Effect of surface structure of porous silica microballoons on dynamic mechanical properties of amine cured epoxy resin composites

Dynamic mechanical properties were studied for epoxy resin filled with porous silica microballoons with varying surface area, pore radius, pore volume and adsorbed water. The glass transition temperature (T_g) of the composites is 12–14°C lower than the T_g of the unfilled epoxy resin. This T_g depression is attributed to the preferential adsorption of curing agents on the porous silica microballoons. Tg of the composite increases with increase in the adsorbed water on fillers. The storage modulus has a distinct correlation with the Hg-surface area of silica microballoons, which corresponds to the sum of the surface area of pores with radii larger than about 4 nm. Tan δ_c tan δ_m decreases with increasing Hg-surface area.     

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.     

Super-Toughened Fumed-Silica-Reinforced Thiol-Epoxy Composites Containing Epoxide-Terminated Polydimethylsiloxanes

In response to the demand for high-performance materials, epoxy thermosetting and its composites are widely used in various industries. However, their poor toughness, resulting from the high crosslinking density of the epoxy network, must be improved to expand their application to the manufacturing of flexible products. In this study, ductile epoxy thermosetting was produced using thiol compounds with functionalities of 2 and 3 as curing agents. The mechanical properties of the epoxy were further enhanced by incorporating fumed silica into it. To increase the filler dispersion, epoxide-terminated polydimethylsiloxane was synthesized and used as a composite component. Thanks to the polysiloxane–silica interaction, the nanosilica was uniformly dispersed in the epoxy composites, and their mechanical properties improved with increasing fumed silica content up to 5 phr (parts per hundred parts of epoxy resin). The toughness and impact strength of the composite containing 5 phr nanosilica were 5.17 (±0.13) MJ/m³ and 69.8 (±1.3) KJ/m², respectively.     

Thermoreversible rheological responses of biscarbamates and tricarbamates in uncured epoxy composite pastes caused by their self‐assembly in an epoxy matrix

We investigated the rheological behaviors of diglycidyl ether of bisphenol A (epoxy resin) composite pastes with fumed SiO₂, biscarbamates, and tricarbamates with the same terminal alkyl chains of C₁₆, respectively. The rheological measurement results show that the rheological responses of both carbamates in the epoxy composite pastes were stronger than that of fumed silica at the same concentrations, especially at low concentrations, and the rheological behaviors of the epoxy composites with them were thermally reversible and concentration dependent. IR, thermal, differential scanning calorimetry, and polarized microscopic analyses demonstrated that their different excellent rheological responses in epoxy composite pastes came from their different self‐assemblies in the epoxy matrix, which were caused by the different intermolecular interactions, mainly including hydrogen‐bonding and van de Waals interactions, and the intermolecular interactions for carbamates were closely related to their molecular structures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46032.     

Optimization of Preparation Conditions for PDMS-Silica Composite Pervaporation Membranes Using Response Surface Methodology

In this article, response surface methodology was used to optimize the preparation conditions of fumed silica filled polydimethylsiloxane/cellulose acetate composite membranes. The silica loading, polydimethylsiloxane concentration, and NH₂-C₃H₆-Si(OC₂H₅)₃/silica weight ratio were considered as factors. Two regression equations, which described the effects of the three factors on the permeation flux and selectivity of the membranes, were derived from the results of 20 experiments by using a statistical software Design-Expert 7.1.4. The results revealed that the three factors had important effects on the permeation flux and the selectivity. The obtained regression equations were confirmed with another four groups of experiments. According to the regression equations, for the separation of an ethanol aqueous solution with the concentration of 10 wt%, the maximum selectivity of the membrane, 11.5 could be obtained at the feed temperature of 40°C, and the corresponding permeation flux was 197.3 g · m^?2 · h^?1. The preparation conditions for making the composite membrane with the above separation performances were: the silica loading was 5.21 wt%, the polydimethylsiloxane concentration was 13.36 wt%, and the NH₂-C₃H₆-Si(OC₂H₅)₃/silica weight ratio was 0.59.     

Frontal cationic curing of epoxy resins in the presence of defoaming or expanding compounds

Thermal frontal polymerization was carried out with trimethylol propane triglycidyl ether using two different BF₃‐amine complexes, B‐950 and B‐110 from Leepoxy, as initiators for cationic polymerization. The amounts of filler (kaolin or fumed silica), defoaming, or expansion agents were varied to study how the compositions affected the front velocity, expansion, and flexural modulus of the resulting epoxy resins. The polymer produced with B‐950 initiator showed higher modulus than the polymers produced with B‐110. Moreover, fumed silica created stronger materials than kaolin. The presence of BYK as a defoamer or an expansion agent such as the Expancel #80 was also able to affect significantly the mechanical properties. differential scanning calorimetry studies indicated that the conversion was complete and that kaolin and silica increased the rate of reaction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40339.     

Physical properties of a bisphenol-F epoxy containing a silica filler treated with silane coupling agents

A model epoxy system consisting of a diglycidyl ether of bisphenol-F epoxy resin, 1,4-butanediol, and cured with 4-methyl-2-phenylimidazole has been investigated. Thermal analysis indicated that 3 parts per hundred resin (phr) is the optimum amount of curing agent for this system. The influence of silane-treated amorphous fumed silica fillers on properties of the cured epoxy was also examined. Silica particles were treated with 3-aminopropyldiethoxymethylsilane (APDS) and3-aminopropyltriethoxysilane (APTS) coupling agents. No change in glass transition temperatures was observed with the addition of the filler (with or without coupling agents) to the epoxy. Addition of the filler led to a slight increase in the activation energy for the glass transition; however, no change in activation energy was observed when using the coupling agent. Addition of either coupling agent to the filler surface led to an increase in cooperativity. Fumed silica also did not significantly affect moisture diffusion properties, but a small decrease was observed in the moisture saturation mass with the addition of silica particles treated with APDS.     

Incorporation of silica network and modified graphene oxide into epoxy resin for improving thermal and anticorrosion properties

In this study, the silica network and functionalized graphene oxide (GO) were incorporated into the epoxy coating systems, which was aimed to improve the thermal property and corrosion resistance of epoxy coatings. First, tetraethyl orthosilicate (TEOS) oligomers and epoxy hybrid was fabricated through sol–gel method. Then the (3-aminopropyl) triethoxysilane (APTES) modified graphene oxide (FGO) was added into the epoxy hybrid composite to obtain anticorrosion coatings. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), Raman spectrum, and X-ray photoelectron spectrum were conducted to evaluate the structural information of GO and APTES modified GO nanosheets. The results indicated that the APTES successfully grafted onto the surface of GO sheets. Besides, TGA curves, electrochemical measurements and salt spray test were also carried out to characterize the thermal performance and corrosion resistance of GO based epoxy coatings. The TGA results revealed that the thermal performance of epoxy coating containing silica network and FGO nanofiller (ES/FGO) was significantly strengthened compared to pure epoxy. The initial degradation temperature of epoxy coating was increased from 300 to 343.7°C after incorporation of silica component and FGO. The EIS measurements demonstrated that the impedance modulus of ES/FGO was significantly higher than neat epoxy, which indicated that the corrosion resistance of epoxy was substantially strengthened after introduction of silica component and FGO. The corrosion rate and inhibition efficiency of epoxy composite coatings were also shifted from 1.237 × 10⁻⁷ mm/year and 76.6% (for neat epoxy) to 1.870 × 10⁻⁹ mm/year and 99.6% (for ES/FGO), respectively. The salt spray test also revealed that the silica and FGO can improve the corrosion resistance of epoxy coating. Additionally, the dispersion of GO sheets was also enhanced after the modification of APTES siloxane.     

PHYSICAL PROPERTIES OF A BISPHENOL-F EPOXY CONTAINING A SILICA FILLER TREATED WITH SILANE COUPLING AGENTS

A model epoxy system consisting of a diglycidyl ether of bisphenol-F epoxy resin, 1,4-butanediol, and cured with 4-methyl-2-phenylimidazole has been investigated. Thermal analysis indicated that 3 parts per hundred resin (phr) is the optimum amount of curing agent for this system. The influence of silane-treated amorphous fumed silica fillers on properties of the cured epoxy was also examined. Silica particles were treated with 3-aminopropyldiethoxymethylsilane (APDS) and3-aminopropyltriethoxysilane (APTS) coupling agents. No change in glass transition temperatures was observed with the addition of the filler (with or without coupling agents) to the epoxy. Addition of the filler led to a slight increase in the activation energy for the glass transition; however, no change in activation energy was observed when using the coupling agent. Addition of either coupling agent to the filler surface led to an increase in cooperativity. Fumed silica also did not significantly affect moisture diffusion properties, but a small decrease was observed in the moisture saturation mass with the addition of silica particles treated with APDS.     

Impact of nanoclay on physicomechanical and thermal analysis of polyvinyl alcohol/fumed silica/clay nanocomposites

Polyvinyl alcohol (PVA)/fumed silica/clay nanocomposites are prepared via solution intercalation by exploiting phase separation based on the bridging of particles by polymer chains. PVA/fumed silica/clay nanocomposites are characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, and thermogravimetric analysis. Mechanical properties are determined by universal testing machine. From FTIR results, it indicates that IR spectrum for PVA/fumed silica/clay nanocomposites, especially PVA/fumed silica/clay (1.30E) nanocomposites, is much broader than pure PVA and other clay nanocomposites. The better interfacial bonding between PVA/fumed silica/clay (1.30E) nanocomposites are reflected in the improvement of the mechanical properties as well as thermal stability. The surface area analysis result proves that the PVA/fumed silica/clay (1.30E) nanocomposites have higher surface area and pore volume with less pore size. With the addition of 1.30E clay to the composite system, the tensile strength and modulus had shown the highest values as well as higher activation energy for thermal decomposition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41843.     

The Preparation and Characterization of Silk/Gelatin Biocomposites

There is a growing interest in the use of composite materials. Silk fiber/gelatin biocomposites were fabricated using compression molding. The fiber content in the composite varied from 10–30 wt%. Composite containing 30 wt% silk showed the best mechanical properties. Tensile strength, tensile modulus, bending strength, bending modulus and impact strength, hardness of the 30% silk content composites were found 54 MPa, 0.95 GPa, 75 MPa and 0.43 GPa and 5.4 kJ/m², 95.5 Shore A, respectively. Water uptake properties at room temperature, accelerated weathering aging, irradiation, thermomechanical analysis, and degradation in soil were carried out in this experiment.     

Application of design of experiments,response surface methodology and partial least squares regression on nanocomposites synthesis

We present an integral chemometric treatment for characterization and synthesis of low-density poly(ethylene)/organically modified montmorillonite nanocomposites using direct melt processing method, complementing design of experiment (DOE), response surface methodology (RSM) and partial least squares (PLS) regression. A central composite circumscribed DOE was used to study the influence of four processing parameters—concentration of clay (Clay%), concentration of compatibilizer (Comp%), mixing temperature (T _mix) and mixing time (t _mix)—on six nanocomposites properties: interlayer distance, decomposition temperature, melting temperature, Young’s modulus, loss modulus and storage modulus. PLS-regression was used to simultaneously correlate parameters and responses. RSM was used to explore interactions among parameters and predict nanocomposite properties on the experimental region. The six responses were simultaneously PLS-modeled with R ² = 0.768 (p ≤ 0.05) being Clay% and Comp% the most important parameters and t _mix the least influential. Moreover, significant (p ≤ 0.05) and complex interactions among Clay%, Comp% and t _mix were found. A complementary interpretation of score and loading plots, coefficient plots, variable importance plots and response surface plots are explained to show how to find the optimal combination of processing parameters according the desired nanocomposite properties.     

Thermo-mechanical behaviors and moisture absorption of silica nanoparticle reinforcement in epoxy resins

An investigation of the thermo-mechanical behavior of silica nanoparticle reinforcement in two epoxy systems consisting of diglycidyl ether of bisphenol F (DGEBF) and cycloaliphatic epoxy resins was conducted. Silica nanoparticles with an average particle size of 20 nm were used. The mechanical and thermal properties, including coefficient of thermal expansion (CTE), modulus (E), thermal stability, fracture toughness (K_IC), and moisture absorption, were measured and compared against theoretical models. It was revealed that the thermal properties of the epoxy resins improved with silica nanoparticles, indicative of a lower CTE due to the much lower CTE of the fillers, and furthermore, DGEBF achieved even lower CTE than the cycloaliphatic system at the same wt.% filler content. Equally as important, the moduli of the epoxy systems were increased by the addition of the fillers due to the large surface contact created by the silica nanoparticles and the much higher modulus of the filler than the bulk polymer. In general, the measured values of CTE and modulus were in good agreement with the theoretical model predictions. With the Kerner and Halpin-Tsai models, however, a slight deviation was observed at high wt.% of fillers. The addition of silica nanoparticles resulted in an undesirable reduction of glass transition temperature (T_g) of approximately 20 °C for the DGEBF system, however, the T_g was found to increase and improve for the cycloaliphatic system with silica nanoparticles by approximately 16 °C. Furthermore, the thermal stability improved with addition of silica nanoparticles where the decomposition temperature (T_d) increased by 10 °C for the DGEBF system and the char yield significantly improved at 600 °C. The moisture absorption was also reduced for both DGEBF and cycloaliphatic epoxies with filler content. Lastly, the highest fracture toughness was achieved with approximately 20 wt.% and 15 wt.% of silica nanoparticles in DGEBF and cycloaliphatic epoxy resins, respectively.     

Transmittance and mechanical properties of PMMA-fumed silica composites

The transmittance, flexure strength, Young's modulus, and Vickers hardness of poly(methyl methacrylate) (PMMA), filled with fumed silica, was measured. Transmittance decreased with increasing content of filler. At 2 vol % filler content, composites had a higher transmittance with a lower surface area of fumed silica (larger primary particle size) because the lower surface area filler was better dispersed. At 4 vol % filler content, composites had a higher transmittance with a higher surface area fumed silica (smaller primary particle size). Flexure strength and Young's modulus of the composites was measured using three point bending. Addition of fumed silica led to a decrease of strength. Also, addition of fumed silica led to an increase of Young's modulus and Vickers hardness. © 1992 John Wiley & Sons, Inc.     

Long-range attractive forces extending from alumina nanofiber surface

Aluminum oxide-hydroxide nanofibers, 2 nm in diameter and approximately 250 nm long, are electroadhesively grafted onto glass microfibers, therefore forming a macroscopic assembly of alumina nanofibers on the second solid in highly organized matter. The assembly can be viewed as a straight cylinder with rough surface and charge density of approximately 0.08 C/m². This creates a significant electric field with negligible screening (ka ? 1) in the region close to the surface of the assemblies. This field attracts nano- and micron-size particles from as far as 0.3 mm in less than a few seconds, many orders of magnitude greater than the conventional Derjaguin–Landau–Verwey–Overbeek theory that predicts only nanometer-scale effects arising from the presence of the surface. The strong electric field on the surface is then able to retain particles such as micron-size powdered activated carbon as well as much smaller particles such as fumed silica nanoparticles of 10–15 nm in diameter, viruses, atomically thick sheets of graphene oxide, latex spheres, RNA, DNA, proteins, and dyes.     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

Fully reacted high strength geopolymer made with diatomite as a fumed silica alternative

Geopolymers are formed by mixing of aluminosilicate sources with alkaline meta-silicate solution at room temperature. In the current study, diatomite of Turkish origin was fully utilized as a fumed silica alternative for the preparation of geopolymer, having a typical formula of K₂O•Al₂O₃•4SiO₂•11H₂O. From XRD of this sample, a broad peak centered at 28° 2θ indicated the well-known formation of amorphous geopolymer, as well as a fully reacted microstructure of geopolymer as seen by scanning electron microscopy. Additionally, geopolymer having the same formula was made by using fumed silica, in order to compare with geopolymers prepared from diatomite. The Weibull modulus was calculated from four-point bending and compressive strength testing of both geopolymer composites. The use of diatomite as a fumed silica substitute in geopolymer production resulted in a very close flexure strength 9.2 (± 4.2 MPa) when compared to geopolymer made from fumed silica 10.2 (± 3.3 MPa). There was a significantly higher compressive strength 71 (± 13.9 MPa) and Weibull modulus (5.4), than comparable properties of geopolymer made from fumed silica, which had a compressive strength 54 (± 25.8 MPa) and Weibull modulus of 2.0. The discrepancy was attributed to some self-reinforcement of the geopolymer matrix due to unreacted diatomite.     

Graphite-Filled Polyethylene/Epoxy Blend for High-Conductivity Applications: The Immiscibility Edge

ABSTRACT

Polyethylene (PE)/epoxy blends filled with graphite were prepared and studied in this work. The in-plane and through-plane conductivities of the composites increased from 11.68 Scm^?1 to 73.11 Scm^?1 and 0.20 Scm^?1 to 4.12 Scm^?1, respectively, as graphite content increased from 30 to 80 wt%. Phase bonding effect of the compatibilizer and reinforcing effect of the filler enhanced the flexural modulus and strength of the composites up to 70 wt% filler content. The electrical conductivities attained by these composites being significantly higher than comparable composite formulations in literature show the edge of immiscible PE/epoxy blend for achieving high-conductivity polymer composites.     

The mechanisms and mechanics of the toughening of epoxy polymers modified with silica nanoparticles

The present paper considers the mechanical and fracture properties of four different epoxy polymers containing 0, 10 and 20 wt.% of well-dispersed silica nanoparticles. Firstly, it was found that, for any given epoxy polymer, their Young’s modulus steadily increased as the volume fraction, v_f, of the silica nanoparticles was increased. Modelling studies showed that the measured moduli of the different silica-nanoparticle filled epoxy polymers lay between upper-bound values set by the Halpin-Tsai and the Nielsen ‘no-slip’ models, and lower-bound values set by the Nielsen ‘slip’ model; with the last model being the more accurate at relatively high values of v_f. Secondly, the presence of silica nanoparticles always led to an increase in the toughness of the epoxy polymer. However, to what extent a given epoxy polymer could be so toughened was related to structure/property relationships which were governed by (a) the values of glass transition temperature, T_g, and molecular weight, M_c, between cross-links of the epoxy polymer, and (b) the adhesion acting at the silica nanoparticle/epoxy-polymer interface. Thirdly, the two toughening mechanisms which were operative in all the epoxy polymers containing silica nanoparticles were identified to be (a) localised shear bands initiated by the stress concentrations around the periphery of the silica nanoparticles, and (b) debonding of the silica nanoparticles followed by subsequent plastic void growth of the epoxy polymer. Finally, the toughening mechanisms have been quantitatively modelled and there was good agreement between the experimentally-measured values and the predicted values of the fracture energy, G_c, for all the epoxy polymers modified by the presence of silica nanoparticles. The modelling studies have emphasised the important roles of the stress versus strain behaviour of the epoxy polymer and the silica nanoparticle/epoxy-polymer interfacial adhesion in influencing the extent of the two toughening mechanisms, and hence the overall fracture energy, G_c, of the nanoparticle-filled polymers.     

Effect of Polyolefin Fibers and Supplementary Cementitious Materials on Corrosion Behavior of Cement-Based Composites

The present study evaluated the corrosion behavior of cement-based composites containing polyolefin fibers and supplementary cementitious materials by the impressed voltage corrosion test and the impressed current corrosion test. Material variables included the addition of polyolefin fiber (0, 0.4, 0.8 and 1.6 %), the dosage of ultrafine slag (40 and 60 %), the dosage of fumed silica (2 and 5 %) and mixed cementitious materials (35 % slag plus 5 % fumed silica and 55 % slag plus 5 % fumed silica). The test results indicate that a small amount of polyolefin fibers extends the time that a chlorine ion reaches to the surface of the rebar and decreases the corrosion rate of rebar. Nevertheless, the fiber is not very useful for the corrosion resistance of steel when the chlorine ions reach the surface of the rebar and corrode it. In addition, the inclusion of ultrafine slag or fumed silica can arrest the rebar corrosion and improve the compactness through pozzolanic reactivity and pore filling effects. According to the corrosion behavior and economy performance of the concrete structure, the combination of 55 % ultrafine slag, 5 % fumed silica and 0.8 % polyolefin fibers provides the best corrosion resistance of the tested cement-based composites.