Synthesis and characterization of liquid crystalline epoxy and co-polymerisation with a non-mesomorphic epoxy resin

A novel liquid crystalline epoxy resin based on the imine group was synthesised and structurally characterised by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The mesogenic behaviour of the monomer was measured by differential scanning calorimetry (DSC) and polarised optical microscopy (POM), and presented various textures in the extensive temperature range. Methyl nadic anhydride (MNA) was employed to cure the liquid crystalline epoxy resin and the curing process was investigated using POM and wide-angle X-ray diffraction (WAXD). Information about distribution of liquid crystalline epoxy resin in the blending system resulted from the FT-IR Imaging System, indicating that molecules of liquid crystalline epoxy resin can agglomerate to form anisotropic domains. The improvement in mechanical properties of diglycidyl ether of biphenol A (DGEBA) modified with liquid crystalline epoxy was achieved. Scanning electronic microscopy (SEM) showed that an extremely rough and highly deformed fracture surface can be obtained. DGEBA modified with liquid crystalline epoxy resin was characterised by dynamic mechanical analysis (DMA) for its thermal properties. The results indicate that the presence of the liquid crystal phase influences glass transition temperature (Tg).     

Preparation of highly exfoliated epoxy/clay nanocomposites by clay grafted with liquid crystalline epoxy

Epoxy/clay nanocomposites with a high degree of exfoliation were achieved by intercalating liquid crystalline epoxy into clay intragallery as well as using a so-called ‘solution compounding’ process. In this process, clay modified was first treated with trichloromethane to form organoclay-trichloromethane suspension followed by liquid crystalline epoxy modification. The liquid crystalline epoxy grafted clay was then mixed extensively with epoxy to form epoxy/nanoclay composites. The mechanism of exfoliation was explored by monitoring the change of morphology of organoclay during each stage of processing with X-ray diffraction (XRD). The liquid crystalline epoxy grafted clay synthesised was characterised by fourier transform infrared spectroscopy (FT-IR) and polarising optical microscopy (POM). The clay platelets uniformly dispersed and highly exfoliated in the whole epoxy matrix were observed using transmission electron microscopy (TEM) and FT-IR imaging system. The epoxy nanocomposites were fabricated by incorporating different liquid crystalline epoxy grafted clay loading. The results revealed that the incorporation of liquid crystalline epoxy grafted clay resulted in a significant improvement in glass transition temperature (Tg) derived from dynamic mechanical analysis (DMA) and thermal stability measured by thermogravimetric analysis (TGA).     

Synthesis and characterization of liquid‐crystalline epoxy and its blend with conventional epoxy

Terephthaloyl chloride was reacted with 4‐hydroxy benzoic acid to get terephthaloylbis(4‐oxybenzoic) acid, which was characterized and further reacted with epoxy resin [diglycidyl ether of bisphenol A (DGEBA)] to get a liquid‐crystalline epoxy resin (LCEP). This LCEP was characterized by Fourier transform infrared spectrometry, ¹H and ¹³C NMR spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). LCEP was then blended in various compositions with DGEBA and cured with a room temperature curing hardener. The cured blends were characterized by DSC and dynamic mechanical analysis (DMA) for their thermal and viscoelastic properties. The cured blends exhibited higher storage moduli and lower glass‐transition temperatures (tan δ_max, from DMA) as compared with that of the pure DGEBA network. The formation of a smectic liquid‐crystalline phase was observed by POM during the curing of LCEP and DGEBA/LCEP blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3375–3383, 2003     

Synthesis and characterization of novel epoxy monomers and liquid crystal thermosets

Four new epoxy monomers have been synthesized and characterized as part of a program to prepare novel liquid crystal thermoset (LCT) materials. Three of the new epoxy monomers contained a biphenyl mesogen and were not liquid crystalline (LC). The remaining epoxy monomer, which contained a 1,4-dibenzoyloxybenzene mesogen, was synthesized in an overall yield of 30% and displayed a broad (83°C) nematic liquid crystalline phase. The new liquid crystalline epoxy monomer was cured at 120°C and postcured at 175°C with a stoichiometric amount of 1,4-phenylenediamine. The thermal transitions of the resulting LCT were studied by differential scanning calorimetry (DSC), polarized light optical microscopy (POM), thermomechanical analysis (TMA), and wide angle x-ray diffraction (WAXD) as a function of cure time and temperature. A process characterization diagram was constructed which shows that LCTs based on this new LC monomer can be processed in the liquid crystalline phase over a broad range of times and temperatures. Qualitative agreement with previous epoxy LCT results was found, as LCT's with smectic phases and without clearing temperatures were observed at long cure times (high crosslink densities), whereas nematic phases with clearing temperatures predominated in networks at short cure times (low crosslink densities). © 1993 John Wiley & Sons, Inc.     

Effect of Pickering emulsion on the mechanical performances and fracture toughness of epoxy composites

The improvement of mechanical properties and toughness of nanoparticles for epoxy composites was mostly dependent on the disperse state of nanoparticles in epoxy matrices. When the content of nanoparticles was higher than a threshold value, it was easy to aggregate and then affect the improvement effect. Pickering emulsion was prepared using SiO₂ nanoparticles as emulsifier and functional monomer as oil phase. The influence of Pickering emulsion on the curing process was investigated. The effect of Pickering emulsion on the mechanical properties, toughness, and glass transition temperature (Tg) was studied. Impact and tensile fracture surface were observed by scanning electron microscopy (SEM). Results from differential scanning calorimeter (DSC), tensile, impact, and fracture toughness tests are provided. The results indicated that the introduction of Pickering emulsion can eliminate the residual stress and accelerate curing reaction. Epoxy composites were capable of increasing tensile strength by up to 29.9%, impact strength of three‐fold, fracture toughness of 35%, and Tg of 20.7°C in comparison with the reference sample. SEM images showed that SiO₂ nanoparticles exhibit a good dispersion in epoxy matrix. The increases in mechanical properties, toughness, and Tg of epoxy composites were attributed to the “Second Phase Toughness” mechanism.     

Synthesis of Liquid Crystalline Epoxy Oligomers: Effect of Molecular Weight on the Phase Behavior

A series of epoxy‐terminated liquid crystalline oligomers with different molecular weights having α‐methylstilbene as the mesogenic unit were synthesized and characterized by means of ¹H NMR and FT‐IR spectroscopy, differential scanning calorimetry (DSC), polarized‐light optical microscopy (POM) and X‐ray diffraction. The effect of the initial ratio between epichlorohydrin and diol on the molecular weight was not significant enough to change the thermal behavior of the oligomers essentially. The copolymerization of epoxy‐ and hydroxyl‐terminated comonomers yielded high‐molecular weight oligomer, whose enantiotropic liquid crystalline character was proved by means of DSC, POM and X‐ray diffraction.     

Thermal and mechanical properties of epoxy resin toughened with epoxidized soybean oil

A series of new modified epoxy resin (EP) cured products were prepared from epoxidized soybean oil and commercial epoxy resin, with methyl nadic anhydride as curing agent and 1-methylimidazole as promoting agent. The thermal properties of the resins were characterized by DMA and TG; DSC was used to determine the curing process. Fourier transform infrared spectroscopy was utilized to investigate their molecular structures and scanning electron microscopy was used to observe the micro morphology of their impact fracture surfaces. Tensile and impact testing was employed to characterize the mechanical properties of the cured products. The combination of commercial EP with 20 wt% ESO resulted in a bioresin with the optimum set of properties: 130.5 °C T _g, 396.9 °C T _50 %, 74.89 MPa tensile strength, and 48.86 kJ m^?2 impact resistance.     

Chemical recycling of carbon fibre reinforced epoxy resin composites in subcritical water: Synergistic effect of phenol and KOH on the decomposition efficiency

The combination of phenol and potassium hydroxide (KOH) was used to chemically recycle carbon fibre reinforced epoxy resin cured with 4,4′-diaminodiphenylmethane in subcritical water. This combination had a synergistic effect on decomposing this kind of epoxy resin. The main decomposition products from the epoxy resin were identified by means of GC-MS, and a possible free-radical reaction mechanism for the decomposition of epoxy resin is proposed. The recovered carbon fibres were characterized using single fibre tensile tests, scanning electron microscopy and X-ray photoelectron spectroscopy. Compared to virgin carbon fibres after sizing removal, the surface compositions of the recovered carbon fibres had little change and the tensile strength of the recovered carbon fibres was well retained.     

Development and characterization of a novel skeletal modified tetraglycidyl epoxy toughened DGEBA epoxy matrices

The present work investigates the improvement in mechanical properties observed for commercially available diglycidyl ethers of bisphenol-A (DGEBA) with the incorporation of a new type of skeletal modified tetra glycidyl epoxy resin TGBAPB as modifier. Varying weight percentages of TGBAPB have been blended with DGEBA and cured with diaminodiphenylmethane (DDM). The chemical structure of TGBAPB was confirmed by FTIR, NMR, and molecular weight determination was carried out by ESI-MS spectroscopic techniques. The thermal properties were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and mechanical properties like tensile strength, flexural strength, impact strength were also studied by universal testing machine (UTM). Scanning electron microscopy (SEM) investigates the morphological behavior of the neat and blend epoxy resins. The results from different studies indicate that the blend epoxy resin system “B” comprising 75% DGEBA/25% TGBAPB has shown improvements in both toughness and stiffness, despite the fact that it is often found that the enhancement of these two properties together in a material cannot be simultaneously achieved. These aspects of this work are novel.     

Curing behavior and kinetics of epoxy resins cured with liquid crystalline curing agent

This article describes the synthesis of a liquid crystalline curing agent 4,4′-bis-(4-amine-butyloxy)-biphenyl (BABB), and its application as a curing agent for the epoxy resin (DGEBA) in comparison with normal curing agent, 4,4′-diaminobiphenyl (DABP). BABB was investigated with polarized optical microscopy, differential scanning calorimetry, and small-angle X-ray scatting, and the results showed that BABB displayed smectic liquid crystalline phase. The curing behaviors of DGEBA cured with BABB and DABP were studied by using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and dynamic mechanical analysis (DMA). The results indicated that BABB showed a higher chemical reactivity than DABP. The kinetics was studied under isothermal conditions using an isoconversional method, and the isothermal DSC data can be fitted reasonably by an autocatalytic curing model. The nematic droplet texture was observed for the resulting polymer network of DGEBA/BABB system, while the DGEBA/DABP system showed an isotropic state. The storage modulus of DGEBA/BABB system was enhanced in comparison with DGEBA/DABP system because of the formation of LC phase, whereas the glass transition temperatures decreased because of the introduction of flexible spacer group.     

High mechanical and thermal performance of Sasobit-modified epoxy resin,prepared via vacuum shock technique

In this study, thermal and mechanical properties of novel nanocomposite, epoxy resin reinforced with octadecylamine functionalized graphene oxide (GO-ODA) and Sasobit, prepared via creative vacuum shock technique, were investigated. By introducing 1, 3 and 5 wt% Sasobit to the neat epoxy resin, the tensile strength increased remarkably by 104%, 315% and 266%, respectively due to the unique stiff and crystalline structure of Sasobit. In addition, considerable enhancement of 125% in Young's modulus, 351% in toughness, 562% in impact resistance, ~19 °C in thermal stability and ~7 °C in glass transition temperature of epoxy resin with 3 wt% Sasobit loading was demonstrated. The composite containing 3 wt% Sasobit alone, were found to have even superior properties than GO-ODA/epoxy nanocomposite, as surprisingly 3, 2.9, 2.2 and 2 times more improvement, respectively in tensile strength, toughness, impact strength and thermal stability of epoxy resin compared to reinforcement with GO-ODA were obtained.     

Development of Liquid Crystalline Order During Cure of Mesogenic Epoxy Resins

In the present paper we describe the curing process of a new liquid crystalline epoxy monomer with 4,4′-diaminodiphenylenemethane (DDM). The characteristic of cured product is presented. Both the monomer and cured product have been characterized by IR and NMR spectroscopy, differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and dielectric relaxation spectroscopy (DRS).The curing process was analysed with the use of DSC and real-time DRS.     

Curing of liquid crystalline epoxy resins with a biguanide

This work extends the authors' investigations on liquid crystalline epoxy resins prepared from diglycidyl ether of 4,4′-dihydroxybiphenyl (DGE-DHBP) and aliphatic dicarboxylic compounds (ADC) or difunctional aromatic compounds. Syntheses and properties of these liquid crystalline epoxy resins are described elsewhere. In this paper a study on the curing reaction of the above mentioned liquid crystalline epoxy resins is presented. Ortho-tolylbiguanide was applied as the curing agent. The curing reactions were investigated by differential scanning calorimetry, microscopic observations and IR spectroscopy. Depending upon the temperature program of curing, it was possible to obtain polymeric networks with liquid crystalline order. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2739–2745, 1997     

Surface modification of cellulose nanowhiskers for application in thermosetting epoxy polymers

Cellulose nanowhiskers (CNWs) were chemically modified with dodecenyl succinic anhydride to obtain hydrophobic CNWs called DCNWs. Surface modification was confirmed by infrared spectroscopy, transmission electron microscopy, and X-ray diffraction. The surface substitution degree determined by X-ray photoelectron spectroscopy was 0.30. Nanocomposites were prepared by incorporating different amounts of DCNWs pre-dispersed in a small amount of acetone into an epoxy matrix. Scanning electron microscope demonstrated that DCNWs dispersed well in the epoxy matrix. A strong interaction was proved between the DCNWs and epoxy matrix, as results of which the nanocomposites exhibited an obvious increase in T _g by about 30 °C, simultaneous increases in tensile strength, Young’s modulus, and strain at break; and an improvement in the hydrothermal properties. Compared with the neat epoxy, the nanocomposite containing 3.5 wt% of DCNWs exhibited an increase in tensile strength by 82 %, Young’s modulus by 21 %, and a strain at break by 198 %.     

Synthesis,characterization and comparative study of mesomorphic properties of some new compounds containing both 1,2,4- and 1,3,4-oxadiazole moieties linked in the same molecule

One new homologous series of compounds containing 1,2,4- and 1,3,4-oxadiazole rings in the same molecule was synthesized. 3-(4-Butoxyphenyl)-5-{4-[5-(4-alkoxyphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-1,2,4-oxadiazole (VII)_1–8 were synthesized by several procedures. This series has been characterized by FT-IR and ¹H NMR spectroscopy. Their liquid crystalline properties were studied by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). This series did not show any liquid crystalline behaviors and only crystal to isotropic liquid transition was observed.     

Synthesis of new monodendrons,gallic acid derivatives,self- assembled in a columnar phase

This article describes the synthesis and liquid crystal properties of new compounds that are derived from gallic acid. All the compounds were characterised by ¹H and ¹³C nuclear magnetic resonance spectroscopy (¹H NMR and ¹³C NMR), Infrared spectroscopy (IR) and Elemental analysis (CHN). The mesophases of these compounds were characterised using polarising optical microscopy (POM), differential scanning calorimetry (DSC) and SAXS measurements. The morphology of the surface of the films was investigated using atomic force microscopy (AFM). Compounds 9 and 13, which remain in a supercooled state until room temperature, do not exhibit liquid crystalline behaviour. The other compounds (i.e., 5, 7 and 8) self-assemble into tubular supramolecular architectures generating hexagonal columnar (Col_h) mesophases, which was confirmed by SAXS measurements.     

Poly（vinylidene fluoride）/Clay Nanocomposites by Melt Compounding

The crystalline structures, morphologies, and mechanical properties of poly（vinylidene fluoride）/clay nanocomposites were studied using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Fourier transform infrared spectroscopy（FTIR）, polarized optical microscopy（POM）, and tensile tests. The results of XRD and TEM show that organoclays are dispersed in the poly（vinylidene fluoride）（PVDF） matrix. A clay-induced crystal transformation from α-phase to β-phase of PVFD was confirmed by XRD and FTIR. Clay layers restricted the growth of spherulite. The tensile tests indicate that the tensile modulus and yield strength as well as the elongation at break decrease when clay is loaded.     

Bio-based tri-functional epoxy resin (TEIA) blend cured with anhydride (MHHPA) based cross-linker: Thermal,mechanical and morphological characterization

A novel renewable resource based tri-functional epoxy resin from itaconic acid (TEIA) was blended with petroleum based epoxy resin (DGEBA) and fabricated at different ratios. Then, it was by thermally cured with methylhexahydrophthalic anhydride (MHHPA) in presence of 2-methylimidazole (2-MI) catalyst. The tensile, modulus, strength of virgin epoxy resin (41.97 MPa, 2222 MPa) increased to 47.59 MPa, 2515 MPa, respectively, with the addition of 30% of TEIA. The fracture toughness parameter, critical stress intensity factor (K_IC) revealed enhancement of toughness in the TEIA bio-based blends system. The thermomechanical properties of TEIA (tri-functional epoxy resin from itaconic acid) modified petroleum-epoxy networks were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The fracture morphology was also studied by the scanning electron microscopy and atomic force microscopy respectively.     

Crystallization behavior and toughening mechanism of poly(ethylene oxide) in polyoxymethylene/poly(ethylene oxide) crystalline/crystalline blends

In this study, the unique crystallization behavior of poly(ethylene oxide) (PEO) in polyoxymethylene (POM)/PEO crystalline/crystalline blends was examined in detail. This study was the first to report the typical fractionated crystallization of PEO in POM/PEO blends when PEO is fewer than 30 wt.%. The delayed crystallization temperature of PEO was confirmed at about 5°C to 14°C by using differential scanning calorimetry and perturbation–correlation moving‐window 2D correlation IR spectroscopy. Wide‐angle X‐ray diffraction indicates that no new crystal structures or co‐crystals were generated in POM/PEO. The statistical calculations of scanning electron microscopy photos show that the average diameter of PEO particles is 0.227 µm to 1.235 µm and that the number of small particles is as many as 10⁹ magnitudes per cm³. Theory analysis establishes that the delayed crystallization of PEO is a heterogeneous nucleation process and not a homogeneous nucleation process. A significant toughening effect of PEO to POM was also observed. The impact strength of POM/PEO acquires a maximum of 10.5 kJ/m² when PEO content is 5%. The impact strength of the blend increases by 78.0% compared with pure POM. To improve the toughening effect, the best particle size is established between 0.352 and 0.718 µm, with a PEO particle spacing of 0.351 µm to 0.323 µm. The number of corresponding particles was 0.887 × 10⁹ per cm3 to 3.240 × 10⁹ per cm³. A PEO toughening model for POM was proposed to provide a new and effective way to solve the problem of POM toughening. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation and cryogenic mechanical properties of epoxy resins modified by poly(ethersulfone)

A thermoplastic, poly(ethersulfone) (PES) was used to modify a bisphenol‐F based epoxy resin cured with an aromatic diamine. The initial mixtures before curing, prepared by melt mixing, were homogeneous. Scanning electron microscopy (SEM) micrographs of solvent‐etched fracture surfaces of the cured blends indicated that phase separation occurred after curing. The cryogenic mechanical behaviors of the epoxy resins were studied in terms of tensile properties and Charpy impact strength at cryogenic temperature (77 K) and compared to their corresponding behaviors at room temperature (RT). The addition of PES generally improved the tensile strength, elongation at break, and impact strength at both RT and 77 K except the RT tensile strength at 25 phr PES content. It was interesting to observe that and the maximum values of the tensile strength, elongation at break, and impact strength occurred at 20 phr PES content where a co‐continuous phase formed. Young's modulus decreased slightly with the increase of the PES content. Moreover, the tensile strength and Young's modulus at 77 K were higher than those at RT at the same composition, whereas the elongation at break and impact strength showed the opposite results. Finally, the differential scanning calorimetry analysis showed that the glass transition temperature (T_g) was enhanced by the addition of PES. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 612–624, 2008