Curing behavior and physical properties of an epoxy nanocomposite with amine-functionalized graphene nanoplatelets

Amine-functionalized graphene nanoplatelets (AGNPs) were prepared via an easy simple one-step process, treating graphite powder with 4-aminobenzoic acid in polyphosphoric acid, and then the effects of the AGNPs on the curing and physical properties of an epoxy resin were studied. The formation of the AGNPs was confirmed by scanning electronic microscopy (SEM), Fourier transform infrared spectroscopy, and thermogravimetric analyzer. Curing behavior of the epoxy/AGNPs nanocomposite was investigated by differential scanning calorimeter. The AGNPs made the epoxide curing reaction with amine groups slightly faster. The physical properties of the epoxy/AGNPs nanocomposite were investigated by dynamic mechanical analyzer, thermomechanical analyzer, and impact test. The AGNPs improved T_g by 21.4 °C, and storage modulus and impact strength of the epoxy resin 23 and 73%, respectively, much more effective than the graphite powder at the same filler loading of 1 phr. SEM images for the fracture surfaces of the epoxy/AGNPs nanocomposite showed improved interfacial bonding between the epoxy matrix and the nanofillers due to the amine functional groups of the AGNPs.     

Nature of the adhesion bond between epoxy adhesive and steel

The potential difference that appears in the epoxy resin located between two grade 3 steel plates is studied. One of them is stored in epoxy resin to reach equilibrium, and the second plate is coated with an asprepared mixture of epoxy resin with a hardener. It is found that the potential difference decreases in time because of charge transfer by Fe²⁺ ions through epoxy resin. The luminescence and infrared absorption spectra of the epoxy adhesive on the grade 3 steel surface are recorded. An analysis of these spectra shows that Fe²⁺ ions penetrate into the as-prepared mixture of epoxy resin with the hardener, and interact with CN groups in the mixture, and form coordination compounds. As a result, a diffusion layer saturated by the coordination compounds forms at the interface between the steel and the adhesive.     

Comparative Study of the Effect of Addition of Silica and Silicate Nanofillers on the Properties of Epoxy Coatings

The effect of adding different amounts (0.5–3 wt%) of nanosilica (NS) and organomodified montmorillonite (MMT) to diglycidyl ether bisphenol A (DGEBA) cured with isophorone diamine at different temperature on the viscoelastic, topographical and gelation properties of epoxy resin was studied. Gel time measurements revealed that both NS and MMT accelerated the curing reaction of DGEBA with IPDA. Both nanofillers were adequately dispersed in DGEBA. The particle size distribution depended on the amount of nanofiller. A broader distribution for NS than for MMT filled epoxy was obtained. On the other hand, an increase in the curing temperature was required to obtain the intercalation of the epoxy into the MMT tactoids. At room temperature, the addition of NS increased both the stiffness (high storage modulus) and the toughness (an increase in the area and height of the tan δ curve) of epoxy, but no significant differences were found by curing at higher temperature. Epoxy/MMT composites showed higher storage modulus in the rubbery region. The improved properties imparted by NS can be ascribed to the interactions between the silanol moieties on the nanosilica surface and the polar groups in the epoxy, whereas the improvement imparted by MMT organoclay was related to tactoid intercalation within the epoxy matrix.     

Modification of Epoxy Resin with Cycloaliphatic-Epoxy Oligosiloxane for Light-Emitting Diode (LED) Encapsulation Application

A novel cycloaliphatic-epoxy oligosiloxane (EHDM) was incorporated into 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ERL-4221) for use as a light-emitting diode (LED) encapsulant. EHDM, with reactable epoxy groups and flexible Si-O-Si chains, was obtained by the hydrolytic condensation reaction between 2-(3,4-epoxycyclo-hexyl)ethyl-trimethoxysilane (EHETMS) and dimethyldiethoxylsilane (DMDES). The results of Fourier transform infrared spectroscopy, ²⁹Si nuclear magnetic resonance, and gel permeation chromatography indicated that EHDM had a narrow molecular weight distribution and high epoxy graft degree. The thermal and mechanical properties, morphologies, and light transmittance of the cured neat epoxy resin and EHDM-modified epoxy were investigated by differential scanning calorimetry, thermogravimetric analysis, tensile and impact testing, scanning electron microscopy, and ultraviolet-visible spectrophotometry. The experimental results demonstrated that the cured EHDM-10 hybrimer with 10 pph of EHDM relative to ERL-4221 maintained the neat ERL-4221 epoxy transmittance of 85% at 450 nm. With respect to the corresponding properties of the neat epoxy resin, EHDM-10 hybrimer possessed a higher glass transition temperature, better thermal stability, better fracture toughness, and lower water absorption ratio, indicating EHDM effectively improved the properties of ERL-4221 for LED packaging applications.     

Friction,adhesion and wear durability of an ultra-thin perfluoropolyether-coated 3-glycidoxypropyltrimethoxy silane self-assembled monolayer on a Si surface

The tribological properties, such as coefficient of friction, adhesion and wear durability of an ultra-thin (<10?nm) dual-layer film on a silicon surface were investigated. The dual-layer film was prepared by dip-coating perfluoropolyether (PFPE), a liquid polymer lubricant, as the top layer onto a 3-glycidoxypropyltrimethoxy silane self-assembled monolayer (epoxy SAM)-coated Si substrate. PFPE contains hydroxyl groups at both ends of its backbone chain, while the SAM surface contains epoxy groups, which terminate at the surface. A combination of tests involving contact angle measurements, ellipsometry, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) was used to study the physical and chemical properties of the film. The coefficient of friction and wear durability of the film were investigated using a ball-on-disk tribometer (4?mm diameter Si₃N₄ ball as the counterface at a nominal contact pressure of ～330?MPa). AFM was used to investigate the adhesion forces between a sharp Si₃N₄ tip and the film. This dual-layer film had a very low coefficient of friction, adhesion and wear when compared to epoxy SAM-coated Si only or bare Si surface. The reasons for the improved tribological performance are explained in terms of the lubrication characteristics of PFPE molecules, low surface energy of PFPE, covalent bonding between PFPE and epoxy SAM coupled with reduced mobile PFPE. The low adhesion forces coupled with high wear durability show that the film has applications as a wear resistant and anti-stiction film for microcomponents made from Si.     

Preparation and Characterization of Nano-Calcium Carbonate/Silane Coupling Agent Master Batch and Its Effect on Epoxy Resin

A nano-calcium carbonate (CaCO₃)/silane coupling agent (NCC/SCA) master batch was prepared by the reaction of SCA (γ-aminopropyl triethoxy silane, trade name KH550) with the hydroxyl groups of nano-CaCO₃. Both Fourier transform infrared spectroscopy and thermal gravimetric analysis indicated that the nanoparticles were grafted by SCA. An epoxy resin was modified by adding the NCC/SCA master batch. A simple dipping test suggested that a better dispersion of the treated NCC in epoxy could be obtained than that of the untreated NCC. Then samples of epoxy nano-composites were prepared by a hot press process. The compressive property of epoxy nano-composites was investigated; the results of these mechanical property tests revealed that the compressive strength, elastic modulus, and the total fracture work of the epoxy matrix filled with the treated NCC were significantly improved relative to that filled with the untreated NCC.     

基于密度泛函理论的外电场下双酚A型环氧树脂分子的结构及特性

采用密度泛函m062x的方法在6-31g(d)基组上对双酚A型环氧树脂分子进行优化得到了它的稳定结构,并且研究了不同外电场(0-0.013 a.u., 1 a.u.=5.142×10~(11) V/m)作用下双酚A型环氧树脂分子的分子结构、电偶极矩和分子总能量,偶极矩、极化率、前线轨道的能级和成分,原子之间的键能和红外光谱的变化.研究表明:随着外加电场的增大,双酚A型环氧树脂分子从倒V型结构逐渐变成线性结构,总能量降低,偶极矩和极化率都升高,且双酚A型环氧树脂分子的稳定性随着外加电场的增大而降低;最高占据轨道能级随着外加电场的增大而增大,沿逆电场方向分子链端表现出亲核反应活性,最低空轨道能级随着外加电场的增大而减小,沿电场方向分子链端表现出亲电反应;位于分子两端环氧基团上的C-C,C-O容易发生断裂,进而破环了双酚A型环氧树脂分子的稳定性;分子红外光谱在高频区的吸收峰出现了明显的红移现象.     

Influence of covalent and non-covalent modification of graphene on the mechanical,thermal and electrical properties of epoxy/graphene nanocomposites: a review

Abstract

Graphene is emerged as a highly sought after reinforcing filler for epoxy matrix in view of its superior electrical, mechanical and thermal properties. Dispersion of low concentration of graphene can significantly enhance the epoxy/graphene nanocomposites properties. Dispersion of graphene in epoxy matrix depends on processing protocols used, and interfacial interaction between epoxy matrix and graphene. Interfacial interaction between epoxy matrix and graphene can be achieved by covalent and non-covalent modification of graphene. This paper comprehensively review the influence of different processing protocols adopted for the processing of epoxy/graphene nanocomposites, and its effect on mechanical, thermal and electrical properties. In addition, covalent and non-covalent strategies adopted for modification of graphene, and its influence on mechanical, thermal and electrical properties of epoxy/graphene nanocomposites are extensively discussed. The future challenges associated with graphene reinforced epoxy nanocomposites processing have been discussed.     

MONITORING OF CURING PROCESS BY FLUORESCENCE TECHNIQUE. FLUORESCENCE PROBE AND LABEL BASED ON 5-DIMETHYLAMINONAPHTHALENE-1-SULFONAMIDE DERIVATIVES (DNS)

The curing reaction of glycidyl ether bisphenol A (DGEBA) with n-butyl amine and/or N-methylethylenediamine was monitored by fluorescence spectroscopy. 5-Dimethylaminonaphthalene-1-sulfonamide (DNS) fluorophore was used as a probe and/or label. Fourier transform infrared (FTIR) analysis revealed that the rate constant for the addition reaction of the primary amino group hydrogen of n-butylamine to the epoxide ring is more than four times larger than that arising from a secondary amine. Significant differences have been observed between the fluorescence behavior of the DNS as a probe and label, especially in the system DGEBA–n-butyl amine. Integrated fluorescence intensity for the DNS label, in contrast to the DNS probe, indicates the most important changes in chemical transformations of this reaction mixture (the onset of tertiary amino groups and maximum concentration of secondary amino groups). Similarly, the dependence of the half-bandwidth on the epoxy groups conversion for the DNS label shows these stages of the curing reaction as well. In the system DGEBA–N-methylethylenediamine, the reactivity of the secondary amino group hydrogen is higher than that of the primary amino group. A change in slope of the dependence of integrated fluorescence intensity on epoxy group conversion clearly indicates the gel point and entry of the system into the glassy state. The DNS probe does not sense any of these changes. From the emission spectra of the DNS probe and/or label, the average value <v> = ΣI_F (ν)ν/ΣI_F (ν) of the emission band position has been correlated with the epoxy group conversion determined by FTIR. Smooth dependencies were obtained in all cases. This enables one to monitor on line and in real time the epoxy group conversion.     

Thermodynamic approach to enhance the dispersion of graphene in epoxy matrix and its effect on mechanical and thermal properties of epoxy nanocomposites

Graphene-reinforced polymer nanocomposites are under intense investigation in recent years. In this work, graphene nanosheets have been prepared using chemical reduction method of graphene oxide. Graphene-reinforced epoxy nanocomposites show an enhancement in mechanical and thermal properties at 0.05 wt.% of graphene in epoxy matrix. Modification of graphene with polyvinylpyrrolidone (PVP) shows the significant enhancement in mechanical and thermal properties of epoxy nanocomposites. PVP-modified graphene nanosheets reduces the gap of enthalpic and entropic penalties and facilitates improved dispersion of graphene in epoxy matrix. In addition, enhanced dispersion of PVP-modified graphene in epoxy matrix results in better load transfer across graphene–epoxy interface. Glass transition temperature (T_g) of PVP-modified graphene epoxy nanocomposites increases as compared to pure epoxy because there exist an interaction between epoxy and PVP. Fractography study reveals the localized ductile fracture.     

Thermal resistance of CNTs-based thermal interface material for high power solid state device packages

Vertically aligned carbon nanotubes (VACNTs) were synthesized over copper substrate. The diameter and length of the CNTs were 100 nm and 2–3 μm, respectively. Synthesis of CNTs was confirmed by Raman spectrum and verified by TEM as multi walled CNTs. SEM images showed the vertically aligned CNTs over Cu substrate. Strengthening of CNTs was performed by filling with Cu and SU-8 epoxy sealant in gap between the CNTs. The observed density was high for epoxy sealed CNTs. The bending ability of CNTs was checked and observed as low for epoxy sealed CNTs. The thermal resistance of the samples was measured by JESD51-2 standard for various loads. The observed resistance was low (0.277 cm²?K/W) for epoxy sealed CNTs at 1100 kPa. The calculated resistance of CNTs alone was 0.097 cm²?K/W for epoxy sealed at 900 kPa.     

Comparison of the immunolabeling of heated and deplasticized epoxy sections on the electron microscopical level.

The purpose of this study was to compare the yield of immunogold labeling of heated epoxy sections with the yield of labeling of deplasticized epoxy sections, and to compare the immunolabeling of deplasticized high-accelerator epoxy sections and deplasticized low-accelerator epoxy sections. Renal swine tissue and human thyroid tissue were embedded in both high- and low-accelerator epoxy resin and also in LR-White resin. Immunogold labeling was performed on deplasticized (ethoxide-treated), heated and non-treated ultrathin sections from these specimens. The renal tissue was immunolabeled with anti-IgG, and the thyroid tissue was immunolabeled with anti-thyroglobulin. The ethoxide treatment of the epoxy sections induced complete deplasticizing. The immunogold labeling with anti-IgG on deplasticized epoxy sections of renal tissue demonstrated significantly more intense immunolabeling of immune complex deposits than the corresponding epoxy sections which were exposed to heat in citrate buffer. The results for labeling areas of thyroglobulin substance with anti-thyroglobulin showed no significant differences between deplasticized and heated epoxy sections, probably because the sodium ethoxide partly destroys the antigenicity. Deplasticized high-accelerator epoxy sections showed significantly higher yield of immunolabeling than deplasticized low-accelerator epoxy sections and LR-White sections both for anti-IgG and anti-thyroglobulin. This can be explained by the reduced tendency for the knife to cleave proteins when cutting high-accelerator epoxy sections. High-accelerator epoxy sections which were exposed to heat in citrate buffer were more intensely immunolabeled than similarly treated low-accelerator epoxy sections, in agreement with previous results. The ultrastructural preservation of the tissues of deplasticized epoxy sections was inferior compared with the other sections. This study shows that the choice between deplasticizing technique or heating of epoxy sections has to be considered with respect to the nature of the antigen and to the requirement for ultrastructural preservation.     

Real-time and label-free detection of biomolecular interactions by oblique-incidence reflectivity difference method

We successfully conduct the label-free and real-time detection of the interactions between epoxy groups and rabbit IgG and 5' CTT CAG GTC ATG AGC CTG AT 3' oligonucleotide, and between the hybridization of 5' CTT CAG GTC ATG AGC CTG AT 3' and its complementary 3' GAA GTC CAG TAC TCG GAC TA 5' oligonucleotide, by the oblique-incidence reflectivity difference (OI-RD) method. The dynamic curves of OI-RD signals, corresponding to the kinetic processes of biomolecular combination or hybridization, are acquired. In our case, the combination of epoxy groups with rabbit IgG and 5' CTT CAG GTC ATG AGC CTG AT 3' oligonucleotide need almost one and a half hours and about two hundred seconds, respectively; and the hybridization of the two oligonucleotides needs about five hundred seconds. The experimental results show that the OI-RD is a promising method for the real-time and label-free detection of biomolecular interactions.     

Effects of corona discharge on the surface structure, morphology and properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were modified by corona discharge and then heat treated in the air. The influences of corona discharge parameters such as treatment time and processing power were investigated. The results of energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA) indicated the introduction of oxygen-containing functional groups onto the surface of the MWCNTs after heat treatment. The water contact angle tests showed that the hydrophobicity of the MWCNTs was decreased to some extent. The static water contact angle was reduced from 146° to 122° when the time of the corona discharge treatment reached 3 min at the processing power of 200 W. The enhanced thermomechanical and mechanical properties of epoxy nanocomposites filled with the corona discharge treated MWCNTs were observed. The modified MWCNTs conferred better properties on the composites than the pristine MWCNTs because of the improved dispersion of MWCNTs in matrix and the enhanced interfacial interaction between the treated MWCNTs and epoxy.     

H2S在氧化石墨烯表面的吸附和分解的理论研究

用周期性密度泛函方法对H₂S在氧化石墨烯(GO)上的吸附和分解进行了理论计算, 讨论了H₂S和GO上的羟基和环氧基团的反应过程．结果表明,反应过程是通过H₂S或-SH上的H转移使得GO的环氧基开环和羟基氢化,当GO相反面存在羟基时有助于环氧基团的开环和羟基氢化反应．H₂S在GO上吸附和分解到S原子的反应机理中引入了相应的中间态,计算两次脱氢过程能垒分别为3.2和10.4 kcal/mol,第二个H原子的转移是GO还原过程的速率决定步骤．结果还表明GO上的羟基和环氧基团有助于加强S原子和石墨烯的结合．     

Production of tung oil epoxy resin using low frequency high power ultrasound

Epoxy resins made from vegetable oils are an alternative to synthesize epoxy resins from renewable sources. Tung oil is rich in α -eleostearic fatty acid, which contains three double bonds producing epoxy resins with up to three epoxy groups per fatty acid. This work studied the production of tung oil epoxy resin using hydrogen peroxide as an oxidizing agent and acetic and formic acid as percarboxylic acid precursors, applying low frequency high power ultrasound. This study evaluated the effects of ultrasound power density, hydrogen peroxide concentration, acetic acid concentration, and formic acid concentration on the yield into epoxy resin, selectivity, and by-products formation. Application of ultrasound was carried out using a 19 kHz probe ultrasound (horn ultrasound) with a 1.3 cm diameter titanium probe, 500 W nominal power, 2940 W L⁻¹ maximum effective power density applied to the reaction mixture. Ultrasound technology yielded up to 85% of epoxy resin in 3 h of reaction. The use of formic acid resulted in a slightly lower oil conversion than acetic acid but with a much higher selectivity towards epoxidized tung oil. However, using acetic acid resulted in the production of high-value by-products, such as 2-heptenal and 2,4-nonadienal. The ultrasound-assisted epoxidation showed to be particularly efficient when applied to oils containing conjugated double-bonds.     

Influence of Mechanical Stretching on Adsorption Properties of Nitrogen-Doped Graphene

This paper presents the results of quantum chemical modeling of chemisorption of atomic hydrogen and epoxy, carboxyl, and hydroxyl functional groups on nitrogen-doped graphene. It is shown that the substitutional nitrogen atom does not bind to adsorbing groups directly, but significantly increases the adsorption activity of neighboring carbon atoms. Mechanical stretching of doped graphene reduces the adsorption energy of all the aforementioned radicals. This reduction is significantly greater for the epoxy group than for the other functional groups. The results obtained confirm that, upon a sufficient stretching of a nitrogen-doped graphene sheet, the dissociation of molecular hydrogen and oxygen with subsequent precipitation of the resulting radicals onto graphene can be energetically favorable.

     

Effect of processing on rheological properties and structure development of EPOXY/MWCNT nanocomposites

Polymer nanocomposites of epoxy resin containing multiwall carbon nanotubes (external diameter ~30 ± 10 nm, approximate length 10–20 μm) are studied using a rheological approach to determine the stage of debundling of the nanofiller in the epoxy matrix and the development of the rheological properties and structure with time. The role of processing for nanotube dispersion and structure formation is also determined by polarized microscopy and Raman spectrometry. Functionalization with amine groups is applied for part of the samples (mixing the nanotubes in amine hardener followed by mixing in appropriate amounts of epoxy resin). Further on the experimental procedure has been optimized and samples within the concentration range from 0 to 1.0 wt% have been prepared by applying high speed mechanical mixing and ultrasonic treatment with power of 250 W. The results show that chemical functionalization with amine groups contributes to significant changes in the rheological properties and hence in the structure of the composites, as proved by Raman and POM results, indicating better deaggregation of the carbon nanotubes in the amine hardener and chemical bonding of the amine groups attached to the functionalized nanotube surface with the epoxy matrix. The evolution of the dynamic viscosity in the process of polymerization reveals some interesting aspects as retarded curing in the viscometer cell, compared to the control sample under the same conditions, prolonged polymerization time owing to the applied shear rates and carbon nanotube content.     

Miscibility of a DGEBA Based Epoxy Resin Blended with Thermoplastic Mixtures of Poly(styrene) and Block Copolymers: Influence of the Copolymer Content and Chemical Nature

The miscibility and phase behavior of ternary systems formed by a DGEBA based epoxy resin, polystyrene (PS), and diblock copolymers has been investigated through phase diagrams experimentally obtained by using a light transmission device. The analysis has been done in the absence and in the presence of a curing agent. In both cases, the influence of the copolymer content and chemical nature (PS-b-PMMA or PS-b-PHEMA) has been discussed. The results show that miscibility is enhanced as the copolymer content in the ternary blend is increased, due to specific H-bonding interactions between the H-donor hydroxyl groups on the epoxy resin and the H-acceptor carbonyl groups in the copolymer, the effect being more pronounced with PMMA than with PHEMA. Experimental results have been fitted with the Flory-Huggins theoretical model by using interaction parameters depending both on temperature and composition. The morphological evolution of the epoxy networks has been examined by scanning electron microscopy (SEM).     

Effects of different parameters on thermal and mechanical properties of aminated graphene/epoxy nanocomposites connected by covalent: A molecular dynamics study

This paper is devoted to studying the thermal and mechanical properties of aminated graphene (AG)/epoxy nanocomposites connected by covalent bond using molecular dynamics (MD) simulation. The effects of crosslinking degree, mass fraction and functionalized graphene (FG) type on AG/epoxy nanocomposites are considered. The elasticity modulus (E), the glass transition temperature (T_g), the coefficient of thermal expansion (CTE) and the interfacial energy (E_int) are also investigated. The MD simulation results indicate that, when the mass fraction of AG is between 1.2% and 3.1% and crosslinking degree reaches about 70%, the E, T_g, E_int and CTE of AG/epoxy nanocomposites are significantly improved compared with those of pure epoxy and graphene/epoxy nanocomposites. The reason is that AG not only possesses some excellent thermodynamic properties of graphene, but also has the function of curing agent to crosslink with epoxy monomer to form the carbon-nitrogen (C–N) covalent bond. A better interfacial interaction between nanoparticles and epoxy is essential in enhancing the thermal and mechanical properties of nanocomposite materials, which will provide a microscopic theoretical basis for the study of epoxy nanocomposites.