Effect of clay dispersion methods on the mechano-dynamical and electrical properties of epoxy–organoclay nanocomposites

The effect of different clay dispersion methods on the mechano-dynamical and electrical properties of epoxy/clay nanocomposites was investigated. Three different clay dispersion methods (high-speed mechanical shearing, ultrasonication (US), and an optimal combination of high-speed shearing and US) were used for the dispersion of the clay in the epoxy resin. 3 wt% of an organoclay, cloisite 30B, was used as the nanoclay. Wide-angle X-ray diffraction technique and electron microscopic techniques (SEM and TEM) were used to study the morphology of the nanocomposites. Dynamic mechanical analysis was used to study the dynamo-mechanical properties. Studies on the dielectric breakdown strength (EBD) of the nanocomposites show that the EBD strongly depends on the clay dispersion time and clay dispersion method. Pulsed electro-acoustics method measurement shows that the space charge accumulation was considerably reduced in the nanocomposites. In particular, reduction in space charges after polarization depends on the dispersion of the nanofillers, the better the degree of dispersion, the lower the space charges observed.     

The influence of temperature and interface strength on the microstructure and performance of sol–gel silica–epoxy nanocomposites

A series of silica–epoxy nanocomposites were prepared by hydrolysis of tetraethoxysilane within the organic matrix at different processing temperatures, i.e., 25 and 60 °C. Epoxy matrices reinforced with 2.0–10.0 wt% silica were subsequently crosslinked with an aliphatic diamine hardener to give optically transparent nanocomposite films. Interphase connections between silica networks and organic matrix were established by in situ functionalization of silica with 2.0 wt% γ-aminopropyltriethoxysilane (APTS). The microstructure of silica–epoxy nanocomposites as studied by transmission electron microscopy indicated the formation of very well-matched nanocomposites with homogeneous distribution of silica at relatively higher temperatures and in the presence of APTS. Thermogravimetric and static mechanical analyses confirmed considerable increase in thermal stability, stiffness, and toughness of the modified composite materials as compared to neat epoxy polymer and unmodified silica–epoxy nanocomposites. A slight improvement in the glass transition temperatures was also recorded by differential scanning calorimetry measurements. High temperature of hydrolysis during the in situ sol–gel process not only improved reaction kinetics but also promoted mutual solubility of the two phases, and consequently enhanced the interface strength. In addition, APTS influenced the size and distribution of the inorganic domain and resulted in better performance of the modified silica–epoxy nanocomposites.     

Effect of particle morphology on viscoelastic and flexural properties of epoxy–alumina polymer nanocomposites

Nanocomposites were synthesised by dispersing two different types of alumina nanoparticles in epoxy matrix by ultrasonication. Alumina nanoparticles of two shapes, rod and spherical were selected to investigate the effect of particle morphology on viscoelastic and flexural properties of nanocomposites. Specific surface area of both the selected nanoparticles was kept in the similar range. Good dispersion of nanoparticles was observed through transmission electron microscopy. The addition of nanoparticles in epoxy had significant enhancement in the viscoelastic properties and moderate improvement in flexural properties of composites. Composites having alumina nanorods showed higher improvement both in storage modulus as well as in flexural properties in comparison to composites having spherical alumina nanoparticles. Efficacy of Mori-Tanaka method was explored in modelling storage modulus of nanocomposites. Assorted size of alumina nanorods based on particle size distribution was used to model composites with nanorods to see the effect of size assortment on storage modulus.     

Effect of number of graphene layers on mechanical and dielectric properties of graphene–epoxy nanocomposites

In this study, mechanical and dielectric properties of epoxy nanocomposites with two types of graphene, <?10 layer stacks (GEC10) and <?30 layer stacks (GEC30) were investigated. Results showed that the number of graphene layers remarkably affected the dielectric properties of epoxy nanocomposites. The real and imaginary parts of relative permittivity and loss tangent of GEC10 samples were noticeably enhanced and reached to 1.29, 20 and 15.6 times respectively for 1?wt-% graphene sample compared to GEC30 samples. Meanwhile, tensile tests showed a peak for tensile strength of GEC10 and GEC30 samples with 0.1?wt-% graphene, which improved by 13 and 7.9% with respect to pure epoxy respectively. In addition, flexural properties did not change significantly compared to the pure epoxy.     

Role of epoxy functionality in microstructure–property relationships within elastomeric nanocomposites

Abstract

The contribution of epoxy functionalities in hybrid filler microstructures and interfaces within different binary and ternary particulate elastomeric nanocomposites, prepared by open two-roll mixing, was analysed. The epoxy percentages of the elastomeric phase were varied at three different levels (e.g. 0, 25 and 50%). Among the ternary samples, the most uniform distribution and dispersion were achieved in the case of the sample based on ENR-25 (epoxidised natural rubber matrix having 25 mol-% of epoxy group), as observed by small angle X-ray scattering (interfacial roughness) and transmission electron microscopy. Clay and carbon black jointly form hybrid microstructures like ‘nanounit’. Uniform distributions of such morphologies are reflected in tensile strength, elongation at break and half height width of the tan?δ peak. Although the cross-link density improves as the epoxy percentage is increased, the level of synergism between two different fillers in terms of cross-linking density gradually reduces with the increased epoxy percentages. Except for solely clay filled samples, the thermal stability enhances as the epoxy percentage is increased.     

Effect of polypyrrole–montmorillonite nanocomposites powder addition on corrosion performance of epoxy coatings on Al 5000

The synthesis of hybrid polypyrrole–montmorillonite (Ppy–MMT) nanocomposites and their effects on the improvement of the protection efficiency of the epoxy coatings on aluminum corrosion were studied. In order to understand the effect of MMT and Ppy on the corrosion inhibition performance of the epoxy coatings in 3.5% NaCl solution, the epoxy (E), epoxy blend with MMT (EM) and polypyrrole (EP) coatings were investigated by electrochemical impedance spectroscopy (EIS). It was shown that EM and EP systems could not provide a good corrosion protection for long-time applications. The results showed that the incorporation of Ppy–MMT nanocomposites inside the epoxy notably increases the resistance of the coating in comparison to the other coatings for long-time period. These phenomena can be attributed to specific morphology of the nanocomposite. The structure and morphology of nanocomposites were studied by FT-IR and XRD techniques, as well as, scanning electron microscopy (SEM).     

Electrical and mechanical tuning of 3D printed photopolymer–MWCNT nanocomposites through in situ dispersion

An electric field-assisted in situ dispersion of multiwall carbon nanotubes (MWCNTs) in polymer nanocomposites, fabricated through stereolithography three-dimensional (3D) printing technique, was demonstrated. The introduction of MWCNTs increased the elasticity modulus of the polymer resin by 77%. Furthermore, the use of an electric field for in situ MWCNT dispersion helped improving the average elongation at break of the samples with MWCNTs by 32%. The electric field also increased the ultimate tensile strength of the MWCNT reinforced nanocomposites by 42%. An increase of over 20% in the ultimate tensile strength of in situ dispersed MWCNT nanocomposites over the pure polymer material was observed. Finally, it was demonstrated that the magnitude and direction of the electrical conductivity of MWCNT nanocomposites can be engineered through the application of in situ electric fields during 3D printing. An increase of 50% in the electrical conductivity was observed when MWCNTs were introduced, while the application of the electric field further improved the electrical conductivity by 26%. The presented results demonstrated the feasibility of tuning both electrical and mechanical properties of MWCNT reinforced polymer nanocomposites using in situ electrical field-assisted 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47600.     

Construction of improved isothermal TTT cure diagram based on an epoxy–amine thermoset

Cure degree plays a pivotal role in determining the final properties of thermosetting resin, while the parameter cannot be visually presented by the classic isothermal time–temperature-transformation (TTT) diagram. An improved isothermal TTT cure diagram is built for an epoxy–amine thermoset with the visual relationship between temperature, time, and cure degree during the whole curing. As for the improved isothermal TTT cure diagram, the curing surface and the gelation plane were developed using Vyazovkin method and rheological analysis in turn, and the variation between glass transition temperature (T _g) and curing degree was described by Dibenedetto's equation. The obtained improved isothermal TTT diagram of epoxy–amine thermoset was constructed by the combination of calorimetric and rheological analysis. The fitting results of vitrification surface and gelation plane obtained via improved isothermal TTT diagram were in good agreement with experimental results. In addition, the experimental gelation curve of epoxy–amine thermoset is directly linked to the steepest location of curing surface. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47279.     

Atomistic analyses of the effect of temperature and morphology on mechanical strength of Si–C–N and Si–C–O nanocomposites

3-D molecular dynamics (MD) analyses of SiC–Si₃N₄ nanocomposite deformation and SiCO nanocomposite deformation are performed at 300 K, 900 K, and 1500 K. In SiC–Si₃N₄ nanocomposites, distribution of second phase SiC particles, volume fraction of atoms in GBs, and GB thickness play an important role in temperature dependent mechanical behavior. The deformation mechanism is a trade-off between the stress concentration caused by SiC particles and Si₃N₄–Si₃N₄ GB sliding. The temperature increase tends to work in favor of GB sliding leading to softening of structures. However, microstructural strength increases with increase in temperature when GBs are absent. In the case of SiCO nanocomposites, findings indicate that temperature change dependent amorphization of nanodomains, the nanodomain wall placement, the nanodomain wall thickness, and nanodomain size are important factors that directly affect the extent of crystallinity and the strength against mechanical deformation.     

Characterisation and modelling of CNT–epoxy and CNT–fibre–epoxy composites

Abstract

This research presents an experimental and theoretical investigation on the effects of carbon nanotube (CNT) integration within neat epoxy resin (nanocomposites) and a carbon fabric–epoxy composite (multiscale composites). An approach is presented for the prediction of mechanical properties of multiscale composites. This approach combines woven fibre micromechanics (MESOTEX) with the Mori-Tanaka model which was used for the prediction of mechanical properties of nanocomposites in this research. Nanocomposite and multiscale composite samples were manufactured using cast moulding, resin infusion, and hand lay-up process. The CNT concentrations in the composite samples were from 0 to 5 wt-%. The samples were characterised using tensile, shear and flexural tests. The discrepancy between the theoretical predictions and the experimental observations was hypothesised to be due to dispersion and bonding issues and SEM images are presented in support of the hypothesis.     

Investigation of the curing kinetics of alkyd–melamine–epoxy resin system

Properties of coatings based on alkyd resin can be improved via blending with other suitable resins. Recent studies assessed that many properties could be improved by blending with epoxy resins as well as with melamine resins. The aim of this work was to investigate the effect of epoxy resin content on the curing process in alkyd–melamine–epoxy three component blends. The coatings with two mixing ratios of alkyd/melamine (70:30 and 80:20) were formulated. They were made into baking enamels by blending with 3 and 5 wt% of epoxy resin on total resin solid. Curring kinetics was investigated by differential scanning calorimetry (DSC) and application of Ozawa isoconversional method. Fourier transform infrared spectroscopy (FTIR) was used to follow major curing reactions. The absorbance of –OH and –N–CH₂R, showed significant reduction and confirmed that the epoxy resin reacts and inserts in enamel structure. It was found that resin system with alkyd/melamine ratio of 70:30 and 3 wt% of epoxy resin has the lowest apparent activation energy of 141.5 kJ mol⁻¹ and needs the shortest time of 34.2 min to reach final apparent degree of cure. Isothermal DSC experiments have confirmed these findings. The samples with 30 wt% of melamine resin had higher hardness of baked enamels then samples with 20 wt%. They also showed an increase of hardness with the increase of epoxy resin content.     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.     

Molecular-level dispersion of phosphazene–clay hybrids in polyurethane and synergistic influences on thermal and UV resistance

Amine substitution of hexachlorocyclotriphosphazene with poly(oxyethylene-oxypropylene)-monoamines afforded aminophosphazenes (AP) at molecular level with the structure of rigid phosphazene core and flexible alkoxy shell. Sodium montmorillonite were modified by using HCl-treated AP to prepare AP-exfoliated MMT clay (AP/EMMT) nanohybrids. When blending the nanohybrid into PU, the presence of silicate platelets promoted the PU stability and retarded the degradation for more than 60 °C under the standard TGA measurement. The co-existence of AP and EMMT at various weight ratios demonstrated a synergistic effect on the improvements of thermal stability as well as the UV resistance under the standard test of UV exposure in wavelength range of 365–400 nm. The molecular-level dispersion of AP and silicate platelets had synergistically contributed to the PU thermal and UV stability.     

Role of vermiculite and zirconium–vermiculite on the formation of zircon–cordierite nanocomposites

The Zr^4 +–vermiculites were studied in their new role of the zircon precursor in the clay minerals mixtures which were prepared for firing of the zircon–cordierite nanocomposites. Currently there is a lack of data available about the structure of Zr^4 +–vermiculites, on which this study was performed. The modeling of the arrangement of interlayer material in the Zr^4 +–vermiculite led to new findings that water molecules are attracted more strongly by Mg^2 + cations than by Zr-tetrameric cations, and that both the tetrameric cations [Zr₄(OH)₁₄(H₂O)₁₀]^2 + and [Zr₄(OH)₈(H₂O)₁₆]^8 + may be present in the interlayer space of the Zr^4 +–vermiculites. Vermiculites from two different localities Czech Republic (Verm1) and from Brazil (Verm2) were intercalated using the zirconyl chloride (ZrOCl₂–30% solution in HCl) and the prepared Zr^4 +–vermiculites were designated as Zr^4 +–Verm1 and Zr^4 +–Verm2, respectively. Influence of the Zr^4 +–Verm1 and Zr^4 +–Verm2 in the mixtures of clay minerals on the properties of zircon–cordierite nanocomposites were investigated by their comparison with the properties of the zircon–cordierite nanocomposites, which were prepared using saturation of the clay minerals mixtures containing Verm1 and Verm2 with the zirconyl chloride (ZrOCl₂–30% solution in HCl). The zircon–cordierite nanocomposites fired from the clay mineral mixtures containing Zr^4 +–Verm1 and Zr^4 +–Verm2 showed a maximum porosity of P = 58 and 60%, skeletal density SD = 3.2 and 3.6, and the smallest pores with a median pores diameter MDP = 18 and 15 μm, respectively, in comparison with the zircon–cordierite nanocomposites fired from the clay mineral mixtures containing Verm1 and Verm2 and saturated with zirconyl chloride solution. The type of vermiculite Verm1 or Verm2 in the clay mineral mixtures did not affect the contents of the crystalline mineral phases in cordierite and zircon–cordierite nanocomposites.     

Improved dispersion of the graphene and corrosion resistance of waterborne epoxy–graphene composites by minor cellulose nanowhiskers

The uniform dispersion of graphene (GN) in a polymer matrix is still challenging at high loadings. In this study, we introduced a tiny number of cellulose nanowhiskers (CNWs; CNWs/GN = 1:20 w/w) to improve the dispersion of GN nanoplatelets in a waterborne epoxy (WEP) matrix at a GN loading of 1.0 wt %. Compared with that of 1.0% GN–WEP, the Young's modulus of the 1.0% GN–WEP–CNWs was enhanced by about 20.5%. The glass-transition temperature increased from 70.4°C for 1.0% GN–WEP to 72.8°C for 1.0% GN–WEP–CNWs. The water contact angle of composite film increased by 17°, from about 79° for the film without CNWs to about 96° for the film with CNWs. The anticorrosion efficiency of the coatings was also evaluated with the potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The results reveal the CNW-containing coating showed better corrosion resistance for mild steel and could be applied as a green dispersant for GN in WEP coatings. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47631.     

Study on interfacial interaction energy of Cu–SAM–epoxy systems in a hot and humid environment

Due to poor adhesion, the interfacial delamination is one of the typical failure modes in electronic packages. In this paper, two kinds of self-assembly monolayers (SAMs), SAMA and SAME, are added to Cu–epoxy interface and the effects of temperature, moisture, and cross-link conversion on the modified interfaces are investigated with molecular dynamics (MD) simulation. The results show that the interfacial interaction energy of the systems with SAMA increases with the increasing temperature, decreasing moisture content, and cross-link conversion. However, the interfacial interaction energy of the systems with SAME decreases with the increasing temperature and moisture content, while it is reluctant to the cross-link conversion. In addition, the simulation reveals that the covalent bonds between SAMA and epoxy enhance the interfacial adhesion of Cu–epoxy. However, the nonbond interactions of SAME and epoxy resin weaken the interfacial adhesion. This paper provides a new method for research and valuation the effects of SAM or other adhesive on interfacial adhesion. MD simulation is an efficient tool in predicting the performances of materials.     

Synthesis and modification of silica-based epoxy nanocomposites with different sol–gel process enhanced thermal and mechanical properties

This research article describes the results of nano-silica composites filled with different epoxy contents containing nano-SiO₂ particles from (5–25 wt%). Reinforcing hybrid composites enhance thermal and mechanical properties to achieve vital and sustainable products. Silica-based nanocomposites with high purity were prepared and used for the surface modification of nanosized silica particles. The surface structure's composition and physical properties of modified nano-SiO₂ particles were characterized through Fourier transferred infrared spectrometer, X-ray photoelectron spectroscopy, thermogravimetric analyzer, and scanning electron microscopic. Silica-based nanocomposites were prepared by incorporating of modified nano-SiO₂ as an enhancing filler. The morphology of fracture surface and dynamic mechanical properties were investigated. Results showed that the silica-based epoxy nanocomposites are bearing a long chain structure that could improve the compatibility of silica nanocomposites with epoxy resin and contribute to a better dispersion state in the matrix, which enhanced the overall performance of epoxy-cured products.     

High-performance waterborne UV-curable polyurethane dispersion based on thiol–acrylate/thiol–epoxy hybrid networks

Synthesis, characterization, and film performance of waterborne thiol–acrylate/thiol–epoxy hybrid coatings are highlighted in this article. A dimer acid-modified epoxy (DME) polyol, containing both hydroxyl and epoxy functional groups, was prepared by reacting epoxy resin (EEW = 190 g/equi) with dimer fatty acid at 2:1 molar ratio. Further, a base UV-curable polyurethane acrylate dispersion (UV-PUD), with a pendant epoxy functional group, was prepared by reacting polyol (DME), isophorone diisocyanate, and dimethylol propionic acid and end-capped with hydroxyethyl methacrylate with subsequent dispersion in water. Prepared intermediates were characterized for the parameters relevant to the study by physical, spectroscopic, and chemical methods. UV-curable thiol–acrylate/thiol–epoxy hybrid coatings were prepared by blending UV-PUD with trimethylolpropane tris(3-mercaptopropionate) (TMPMP) at four different thiol ratios (0, 0.3, 0.6, and 1.0) with respect to acrylate/epoxy groups. Cured films of the hybrid coating were identified by FTIR spectroscopy. The impact of thiol ratio on film performance was evaluated in terms of mechanical, chemical, thermal, and coating properties. The gel content measurements confirm that the addition of TMPMP increased the double bond conversion along with the epoxy group. Evaluation of cured samples shows the significant improvement in storage modulus, glass transition temperature, tensile strength, and hardness with increase in thiol ratio. The cured films possessed excellent water and acid resistance (<4%) even after 28 days of immersion. Moreover, the notable improvement was alkali resistance of cured films, i.e., as thiol ratio was increased from 0 to 1, weight loss in alkaline environment deceased from 49.5 to 4.5% after 28 days. Better properties of the thiol–acrylate/thiol–epoxy hybrid films will allow it as a potential application in low-volatile high-performance coatings.     

Effects of nanosilica and titanium oxide on the performance of epoxy–amine nanocoatings

Different types of composite coatings were prepared by the blending of colloidal nanosilica (SiO₂) and titanium dioxide (TiO₂) in epoxy resin to investigate their coating performances. A fixed amount of silica nanoparticles (20 wt %) and different amounts (5, 10, and 15 wt %) of microsized TiO₂ particles were used in the coatings. The functional groups of the formulated coatings were confirmed by Fourier transform infrared spectroscopy. These results indicate that the SiO₂–TiO₂ particles interacted well with epoxy. Scanning electron microscopy images of the composite coatings revealed a good dispersion of TiO₂ particles at a lower amount of loading; this improved the adhesiveness, glass-transition temperature, thermal stability, and chemical resistance properties. At higher loadings, the performances decreased. The composite coatings were also characterized by their UV radiation-absorption properties with an ultraviolet–visible spectrophotometer. Interestingly, this property was found to be enhanced at higher loadings. An impressive result was noticed in the nanocomposites in terms of oxygen transmission rate performance compared to that of the neat epoxy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47901.     

Investigation on Production and Markets of Silica Bricks in China

The annual output of China‘s silica brick amounts up to over 300 thousand tons, which accounts for more than 70% of the total oupout of silica bricks in the world. Besides satisfying domestic markets, China‘s silica bricks have been exported to many countries and retions such as Japan, USA etc. In this paper, the situation of silica bricks production, technology, sales and exporting have been described. Also suggestions on improvement of silica bricks quality and exporting, corporation with foreign partners have been put forward in order to win larger market share both aat home and abroad.