Morphology and Fracture Toughness of Nanostructured Epoxy Resin Containing Amino-Terminated Poly(propylene oxide)

Amino-terminated poly(propylene oxide) (ATPPO) was incorporated into epoxy resin to toughen thermosets. It was found that nanostructured thermosets were obtained; the nanostructures were characterized by means of atomic force microscopy and small-angle X-ray scattering. The formation of the nanostructures is interpreted on the basis of the occurrence of the reaction of terminal groups of ATPPO with diglycidyl ether of bisphenol A; this reaction is suggested to result in the formation of star-shaped block copolymers composed of poly(propylene oxide) (PPO) and epoxy blocks. Due to the presence of the star-shaped block copolymer produced in situ, the phase separation of PPO induced by the reaction was confined to the nanometer scale. The glass-transition behavior and fracture toughness of the nanostructured thermosets were investigated by means of differential scanning calorimetry, dynamic mechanical thermal analysis, and the measurement of critical stress intensity factors. The epoxy thermosets were significantly toughened by the inclusion of a small amount of ATPPO. The thermal and mechanical properties of the nanostructured thermosets are compared to the binary blends of epoxy resin containing hydroxyl-terminated poly(propylene oxide) (HTPPO) with identical molecular weight. With the identical composition, the nanostructured thermosets displayed higher fracture toughness than that of their binary blends. The difference in morphology and properties is interpreted in terms of the formation of the nanostructures.     

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 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.     

新型腰果酚基不饱和树脂的结构及其紫外光固化行为的红外光谱研究

以天然产物腰果酚为原料,利用其酚羟基与环氧基的反应活性,通过开环醚化反应制备了两种腰果酚基不饱和树脂单体。通过傅里叶红外光谱研究了合成过程中主要活性基团的变化,结合核磁共振氢谱及凝胶渗透色谱分析进一步确定了合成树脂单体的分子结构,并利用红外光谱法对树脂单体的紫外光固化行为进行了研究,且对其光固化物进行了热重分析。研究表明：分子结构分析确认了目标产物的成功合成,树脂单体的分子结构以及不饱和双键含量对树脂的固化速度和固化物的热稳定性有着重要影响,两种单体在30 s内均已基本达到最高固化水平,光固化物的主分解初始温度均可达到350 ℃以上。     

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.     

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.     

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.     

两种含硅炔基树脂的固化行为研究

综合采用红外光谱（FTIR）、核磁碳谱 (13C NMR)、差示扫描量热（DSC）,热失重测试(TGA)等多种表征手段,研究了聚硅芳炔（PAR）和聚硅乙炔（PMR）两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明：PAR和PMR树脂的固化机理不同,PAR主要通过炔基间的加成和Diels-Alder反应实现分子间的固化交联,并最终形成由苯环和稠芳环组成的芳构网络;PMR则主要通过硅氢基、炔基、烯基之间的加成反应实现固化,并成形饱和的碳硅Si—C(sp3)网络结构。固化成型的芳构网络和Si—C(sp3)网络结构分别赋予了PAR和PMR树脂固化物良好的热稳定性能,它们的热分解温度T_d5均大于600 ℃,900 ℃残重率均达到85%以上。     

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.     

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。     

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.     

Quantitative evaluation of interfacial adhesion between fiber and resin in carbon fiber/epoxy composite cured by semiconductor microwave device

Interfacial adhesion between carbon fiber (CF) and epoxy resin in carbon fiber-reinforced epoxy composite, which was prepared by different heating process such as semiconductor microwave (MW) device and conventional electric oven, has been evaluated quantitatively. The interfacial shear strength (IFSS) between CF and epoxy resin, which was an indicator of adhesion on the interface, was measured by a single fiber fragmentation test. The single fiber fragmentation test showed that the IFSSs of the prepared specimens were different by heating methods. In the case of MW process, the curing reaction of epoxy resin on the CF interface would be progressed preferentially due to the selective heating of CF, resulting that the IFSSs of specimens prepared by MW irradiation were increased by enhancing the output power of MW. However, the IFSSs of the specimens were decreased by excessively high output power because the matrix resin on the CF interface was thermally degraded. As results, by optimizing the MW conditions of output power and irradiation time, the IFSS of the sample cured by MW was increased by 21% as compared to oven-heated one. It was found that the interfacial adhesion between CF and epoxy resin would be improved by the MW-assisted curing reaction on the surface of CF.     

长亚甲基链段改性固化剂的制备与性能

采用二官能度环氧树脂对己二胺进行改性,得到了含多段长亚甲基链段的柔性固化剂。利用红外光谱表征其基本结构。采用环氧树脂E-44与之进行固化,通过不同温度下固化时间对力学强度影响的分析,初步确定其最佳固化条件为80 ℃,6 h。通过热重分析检测不同固化比例下固化产物的热稳定性,并采用差示扫描量热法研究该固化剂的固化动力学参数、反应活性、最佳固化温度及时间。对其固化物拉伸剪切强度进行测试,测试结果表明:在固化比例为1:0.5时,在-196 ℃、室温、60 ℃下的拉伸剪切强度分别为16.84,14.73和13.52 MPa,基本满足实际应用的需求。     

Temperature dependence of the stress transfer for thermal resistance polymer composites by X-ray diffraction

Temperature dependence of the stress transfer from the matrix resin to the incorporated fiber has been measured for poly(p-phenylene benzobisoxazole) (PBO) fiber/bismaleimide (BMI) resin composite by a novel X-ray diffraction method. At 120°C, stress transfer and tensile strength of the PBO/BMI composite are superior to that of the PBO/epoxy composite, due to the excellent thermal resistance and good mechanical property of BMI resins. The PBO/BMI composite possesses good adhesion and excellent mechanical properties at high temperature, which are suitable for thermal resistance applications.     

Influence of Curing Pressure on the Structure and Properties of Epoxy Adhesive Films

The effects of different curing pressures on the structure and properties of bisphenol A type epoxy adhesive film (METLBOND 1515-4, Cytec Industries Inc. Germany) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), nano-indentation analysis, and tensile testing. When the curing pressure was increased from 0?MPa to 0.5?MPa FTIR showed that more rigid carbonyl groups were found in the polymers. In addition, the microscopic and macroscopic mechanical properties of the cured adhesive films were improved. Nano-indentation analysis showed that the elastic modulus of the cured product increased significantly, from 2.92?GPa to 3.49?GPa. However, the tensile tests showed that the breaking-elongation increased only slightly, from 3.10% to 3.73%, when the curing pressure was increased from 0?MPa to 0.5?MPa. DMA results showed that the crosslinking densities of the cured epoxy films were improved by the increased curing pressure. These results indicated that a higher modulus of the cured product could be gained by increasing the curing pressure appropriately.     

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.     

Glass Transition Temperatures of Epoxy Modified with Pendent Nano‐Organic Rigid‐Rod Compounds

Pendent nanoscale organic rigid‐rod compounds are molecular fiber‐like materials that can be used to reinforce the polymer matrix. In this study, 4,4′‐diphenylmethane diisocyanate (MDI) was used to covalently connect a number of organic rigid‐rod compounds [4′‐hydroxyphenyl‐4‐hydroxy‐benzoate (HPHB), phenyl 4‐hydroxybenzoate (HPB), 4,4′‐isopropylidenediphenol (BSPA), and 2‐naphthol (NPT)] to the secondary hydroxyl groups of the epoxy resin. These reactions were monitored using Fourier transform infrared (FT‐IR) spectroscopy; the products were characterized using nuclear magnetic resonance (NMR) spectroscopy. The glass transition temperatures of the organic rigid‐rod compounds modified epoxy resins were investigated through differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Thermogravimetric analysis (TGA) was used to detect the values of Td and the thermal stabilities of the polymers.     

Improving the Flame Retardancy of Polybenzoxazines with a Reactive Phosphorus-Containing Compound

A novel flame retardant resin was prepared by modifying benzoxazines with a reactive phosphorus-containing compound, 2-(6-Oxido-6H-dibenzo[c,e][1,2]oxa-phosphorin-6-yl) 1,4-benzenediol (ODOPB). The curing reactions of the benzoxazines containing ODOPB (ODOPB-BOZ) and a type of bifunctional benzoxazine (B-BOZ) were investigated via differential scanning calorimetry. The ODOPB-BOZ precursors exhibited lower curing temperature in comparison with the B-BOZ. Through dynamic mechanical analysis tests, it was found that the glass transition temperature and storage modulus of the cured ODOPB-BOZ were lower than those of the cured B-BOZ. Moreover, the tensile and flexural properties of the cured ODOPB-BOZ were also lower than those of the cured B-BOZ. The TGA tests proved that, owing to the presence of ODOPB, the char yield of the polybenzoxazines were remarkably raised while the decomposition rates at higher temperature were reduced. It was found that the flame retardancy of cured ODOPB-BOZ attained V-0 grade upon the UL-94 tests while that of cured B-BOZ was V-1 grade. SEM images showed that more compact char layers were formed in the cured ODOPB-BOZ after combustion, resulting in the improvement of flame retardance.     

Plasma treatment of carbon fibers: Non-equilibrium dynamic adsorption and its effect on the mechanical properties of RTM fabricated composites

The effect of oxygen plasma treatment on the non-equilibrium dynamic adsorption of the carbon fabric reinforcements in RTM process was studied. 5-Dimethylamino-1-naphthalene-sulfonylchloride (DNS-Cl) was attached to the curing agent to study the change of curing agent content in the epoxy resin matrix. Steady state fluorescence spectroscopy (FS) analysis was used to study this changes in the epoxy resin at the inlet and outlet of the RTM mould, and XPS was used to study the chemical changes on the carbon fiber surfaces introduced by plasma treatment. The interlaminar shear strength (ILSS) and flexural strength were also measured to study the effects of this non-equilibrium dynamic adsorption progress on the mechanical properties of the end products. FS analysis shows that the curing agent adsorbed onto the fiber surface preferentially for untreated carbon fiber, the curing agent content in the resin matrix maintain unchanged after plasma treatment for 3 min and 5 min, but after oxygen plasma treatment for 7 min, the epoxy resin adsorbed onto the fiber surface preferentially. XPS analysis indicated that the oxygen plasma treatment successfully increased some polar functional groups concentration on the carbon fiber surfaces, this changes on the carbon fiber surfaces can change the adsorption ability of carbon fiber to the resin and curing agent. The mechanical properties of the composites were correlated to this results.     

Processing and properties of carbon nanofibers reinforced epoxy powder composites

Commercially available CNFs (diameter 30–300 nm) have been used to develop both bulk and coating epoxy nanocomposites by using a solvent-free epoxy matrix powder. Processing of both types of materials has been carried out by a double-step process consisting in an initial physical premix of all components followed by three consecutive extrusions. The extruded pellets were grinded into powder and sieved. Carbon nanofibers powder coatings were obtained by electrostatic painting of the extruded powder followed by a curing process based in a thermal treatment at 200 °C for 25 min. On the other hand, for obtaining bulk carbon nanofibers epoxy composites, a thermal curing process involving several steps was needed. Gloss and mechanical properties of both nanocomposite coatings and bulk nanocomposites were improved as a result of the processing process. FE-SEM fracture surface microphotographs corroborate these results. It has been assessed the key role played by the dispersion of CNFs in the matrix, and the highly important step that is the processing and curing of the nanocomposites. A processing stage consisted in three consecutive extrusions has reached to nanocomposites free of entanglements neither agglomerates. This process leads to nanocomposite coatings of enhanced properties, as it has been evidenced through gloss and mechanical properties. A dispersion limit of 1% has been determined for the studied system in which a given dispersion has been achieved, as the bending mechanical properties have been increased around 25% compared with the pristine epoxy resin. It has been also demonstrated the importance of the thickness in the nanocomposite, as it involves the curing stage. The complex curing treatment carried out in the case of bulk nanocomposites has reached to reagglomeration of CNFs.