Influence of nanosilica particles on the cure and physical properties of an epoxy thermoset resin

Measurements are reported on the cure and physical properties of an epoxy resin created using a functionalised nanosilica filler. The filled bisphenol A epoxy (Nanopox A410) contained 40 wt% silica nanoparticles and was blended with two bisphenol A resins of molecular weights of 355 and 1075 g mol^?1, respectively. Cure was achieved using 3,3‐diaminodiphenylsulfone. The functionality of the mixture containing the epoxy nanoparticles was determined using NMR analysis. Cure times showed a progressive decrease with increasing silica level. Dynamic mechanical thermal analysis showed a decrease in the value of the glass transition temperature (T_g) with increasing silica level. T_g was further studied using differential scanning calorimetry. The ability of the nanosilica to create a stable network structure was demonstrated by the variation of the high‐temperature modulus with silica composition. Thermomechanical analysis carried out below and above T_g showed a progressive decrease in the expansion coefficients with increasing silica level, indicating the effectiveness of the functionalised silica nanoparticles in forming a network. The network formed during cure in the nano‐modified epoxy is unable to undergo the densification possible in the pure resin material and explains the observed lowering of T_g with increasing nanosilica content. Copyright © 2009 Society of Chemical Industry     

The effects of alumina and silica nanoparticles on the cure kinetics of bisphenol E cyanate ester

Nanoparticles can be used as fillers to reinforce polymers, forming nanocomposites with better thermomechanical properties than composites with macrosized fillers. Furthermore, the addition of nanoparticles may influence the curing behavior of the polymer matrix during processing. In this study, the effect of various loadings of alumina or silica nanoparticles on the cure kinetics of bisphenol E cyanate ester (BECy) is investigated by differential scanning calorimetry (DSC). Alumina nanoparticles are shown to have a catalytic effect on the cure of BECy. The greater catalytic effect of alumina nanoparticles, compared with silica, is attributed to the increased number of hydroxyl groups on the surface and the Lewis acidity of γ‐phase alumina. Kinetic parameters were obtained from dynamic DSC experiments. For an autocatalytic model of the cure process, the kinetic parameters obtained from the model suggest that the addition of alumina nanoparticles changed the cure reaction mechanism of BECy. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Modeling the curing kinetics for a modified bismaleimide resin using isothermal DSC

The kinetics of curing for a modified bismaleimide (BMI) resin was investigated to ascertain a suitable cure model for the material. The resin system used in this study was composed of 4,4′‐bismaleimidodiphenylmethane (BMIM) and 0,0′‐diallyl bisphenol A (DABPA, DABA). The BMIM was the base monomer and the DABPA was the modified agent. A series of isothermal DSC runs provided information about the kinetics of cure in the temperature range 170–220°C. Regardless of the different temperatures, the shape of the conversion curves was similar, and this modified BMI resin system underwent an nth‐order cure reaction. Kinetic parameters of this BMI resin system, including the reaction model, activation energy, and frequency factor, were calculated. From the experimental data, it was found that the cure kinetics of this resin system can be characterized by a first‐order kinetic model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3338–3342, 2004     

Thermally and mechanically enhanced epoxy resin‐silica hybrid materials containing primary amine‐modified silica nanoparticles

In this article, a series of hybrid materials consisted of epoxy resin matrix and well‐dispersed amino‐modified silica (denoted by AMS) nanoparticles were successfully prepared. First of all, the AMS nanoparticles were synthesized by performing the conventional acid‐catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS), which acts as acceded sol–gel precursor in the presence of 3‐aminopropyl trimethoxysilane (APTES), a silane coupling agent molecules. The as‐prepared AMS nanoparticles were then characterized by FTIR, ¹³C‐NMR, and ²⁹Si‐NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in situ thermal ring‐opening polymerization reactions of epoxy resin in the presence of as‐prepared AMS nanoparticles and raw silica (RS) particles (i.e., pristine silica). AMS nanoparticles were found to show better dispersion capability in the polymer matrices than that of RS particles based on the morphological observation of transmission electron microscopy (TEM) study. The better dispersion capability of AMS nanoparticles in hybrid materials was found to lead enhanced thermal, mechanical properties, reduced moisture absorption, and gas permeability based on the measurements of thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and gas permeability analysis (GPA), respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of organosilane coupling agents on microstructure and properties of nanosilica/epoxy composites

Three types of silane coupling agents, γ‐aminopropyltriethoxysilane, γ‐glycidoxypropyltrimethoxysilane, and γ‐methacryloxypropyltrimethoxysilane, were used as modifiers to modify the surface of the nanosilica, respectively, and the nanocomposites of the epoxy resin filled with nano‐sized silica modified by three silane coupling agents were prepared by physical blending. The properties of the modified silica nanoparticles were characterized by Fourier transform infrared spectrum and particle‐size analyzer. The microstructure, mechanical behavior, and heat resistant properties of the nanocomposites were investigated by transmission electron microscopy, scanning electron microscopy, thermo gravimetric analyses, differential thermal gravity, differential scanning calorimetry, and flexural tests. The results showed that these modifiers are combined to the surfaces of nanosilica by the covalent bonds, and they change the surface properties of nanosilica. The different structures of coupling agents have different effects on the dispersibility and stability of modified particles in the epoxy matrix. In comparison, the silica nanoparticles modified by γ‐glycidoxypropyltrimethoxysilane exhibit a good dispersivity. The nanocomposites with 4 wt% weight fraction nanosilica modified by γ‐glycidoxypropyltrimethoxysilane have higher thermal decomposing temperature and glass transition temperature than those of the other two composites with the same nanosilica contents, and they are raised by 43.8 and 8°C relative to the unmodified composites, respectively. The modified silica nanoparticles have good reinforcing and toughening effect on the epoxy matrix. The ultimate flexural strengths of the composites with 4 wt% nanoparticles modified by γ‐aminopropyltriethoxysilane, γ‐glycidoxypropyltrimethoxysilane, and γ‐methacryloxypropyltrimethoxysilane are increased by 10, 30, and 8% relative to the unmodified composites, respectively. The flexural fracture surfaces of modified composites present ductile fracture features. POLYM. COMPOS. 2012. © 2012 Society of Plastics Engineers     

A new extra situ sol–gel route to silica/epoxy (DGEBA) nanocomposite. A DTA study of imidazole cure kinetic

Silica nanoparticles were obtained through the Stöber method, from mixtures of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTS). The nanoparticles were dispersed in tetrahydrofuran (THF) and coupled to bisphenol A epoxy resin (DGEBA) through surface amino groups. After removing THF non-isothermal cure was performed at different heating rates (2–20°C/min), using imidazole (2–4 wt%) as curing agent. For the sake of comparison bare DGEBA epoxy polymers were also prepared with similar schedule A nanocomposite of well-dispersed silica nanoparticles (5 wt%) in a fully cured epoxy matrix was easily obtained. Lower cure kinetics were observed with silica addition. This was attributed to reduction of the imidazole volume concentration. Cure activation energy was not influenced by silica presence, whereas it changed with the imidazole content. Therefore, experimental results suggested that silica had only an indirect effect (the reduction of the imidazole molar concentration) on the epoxy matrix cure kinetics. Glass transformation temperatures, T _g, as high as 175°C were recorded. The nanocomposite glass transformation temperature depended on the heating rate of the cure process, the imidazole and silica content. T _g changes as high as 40°C were detected as a function of the heating rate. At higher imidazole content no differences in T _g values between bare polymer and the nanocomposite were observed. This suggests that a higher imidazole content assures a better interconnection between the compatibilizing epoxy shell around the nanoparticles and the epoxy matrix. The new proposed methodology is an easy route to engineer both nanocomposites structure and interfacial interactions, thus tailoring their properties.     

Silica nanoparticles modified with vinyltriethoxysilane and their copolymerization with N,N′‐bismaleimide‐4,4′‐diphenylmethane

The synthesis and characterization of the vinyltriethoxysilane‐modified silica nanoparticles were investigated. It was shown that the vinyltriethoxysilane molecules had been successfully grafted onto the silica nanoparticles. The native and silane‐modified silica dispersions in N‐methyl‐2‐pyrrolidone with the total solids contents within the range 1–6 wt % exhibited dramatically different flow behaviors. The polymerization of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) initiated by barbituric acid in the presence of the native or vinyltriethoxysilane‐modified silica nanoparticles were then carried out in γ‐butyrolactone (total solids content = 20%). The higher the level of silica, the better the thermal stability of the BMI/silane/silica composite particles. The silane‐modified silica particles significantly improved their dispersion capability within the continuous BMI oligomer matrix. Furthermore, the degree of dispersion of the vinyltriethoxysilane‐modified silica particles in the BMI oligomer matrix decreased with the weight percentage of silica based on total solids increased from 20 to 40 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: Sci 103: 3600–3608, 2007     

Rheology and dynamic mechanical analysis of bisphenol E cyanate ester/alumina nanocomposites

Alumina nanoparticles were functionalized with 3‐glycidyloxypropyl trimethoxysilane for compatibility with a low viscosity bisphenol E cyanate ester (BECy) resin. The functionalized alumina nanoparticles were characterized with Fourier transform infrared and thermogravimetric analysis. The alumina nanoparticles, which increase the viscosity of the BECy/alumina suspension, show a concurrent catalytic effect on the cure of the BECy resin, as indicated by reduced gelation times under isothermal cure conditions. Transmission electron microscopy micrographs reveal that most of the alumina nanoparticles are well dispersed in the BECy matrix, but a small fraction of particles formed agglomerates. The thermal‐mechanical properties of cured BECy composites reinforced with either bare alumina or functionalized alumina are evaluated by dynamic mechanical analysis. The storage modulus increases with both bare and functionalized alumina loading. Although the glass transition temperatures (T_g) of bare and functionalized alumina/BECy nanocomposites decrease with increasing filler content, the reduction in T_g is less severe when the alumina nanoparticles are first functionalized. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Compatibilization of immiscible blends of polypropylene and isosorbide containing copolyester with silica nanoparticles

In the present study, compatibilization of immiscible blends of polymers was investigated based on the Pickering emulsion concept with various mixing procedures. Silica nanoparticles were incorporated into poly (1,4-cyclohexanedimethylene isosorbide terephthalate) (PEICT)/isotactic polypropylene (iPP) blends. Localization of nanoparticles was effectively modified by varying mixing procedures. Relocation of hydrophilic silica occurred in a secondary mixing procedure with the PEICT, which has relatively high affinity when primarily mixed with iPP. The final location of the silica nanoparticles was confirmed by SEM images. SEM and an optical microscope were used to follow morphological change. By simply changing the mixing procedure, the hydrophilic silica nanoparticles were able to perform the role of a morphology modifier successfully without modifying the surface characteristics. The mechanical properties and crystallization behavior were also compared depending on the surface characteristics of the silica nanoparticles and their final localization.     

Cure behavior of epoxy resin/CdS/2,4-EMI nanocomposites investigated by dynamic torsional vibration method (DTVM)

Summary Epoxy resin/CdS nanocomposite was prepared by a novel method and its cure behavior was investigated by the HLX-II Resin Curemeter based on the dynamic torsional vibration method (DTVM). The non-equilibrium thermodynamic fluctuation theory, the Avrami equation and the Flory’s gelation theory have been used to analysis the cure behavior of the composite systems with different CdS and cure agent loadings at various temperatures. The results show that the addition of CdS nanoparticles reduces the gel time t_g, but has little effect on the mechanism of the cure reaction. The theoretical prediction is in good agreement with the experimental results. The Avrami exponent of n decreases a little when the temperature increases.     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Degree of conversion and mechanical properties studies of UDMA based materials for producing dental posts

Nanocomposites are a relatively new material in producing fiber re‐enforced dental posts. The mechanical properties of nanocomposites, which strongly associate with the resin matrix, nanoparticles, and the interface between inorganic fillers and organic matrix, play an important role in determining the quality of dental posts. This work was to investigate the effect of degree of conversion (DC) and silanization of fillers on the mechanical properties of nanocomposties. Experimental Urethane dimethacrylate (UDMA) based dental composites containing unsilanized and silanized SiO₂ filler and various amount of triethylene glycol dimethacrylate (TEGDMA) were prepared at the first step. The DC of composites at different ratios of UDMA/TEGDMA, cure temperature and cure time was measured by Fourier transform infrared spectroscopy. The results showed that DC increases with the increase of TEGDMA content in resin matrix. Both increase of the cure temperature and cure time can cause the increase of DC. The incorporation of fillers, either silanized, or unsilanized filler, caused the decrease of DC. However, composites reinforced with silanized silica showed relatively lower DC, and DC decreased with the increase of silanized filler content. The effect of incorporation of fillers on the mechanical properties was investigated. Silanized silica can effectively improved the flexural strength and flexural modulus of material, and these properties increased with the increase of silica content. Thermomechanical analysis (DMA) provided the similar results to the static property measurements. SEM images of fracture surfaces of specimens from flexural testing revealed the surface morphology is strongly related to the quality of interface between inorganic fillers and organic matrix. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Processability studies of silica‐thermoset polymer matrix nanocomposites

The aim of this study is to investigate the processability of silica‐thermoset polymer matrix nanocomposites in terms of dispersion of silica nanoparticles and their effect on curing. Two thermosetting resins were considered, an epoxy and a polyester resin, with 5% silica, although 1% silica was also used in preliminary studies in the polyester system. Various combinations of mechanical mixing and sonication were investigated for the dispersion of silica nanoparticles under different processing conditions and times in solvent‐free and solvent‐containing systems. It was found that the best dispersion route involved a solvent‐aided dispersion technique. Consequently, different procedures for the solvent removal were investigated. Optical microscopy and SEM were used to characterize the resulting nanocomposites. DSC and rheological DMTA tests demonstrated that the silica nanoparticles shorten the gel time and promote curing in these thermosetting systems. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Estimation of silica flocculation in SBR/BR compounds reinforced with different silica contents from their rheocurves

The rheocurves of silica-filled styrene–butadiene/polybutadiene rubber (SBR/BR) compounds containing 3-octadecyltriethoxy silane (OTES) and bis-[triethoxysilylpropyl]tetrasulfide (TESPT) were investigated to examine the effects of silica content and silanes on silica flocculation during mixing and cure. SBR/BR compounds without curatives were also prepared to infer the effect of cure on silica flocculation. The maximum torque of the compounds could be deconvoluted to individual source torques such as silica flocculation during mixing and cure, crosslinking of rubber, and coupling between rubber and silica by assuming the independence of silica flocculation from cure and coupling. Torque due to silica flocculation increased with the silica content of the SBR/BR compounds, but its effect was significantly reduced by the addition of OTES or TESPT. TESPT suppressed silica flocculation and facilitated coupling, thus yielding enhanced tensile properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48559.     

Effect of the chemical characteristics of mesoporous silica MCM‐41 on morphological,thermal, and rheological properties of composites based on polystyrene

Mesoporous silica nanoparticles (MCM‐41) with an average diameter of ～ 20 nm were synthesized by a sol‐gel method using binary surfactant system. Polystyrene (PS) composites containing mesoporous silica nanoparticles were prepared by in situ polymerization of styrene monomers. Similar in situ polymerized PS composites were prepared based on the modified silica functionalized with methyl and vinyl groups. The effects of silylation on thermal and rheological properties of the PS/silica composites are investigated. Of particular importance is that the in situ polymerization of monomers within the mesoporous silica may trap some polymer chains, if not all, thereby affording a greater physical interaction between polymer and the porous fillers, whereas the chemical modification of silica surface promotes the polymer–filler interaction, which in turn enhances the thermal stability of composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Layered silicate nanocomposites based on various high‐functionality epoxy resins: The influence of an organoclay on resin cure

The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p‐amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems.     

Properties and curing behavior of reactive blended allyl novolak with bismaleimide using dicumyl peroxide as a novel curing agent

For reducing the cure temperature and improving the thermal stability and mechanical properties, a thermosetting resin system composed of novolak and bismaleimide (BMI) was developed by reactive blending and using dicumyl peroxide (DCP) as a novel curing agent. Novolak was allylated and reacted with BMI to produce bismaleimide allylated novolak (BAN), and the effect of DCP on flexural, impact and heat distortion temperature of cured resin were investigated. On the basis of improved mechanical and thermal properties at 0.5% DCP contents, the curing behavior of DCP/BAN resin system was evaluated by DSC analysis. Ene, Diels‐Alder, homo‐polymerization and alternating copolymerization which occurred in DCP/BAN resin system were further verified using FTIR at sequential cure conditions from 140 to 200°C. Kissinger and Ozawa‐Flynn‐wall methods were used to optimize the process and curing reactions of DCP/BAN resin system. The results showed that the addition of 0.5% DCP in BAN reduced the curing temperature and time of the modified resin. For evaluating process ability of the modified system, composite samples using polyvinyl acetyl fiber were molded and tested for flexural properties. The resulting samples showed better flexural properties when compared with the composite made with neat BAN. The modified 0.5% DCP/BAN resin system with good mechanical properties and manufacturability can be used for making bulk molding compounds and fiber reinforced composites required in various commercial and aerospace applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41829.     

Improvement of Hardness and Wear Resistance of Glass Fiber-Reinforced Epoxy Composites by the Incorporation of Silica/Carbon Hybrid Nanofillers

The tribological performance of hybrid composite (epoxy reinforced with woven, nonwoven tissue glass fibers, silica and carbon black nanoparticles) was investigated. Two methods were used to ensure good dispersion of nanoparticles in epoxy resin which were ultrasonic processor and magnetic stirrer. The effect of silica and/or carbon black nanoparticle content on microindentation hardness and wear properties of the neat glass fiber-reinforced epoxy composites was investigated. The results from the wear test indicated that, under all applied loads, incorporation of silica and carbon black nanoparticles either single or combined significantly improved the wear resistance of neat glass fiber reinforced epoxy. A significant increase in hardness of the hybrid nanocomposite laminates was achieved. Analysis of variance was developed to study the optimal wear testing parameters on composite samples. The most significant parameter is the time, followed by nanoparticle (silica and carbon black) content.     

SiO2/聚氨酯纳米复合物的在位合成及其在环氧树脂中分散行为的研究

以水性阳离子聚氨酯纳米粒子为纳米微囊,利用原位水解法使正硅酸乙酯(TEOS)在囊内水解、聚合生成二氧化硅(SiO2)纳米粒子,从而合成出SiO2/聚氨酯纳米复合物的稳定水基乳液,实现纳米复合物中SiO2纳米粒子的均匀分散和良好的界面结合。并以此作为已表面改性的纳米粒子实现SiO2纳米粒子在环氧树脂的均匀分散。通过能谱扫描、透射电镜和乳液粒子粒径与分布等测试方式对含有环氧树脂的水性SiO2/聚氨酯纳米复合物进行测试。结果表明,SiO2/聚氨酯纳米复合物可以在环氧树脂中均匀分散且不团聚,同时也可促进环氧树脂在水中的分散。     

Studying the mechanical properties of composites made of Kenaf‐Nylon 66 fabric,silica nanoparticles,and epoxy resin

In this study, the effect of the relationship between yarn material and yarn count tex on the mechanical behavior of plainly woven hybrid fabrics impregnated with silica nanoparticles and epoxy resin has been investigated. First, various types of bicomponent and single‐component fabrics with plain weaves are prepared using kenaf and nylon‐66 yarns with yarn tex count of 334 and 427. To prepare the composite, silica nanoparticles with a particle size of 200 nm are mechanically mixed into glycol polyethylene with a molecular weight of 200 along with ethanol in proportions of 6:1. The weight percent of silica particles in the suspension has been selected as 60%. Using a round edge indenter, the concentrated indentation force test has been performed based on the 6264D standard to determine the strength of each fabric sample. Then, by impregnating the mentioned fabrics with polymer materials (silica nanoparticles and epoxy resin) and performing the concentrated force tests again, it is found that the hybrid fabrics with a yarn tex count of 427 and impregnated with polymer material enjoy the highest shear thickening properties. POLYM. COMPOS., 37:674–683, 2016. © 2014 Society of Plastics Engineers