Studies on the Thermal Properties of Epoxy Resins Modified with Two Kinds of Silanes

Dimethyldiethoxysilane (DMDES) and diphenyldimethoxysilane (DPDMS)-containing epoxy resins were synthesized by dehydration polycondensation. The chemical structures were determined by FT-IR, ¹H NMR, and ¹³C NMR. The cured samples, with 4, 4′-diaminodiphenylmethane (DDM) as curing agent, were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile and impact testing. Results showed that DMDES and DPDMS-modified epoxy resins possess higher glass transition temperatures, better thermal stability, and better fracture toughness than the neat epoxy resin.     

Preparation and Properties of Novel Inherent Flame-Retardant Cyclotriphosphazene-Containing Epoxy Resins

A novel flame-retardant cyclotriphosphazene-based epoxy resin (CPEP) was successfully prepared by epoxidation of bis-(4-hydroxyphenylsulfonylphenoxy) tetraphenoxycyclotriphosphazene with epichlorohydrin, and was characterized by ¹H nuclear magnetic resonance (NMR), Fourier transform infrared, and gel permeation chromatography (GPC). Then the blends of CPEP and diglycidyl ether of bisphenol A (E51) with different mass ratios were cured using 4,4′-diaminodiphenylmethane as a curing agent. The curing behaviors and the glass transition temperatures of the resulting thermosets were studied by differential scanning calorimetry. The thermal stabilities and flame-retardant properties of the cured resins were studied by thermogravimetric analysis and UL94 tests, respectively. In addition, mechanical, hydrophobic, and electrical properties were also characterized. Compared to the corresponding E51-based thermosets, the cured resins with a mixture of CPEP and E51 showed better thermal stabilities, higher char yields, and greatly improved flame-retardant properties. Furthermore, relatively good mechanical properties, hydrophobicity, and electric resistance were maintained. The cured resins of CPEP/E51 (mass ratio 1:1) achieved UL94 V-0 rating, indicating that the epoxy resin prepared in this study could be used as a flame-retardant coating material.     

Synergistic Effect of Polyhedral Oligomeric Silsesquioxane and Multiwalled Carbon Nanotubes on the Flame Retardancy and the Mechanical and Thermal Properties of Epoxy Resin

A novel polyhedral oligomeric silsesquioxane containing phosphorus and boron (PB-POSS) was synthesized. The resulting PB-POSS and multiwalled carbon nanotubes (MWCNTs) were incorporated into an epoxy resin (EP) to prepare PB-POSS/MWCNTs/EP composites through a solution mixing method. The synergistic effect of MWCNTs and PB-POSS on the thermal and mechanical properties and the flame retardancy of these flame retardant composites were studied. The experimental results showed that the introduction of PB-POSS or MWCNTs further improved the LOI values of the epoxy resin, and the highest LOI value (32.8%) was obtained for the formulation containing 14.6 wt% PB-POSS and 0.4 wt% MWCNTs. In addition, the incorporation of both PB-POSS and MWCNTs significantly improved the thermal and mechanical properties of the composites. The mechanical properties of composites containing 14.7 wt% PB-POSS and 0.3 wt% MWCNTs reached the maximum. The impact strength and flexural strength increased by 42% and 7%, respectively, compared to the neat epoxy resin. Thus, a combination of PB-POSS and MWCNTs in the appropriate ratio could effectively enhance the thermal and mechanical properties and the flame retardancy of the epoxy resin matrix.     

Preparation and Properties of Nano‐SiO2/Epoxy Composites Cured by Mannich Amine

Nano‐SiO₂/epoxy composites cured by Mannich Amine (type T‐31) were prepared and studied and the results are reported in this paper. The nano‐SiO₂ was pretreated by a silane coupling agent (type KH‐550) and mixed with epoxy resin (type E‐51) using an ultrasonic processor. Amounts of filler loading ranged from 1% to 5% of the weight of the epoxy resin. Some properties of the resulting composites were characterized by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results of tensile tests and impact tests showed that the composite with 3% nano‐SiO₂ loading presented the best mechanical performances. The tribological performance and thermal stability of the materials were also improved with the addition of nano‐SiO₂.     

Phase Separation in Poly(Methyl Methacrylate)-Epoxy Blend

Diglycidyl ether of bisphenol A (DGEBA) epoxy resin was modified with high molecular weight poly(methyl methacrylate) (PMMA). Morphological variations of a 2 wt% PMMA-modified epoxy mixture were studied by optical microscopy and scanning electron microscopy (SEM). A PMMA-epoxy blend cured at 100°C revealed that a secondary phase morphology was observed in both epoxy and PMMA phases from the early stages of the phase separation process. A morphology consisting of a rough striated continuous phase along with large smooth regions was observed by SEM, confirming the secondary phase separation. The dynamic mechanical thermal analysis showed that the PMMA modification of epoxy at such a low PMMA concentration of 2 wt% has no major influence on the glass transition temperature of the epoxy-rich phase. The PMMA-epoxy blend showed a slight increase in the flexural properties and the fracture toughness.     

Magnetic, dielectric and thermal stability of Ni-Zn ferrite-epoxy composite thin films for electronic applications

The fabrication of flexible epoxy thin film composites was investigated in this study. Neat epoxy with a resin-to-hardener ratio of 100:32 exhibits higher tensile properties and thermal stability than neat epoxy with a resin-to-hardener ratio of 100:45. In addition, the thermal stability of epoxy composites decreased as the NiZn ferrite content in the epoxy was increased. This result could be caused by the catalytic effect of ferrite. Vibration sample magnetometer results revealed the ferrimagnetic behavior of the ferrite-filled epoxy composites. The degree of saturation magnetization of the epoxy composites increased with the addition of NiZn ferrite nanoparticles. Dielectric tests were performed at room temperature and at frequencies ranging from 10⁴ Hz to 10⁶ Hz. These findings indicate that the dielectric constant and the dielectric loss are dependent on the filler concentration and test frequency.     

Fabrication of optically transparent chitin nanocomposites

This paper demonstrates the preparation of chitin nanofibers from crab shells using a simple mechanical treatment. The nanofibers are small enough to retain the transparency of neat acrylic resin. Possessing hydroxyl and amine/N-acetyl functionalities, water suspension of chitin nanofibers was vacuum-filtered 9 times faster than cellulose nanofibers to prepare a nanofiber sheet of 90 mm in diameter. This is a prominent advantage of chitin nanofibers over cellulose nanofibers in terms of commercial application. Interestingly, chitin acrylic resin films exhibited much higher transparency than cellulose acrylic resin films owing to the close affinity between less hydrophilic chitin and hydrophobic resin. Furthermore, the incorporation of chitin nanofibers contributes to the significant improvement of the thermal expansion and mechanical properties of the neat acrylic resin. The properties of high light transmittance and low thermal expansion make chitin nanocomposites promising candidates for the substrate in a continuous roll-to-roll process in the manufacturing of various optoelectronic devices such as flat panel displays, bendable displays, and solar cells.     

The effect of mechanical relaxation on ultra-fast charge pulses in flexible epoxy resin nanocomposites

Previously we have reported the existence of small-amplitude charge pulses in crosslinked Polyethylene (XLPE) and epoxy resin with a mobility several orders of magnitude higher than that found for the incoherent charge transport relevant to the steady state current. Here the relationship of this phenomenon to mechanical relaxation in the material is investigated by using a series of epoxy resin nanocomposites based on a resin that has its flexibility increased above that of the fully cured glassy epoxy network by the addition of a suitable flexibilizing chemical. Differential Scanning Calorimetry (DSC) measurements show that the stiffness of the nanocomposite is progressively increased as the nanoparticle concentration increases. Pulsed Electro-Acoustic (PEA) measurements reveal that both positive and negative fast charge pulses exist in the unfilled epoxy at 45 and 70°C under a field of 10?kV/mm with mobility 5×10^?10 to 9×10^?10 m²?V^?1?s^?1, amplitude between 2×10^?5 and 3.6×10^?5 C?m^?2 and repetition rates between 8 and 12?s^?1. These values are reduced progressively as the nanoparticle concentration is increased from 0% in the unfilled epoxy. A???-mode mechanical relaxation is identified in the loss modulus by Dynamical Mechanical Analysis (DMA), whose activation energy moves to higher values with increasing nanoparticle concentration. It is shown that the repetition rates of both positive and negative pulses have similar values and are correlated with the ??-mode activation energy; a similar correlation is found for the activation energy of the mobility of positive pulses. The correlation of the activation energy of the mobility of negative pulses and that of the ??-mode is weaker although both show a progressive increase with nanoparticle concentration. The modification of the fast charge pulse properties by the mechanical stiffness of the epoxy nanocomposite is discussed in terms of the theory presented previously for their formation and transport.     

Preparation and Characterization of Two Types of Cyanate Ester-epoxy Resin Interpenetrating Network Matrix/Butadiene-acrylonitrile Rubber Composites

Two types of butadiene-acrylonitrile rubbers (i.e., carboxyl randomized butadiene-acrylonitrile rubber (CRBN) and hydroxyl terminated butadiene-acrylonitrile rubber (HTBN)) have been used for modifying an interpenetrating network of cyanate ester (CE)/epoxy resin (EP) (70/30). The toughness of the matrix can be improved effectively with addition of rubbers. The values of impact strength (11.6 KJ/m²) show a maximum for the CE/EP/HTBN (70/30/8) blend. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that CRBN and HTBN have a different dispersion state in the CE/EP matrix. CRBN aggregates to form regular spheres with a size of about 1 μm. HTBN disperse homogeneously with its size of the nano-level (about 10 nm). Fourier transform infrared spectrum (FTIR) and differential scanning calorimetric (DSC) analysis shows that the CRBN has higher reactivity than HTBN. The thermal gravimetric analysis (TGA) results shows that T ₁₀ (temperature of 10% weight loss) of the CE/EP system decreases with the addition of rubbers. For the CE/EP/CRBN system, both T ₃₀ (temperature of 30% weight loss) and T ₅₀ (temperature of 50% weight loss) are lower than neat CE/EP. However, for the CE/EP/HTBN system, both T ₃₀ and T ₅₀ are near to neat CE/EP. Different reactivity and compatibility between the rubbers and CE/EP matrix is the main determining factor for the thermal stability of the blends.     

环氧树脂胶的太赫兹光谱特性研究

环氧树脂是纤维增强复合材料加工中的一种重要的胶粘剂,太赫兹时域光谱技术已成为纤维增强复合材料无损检测的有力补充手段。固化温度是环氧树脂的重要参数之一,不同的固化温度会影响环氧树脂胶的性能,因此采用太赫兹时域光谱技术分别对室温和高温下固化的环氧树脂胶的太赫兹透射光谱特性进行了系统研究,计算得到了不同温度下固化的环氧树脂胶的折射率和吸收系数,并进行了对比分析。研究表明,由于室温下固化的环氧树脂样本基本没有气泡,而高温下固化的样本存在微量气泡,气泡的存在降低了样品的密度,因此室温下固化的环氧树脂胶样品的折射率和吸收系数均大于高温下固化的样品。在同种固化条件下制备的不同样品间折射率差别较小,同时,室温下固化不同样品间的吸收系数差别亦较小,但高温下固化样品间的吸收系数在0.6～1.5 THz差别逐渐变大,这主要是因为高温下制备的不同样本间的气泡分布不均匀,即密度分布存在差异。室温和高温下固化样品的吸收系数在整体上均随着频率的增加而增加,并且没有明显的吸收峰。此外,由于法布里-珀罗干涉效应的存在,导致有些厚环氧树脂样本的能量透过率在共振峰处要远大于薄样本。该研究对纤维增强复合材料的太赫兹无损检测具有重要的研究意义。     

Study on the Structure and Properties of UHMWPE/Epoxy Resin Composite Fiber

The preparation, crystallization behavior, and fiber structure and properties of ultrahigh molecular weight polyethylene (UHMWPE) epoxy resin composite fiber were studied by means of differential scanning calorimeter (DSC), X‐ray diffraction (XRD), Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and tensile testing. The morphology showed a different behavior from pure polyethylene (PE) fiber. The fiber mechanical properties, creep behavior, and thermal properties of UHMWPE fiber can be improved by adding epoxy resin. It's believed that the epoxy can serve as a physical cross‐linking agent to limit the motion or migration of PE molecules and consequently improve the fiber creep property. However, when the content of epoxy resin is higher than 5 wt%, all of the behavior and properties deteriorate.     

Thermal and Mechanical Properties of Epoxy/Carbon Fiber Composites Reinforced with Multi-walled Carbon Nanotubes

Multi-scale hybrid composite laminates of epoxy/carbon fiber (CF) reinforced with multi-walled carbon nanotubes (MWCNTs) were fabricated in an autoclave. For laminate fabrication, 0.5 wt% of pristine MWCNTs or silane-functionalized MWNCTs (f-MWCNTs) were dispersed into a diglycidyl ether of bisphenol-A epoxy system and applied on the woven carbon fabric. The neat epoxy/CF composite and the MWCNTs-reinforced epoxy/CF hybrid composites were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), tensile testing, and field emission scanning electron microscopy (FE-SEM). A significant improvement in initial decomposition temperature and glass transition temperature of epoxy/CF composite was observed when reinforced with 0.5 wt% of f-MWCNTs. The coefficient of thermal expansion (CTE), measured by TMA, diminished by 22% compared to the epoxy/CF composite, indicating an improvement in dimensional stability of the hybrid composite. No significant improvement in tensile properties of either MWCNTs/epoxy/CF composites was observed compared to those of the neat epoxy/CF composite.     

On the Thermal Degradation of a Novel Epoxy-Based Nanocomposite Cured With Tryptophan as an Environment-Friendly Curing Agent

The thermal degradation kinetics of diglycidyl ether of bisphenol-A (DGEBA) cured with tryptophan (Trp) in the presence of silica nanoparticles (SiNP) was investigated by thermogravimetry analysis. The activation energies of the solid-state decomposition process were evaluated using the advanced isoconversional method. The dependence of conversion (degradation) on the temperature and activation energy was determined allowing the calculation of master plots. The experimental master plots agreed with the first-order (F1) kinetic function for both neat epoxy and nanocomposite in the conversion range of 0.45–0.85. Using the kinetic model and the calculated kinetic parameters, the times at half conversion (α = 0.5) were computed for different degradation temperatures. The kinetic analysis showed that the degradation rate of the epoxy nanocomposite was lower than that of the neat epoxy for conversions between 0.45 and 0.85. Therefore, we concluded that adding SiNP to DGEBA/Trp can improve the thermal stability in the conversion range of 0.45–0.85.     

Carbon nanotube (CNT)–epoxy nanocomposites: a systematic investigation of CNT dispersion

A systematic investigation of the dispersion of carbon nanotubes (CNTs), 1–6 nm in diameter and a few microns in length, in a bisphenol F-based epoxy resin has been presented. Several dispersing techniques including high-speed dissolver, ultrasonic bath/horn, 3-roll mill, etc. have been employed. Optical microscopy has been extensively used to systematically characterise the state of CNT dispersion in the epoxy resin during the entire processing cycle from mixing CNT with resin to adding and curing with hardener. Complimentary viscosity measurements were also performed at various stages of nanocomposite processing. A method to produce a good CNT dispersion in resin was established, but the state of CNT dispersion was found to be extremely sensitive to its physical and chemical environments. The cured nanocomposites were further tested for their thermo-mechanical properties by dynamic mechanical thermal analysis (DMTA), and for flexural and compressive mechanical properties. The measured properties of various nanocomposite plates were then discussed in view of the corresponding CNT dispersion.     

Formation of silver nanoparticles during deposition onto viscous-fluid epoxy resin

A new method is proposed for synthesizing metallic nanoparticles in a polymer matrix. These nanoparticles are synthesized during thermal vacuum evaporation of a metal (4.8 × 10⁻⁶ g/cm²) onto the surface of viscousfluid epoxy resin (at a viscosity of 20–120 Pa s) having room temperature, which is well below the glass transition temperature of the polymer. As a result, epoxy resin layers containing silver nanoparticles in their volume form; these nanoparticles are studied by transmission electron microscopy and optical absorption spectroscopy. Various types of disperse structures formed by metallic nanoparticles in the polymer are detected. The morphology of the composite material is found to be controlled by the polymer viscosity and the metal deposition time.     

Role of curing conditions and silanization of glass fibers on carbon nanotubes (CNTs) reinforced glass fiber epoxy composites

Curing behavior of amino-functionalized carbon nanotubes (ACNT) used as reinforcing agent in epoxy resin has been examined by thermal analysis. Experiments performed as per supplier’s curing conditions showed that modification of the curing schedule influences the thermo-mechanical properties of the nanocomposites. Specifically, the glass transition temperature (T_g) of ACNT-reinforced composites increased likely due to the immobility of polymer molecules, held strongly by amino carbon nanotubes. Further, a set of composites were prepared by implementing the experimentally determined optimal curing schedule to examine its effect on the mechanical properties of different GFRP compositions, while focusing primarily on reinforced ACNT and pristine nanotube (PCNT) matrix with silane-treated glass fibers. From the silane treatment of glass fibers in ACNT matrix composition it has been observed that amino silane is much better amongst all the mechanical (tensile and flexural) properties studied. This is because of strong interface between amino silane-treated glass fibers and modified epoxy resin containing uniformly dispersed amino-CNTs. On the other hand, PCNT GFRP composites with epoxy silanes demonstrated enhanced results for the mechanical properties under investigation which may be attributed to the presence of strong covalent bonding between epoxy silane of glass fiber and epoxy–amine matrix.     

Carbon fiber/epoxy composite materials cured thermally and with microwave irradiation

In this paper, composite materials of short carbon fibers (CFs) and a thermosetting epoxy were prepared in three different ways: without curing, thermal curing, and thermal curing followed by microwave irradiation. Mechanical properties of the three kinds of CF reinforced plastic (CFRP) composites were studied to explore the effect of microwave irradiation. Microscopic study with the aid of a scanning electron microscope (SEM) was performed on fractured composite surfaces to identify the principle features of failure. Degree of polymerization of the epoxy resin in the three CFRP composites was evaluated by infrared (IR) spectroscopy. The microwave irradiated CFRP exhibited mechanically ductile behavior even though its highest degree of polymerization. Use of microwaves and resultant stronger physico-chemical linkage at the interface between CF and epoxy resin are the main feature of this study.     

Anisotropic orientation of the carbon fiber/liquid crystalline epoxy resin composites

Anisotropic orientation of carbon fiber (CF)/liquid crystalline epoxy (LCE) resin composite was readily induced during curing on a CF surface along a long molecular axis of CF. Orientation of LCE was confirmed with polarized optical microscope (POM) and wide angle X-ray diffractometer (WAXD). In addition, anisotropic ordering of LCE was correlated with curing rate, dynamic mechanical properties and thermal expansion behaviors of CF/LCE composite. Curing of LCE was accelerated in the presence of CF and the rubbery modulus of the CF/LCE composites cured at low temperature was enhanced by long-range, long axis orientational ordering of the LCE resin along a CF surface. Fully cured CF/LCE composite showed a negative coefficient of thermal expansion in the fiber direction. These results obtained in this study are interpreted in terms of structural changes occurring during curing.     

Synthesis and Curing Kinetics of UV-Curable Waterborne Bisphenol-S Epoxy-Acrylate/Polyurethane-Acrylate/Methylacryloylpropyl-POSS Nanocomposites

In order to prepare waterborne UV-curable polyurethane-acrylate (PUA) /epoxyl-acrylate (ERA) nanocomposites, the PUA, bisphenol-S epoxy acrylate (BPSEA) and methylacryloylpropyl polyhedral oligomeric silsesquioxanes (MAP-POSS) were synthesized. UV-curable BPSEA/PUA/MAP-POSS nanocomposites were prepared. The curing process, kinetics, and properties of the nanocomposites were investigated by Fourier transform infrared spectrometer (FTIR), differential scanning calorimeter (DSC) and dynamic mechanical analyzer (DMA). The base-acid resistance ability, adhesive strength, and hardness of coating films were determined. The results showed that these nanocomposites could be cured by both UV-light irradiation and a thermal free radical polymerization. Under the UV-light irradiation, they could be cured basically completely in about 20 min. The thermal free radical curing reaction could be described by a two-parameter autocatalytic ?esták-Berggren (S-B) model. The dynamic mechanical loss peak temperature, T_p, of the cured nanocomposites increased with increasing MAP-POSS content up to 8 wt%, an enhancement of 5.8°C over the pure BPSEA/PUA system, and then decreased. Films of the nanocomposites also had better base-acid resistance ability and hardness than pure BPSEA/PUA.     

Identification des propriétés thermiques de composites fibres de verre/résines thermodurcissables: Application à l'optimisation des procédés de moulage

Identification of glass fiber/thermosetting resins composites thermal properties. Application to the optimization of molding processes. A procedure has been developed to optimize molding processes of thermosetting composite materials. Three stages have been distinguished. In the first one, some thermal and kinetic properties have been measured by differential scanning calorimetry. Thermal conductivities have been identified afterwards in thick instrumented pieces, placed in a thermally regulated press. High dependences of thermal conductivities on temperature and transformation degree have been shown. Secondly, coupled heat transfers have been numerically simulated and results have been satisfactorily compared with experimental thermograms. Finally, optimization technics based on effective inverse methods have been used.These points have been illustrated with two examples : glass fiber/epoxy resin and glass fiber/polyester. Sufficient mechanical characteristics of the first one, which is cured in oven, and good surface aspect of the second, that is made by injection in heated and closed molds, had to be obtained. The results let foresee real improvement of the corresponding molding processes.