Synthesis and curing of liquid crystalline epoxy resin based on asymmetric mesogen

A novel liquid crystalline epoxy resin (LCER) derived from asymmetric mesogen unit was synthesized. Its structure and liquid crystalline behavior were characterized by hydrogen nuclear magnetic resonance (H‐NMR), differential scanning calorimetry (DSC), polarized optical microscopy (POM). The results indicated that the LCER converted to a nematic phase at 85°C during heating and finally became isotropic at 145°C. The curing behavior and phase behavior of the LCER with 4,4′‐diaminodiphenyl methane and methyl hexahydrophthalic anhydride were also studied by DSC and POM, respectively. Their apparent activation energy (E_a) was evaluated according to the Ozawa's isoconversional method. The results suggested that autocatalytic reaction had occurred in these two systems. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of a liquid crystalline epoxy containing azomethine mesogen for modification of epoxy resin

A novel liquid crystalline epoxy monomer, 1,1′‐bis [4‐(2,3‐epoxypropoxyphenyleneininomethyl)]‐2,2′‐dimethylbiphenylene (BMPE) was synthesized and characterized by infrared (IR) and Nuclear magnetic resonance (NMR) spectroscopy. The effect of BMPE content on mechanical and thermal properties of its blends with Diglycidyl Ether of Biphenol A (DGEBA) was investigated. BMPE presented a Schlieren texture in the range of 150 to 215°C as observed by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The improvement of mechanical properties of DGEBA modified with BMPE was achieved without sacrificing thermal resistance. Scanning electronic microscopy (SEM) graphs of fracture surfaces of the cured blends showed that microfiber‐like structure formed in the cured blends, which would be a result of self‐oriented alignment of azomethine mesogen component. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nucleation effect of polyamide on polyoxymethylene

The crystallization behavior and morphology of polyoxymethylene (POM) and POM with polyamide (PA) were studied by polarized light microscopy (PLM), isothermal and nonisothermal differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The isothermal crystallization kinetics were analyzed with the Avrami equation. Compared with the virgin POM, the addition of PA can reduce the spherulites size and improve the crystallization growth rate and crystallinity (X_c) of POM, which demonstrates that the nucleation effect of PA as the high‐molecular nucleus is favorable to the mechanical properties and dimension stability of POLYM. ENG. SCI., 45:1174–1179, 2005. © 2005 Society of Plastics Engineers     

Synthesis,characterization, and thermomechanical properties of liquid crystalline epoxy resin containing ketone mesogen

This study focuses on the synthesis of a novel liquid crystalline epoxy resin (LCER) based on ketone mesogenic group. The chemical structure, melting range, and liquid‐crystalline phase transition behavior of the LCER were characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). Two endothermal peaks and one exothermal peak appeared in the DSC curves. A birefringent liquid crystalline texture was observed with POM during heating. The curing reaction of the LCER was monitored by DSC using diaminodipheylmethane (DDM) and diaminodiphenylsulfone (DDS) as curing agents, respectively. The results showed that the curing reaction of LCER/DDM proceeded faster than that of LCER/DDS in the initial stage. Birefringence was observed with POM during the curing processes. The results of thermomechanical properties showed that the glass transition temperatures of the cured LCERs were higher than 230°C, and that the LCER crosslinked networks were thermally stable up to 360°C. The LCER crosslinked networks showed much higher glass transition temperature, storage modulus, and thermal conductivity, and a lower coefficient of thermal expansion both in the glassy region and the rubbery region compared to those of a common epoxy resin (diglycidyl ether of bisphenol A). POLYM. ENG. SCI., 57:424–431, 2017. © 2016 Society of Plastics Engineers     

Synthesis and characterization of the two novel liquid crystalline epoxy resins based on bisphenol‐s mesogen

Two novel liquid crystalline epoxy resins (LCER) based on bisphenol‐S mesogen, 4,4′‐Bis‐(2,3‐epoxypropyloxy)‐sulfonyl bis(1,4‐phenylene) (p‐BEPSBP) and sulfonyl bis(4,1‐phenylene) bis[4‐(2,3‐epoxypropyloxy)benzoate] (p‐SBPEPB), were synthesized. Their liquid crystalline behavior and structure were characterized by Fourier transmittance infrared ray (FTIR), differential scanning calorimetry (DSC), ¹HNMR, polarized optical microscopy (POM) and X‐ray diffraction (XRD). The results show that p‐BEPSBP is a kind of thermotropic liquid crystal and has a smectic mesophase with a melting point (T_m) at 165°C; the p‐SBPEPB is a kind of nematic mesophase with the temperature range of 155–302°C from the T_m to the clearing point T_i. The curing behaviors and texture of the liquid crystalline epoxy resins with 4,4′‐diaminodiphenyl ether (DDE) were also studied by DSC and some kinetic parameters were evaluated according to the Ozawa's method. The dynamic mechanical properties of curing products were also investigated by torsional braid analysis (TBA), and the results suggest that the dynamic mechanical loss peak temperature (T_p) of p‐BEPSBP/DDE and p‐SBPEPB/DDE is 120 and 130°C, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hierarchical macroporous epoxy resin templated from single semi-fluorinated surfactant

A hierarchical macroporous epoxy resin monolith has been successfully synthesized via a single semi-fluorinated surfactant (FSO-100) templating approach. The hierarchical macroporous material is characterized by variety of techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric (TG), infrared (IR) and X-ray diffraction (XRD). The results show that this material features a hierarchical macropore distribution with pore sizes at 0.4–2 μm and 20–100 nm, respectively. Additionally, the semi-fluorinated surfactant (FSO-100) disperses homogenerously in the epoxy resin, which imparts mesoscopic features.     

Studies on novel composites of polyoxymethylene/ polyamide 6

A series of new composite of polyoxymethylene/polyamide 6 (POM/PA 6) were synthesized by using ε‐caprolactam as a reactive solvent with POM soluble in it. Incorporating a small content of POM (1–4 wt %) into PA 6 led to a great improvement of impact resistance POM/PA 6. The effects of POM content on the mechanical, morphological, and thermal properties of the composites were investigated. Incorporating minor POM (1 wt %), disposed in finely dispersed level (about 1 μm), into PA 6 matrix can greatly reduce the crystallization rate and crystallinity of PA 6. Scanning electron microscopy measurements indicated that much microfibers with aspect ratio about 10 appeared with the addition of 3 wt % POM because of the change of phase separation mechanisms. As a result, with a small content of PA 66 (1–4 wt %) incorporated, the impact strength and elongation of POM/PA 6 were improved markedly, with retention of good tensile strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 335–339, 2006     

Polyoxymethylene/polyurethane/alumina ternary composites: Structure,mechanical, thermal and dielectric properties

Ternary composites composed of polyoxymethylene (POM), polyurethane (PU), and boehmite alumina were produced by melt blending with and without latex precompounding. Latex precompounding served for the predispersion of the alumina particles. The related masterbatch (MB) was produced by mixing the PU latex with water‐dispersible boehmite alumina. The dispersion of the alumina was studied by transmission and scanning electron microscopy techniques (TEM and SEM, respectively) and discussed. The crystallization of POM was inspected by means of differential scanning calorimetry (DSC) and polarized optical microscopy (DSC and polarized light microscopy, respectively). The mechanical and thermomechanical properties of the composites were determined in uniaxial tensile, dynamic‐mechanical thermal analysis (DMTA), short‐time creep tests (performed at various temperatures), and thermogravimetric analysis (TGA). The melt flow of the composites was characterized in a plate/plate rheometer. In addition, the dielectric response of the nanocomposites was investigated by means of broadband dielectric spectroscopy at an ambient temperature. The composites produced by the MB technique outperformed the direct melt (DM) compounded composites in respect to the thermal and mechanical characteristics. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of a synthetic ureido nucleating agent on crystallization behavior and mechanical properties of polyamide 6

A synthetic ureido mixture prepared from the reaction of 4,4′‐diphenylmethane disocynanate (MDI) and cyclohexylamine without using any harmful organic solvents, has been used as a nucleating agent (PNA) for polyamide 6 (PA6). The effect of PNA on the crystallization and mechanical properties of PA6 has been studied by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM), tensile test, melt flow index (MFI), and X‐ray diffraction (XRD). The results show that PNA is an effective nucleation agent for PA6. PNA affects the nucleation mechanism of PA6, and substantially accelerates the crystallization rate of PA6 and gives rise to smaller crystal size. In comparison with PA6, the crystallization temperature (T_c) of PA6/PNA (100/0.5) increases 21.3°C and the degree of sub‐cooling (ΔT_c) decreases 23.7°C. Furthermore, because of the heterogeneous nucleation induced by PNA, the spherulites of PA6 become even and tiny based on POM observation. Polymorph transform has been obtained from XRD analysis. The virgin PA6 is free of γ‐phase crystals, presented as α‐phase crystals in this study, but γ‐phase crystal appears after the introduction of PNA. The mechanical and thermal properties of PA6 are obviously improved by the addition of PNA. POLYM. ENG. SCI., 55:2011–2017, 2015. © 2015 Society of Plastics Engineers     

Studies on epoxy/calcium carbonate nanocomposites

The article describes the preparation of epoxy‐calcium carbonate nanocomposites using diaminodiphenyl sulfone (DDS) as a curing agent. The curing behavior of diglycidyl ether of bisphenol‐A (DGEBA) (1 mol) in the presence of varying amounts of nanocalcium carbonate was investigated by differential scanning calorimetry (DSC) using stoichiometric amounts of diaminodiphenyl sulphone (0.5 mol) as curing agent. The amount of calcium carbonate (～ 44 nm) was varied from 2% to 10% (w/w). In the DSC scans of these samples, a broad exothermic transition due to curing was observed in the temperature range of 110–335°C. As expected, heat of curing decreased with increasing amount of nanocalcium carbonate; however it did not affect the curing characteristics, thereby indicating that the filler did not hinder the curing reaction. Thermal stability of DGEBA in the presence of varying amounts of nano‐CaCO₃ after isothermal curing [(i.e., by heating in an air oven at 80°C (1 h), 100°C (1 h), 120°C (1.5 h), and 180°C (4 h)] was evaluated by thermogravimetry. All the samples were stable upto 350°C, and char yield at 800°C increased with increasing amount of nanocalcium carbonate. Rectangular bars were prepared by mixing DGEBA, DDS, and varying amounts of CaCO₃ using silicone mold. The nanocomposites were characterized by X‐ray, scanning electron microscopy (morphological characterization), and dynamic mechanical analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and thermal properties of liquid crystal p‐PAEB/n‐propyl methacrylate copolymers

The copolymers of p‐phenylene di{4‐[2‐(allyloxy) ethoxy]benzoate} (p‐PAEB) with n‐propyl methacrylate (PMA) were synthesized. The liquid crystalline behavior and thermal properties of copolymers were studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X‐ray diffractometer (XRD), and torsional braid analysis (TBA). The results of XRD, POM, and DSC demonstrate that the phase texture of copolymers is affected by the composition of liquid crystal units in copolymers. The POM and XRD reveal that liquid crystal monomer (p‐PAEB) and copolymers of p‐PAEB with PMA are all smectic phase texture. The dynamic mechanical properties of copolymers are investigated with TBA. The results indicate that the phase transition temperatures and dynamic mechanical loss peak temperature T_p of copolymers are affected by the composition of copolymers and liquid crystal cross networks. The maximal mechanical loss T_p is 114°C and is decreased with added PMA. The behaviors of phase transition are affected by the crosslinking density, and it is revisable for lightly crosslinking LC polymer networks, but it is nonreversible for the densely crosslinking of LC polymer networks. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical behavior of tetrafunctional/phenol novolac epoxy mixtures cured with a diamine

An amine‐cured epoxy system based on tetraglycidyldiaminodiphenylmethane and a novolac glycidyl ether resin was studied. Epoxies were prepared by varying the cure schedules and using the isothermal time–temperature–transformation diagram of the system. The materials were characterized using dynamic‐mechanical analysis (DMA), tensile stress–strain tests over a range of temperatures and testing speeds, impact, and hardness tests. Optical microscopy was used to study the fracture surfaces of the samples. Some interrelations between the behavior and the microstructure of the system are discussed. In addition, the effect of thermal aging on the mechanical properties has been studied. DMA analysis seemed to reveal a structure that tended to be less heterogeneous with increasing the crosslink density. The advance in the etherification reactions or the thermal aging has reduced the mechanical properties related with the consumption of energy to break. The optimal cure schedule according to the global properties has been established. The morphology of fractured surfaces by optical microscopy showed a clear correlation with the variation of the tensile properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2305–2313, 2000     

Structure and properties of poly(ethylene oxide)‐organo clay nanocomposite prepared via melt mixing

Poly(ethylene oxide) (PEO)/organo clay nanocomposites were prepared by melt‐mixing using a laboratory kneader followed by compression molding. The nanocomposites were characterized by X‐ray diffraction, atomic force microscopy, and scanning electron microscopy. Their crystallization behavior in hot stage was investigated by polarized optical microscopy (POM). A decrease in size and regularity were observed as a result of incorporation of clay into the PEO matrix. The dynamic viscoelastic behavior of PEO/organo clay nanocomposites was assessed using a strain‐controlled parallel plate rheometer. The effects of clay concentration and the processing temperature on the rheological properties of the nanocomposites were extensively studied. A significant increase in the viscosity and storage modulus of the nanocomposites was found with the increasing clay content. The flow activation energy decreased with the incorporation of clay. The reinforcing effect of the organoclay was determined in dynamic mechanical analysis and tensile testing. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Dimeric liquid crystalline thermosets from azo-containing diglycidyl ether cured by anhydride

A series of dimeric liquid crystalline (LC) epoxy monomers containing azobenzene group with central spacers of different lengths were synthesized and structurally characterized by ¹H NMR, ¹³C NMR, and elemental analysis. The mesogenic behavior of these monomers was measured by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD). Like other dimeric LC epoxy monomers, the melting points, clear points, and mesophase of these compounds are influenced by the carbon numbers of central spacers. Anhydride was employed to cure the monomers and LCTs with nematic phase were obtained. Thermal properties, dynamic mechanical properties and UV–Vis spectra of the LCTs were studied. The decomposition of the LCTs occurred near 220 °C and followed three stages. The LCTs also had the natural absorbance bonds of azo compounds.     

Preparation and characterization of epoxy nanocomposites containing surface‐modified graphene oxide

A three‐step grafting procedure has been used to graft the epoxy monomers (DER332) and the curing agents (diamino diphenyl methane (DDM), onto graphene oxide (GO) surface. The surface modification of GO has been performed by grafting of Jeffamine D‐2000, followed with subsequent grafting of DER332 and DDM, respectively. Fourier transform spectroscopy and thermogravimetric analysis indicate successful surface modification. The resulting modified GO, that is, (DED)‐GO, can be well dispersed in the epoxy monomers. The epoxy nanocomposites containing different GO contents can then be prepared through curing processes. The dispersion of GO in the nanocomposites is characterized by transmission electron microscopy. It is found that the tensile strength and elongation at break of epoxy nanocomposite with only 0.2 wt % DED‐GO are increased by 30 and 16% as compared with the neat epoxy resin, respectively. Dynamic mechanical analysis results show that 62% increase in storage modulus and 26°C enhancement in the glass transition temperature of the nanocomposite have been achieved with the incorporation of only 0.2 wt % of DED‐GO into the epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40236.     

含异氰酸酯基的低聚物和聚醚增容改性POM/TPU共混物

利用双螺杆挤出机制备了聚甲醛(POM)/热塑性聚氨酯弹性体(TPU)、POM/TPU/含异氰酸酯基的低聚物(Z)以及POM/TPU/Z/聚醚3种共混物。采用力学性能测试、差示扫描量热分析(DSC)、偏光显微镜(PLM)、傅里叶转换红外线光谱 (FTIR)、扫描电子显微镜(SEM)、动态力学性能分析(DMA)等,研究了3种共混物的力学性能、结晶行为及形态结构。结果表明：共混物的缺口冲击强度和断裂伸长率随TPU含量的增加而提高;异氰酸酯基低聚物（Z）和聚醚在促进分散相分散、增强两相间的相容性方面发挥重要作用,降低了聚甲醛的结晶度,能够有效地提高共混物的缺口冲击强度和断裂伸长率。     

Improvement of mechanical and electrical properties of epoxy resin with carbon nanofibers

In the present research, the reinforcement effect of vapor grown carbon nanofiber (VGCNF) was studied in relation to the mechanical properties and electrical conduction behavior of fabricated nanocomposites. Different weight fractions of nanofillers into epoxy resin, from 0.05 to 1 wt% and up to 2 wt% for mechanical and electrical properties were investigated. It was found that the optimum improvement in mechanical properties of nanocomposite is obtained at 0.25 wt% of carbon nanofibers. At this filler content, 23 % enhancement in tensile strength and 10 % in flexural strength have been observed. The degree of the VGCNF dispersion has been monitored by means of viscosity variation of the suspension during the sonication process to obtain the optimum sonication time. Finally, the quality of the dispersion for post-cured nanocomposites is characterized by fractured surfaces using the scanning electron microscopy. Agglomerates had a direct effect on the reduction of tensile and flexural strength of nanocomposites. The electrical conductivity was obtained by means of surface measuring method. The optimum amount of filler for the generation of a fine electrical conductivity was found to be around 0.5 wt% of VGCNF. After the threshold point, the electrical conductivity of nanocomposites was slightly raised in spite of adding more filler contents.     

Enhancement in the thermal and dynamic mechanical properties of high performance liquid crystalline epoxy composites through uniaxial orientation of mesogenic on carbon fiber

In this work, a high performance liquid crystalline epoxy composite was prepared and the effect of the alignment of LCE with long lateral substituent on the carbon fiber surface curing at low temperature on fracture toughness, dynamic mechanical, and thermal properties of liquid crystalline epoxy with lateral substituent (LCE6) was investigated by polarized optical microscopy (POM), wide angle X‐ray diffraction measurements (WAXS), dynamic mechanical analysis (DMA), thermogravimetric (TGA), and scanning electron microscopy (SEM). Curing degree of the composite was observed by FTIR. The experimental results indicate that the fracture toughness, glass transition temperature (T_g), thermal stability, degradation kinetics are associated with the alignment of LCE6 along long axis of carbon fiber. The alignment of LCE6 on carbon fiber surface can increase mesogen network density, which leads to higher fracture toughness, higher thermal stability, increase of the activation energies and higher T_g of the composite. The dynamic mechanical analysis shows that the compoaite possesses extremely higher dynamic storage moduli, which indicates that this LCE6/DDM/CF composite can be a high performance composite. Thus, the compoaite can be a potential candidate for advanced composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40363.     

Synthesis,phase behaviors,and mechanical properties of biphenyl‐type epoxy resins and composites

Diglycidyl ether of 3,3′,5,5′‐tetramethyl‐4,4′‐biphenyl (TMBPDGE) which has been found great applications in semiconductor packaging was synthesized. The liquid crystalline phases of diglycidyl ether of 4,4′‐dihydroxybiphenol (BPDGE) cured with phenol novolac (PN) were studied by wide angle X‐ray diffraction (WAXD) and polarized optical microscopy (POM). BPDGE was in situ copolymerized with TMBPDGE to improve its thermal and mechanical properties by means of the LC domains retained in the crosslinked networks. The results indicated that a nematic phase was formed and fixed with proper curing schedule when BPDGE was cured with PN that had no neighboring active hydrogens and the LC domains could also be efficiently embedded into the composite systems. Dynamic mechanical properties showed that epoxy networks containing LC domains displayed higher α‐relaxation temperature and linear elastic modulus traces. The impact toughness and T_g were improved with the addition of BPDGE. Scanning electron microscope observation of the fracture surfaces showed that there was a change in failure mechanism in the composite systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

环氧树脂/环氧丙烯酸酯混杂光固化材料的结构与性能

以预聚物双酚A环氧树脂（E-44）和双酚A环氧丙烯酸酯（EA）为主要原料加入一定的单体和引发剂配制成混杂光固化树脂。运用FTIR、DMA、TG及TEM等手段,表征了混杂光固化材料的结构,讨论了环氧树脂含量对材料固化程度和结构变化的影响。结果表明,混杂光固化材料具有2个玻璃化转变温度,具有良好的阻尼性能及热温度性能。