Organic–inorganic microhybrid materials via a novel emulsion mixing method

Water‐dispersible urethane acrylate anionomers (UAAs) were prepared using anionic dimethylol propionic acid and silica emulsion was prepared by a sol–gel process using poly(vinyl pyrrolidone) and tetraethoxysilane. The above two emulsions were mixed, and UAA/silica composite gels were prepared. FTIR, X‐ray diffraction, SEM, and AFM were used to verify the structure and the inclusion of silica in the composite gels. To investigate the influence of silica in UAA gels on the physical properties, the tensile strength and elongation at break were measured, and the annealing effect was evaluated by the physical properties. As the silica content increased, the tensile strength of the composite gels increased; however, up to a certain amount of silica, phase separation was induced and physical properties were reduced. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1597–1605, 1999     

Preparation and characterization of acrylic latex/nano‐SiO2 composites

Acrylic/nano‐silica composite latexes were prepared by blending via high shear stirring (SS) or ball milling (BM) and in situ polymerization (IS). For comparison, composites filled with micro‐silica were also prepared. The mechanical and optical properties of the polymers formed by the composite latex filled with nano‐ or micro‐silica were investigated using an Instron testing machine, by dynamic mechanical analysis, ultraviolet–visible spectrophotometry and transmission electron micrography. The results showed that SS and BM methods could obtain better nanocomposite latex and polymers than the IS method, characterized by better dispersion of nanoparticles, higher tensile strength and T_g for SS and BM than for IS. The increase in absorbance and reduction in transmittance of UV (290–400 nm wavelength) were observed as nano‐silica content increased, whereas the UV absorbance or transmittance basically were kept unchanged for the composites filled with micro‐silica. © 2002 Society of Chemical Industry     

The influence of silane treatment on nylon 6/nano‐SiO2 in situ polymerization

Silane treatment has been applied to the preparation of nylon 6/nano‐SiO₂ composites through in situ polymerization. The influence of such treatment on the reactivity of silica, polymerization of nylon 6, and the mechanical properties of the achieved composites has been studied. Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA) of silicas isolated from the composites have shown that the conversion of surface silanol groups to amino and epoxy groups did not cause a significant change in the reactivity of silica and that the percentage of silica surface grafting was around 15% for all treated and untreated silicas. End group analysis has shown that the presence of silica (pretreated or not) in the composite system resulted in the decrease of the average molecular weight of the polymer matrix. However, dynamic mechanical analysis and mechanical tests revealed that treating silica with silane improved the strength and toughness of the composite materials, while untreated silica improved their strength at the expense of toughness. This can be attributed to the existence of the flexible interlayer introduced by silane treatment. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 827–834, 2002; DOI 10.1002/app.10349     

Studies on the preparation and mechanical properties of esthetic polymeric dental restoratives using silane treated silica microfiller via freeze‐drying

Polymeric dental restorative composites were prepared using silica filler where the surface was treated with γ‐methacryloxypropyltrimethoxysilane and decanted solvents by the freeze‐drying method. This treatment improved the miscibility of the filler with 2,2′‐bis‐[4‐(methacryloxy‐2‐hydrbxypropoxy)‐phenyl]‐propane/triethyl‐eneglycoldimethacrylate resin matrix and enhanced the esthetic properties of the composite. Diametral tensile strength (DTS) and flexural strength (FS) of the dental composite were measured, and the effect of drying methods in the surface treatment of filler on the mechanical properties of the composite was also investigated. Dental restorative composites prepared by the freeze‐drying method showed substantially higher DTS and FS values than those prepared by the conventional heat‐drying method. This resulted in increasing the loading percentage of filler in the resin matrix, and thereby, DTS values were increased dramatically. Dispersion of silica filler in the resin matrix and surface characteristics were examined by scanning electron microscopy. Various esthetic grades of dental composites were successfully prepared using iron oxide pigments, and its Hunter L. a. b. values of vita color‐shade were also investigated.     

Rice‐husk‐ash‐based silica as a filler for embedding composites in electronic devices

We carried out a feasibility study of the use of black rice husk ash (RHA) as a filler in epoxy resin for embedding material in electrical and electronic applications. We made a comparison by mixing RHA and two commercial fillers, fused and crystalline silica, with epoxy resin at weight fractions ranging from 20–60%. RHA‐filled epoxy resin had higher mixing viscosity, coefficient of thermal expansion, and water absorption percentage than commercial‐silica‐filled epoxy composite. However, the impact strength of all composites was comparable, but the tensile strength and elongation at break of silica‐filled epoxy were slightly superior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3013–3020, 2002     

Effect of different fillers on physical,mechanical, and optical properties of styrenic‐based thermoplastic elastomers

The effects of different fillers on physical, mechanical, and optical properties of styrenic‐based thermoplastic elastomers were investigated by experimental study. Poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] block copolymer (SEBS)‐based thermoplastic elastomer composites were prepared in a co‐rotating intermeshing twin‐screw extruder, using silica and calcite as filler materials with three different particle sizes. The loading ratios in the composites were varied. Hardness, density, tensile strength, tear strength, compression set, wear resistance, transmittance, and haze measurements were performed. Thermal properties and morphological structure were investigated by differential scanning calorimeter (DSC) and scanning electron microscopy (SEM), respectively. The results show that, an interaction between silica and the polymer matrix exists, whereas calcite does not show any interaction with the polymer. Therefore, it is concluded that, calcium carbonate can be used in the composite as filler for cost efficiency, whereas silica can be used as reinforcing material in SEBS‐based thermoplastic elastomer composites, when optical properties are also concerned. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Nanosilica‐reinforced Epoxidized natural rubber nanocomposites: Effect of Epoxidation level on morphological and mechanical properties

Epoxidized natural rubbers (ENRs) with three different epoxide contents (i.e., 20, 35, and 50 mol% indicated as ENR20, ENR35, and ENR50, respectively) were prepared. They were then reinforced with 3‐methyacryloxypropyl trimethoxysilane‐modified nanosilica (MPTS‐SiO₂). Influence of epoxide level in ENR molecules on morphological, mechanical, and dynamic mechanical properties of the ENR nanocomposites was investigated. The scanning electron microscopy results revealed larger agglomerates of SiO₂ were found in the ENR composites with higher epoxide content. Furthermore, the strength and moduli of the ENR nanocomposites increased with increasing epoxide content. However, the optimal tensile strength and elongation at break were observed in the nanocomposites with the intermediate level of epoxide contents. The correlation between the strength properties and the interfacial silica‐matrix adhesion indicated that the maximum interfacial adhesion of the nanocomposites was observed in the nanocomposite with ENR35. Also, DMA results indicated stronger interaction between ENR35 and MPTS‐SiO₂ due to higher storage modulus. POLYM. COMPOS., 38:1151–1157, 2017. © 2015 Society of Plastics Engineers     

Polypropylene–intumescent flame‐retardant composites based on meleated polypropylene as a coupling agent

The phosphoric acid‐pentaerythritol‐melamine copolymer, which is composed of three main components of intumescent flame retardant (IFR) and has optimal intumescent degree, was selected as IFR. The influence of meleated polypropylene (PP‐g‐MAH) on the properties and compatibility of IFR polypropylene (PP) composites were studied. The results obtained from mechanical tests, rheological behavior of composites, and scanning electron microscope showed that PP‐g‐MAH was a true coupling agent for IFR/PP blends and did not change the necessary flame retardancy. The cocrystallization between bulk PP and PP segments of PP‐g‐MAH was also proven by WAXD analysis. Flow test showed that the flow behaviors of composites in the melt are those of a pseudoplastic and it is very small for PP‐g‐MAH affecting rheological behavior of the PP/IFR composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 257–262, 2002     

Mechanical properties of high density packed silica/poly(vinyl chloride) composites

This article focuses on the preparation and mechanical properties of silica/poly(vinyl chloride) (PVC) composites enriched with 60% mass ratio of 130 nm and 30 nm silica sphere fillers. Silica particles were pre‐treated with silane, IO₇ T₇(OH)₃ (trisilanol isooctyl polyhedral‐oligomeric silsesquioxane) to prevent agglomeration. The dispersion and interfacial compatibility of silica particles in a PVC matrix were investigated by scanning electron microscopy. The composite mechanical properties were characterized by tensile test, revealing improved Young modulus and tensile strength. Compared to pure PVC, the stiffness of 30 nm and 130 nm silica/PVC composites is on average increased by 30–40%, respectively. Similar trend was observed for the composite tensile strength on the change of the silica size. In contrast, elongation at break decreased for both composites compared to pure PVC, for 15% in 30 nm and for 30% in 130 nm silica/PVC composite. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Influence of radiation structures on positive‐temperature‐coefficient and negative‐temperature‐coefficient effects of irradiated low‐density polyethylene/carbon black composites

The electrical‐resistivity/temperature behaviors of low‐density polyethylene (LDPE)/carbon black (CB) composites irradiated with ⁶⁰Co γ rays were studied. The experimental results showed that the irradiated composites could be separated into insoluble crosslinking networks with CB (gel) and soluble components (sol) by solvent‐extraction techniques. When the sol of an irradiated LDPE/CB composite was extracted, the electrical conductivity of the system increased. The positive‐temperature‐coefficient (PTC) and negative‐temperature‐coefficient (NTC) intensities of the gels of the irradiated composites became extremely small and independent of the radiation dose. The sols and gels of the irradiated LDPE/CB composites, which had different thermal behaviors, played important roles in the appearances of the PTC and NTC effects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 700–704, 2005     

Nanosilica as dry bonding system component and as reinforcement in short nylon‐6 fiber/natural rubber composite

Nanoscale silica was synthesized by acid hydrolysis of sodium silicate using dilute hydrochloric acid under controlled conditions. The synthesized silica was characterized by SEM, BET adsorption, and XRD. The particle size of silica was calculated to be 13 nm from the XRD results and the surface area was found to be 295 m²/g by BET method. This synthesized nanosilica was used in place of conventional silica in HRH (hexamethylenetetramine, resorcinol and silica) bonding system for natural rubber/Nylon‐6 short fiber composite. Nanosilica was also used as reinforcing filler in natural rubber/Nylon‐6 short fiber hybrid composite. Mechanical, thermal, and dynamic mechanical properties of the composites were evaluated. The introduction of the nanosilica in hybrid composites improved the tensile strength, modulus, and tear strength through improved interaction with the matrix which is facilitated by the higher surface area. Abrasion loss and hardness were also better for the nanosilica composites. Resilience and compression set were adversely affected. The hybrid composites showed anisotropy in mechanical properties. Peak rate of thermal decomposition decreased and temperature of initiation of thermal degradation increased with silica content, indicating improved thermal stability of the hybrid composites. The storage modulus and loss modulus showed two‐stage dependence on frequency at higher fiber loading. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties and structure of poly(vinyl alcohol)/silica composites

The relationships between the properties and structure are discussed for poly(vinyl alcohol)(PVA)/silica composites prepared through the sol‐gel process. The composites became stiff and brittle with increasing the silica content. The properties of the composites were changed drastically at around the composition of PVA/silica = 70/30 wt %. For example, there was no large change in the Young's modulus above 30 wt % of silica content (Pure PVA: 31.8 MPa, silica 30%: 52.6 MPa, silica 50%: 55.2 MPa). Consequently, it was considered that the three‐dimensional network structure of silica could be formed in the composite with more than 30 wt % of silica in PVA. From this behavior, it could be considered that the crystal growth of PVA was remarkably inhibited by silica network. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 133–138, 1999     

Effects of silica surface treatment on the impregnation process of silica fiber/phenolics composites

Effects of silica surface treatment on the impregnation process of silica fiber/phenolics composites were studied. Micro‐Wilhelmy method was used to evaluate the surface characterization of silanized silica fibers. The interlaminar shear strength (ILSS) measurements and the void contents of the silica fiber/phenolics composites were also performed. The interactions occurring between silica fiber and the components of phenolic resin solution can affect the contact angle between silica fiber and phenolic solution and the dynamic adsorption behavior of phenolic resin onto silica fiber. There are competitive adsorptions to different extent for phenolic resin and solvent onto silica fibers. Silica fibers as reinforcement treated by silane‐coupling agent, such as γ‐aminopropyl‐triethoxysilane, γ‐glycidoxypropyl‐trimethoxysilane, trimethylchlorosilane, and γ‐methacryloxypropyl‐trimethoxysilane, influence the mechanical interfacial properties of silica fiber/phenolics composites and the uniformity of resin distribution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis of modified silica spheres used for the preparation of dual ultraviolet‐ and thermo‐cured epoxyacrylate/silica composites

To investigate the interfacial effect on properties of epoxyacrylate–silica composites, submicron‐sized silica spheres were synthesized by sol–gel reaction under a basic environment and their surfaces were endowed with vinyl functional groups by further modification with 3‐methacryloxypropyl trimethoxy silane. The pure silica (PS) and the modified silica (MPS) spheres were characterized by Fourier transform infrared, ²⁹Si‐ and ¹³C‐nuclear magnetic resonance (NMR), scanning electron microscope (SEM), and particle size analyzer. The silica spheres were then added to the presynthesized difunctional epoxyacrylate resin with one vinyl group and one epoxide group at each end, in addition to the photo‐ and thermo‐curing agents. After cure, thermal and mechanical properties of the obtained epoxyacrylate–silica composites were measured and compared. Tensile mechanical properties including initial modulus, ultimate tensile strength, and elongation at break, as well as the fracture energy of the epoxyacrylate–silica composite were all increased by increasing the content of silica spheres. Moreover, the composites filled with MPS had stronger interfacial strength between silica sphere and matrix than those with PS and thus exhibited an additional increase of tensile mechanical properties and fracture toughness. The increase of fracture toughness was owing to the crack deflection and particle–matrix debonding as evidenced by SEM pictures on the fracture surface. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Morphology and thermo‐mechanical properties of compatibilized polyimide‐silica nanocomposites

Polyimide‐silica nanocomposites have been prepared from an aromatic polyamic acid derived from pyromellitic dianhydride and oxydianiline and a silica network using the sol‐gel reaction. Compatibilization of the two components was achieved by modifying the silica network with imide linkages. Morphology, thermal, and mechanical properties of these composite materials were studied as a function of silica content and compared with the one in which reinforcement of the polyimide was achieved using a pure silica network. There was considerable reduction in the silica particle size with more homogeneous distribution in the matrix when imide spacer groups were introduced in the silica network. The tan δ spectra obtained from dynamic thermal mechanical analysis shows a large increase in the glass transition temperature with increasing silica content for the compatibilized system in contrast to the un‐compatibilized one. Mechanical properties of the polyimide composites improved due to better interaction between the organic and inorganic phases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2521–2531, 2005     

Polypropylene/silica micro‐ and nanocomposites modified with poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)

The effects of different silica loadings and elastomeric content on interfacial properties, morphology and mechanical properties of polypropylene/silica 96/4 composites modified with 5, 10, 15, and 20 vol % of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) SEBS added to total composite volume were investigated. Four silica fillers differing in size (nano‐ vs. micro‐) and in surface properties (untreated vs. treated) were chosen as fillers. Elastomer SEBS was added as impact modifier and compatibilizer at the same time. The morphology of ternary polymer composites revealed by light and scanning electron microscopies was compared with morphology predicted models based on interfacial properties. The results indicated that general morphology of composite systems was determined primarily by interfacial properties, whereas the spherulitic morphology of polypropylene matrix was a result of two competitive effects: nucleation effect of filler and solidification effect of elastomer. Tensile and impact strength properties were mainly influenced by combined competetive effects of stiff filler and tough SEBS elastomer. Spherulitic morphology of polypropylene matrix might affect some mechanical properties additionally. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41486.     

The viscoelastic properties of modified thermoplastic impregnated multiaxial aramid fabrics

This study reports the manufacture of new fabric forms from the preparation of hybrid laminated multiaxial composites with enhanced thermo‐mechanical properties. Thermal and dynamic mechanical analysis of polymer matrix films and fabricated hybrid composites were used to determine the optimal material composition and reinforcement content for composites with improved viscoelastic properties. The introduction of 5 wt% silica nanoparticles in a composite of p‐aramid–poly(vinyl butyral) led to significant improvements in the mechanical properties, and the addition of silane coupling agents yielded maximal values of the storage modulus for hybrid nanocomposites. The introduction of silane led to a better dispersion and deagglomeration of SiO₂ particles, and to the formation of chemical bonds between organic and inorganic constituents, or p‐aramid–poly(vinyl butyral) composites. In this way, the mobility of macromolecules was reduced, which can be seen from the decreasing value of damping factor for the p‐aramid–poly(vinyl butyral) composite. Analysis of the glass transition temperature of the composite with amino‐functionalized silica nanoparticles revealed improved thermal stability in addition to the aforementioned mechanical properties of the tested materials. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Methylene blue adsorption from aqueous solutions to flexible poly(vinyl chloride) silica composites

Methylene blue (MB) adsorption studies were performed with poly(vinyl chloride)‐(dioctyl phthalate)‐silica composites, which were obtained by using plastisol‐plastigel technology. The films were flexible, having elastic modulus of 1.0–1.5 GPa. Diminishing MB concentration in the aqueous phase was followed as the adsorption process advanced by using visible spectroscopy. Contributions of the individual components of the composites to adsorption were also investigated. Although the MB adsorption capacity was extensively high for silica, it was moderate for the composite, most likely owing to the occlusion of pores of silica by plasticizer to some extent. The improvement of MB adsorption capacity of the composites as the silica ratio increased was explicitly deduced from the optical microscopy photographs. The diffusion coefficients of MB through the composites were 5 × 10^?13, 6 × 10^?13, and 3 × 10^?13 m² s^?1 with regression coefficients of 0.73, 0.89, and 0.88 for 0, 2, and 16% silica‐containing composites, respectively. Because of the slow diffusion of MB in poly(vinyl chloride)‐silica composites, using them as dynamic column adsorbent was not practical. However, these versatile plastics can be used as plastic labels, colored clothing, leather substitutes, antimicrobial medical devices, and laser printable surfaces. J. VINYL ADDIT. TECHNOL., 21:42–50, 2015. © 2014 Society of Plastics Engineers     

Hybridized reinforcement of natural rubber with silane‐modified short cellulose fibers and silica

Natural‐rubber‐based hybrid composites were prepared by the mixture of short cellulose fibers and silica of different relative contents with a 20‐phr filler loading with a laboratory two‐roll mill. The processability and tensile properties of the hybrid composites were analyzed. The tensile modulus improved, but the tensile strength and elongation at break decreased with increasing cellulose fiber content. The scorch safety improved with the addition of 5‐phr cellulose fiber in the composites. The Mooney viscosity significantly decreased with increasing cellulose fiber content. To modify the surface properties of the cellulose fiber and silica fillers, a silane coupling agent [bis(triethoxysilylpropyl)tetrasulfide, or Si69] was used. The effects of Si69 treatment on the processing and tensile properties of the hybrid composites were assessed. We found that the silane treatment of both fillers had significant benefits on the processability but little benefit on the rubber reinforcement. The strength of the treated hybrid composite was comparable to that of silica‐reinforced natural rubber. Furthermore, to investigate the filler surface modification and to determine the mixing effects, infrared spectroscopic and various microscopic techniques, respectively, were used. From these results, we concluded that the fillers were better dispersed in the composites, and the compatibility of the fillers and natural rubber increased with silane treatment. In conclusion, the hybridized use of short cellulose fibers from a renewable resource and silica with Si69 presented in this article offers practical benefits for the production of rubber‐based composites having greater processability and more environmental compatibility than conventional silica‐filler‐reinforced rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tuning the interlaminar shear strength and thermo-mechanical properties of glass fiber composites by incorporation of (3-mercaptopropyl) trimethoxysilane-functionalized carbon black

The incorporation of functionalized nanoscale fillers into traditional glass fiber/unsaturated polyester (GF/UPE) composites provides a more robust mechanical attributes. The current study demonstrates the potential of 3-mercaptopropyl trimethoxysilane (MPTS)-functionalized carbon black (f-CB) for enhancing the thermo-mechanical properties of GF composites. The composites infused with 1, 3 and 5 wt% of pristine and MPTS-functionalized CB were fabricated by hand lay-up and hot press processing. Tensile testing, interlaminar shear strength (ILSS) testing and dynamic mechanical analysis were used to evaluate the performance of nanocomposites. Fourier transform infrared spectroscopy validated the MPTS functionalization of CB. Pristine CB-loaded nanocomposites exhibited marginal improvement in ultimate tensile strength (UTS), ILSS and thermo-mechanical properties. However, with the addition of f-CB, the improvement in all the studied properties was more substantial. The inclusion of 5 wt% f-CB increased the elastic modulus and UTS by 16 and 22%, respectively, whereas the ILSS was enhanced by 36%, in comparison to the neat GF composite. The scanning electron microscope analysis of fractured ILSS samples revealed better fiber-matrix adhesion and compatibility in f-CB-loaded nanocomposites. At the same filler weight percentage, the storage modulus at 25 °C was ~ 19% higher than that of neat composite. The f-CB inclusion resulted in increment of T _g by ~ 13 °C over the T _g of neat GF/UPE composite (~ 109 °C). These improvements were due to the chemical connection of f-CB to the UPE matrix and GF surface. With such improvements in thermal and mechanical properties, these nanocomposites can replace the conventional GF composites with prominent improvements in performance.