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     

Cationic cure of epoxy resins via benzylsulfonium salts covalently bound to glass surfaces

The cure behavior of epoxy resins in the presence of glass fillers was investigated using differential scanning calorimetry (DSC). A novel benzylsulfonium salt capable of covalently bonding to glass surfaces through a trialkoxysilane moiety were synthesized. Coupling of the salt to silica gel (as a model glass surface), characterization of the bound material, and its ability to initiate the cationic cure of DGEBA resins were investigated. The bound material was characterized by solid-state ¹³C and ²⁹Si CP/MAS NMR, FTIR, and TGA. The sulfonium salt was coupled with silica as the Br anion form because of the insolubility of the SbF₆ salt. After anion exchange, silica-bound salt with SbF₆ counterion was shown to initiate cure of epoxy resins but only at temperatures much higher than with an analogous unbound salt (>200°C and <100°C, respectively). The inability to get complete anion exchange of Br anions for SbF₆ (necessary for cationic initiation activity) after coupling allowed formation of excess tetrahydrothiophene (THT) during heating through decomposition of the residual Br salt, causing temporary termination and a large delay in cure. The temporary termination mechanism involved reaction of THT and the active oxonium ion to give a primary alkylsulfonium salt. In addition, it was discovered that the silica gel itself had an inhibiting effect on the cure of epoxy resins cured with unbound initiator, giving low T_g materials. This was due to inherent surface surface interaction with the salt and not to chemical reaction with the surface or with a physically adsorbed contaminant (such as water). The degree of inhibition increased with increasing filler content. Low surface area glass beads also inhibited cure, although surface modification of the glass beads with bound benzylsulfonium salt (SbF₆ form) improved cure significantly, reducing onset delay and giving high T_g materials. The degree of delay was inversely dependent on the amount of silane coupled to the surface and varied with counterion.     

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.     

Novel nanocomposite of epoxy resin by introduced reactive and nanoporous material

A reactive and nanoporous particle (OG) was introduced to UV-cured epoxy resin to form great low D _k material for electronic industrial. We expected the porous cage of OG to decrease the dielectric constant of UV-cured epoxy resin and multiple reactive functional groups (oxirane ring) of OG reacted with photoinitiator to increase the curing density of UV-cured epoxy resin. The glass transition temperatures (T _g) of epoxy increases with the increase of the OG content up to 10 phr due to the increase of crosslinking density. Excessive aggregation at highest OG content of 15 phr results in the reduced crosslinking density and T _g. The char yield of the composite increases with increase of OG content because stable Si and SiO₂ are formed after thermal decomposition. The presence of OG results in the higher porosity and thus the lower dielectric constant.     

A Study of the Interphase Region in Carbon Fibre/Epoxy Composites using Dynamic Mechanical Thermal Analysis

We have examined the effect of fibre addition on the glass transition temperature (T _g ) of two epoxy resin systems (an amine cured and an anhydride cured epoxy system) using dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The presence of fibres changes the glass transition temperature (T _g ) of an anhydride cured epoxy resin but does not affect that of an amine cured epoxy. The data suggest that two counteracting mechanisms are responsible for these changes: firstly, the presence of fibres causes a restriction of the molecular motion in the resin system, and secondly, the presence of carboxyi and keto-enol groups on the fibre surface inhibit curing of the resin close to the fibre, i.e. in the interphase region. The former increases the T _g and is a long range effect whereas the latter decreases the T _g and is a localised phenomenon. Changes in the dynamic properties of the interphase region are only detected when the samples are loaded in the longitudinal direction and not in the transverse direction where bulk matrix properties dominate. Sizing the fibres before their incorporation into the epoxy resin eliminates the variation in interfacial properties arising from differences in fibre surface chemistry.     

Study of epoxy resin—filler interaction

A bisphenol-type epoxy resin cured with phthalic anhydride was filled with three types of SiO₂ (untreated, silanized and smaller particle size), CaCO₃, dolomite and Al₂O₃. Also, the concentration of silica was varied. Interaction of filler and resin was estimated by measuring the glass transition temperature (T_g) by different methods. Electron microscopy and x-ray diffraction were used to study the structure of the boundary layer and the bulk polymer. It was found that silica forms strong bonds with the resin and that basic fillers (CaCO₃, Al₂O₃) probably affect the crosslinking process with anhydride as hardener causing lowering of T_g.     

Mild processing and characterization of silica epoxy hybrid nanocomposite

Previous research has shown that the inclusion of the spherical silica (SiO₂) nanoparticles into epoxy resin can achieve simultaneous improvement of fracture toughness and modulus. However, the glass transition temperature of the nanocomposite was significantly decreased when loading the nanosilica was higher than 5 wt.%. This perhaps was caused by utilization of the ultrasonication probe in the processing of these materials. In this paper, milder processing procedures were applied to make spherical silica epoxy nanocomposites while investigating if the homogeneous dispersion and morphology of the individual silica nanoparticle dispersed in the epoxy matrix could still be achieved. The results show that even at high loading of the silica nanoparticle, such as 30 wt.% silica, the perfect morphology of the nanocomposite could still be achieved with these milder processing conditions which indicates that ultrasonication is not needed. With the use of milder processing conditions, the glass transition temperature of the nanocomposite of 5 wt.% silica loading did not change, and the drop in the T_g was minimal for silica loading up to 15%, but some effects of self-polymerization of the epoxy were noted on T_g up to 30 wt.% loading of silica. Thermal analysis and flammability testing of the resulting materials suggest that nanosilica has only an inert filler effect (dilution of fuel) on flammability reduction and char yield increase, not a synergistic decrease in heat release as is often observed for clays and carbon nanotubes/nanofibers. So the mild and easy processing procedure only achieved uniform nanoscale morphology with excellent dispersion in the final nanocomposite, but also the effect on the change in the T_g can be minimized as nanosilica loading was increased.     

Reinforcing effect of amine-functionalized and carboxylated porous graphene on toughness,thermal stability,and electrical conductivity of epoxy-based nanocomposites

Epoxy-based nanocomposites reinforced with nonfunctionalized porous graphene (NPG), carboxylated porous graphene (CNPG), and amine-functionalized porous graphene (ANPG) were investigated with regard to mechanical properties, thermal stability, and electrical conductivity. Nanomaterials were added to the epoxy matrix in varying contents of 0.5, 1, and 2 wt %. Generally, mechanical properties were improved as a result of introducing nanomaterials into the epoxy resin. However, the amelioration of toughness was only observed in functionalized NPGs/epoxy nanocomposites. Field emission scanning electron microscopy images showed that functionalized nanomaterials induced a rougher fracture surface compared to the neat epoxy. Dynamic mechanical analysis along with differential scanning calorimetry confirmed an increment in the glass-transition temperature (T_g) of the reinforced nanocomposites. Also, they proved that functionalization made the epoxy network tougher and more flexible. The electrical conductivity and thermal stability of the epoxy resin were also improved when loaded with nanomaterials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47475.     

Effect of silica nanoparticle size on toughening mechanisms of filled epoxy

The addition of silica nanoparticles (23 nm, 74 nm, and 170 nm) to a lightly crosslinked, model epoxy resin, was studied. The effect of silica nanoparticle content and particle size on glass transition temperature (T_g), coefficient of thermal expansion (CTE), Young's modulus (E), yield stress (σ), fracture energy (G_IC) and fracture toughness (K_IC), were investigated. The toughening mechanisms were determined using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and transmission optical microscopy (TOM). The experimental results revealed that the addition of silica nanoparticles did not have a significant effect on T_g or the yield stress of epoxy resin, i.e. the yield stress and T_g remained constant regardless of silica nanoparticle size. As expected, the addition of silica nanoparticles had a significant impact on CTE, modulus and fracture toughness. The CTE values of nanosilica-filled epoxies were found to decrease with increasing silica nanoparticle content, which can be attributed to the much lower CTE of the silica nanoparticles. Interestingly, the decreases in CTE showed strong particle size dependence. The Young's modulus was also found to significantly improve with addition of silica nanoparticles and increase with increasing filler content. However, the particle size did not exhibit any effect on the Young's modulus. Finally, the fracture toughness and fracture energy showed significant improvements with the addition of silica nanoparticles, and increased with increasing filler content. The effect of particle size on fracture toughness was negligible. Observation of the fracture surfaces using SEM and TOM showed evidence of debonding of silica nanoparticles, matrix void growth, and matrix shear banding, which are credited for the increases in toughness for nanosilica-filled epoxy systems. Shear banding mechanism was the dominant mechanism while the particle debonding and plastic void growth were the minor mechanisms.     

Epoxy composites reinforced by different size silica nanoparticles

Three series of epoxy/SiO₂ composites, containing 0.3–7 wt % nanosized SiO₂ with different specific surface area, were prepared by solution blending. The resulting composites exhibit the higher glass transition temperature (T_g) than that of pure epoxy. The T_g of composite showed a maximum increment of 35.3°C by the addition of 7 wt % A300. The trade name of A300 is Aerosil 300. It is one of the fumed silica nanoparticles products of Degussa. The decomposition temperatures (T_d) of composites were always higher than that of pure epoxy and showed a maximum increment of 20.8°C by the addition of 5 wt % A300. The light transmittance of composites was as a function of the SiO₂ content and size. The water permeability of composites decreased with increasing SiO₂ content and the 7 wt % A300 composite exhibits a maximum decrement percentage of 35.6%. The T_g, T_d, storage modulus, and water‐vapor barrier property are as a function of the SiO₂ content and size. These properties increased as the content of SiO₂ increased. The finer SiO₂ are more effective in increasing the T_g, T_d, and water‐vapor barrier property. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Moisture absorption behavior of epoxies and their S2 glass composites

The influence of moisture exposure on the behavior of three toughened epoxy–amine systems (scrimp resins SC11, SC15, and SC79, Applied Poleramic, Inc., Benicia, CA) was investigated. Neat resin samples were conditioned by immersion in distilled water at 71°C and in an environmental chamber at 85% relative humidity and 87.8°C until saturation. The equilibrium weight gain ranged from 1.8 to 3.8% for the resins. The long-chain, low-crosslink-density epoxy system (SC11) absorbed the highest amount of water and was saturated first, and it was followed by the medium-crosslink-density (SC15) and high-crosslink-density materials (SC79). The moisture diffusivity decreased with the increasing crosslink density of the resins. The percentage reduction of the glass-transition temperature (T_g) at equilibrium moisture absorption was highest for the low-crosslink molecule. The percentage reductions for the medium-crosslink and higher crosslink systems were comparable. A net weight loss after drying was observed for the SC11 and SC79 resin systems. Fourier transform infrared analysis confirmed the segment breakage and leaching of molecules from the epoxy–amine network. The effects of moisture cycling on T_g were dependent on the epoxy–amine morphology. During the drying stage, T_g increased to a value higher than that of the unaged dry systems. The S₂ glass composite samples were conditioned under identical conditions for the resin system. Composite systems absorbed less moisture than the neat resins as expected. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Enhanced adhesion of silica for epoxy molding compounds (EMCs) by plasma polymer coatings

Silica for epoxy molding compounds (EMCs) was coated via plasma polymerization using an RF plasma (13.56 MHz) as a function of the plasma power, gas pressure, and treatment time. The monomers utilized for the plasma polymer coatings were 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan, and allyl alcohol. The EMC samples were prepared from biphenyl epoxy resin, phenol novolac, triphenyl phosphine, and plasma polymer-coated silica, and the loading of silica was controlled to 60 wt%. The EMC samples were cured at 175°C for 4 h and subjected to T_g, CTE, and water absorption measurements. The adhesion of silica to epoxy resin was evaluated by measuring the flexural strength of EMC samples and the fracture surfaces were analyzed by SEM. Plasma polymer coatings were also characterized by FT-IR and coating thickness measurements. The plasma polymer coating of silica with 1,3-diaminopropane and allylamine enhanced the flexural strength of EMC samples (167 and 165 MPa), compared with the control sample (140 MPa), and exhibited a higher T_g, a lower CTE, and lower water absorption. The enhanced properties with 1,3-diaminopropane and allylamine plasma polymer coatings can be attributed to the amine functional groups in the plasma polymer coatings.     

Novel effect of barbituric acid on glass transition temperature of bismaleimide–epoxy resin systems

Barbituric acid (BTA) has a novel influence on glass transition temperature (T_g) of bismaleimide (BMI)–epoxy resin systems. It causes the T_g of a BMI–epoxy resin system to rise significantly. The BTA's influence on T_g was investigated by changing the molar ratio of the reactants. In addition, the influence of benzoperoxide (BPO) on T_g was compared with that of BTA. The reaction selectivity of BTA and diamino-diphenyl sulfone (DDS) toward BMI and epoxy individually in the BMI–epoxy blended systems were studied using the DSC and GPC. By controlling the amount of DDS and BTA, epoxy and BMI could form intercrosslinking networks.     

The Use of Dynamic Mechanical Methods to Study the Effect of Absorbed Water on Temperature-dependent Properties of an Epoxy Resin-Carbon Fibre Composite

Dynamic mechanical methods were used to study the effect of absorbed moisture on the properties of an epoxy resin matrix CFRP. The glass transition temperature (T_g)of the matrix resin, determined as the onset of the characteristic fall in dynamic modulus with increasing temperature, was found to decrease with increasing moisture content. Maximum shifts in T_g of 80 to 90°C, relative to the dry material, were observed for a resin moisture content of 5.2% by weight. The effects of sample geometry, fibre orientation, and frequency of oscillation, on the dynamic mechanical properties are discussed. Results are given of an analysis of the observed dependence of T_g on water content using two theoretical models.     

Short term isothermal aging of epoxy resin and epoxy-carbon fiber composites

Short term isothermal aging of a neat epoxy resin and one ply epoxy-carbon fiber composite has been performed. The glass transition temperature, T_g of the neat epoxy resin aged at 204°C increased with aging time. The weight loss of the neat epoxy resin due to aging increased with aging temperature and aging time. The weight loss of the epoxy–carbon fiber composite during aging was slightly less than that of the neat resin. SEM microscopy showed the presence of voids and pores on the surface of the composite due to loss of low molecular weight volatiles. The amount and the size of the voids formed during aging increased with aging temperature and time.     

Viscoelasticity of epoxy resin/silica hybrid material prepared via sol–gel process: Considered in terms of morphology

We investigated the relationship between the morphology and viscoelasticity of epoxy/silica hybrid materials manufactured via two different processes: simultaneous formation of epoxy and silica phases and sequential formation of silica phase in the prepared epoxy phase. The glass transition phenomena of the hybrid materials mostly depended on their silica structure. The particular structure did not affect T_g much, while the silica chain structure greatly raised T_g of the hybrid samples. The storage modulus E′ depended on the volume fraction of the silica phase ζ, rather than the silica structure. In the glassy state, E′ of the hybrid samples slightly decreased when compared with the neat epoxy samples. Lack of chemical reaction between the silica and the epoxy phases could be attributed to this decrease at which the silica structure could have worked as a flaw. In the rubbery state, E′ greatly increased with increasing silica content ζ regardless of the silica structure, and this behavior well agreed with that predicted by the Davies model, because the physical interaction worked very well in the rubbery region. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and thermally stimulated current study of molecular relaxations of the grafted polymethylphenylsiloxane segment in thiodiphenol-modified epoxy resin

A series of grafted polymethylphenylsiloxane (PMPS) segments in thiodiphenyl-containing epoxy resin (ESTP) was prepared. The structure was evaluated by IR, ¹H-NMR, and ¹³C-NMR measurements. DSC measurements on the grafted ESTP epoxy resins showed a decreasing trend for T_g with increasing content of PMPS siloxane. The TSC measurements further confirmed this trend. This result suggests that the matrix of ESTP copolymer was less rigid with grafting of PMPS oligomer, due to the Si—O—C linkage at the opened glycidyl ether chain located approximately between the BPA and 4,4′-thiodiphenoxyl chains in the epoxy backbone. A new and broad sub-T_g transition appeared at −60°C in the TSC spectrum was observed for the cooperative motion of this siloxane moiety. All copolymers showed sub-T_g relaxations of γ- and δ-modes, observed at −100 and −130°C, respectively. These two relaxations may be attributed to the motions of BPA and the terminal groups in the epoxy matrix. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1523–1530, 1998     

Improvement of interfacial adhesion between oxide ceramic nanoparticles and epoxy resin by wet-jet milling

Although ceramic/polymer composites are useful for various applications, such as sensors, electronics, automobiles, and aerospace, the aggregation of nanoparticles can lead to the degradation of the mechanical and functional properties of the composites. To mitigate this, the interfacial adhesion between epoxy resin and the oxide ceramic nanoparticles γ-aluminum oxide (Al₂O₃), silicon dioxide, and magnesium oxide was strengthened by wet-jet milling (WJM) treatment without a chemical modifier. The WJM treatment of the slurry containing nanoparticles and epoxy resin led to the good adsorption of epoxy resin onto the nanoparticle surface, which significantly improved the mechanical properties of the composites. Throughout this process, the amount of epoxy resin adsorbed on the nanoparticle surface and the composite mechanical properties increased with increasing WJM processing pressure, owing to the increased contact between the nanoparticles and epoxy resin droplets and the reduced droplet size. Furthermore, poor solvent was found to be effective for the dispersal of the nanoparticles because the epoxy resin droplets in the slurry were more stable on the nanoparticle surfaces than those in the solvent. When Al₂O₃ nanoparticles were used as a filler, the amount of epoxy resin adsorbed increased from 3.7 to 70.6 mg g⁻¹, and the composite tensile strength increased from 67.1 to 100.3 MPa in poor solvent and under high WJM processing pressure. This optimized WJM treatment will lead to improvements in the mechanical and functional properties of various composite materials.     

Polyamide-silica gel hybrids containing metal salts: Preparation via the sol-gel reaction

The hydrolysis and condensation of tetramethoxysilane in a DMF solution of polyamides containing LiCl, CaCl₂ or ZnCl₂, both in presence and absence of polyoxazoline, resulted in the facile formation of polyamide-silica gel hybrids. Films were cast from the resulting mixtures and evaporation of the solvent resulted in the formation of clear, transparent hybrids with the salts dispersed at the molecular level. Pyrolysis of hybrids at 600 °C gave porous silica. Pore size and surface characteristics of these silica gel samples indicated a porous nature with a pore radius of 1.1 nm for silica gels obtained from hybrids HPA-6 (containing no salt) and HPA-9 (containing ZnCl₂) and a surface area of 213 m² g⁻¹ and 310 m² g⁻¹, respectively. Silica gel from hybrid HPA-7 (containing LiCl) had a pore radius of 1.9 nm and a surface area of 15 m² g⁻¹. The silica gel samples obtained from hybrids HPA-6, HPA-7 and HPA-9 exhibited narrow slit-like pores with a pore volume of 0.68 cm³ g⁻¹. Received: 7 January 1997/Accepted: 6 March 1997     

Catalytic activity of graphite-based nanofillers on cure reaction of epoxy resins

The strong influence of graphite oxide (GO) nanofiller on the glass transition temperature (T_g) of epoxy resins, generally attributed to restricted molecular mobility of the epoxy matrix by the nanofiller or to the crosslinking of GO layers via the epoxy chains, is investigated. The study confirms that large increases of the glass transition temperature of the nanocomposite can be observed in presence of GO. However, similar T_g increases are observed, when the filler is a high-surface-area graphite (HSAG), lacking oxidized groups. Moreover, these T_g differences tend to disappear as a consequence of aging or thermal annealing. These results suggest that the observed T_g increases are mainly due to a catalytic activity of graphitic layers on the crosslinking reaction between the epoxy resin components (epoxide oligomer and di-amine), rather than to reaction of the epoxide groups with functional groups of GO. This hypothesis is supported by investigating the catalytic activity of graphite-based materials on reactions between analogous monofunctional epoxide and amine compounds.