Effect of an epoxy octasilsesquioxane on the thermodegradation of an epoxy/amine system

Polyhedral oligomeric silsesquioxanes (POSS^®) can be added to thermoplastic and thermostable polymers to obtain hybrid materials with only a minor tendency to suffer ignition. The aim of the work reported was to analyse the influence of an octafunctional POSS^® in the pyrolysis of an epoxy/amine system as well as during the combustion process. Thermal degradation of the modified materials, with respect to the unmodified ones, was analysed using thermogravimetric analysis. As the content of POSS^® increased the stability improved and the char/ceramic yields were higher. The Kissinger–Akahira–Sunose method was applied to the modified blends and it showed a decrease in the activation energy with POSS^® content. Empirical kinetic models, as well as generalized master plots, were applied to explain the degradation mechanism for ternary blends. The limiting oxygen index parameter was measured to analyse the fire retardancy effect of POSS^®: it increased from 24.3 to 25.4% with the addition of 2.5 wt% of POSS^®. The mechanism of thermal degradation of the hybrid materials based on an epoxy resin is affected by the presence of the octaepoxy POSS^®. Only small amounts of POSS^® are necessary to enhance the combustion resistance of the system. Copyright © 2009 Society of Chemical Industry     

环氧树脂和环氧/环硫树脂与胺的固化反应动力学

采用非等温DSC法对低黏度体系CY184/IPDA环氧树脂体系及对CY184/ES184/IPDA环氧/环硫树脂体系的固化反应动力学进行了研究。用高级等转化率Vyazovkin积分法求取活化能E_a,通过Málek法确定了固化反应机理函数和动力学参数,得到固化反应动力学方程。结果表明:CY184/IPDA环氧树脂体系的平均活化能为47.04 kJ·mol^-1;CY184/ES184/IPDA环氧/环硫树脂体系的活化能为48.97 kJ·mol^-1。两种体系的模型拟合曲线与实验得到的DSC曲线吻合得较好,均符合esták-Berggren(m,n)模型。     

Dielectric relaxation during isothermal curing of epoxy resin with an aromatic amine

The isothermal curing behavior of an epoxy resin system has been monitored by a dielectric measurement whose sensor consisted of a vertical parallel-plate cell based on a three-terminal method. The materials used in the isothermal cure were the diglycidyl ether of bisphenol-A (DGEBA), which was purified from Epon 825 by recrystallization, and 4,4′-diamino diphenyl methane (DDM). A dielectric relaxation was observed during each isothermal cure at temperatures of 70,80,90, and 100°C, which were below the glass transition temperature (T_g) of the reactive DGEBA–DDM system at the gel point. The relaxation is considered to be caused by the transformation from a liquid state to an ungelled glassy state as a result of an increase in molecular weight because gelation followed by a rubbery state did not exist in the temperature range studied. The dielectric relaxation for the DGEBA–DDM system fits the empirical model of the Havriliak–Negami equation. The T_g of the DGEBA–DDM system, which was estimated from the dielectric relaxation time, agreed with the one experimentally determined by differential scanning calorimetry (DSC).     

Effect of cure temperature on the structure and water absorption of epoxy/amine thermosets

Dielectric and rheological measurements are reported on the effect of cure temperature on the water absorption of tris[(2,3-epoxypropoxy)phenyl] methane cured with a 1 : 1 stoichiometric ratio of 4,4′-diaminodiphenylsulphone. Analysis of the water absorption characteristics of these materials using a combination of dielectric and gravimetric measurements has indicated that water molecules can be found in two distinctly different types of environments. There are water molecules which are strongly interacting with polar groups and water molecules clustered together into sub-micro-scale cavities within the matrix structure. Changes in the final cure temperature have the effect of changing both the extent and distribution of the types of water molecules present in the matrix. Validation of the diffusion coefficients obtained from the dielectric analysis is based on a comparison with gravimetric data and the implications are discussed. Differences observed between these two different types of measurement are related to peculiarity in the dielectric method and its extreme sensitivity to interfacial phenomena.     

Time–temperature-transformation (TTT) diagram of the isothermal crosslinking of an epoxy/amine system: Curing kinetics and chemorheology

Rotational molding is a new process for thermosets, few research works have been done on this subject. The goal of this study is to determine the optimal conditions (time, temperature, viscosity, etc) of this process for an epoxy-amine system. The thermal and rheological analysis help us to investigate the vitrification and the gelation of the reactive system (DGEBA-DETDA) and to draw the TTT diagram. We have completed this diagram by adding the isoviscosity curves to determine the available domain for rotational molding. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of amine/epoxy ratio on the fracture toughness of tetrafunctional epoxy resin

Summary. The effect of amine/epoxy ratio on the fracture toughness (K_Ic) of tetrafunctional epoxy resin was investigated. K_Ic value was measured by single-edge notch-bend test. The K_Ic value of the tetrafunctional epoxy resin increased with increasing the amount of amine curing agent. This result was explained with the structural viewpoint of the epoxy network. The network structure of the tetrafunctional epoxy was analyzed with dynamic thermomechanical measurement and in-situ near IR technique. Received: 19 June 1997/Accepted: 17 Juli 1997     

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 °C) and at 80 °C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration.     

Effect of carbon black silanization on isothermal curing kinetics of epoxy nanocomposites

The present study was carried out to determine the effect of carbon black (CB) nanofiller silanization and loading on isothermal curing kinetics of epoxy nanocomposites. The epoxy resin specimens incorporated with 2, 4, and 8 wt% pristine CB and silanized CB were cured at isothermal temperatures of 43, 60, and 104°C. Differential scanning calorimetry was used to characterize the curing kinetics, Fourier transform infrared spectroscopy was employed to confirm silanization of CB nanofillers, and scanning electron microscopy was utilized to study the morphology of nanocomposite specimens. It was also observed that the silanization did not change the curing kinetics of CB nanocomposites significantly as compared to the neat epoxy resin. However, the curing reactions of the pristine CB nanocomposites were slower than the neat epoxy resin marked by an average 10 and 4% decrease in the final degree of cure for the nanocomposite specimens cured at 43 and 60°C, respectively. The morphological studies revealed that the silanized CB particles exhibited a more stable and homogeneous dispersion in the epoxy resin than the pristine CB particles. Potential applications for the fabricated nanocomposites include sensors, actuators, and conductive coatings for electrostatic dissipation control in plastic parts.     

Erasure below glass‐transition temperature of effect of isothermal physical aging in fully cured epoxy/amine thermosetting system

The erasure below the glass‐transition temperature (T_g) of the effect of isothermal physical aging (at aging temperature T_a) in a fully cured epoxy/amine thermosetting system is investigated using the torsional braid analysis (TBA) dynamic mechanical analysis technique and the differential scanning calorimetry (DSC) technique. From the TBA temperature scans, the intensity of the localized perturbation of the moduli in the vicinity of the T_a (90°C), due to isothermal physical aging, is decreased by heating to below the T_g (T_g∞ = 177°C), indicating that the physical aging effect can be eliminated by heating to below the T_g. The isothermal aging effect in the vicinity of the T_a is almost completely eliminated by heating to 50°C above the T_a (i.e., 140°C); however, a competing aging effect occurs above T_a at higher temperatures during the heating. Erasure below T_g of the isothermal physical aging effect is inferred from DSC experiments from the diminished relaxation enthalpy in the vicinity of the T_g, which is measured from the difference in areas between the aged (T_a = 150°C) and deaged thermograms. A comparison of the TBA and DSC results is made. Implications on the heterogeneous nature of the amorphous glassy state of polymers are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 396–404, 2001     

Dielectric analysis of the cure of thermosetting epoxy/amine systems

A low molecular weight epoxy resin is cured isothermally with an aromatic amine hardener, and the dielectric properties are measured as a function of the frequency, reaction time, and cure temperature. At specific stages in the cure, small samples from the reacting mixture are quenched and subsequently analyzed for the glass transition temperature and epoxy group conversion by differential scanning calorimetry. In this manner, the change In dielectric properties can be directly correlated with the network structure. The ionic conductivity is modeled as a function of the cure temperature and the cure-dependent glass transition temperature using a Williams-Landel-Ferry (WLF) relation. Combining this WLF relation with the DiBenedetto equation, a comprehensive model relating conductivity with the extent of reaction and cure temperature has been developed.     

胺类环氧固化剂胺值测定方法的探讨

介绍了伯胺值、仲胺值和叔胺值的测定方法,以及改性胺固化剂理论用量的计算公式。     

Etherification versus amine addition during epoxy resin/amine cure: An in situ study using near-infrared spectroscopy

The reactions between a multifunctional epoxy resin, tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) and a monofunctional amine, methylaniline (mAnil) are studied. Due to the existence of a tertiary amine catalytic center within the TGDDM molecule, the etherification reaction during cure of TGDDM is usually more significant than in other epoxide systems. The importance of this reaction relative to the amine addition reactions is investigated. In situ near-infrared spectroscopy is used to obtain kinetic data during the cure reactions. The reaction rate constants are calculated from linear regression analysis for both amine addition and etherification reactions based on the reaction mechanisms proposed. Arrhenius relationships are observed for all the reaction rate constants involved. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:895–901, 1998     

超支化胺/异佛尔酮二胺/EP固化体系的动力学研究

超支化聚合物改性EP(环氧树脂)是近年来EP应用的研究热点。以超支化聚乙烯亚胺(PEI)/异佛尔酮二胺(IPDA)作为EP的复合固化剂,探讨了PEI/IPDA/EP固化体系的固化行为和固化动力学。研究结果表明:PEI的引入能有效降低IPDA/EP体系的黏度、提高体系的相容性,并且体系的固化活化能从56.12 k J/mol降至52.02 k J/mol。     

酚醛胺/环氧树脂胶粘剂耐化学介质性能研究

以自制酚醛胺作为环氧树脂(EP)的固化剂,研究了酚醛胺/EP胶粘剂的耐化学介质性能和耐久性。结果表明:酚醛胺/EP胶粘剂在水、10%NaOH和2%NaCl溶液中浸泡48 h时,其剪切强度分别为6.61、4.66、5.12 MPa,其强度保留率分别为87.90%、61.97%、68.09%;酚醛胺/EP胶粘剂既具有良好的耐水性、耐碱性和耐盐性,又具有较好的碱、盐耐久性,可作为特种胶粘剂——水下胶粘剂广泛用于房屋、水利、地下建筑、医疗、仿生和养殖等领域,并具有良好的经济效益和应用前景。     

Effect of amine functionalization of CNF on electrical, thermal, and mechanical properties of epoxy/CNF composites

This paper presents experimental results of the effect of amine functionalization of carbon nanofibers (CNF) on the electrical, thermal, and mechanical properties of CNF/epoxy composites. The functionalized and non-functionalized CNFs (up to 3 wt%) were dispersed into epoxy using twin screw extruder. The specimens were characterized for electrical resistivities, thermal conductivity (K), UTS, and Vicker’s microhardness. The properties of the nanocomposites were compared with that of neat epoxy. The volume conductivity of the specimens increased by E12 S/cm and E09 S/cm in f-CNF/epoxy and CNF/epoxy, respectively, at 3 wt% filler loading. The increase in K for former was 106% at 150 °C, while for the latter it was only 64%. Similarly, UTS increased by 61% vs. 45% and hardness 65% vs. 43%. T _g increased with increase in filler content. SEM examinations showed that functionalization resulted in better dispersion of the nanofibers and hence greater improvement in the studied properties of the nanocomposites.     

Effect of a curing accelerator on the glass transition temperature of non-stoichiometric epoxy amine networks

Networks were prepared from Bisphenol A diglycidylether and 4,4′-diaminodiphenylmethane both in the presence of different amounts of imidazole and in the absence of any accelerator. The ratio of epoxy groups to amino hydrogen was varied: the networks were made with amino hydrogen excess, a stoichiometric ratio of epoxy groups to amino hydrogen, and an epoxy excess. The resulting networks were investigated by thermomechanical analysis, by torsion pendulum analysis and by uniaxial compression modulus measurements in the rubbery-plateau zone. Further characterization was done by sol gel analysis of the cured samples. It was shown that imidazole does not significantly influence the glass transition temperature and the soluble content of the samples of an excess of amino hydrogen was used. In the case of a stoichiometric ratio of epoxy groups to amino hydrogen and in the case of an epoxy excess, imidazole considerably influences the glass transition temperature of the networks. A dependence of the soluble content of the samples on imidazole concentration used for network synthesis was found mainly in epoxy excess systems.     

Model compound studies on the amine cure of epoxy resins

Monoepoxy phenyl glycidyl ether, curing agent p-chloroaniline, and the substituted urea type accelerator Monuron were used as a model system for studying the amine cure of epoxies. Reactions were carried out at 120°C with amine to epoxy equivalent rations of 0.25 and 1.0 Reaction mixtures were analyzed primarily by reverse phase high performance liquid chromatography. Three types of reactions occur; simple amine addition to epoxy, homopolymerization of epoxy, and epoxy polymerization involving the addition products. In the absence of accelerator the reaction involved simple addition. With the accelerator, there was competition between addition and polymerization, the balance depending on the amine to epoxy equivalent ratio. Both addition and polymerization were important for a ratio of 1, but polymerization far outweighed addition for a ratio of 0.25.     

Comparison of microwave and thermal cure of an epoxy/amine matrix

An investigation was carried out into the effect ofa microwave cure on an epoxy prepolymer with a cycloaliphatic diamine mixture, as compared to a standard thermal cure. The microwave waveguide and process (propagation mode TE₀₁) were adjusted to obtain large homogeneous samples. The extent of reaction, x, was measured during the microwave processing by size exclusion chromatography and differential scanning calorimetry. A good estimate of x was found using a modified DiBenedetto equation correlating x and the glass transition temperature T_g. The homogeneity of the samples was checked during the last steps of cure, showing the efficiency of the microwave processing and waveguide. The influence of the nature of the mold (metallic or dielectric) on the reaction kinetic was also investigated. Samples cured by both thermal and microwave processing were characterized by dynamic and static mechanical properties and then compared with those of fully crosslinked networks, i.e., postcured at a high temperature.     

新型脂环环氧树脂/胺体系固化动力学及性能研究

采用DSC研究了脂环环氧树脂稀释剂1,4-环己烷二甲醇二缩水甘油醚(CHDMDGE)与异佛尔酮二胺及聚醚胺D230的固化行为,得出其固化反应的活化能、指前因子和反应级数等动力学参数。通过外推法计算出了固化工艺的特征温度,以此为依据制定了固化工艺并对固化后体系的力学性能进行了测试。结果表明,与线形脂肪族环氧稀释剂1,4-丁二醇二缩水甘油醚和1,6-己二醇二缩水甘油醚相比,CHDMDGE的拉伸强度分别提高了0.4倍和2.7倍,断裂伸长率则提高了1.9倍和5.0倍。     

Effect of geometry and surface properties of silicates on nanostructuration of suspension in precursors of an epoxy/amine network

Several lamellar silicates (Montmorillonite, Hectorite, Mica) showing different host structures and aspect ratios were modified with octadecylammonium ions by a cationic exchange process. The resulting organoclays were characterized using thermal gravimetric analysis and X‐ray diffraction, which allowed us to estimate the amount of surfactants within the organoclays and their organization in the interlamellar spacing. Some local pseudo‐organizations were found and checked by differential scanning calorimetry (DSC). The interactions of organophilic silicates were evaluated, without any shear, with the precursors of a rubbery epoxy/amine network. These silicate/monomers interactions were monitored via the measurements of the interlamellar swelling, the surface energies and the physical gel formation. The organoclays used form gels in the monomers above the percolation threshold if no shear is applied and present a gel/sol transition at a critical shear stress. Gel strength determined from storage modulus and viscosity values determined at high shear rates reveal different organizations of clay in the monomers depending on the silicate aspect ratio and silicate/monomers interactions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1380–1390, 2006