio, BSA preserved its native secondary and tertiary structure and maintained its capability for binding and enclosing small molecules. Drug delivery was assessed by a discontinuous method in vitro using 5‐fluorouracil. Degradation tests with trypsin confirmed that the hydrogels were biodegradable. This novel material holds promise for biomedical applications as potentially injectable drug delivery vehicle. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40946.