Influence of the network chain orientation on the fracture toughness of a mesogenic epoxy resin modified with CTBN

A biphenol‐type epoxy resin, which had a mesogenic group in the backbone moiety, was modified with carboxy‐terminated butadiene acrylonitrile copolymer (CTBN) as a reactive elastomer, and its fracture toughness was measured. With the addition of CTBN, the fracture toughness of the biphenol‐type epoxy resin significantly increased and became significantly higher than that of a bisphenol A‐type epoxy resin modified with CTBN. The network chain orientation in the cured biphenol‐type epoxy resin system was clearly observed during the fracture process with polarized microscopy Fourier transform infrared measurements, although such a phenomenon was not observed in the bisphenol A‐type epoxy resin system. The high toughness of the cured biphenol‐type system was clearly due to the consumption of the mechanical energy by a large deformation of the matrix resin due to the orientation of the network chains during the fracture process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1198–1209, 2003     

Thermal properties and fracture toughness of a liquid‐crystalline epoxy resin cured with an aromatic diamine crosslinker having a mesogenic group

A mesogenic‐type curing agent was synthesized to introduce a mesogenic group not only into epoxy resin backbones but also into the crosslink units. In the mesogenic curing agent system, the domain size became larger, and the network arrangement in each domain existed to a greater extent than that in a system cured with the ordinary diamine curing system according to the evidence from polarized optical micrographs and polarized Fourier transform infrared mapping measurements. Moreover, the fracture toughness of the system was considerably improved. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2486–2494, 2006     

Fracture mechanism of liquid‐crystalline epoxy resin systems with different phase structures

A liquid‐crystalline epoxy resin was cured at two different temperatures. The phases of the cured systems clearly showed isotropic and nematic polydomain structures, which depended on the curing temperature. The fracture toughness of the systems was measured, and the fracture mechanism was investigated with polarized IR measurements. The nematic polydomain structure system showed considerably higher fracture toughness than the isotropic structure. Moreover, both systems exhibited a reorientation of the network chains near the fracture surface during the fracture process, and the region of the network reorientation in the nematic polydomain structure system was larger than that in the isotropic structure system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4044–4052, 2004     

Fracture toughness of polymers in the ductile‐to‐brittle transition region: Statistical approach and lower bound determination

A method available in literature was adapted and proposed for treating scatter and nonlinearity effects in fracture toughness of polymers in the ductile‐to‐brittle transition regime. The materials used were polypropylene homopolymer (PPH) and a polypropylene‐elastomeric polyolefin blend (PPH/POes 20 wt %), at room temperature and at 20‐mm/min test rate. Under such conditions, the fracture toughness presents a large scatter and a mean value can not be used as a design parameter because it leads to toughness overestimation. Then, there is a need to find a threshold of toughness, as a safe characteristic value for design. The toughness was evaluated by using the J‐integral approach. Large sets of specimens, 53 samples per each material, were tested with the purpose to reveal a reliable tendency in fracture behavior. As the toughness was considered nonuniform throughout the material, a weakest link model was assumed, and then results were analyzed statistically by means of a three‐parameter Weibull model (3P‐W). The PPH responded well to this 3P‐W model, whereas some deviations from the original model were observed in the PPH/POes blend. However, lower‐bound toughness values could be determined for both materials by censoring nonvalid data (Δa > 0.1b₀). From an engineering point of view, the results are very encouraging, since this methodology allows to obtain a threshold of fracture toughness from a given population, that is suitable to characterize the material fracture toughness at a given temperature and strain rate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3674–3684, 2005     

Relationship between fracture toughness and domain size of liquid‐crystalline epoxy resins having polydomain structure

A liquid‐crystalline (LC) epoxy resin was cured at different temperatures and some types of curing systems having different phase structures (isotropic or polydomain, which have a microscopically ordered LC network structure) were obtained. The diameters of each domain in the polydomain system changed from the small to the larger size. The diameters of the LC domains were evaluated using a polarized optical microscope and the polarized microscopy FTIR mapping method. These systems were used to investigate the relationship between the network arrangement and mechanical properties. The fracture toughness of the cured systems was related to the enlargement of the ordered area in the network structures. With the toughness improvement, the meandering cracks were observed at the fracture surfaces. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 156–165, 2009     

Permeation and separation of benzene/cyclohexane mixtures through liquid-crystalline polymer membranes

The side-chain liquid-crystalline polymer (LCP) was synthesized by the addition of the mesogenic monomer to poly(methylsiloxane) with Pt catalyst. When the benzene/cyclohexane mixtures were permeated through the LCP membranes by pervaporation at various temperatures, the permeation rate increased with increasing benzene concentration in the feed solution and permeation temperature. Though the LCP membranes exhibited a benzene permselectivity, a mechanism of the permeation and separation for the benzene/cyclohexane mixtures was different in the glassy, liquid-crystalline and isotropic state of the LCP membranes. These results suggested that the permselectivity was fairly influenced by the change of the LCP membrane structure, that is, a state transformation. It was found that a balance of the orientation of mesogenic groups and flexibility of siloxane chains is very important for the permeability and selectivity. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 699–707, 1997     

Effect of molecular orientation on the fracture behavior of carbon black-filled natural rubber compounds

The fracture behavior of carbon black-filled natural rubber compounds, differing in filler content, was studied performing tensile tests in biaxial loading conditions, using a central notched cross-shaped specimen. The test consisted of two steps: a drawing step was initially performed loading the specimen in the direction parallel to the notch plane, up to different draw ratios, and then the specimen was loaded in the direction normal to the notch plane up to fracture. Using a fracture mechanics approach, the fracture toughness was evaluated as a function of the draw ratio applied in the drawing step. A correlation between the fracture phenomenology observed and molecular orientability and orientation was attempted. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1509–1515, 2010     

Investigation of fracture mechanism on liquid crystalline epoxy networks arranged by a magnetic field

A liquid crystalline epoxy resin was cured under non‐ and 10T‐magnetic fields, and polydomain and monodomain networks were obtained, respectively. The fracture toughness of these systems was evaluated and it was clarified that the toughness of the magnetic field system showed a higher value. To investigate the toughening mechanism, polarized micro FTIR measurements were carried out. As a result, it was clarified that their mechanisms were quiet different. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1406–1412, 2006     

Optical anisotropy of a photoreacted side-chain liquid-crystalline polymer induced by linearly polarized UV light

Linearly polarized (LP) UV photoreaction of a photo-crosslinkable side-chain liquid-crystalline polymer (SLCP) containing photoreactive cinnamoyl and biphenyl mesogenic groups ( 1 ) was studied. The optical anisotropy of the polymer film was induced by the LP-UV photoreaction and was investigated by the temperature-controlled polarized UV absorption spectroscopy and polarized FT-IR measurements. The reorientation of the nonreacted mesogenic groups along to the Ê direction of the incident LP-UV light during the photoreaction occurred at the LC temperature range of the polymer, and the induced birefringence Δn was about 0.02. Because of the high-density photo-crosslinking, the LP-UV photoreacted film showed orientational stability up to 160°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1521–1526, 1998     

Liquid crystalline epoxy resin with improved thermal conductivity by intermolecular dipole–dipole interactions

To address tremendous needs for developing efficiently heat dissipating materials with lightweights, a series of liquid crystalline epoxy resins (LCEs) are designed and synthesized as thermally conductive matrix. All prepared LCEs possess epoxies at the molecular side positions and cyanobiphenyl mesogenic end groups. Based on several experimental results such as differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction, it is found that the LCEs exhibited liquid crystalline mesophases. When LCE is cured with a diamine crosslinker, the cured LCE maintains the oriented LC domain formed in the uncured state, ascribing to a presence of dipole–diploe and π–π interactions between cyanobiphenyl mesogenic end groups. Due to the anisotropic molecular orientation, the cured LCE exhibits a high thermal conductivity of 0.46 W m^?1 K^?1, which is higher than those of commercially available crystalline or amorphous epoxy resins. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 708–715     

Fracture toughness and fracture mechanism of liquid‐crystalline epoxy resins with different polydomain structures

Liquid‐crystalline (LC) epoxy resins were cured at different temperatures to obtain polydomain LC phase–cured resins. The cured resins had polydomain structures with a nematic LC phase and their domain diameters differed depending on the curing temperatures. The relationship between the domain diameter and fracture toughness of the diglycidyl ether of terephthalylidene‐bis‐(4‐amino‐3‐methylphenol) (DGETAM)/m‐phenylenediamine (m‐PDA) systems with the nematic phase and the previously reported smectic LC phase structures was investigated. It was clarified that the highly ordered LC structure (smectic phase) in each domain could improve the fracture toughness. In addition, the changes in the network orientation of the DGETAM/m‐PDA systems were evaluated by a mapping of the microscopic infrared dichroism in the fracture process and their toughening mechanism was suggested. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Experimental fracture study of MWCNT/epoxy nanocomposites under the combined out-of-plane shear and tensile loading

In order to explore the role of multi-walled carbon nanotubes (MWCNTs) on the fracture behavior of epoxy-based nanocomposites, fracture tests were conducted under the combined out-of-plane shear and tensile loading. Epoxy resin LY-5052 together with MWCNT contents of 0.1, 0.5 and 1.0 wt% were used to produce nanocomposite specimens. The results showed that increasing the contribution of out-of-plane shear from pure mode I towards pure mode III enhanced fracture toughness for both pure epoxy and nanocomposites. Additionally, it was found that in both loading conditions of pure mode III and mixed mode I/III, increasing MWCNT content up to 1.0 wt% enhanced fracture toughness with an ascending trend. The mechanisms involved in the fracture behavior of polymer-based nanocomposites were also studied in detail using the photographs taken from the fracture surfaces by scanning electron microscopy.     

Functionally integrated liquid crystalline photochromic triple block copolymer with locally light‐ and thermal‐controllable sub‐blocks

Photoorientation and reorientation processes induced by illumination of the samples with oppositely directed polarized light and by the thermal treatment were studied for the films of triblock copolymer pAzo₁₀‐b‐pPhM₈₀‐b‐pAzo₁₀ consisting of a nematic phenyl benzoate сentral sub‐block (PhM, DP = 80) with two terminal smectic azobenzene sub‐blocks (Azo, DP = 10). For amorphized films of triblock copolymer, illumination with polarized light (λ = 546 nm) is shown to be by orientation of only Azo‐containing groups, but upon following annealing of the film, PhM groups are adjusted to the orientation of Azo fragments. It was found, that the subsequent illumination of the block copolymer sample with oppositely directed polarized light changes the orientation of azobenzene groups, while the orientation of phenyl benzoate groups is remained unchanged. Thus, the cyclic illumination of the triblock copolymer samples by the linear polarized light and subsequent thermal treatment make it possible to control and fix orientation of azobenzene and phenyl benzoate groups located in different sub‐blocks in the desired and independent manner. The comparison of these results with the data on random p(Azo₇‐ran‐PhM₃₀) copolymer of the similar composition revealed, that in the random copolymer, both Azo and PhM mesogenic groups are involved in the orientational cooperative process regardless of films process treatment. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1602–1611     

Effect of permeation temperature on permeation and separation of a benzene/cyclohexane mixture through liquid-crystalline polymer membranes

When a benzene/cyclohexane mixture of 10 wt % benzene was permeated through side-chain liquid-crystalline polymer (LCP) membranes by pervaporation at various temperatures, the permeation rate increased with increasing permeation temperature. The LCP membranes also exhibited a benzene permselectivity. The permselectivity for the benzene/cyclohexane mixture through the LCP membrane was different in the glassy, liquid-crystalline, and isotropic states. The LCP membrane had different apparent activation energies for permeation at each state. LCP membrane in the liquid-crystalline state had the highest apparent activation energy of the three states. Results suggest that the benzene permselectivity was influenced by changes in the LCP membrane structure, i.e., a state-transformation. It was found that a balance of the orientation of mesogenic groups and the flexibility of the siloxane chains was very important for benzene permselectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 281–288, 1998     

Effect of the network structure on thermal and mechanical properties of mesogenic epoxy resin cured with aromatic amine

The epoxy resin containing a typical mesogenic group such as biphenol was cured with catechol novolak and aromatic diamines which have neighboring active hydrogens. In the biphenol-type epoxy resin cured with catechol novolak, 4,4′ diaminodiphenylmethane, and p-phenylenediamine (PPD), the glass-rubber transition almost disappeared, and thus a very high elastic modulus was obtained in the high temperature region. It is clear that the thermal motion of the network chains is significantly suppressed in these cured systems. In addition, in the PPD-cured system, a characteristic pattern like a schlieren texture was clearly observed under the crossed polarized optical microscope. Thus we conclude that the mesogenic group contained in the epoxy molecule is oriented in the networks when the mesogenic epoxy resin is cured with phenols and diamines which have neighboring active hydrogens. On the other hand, the biphenol-type resin cured with 3,3′,5,5′-tetraethyl-4,4′-diamino diphenylmethane (TEDDM) showed a well-defined glass-rubber transition and, thus, a low rubbery modulus. In this cured system, no characteristic pattern was observed under the crossed polarized light. These results show that the large branches, such as ethyl groups on the network chains, prevent the orientation of network chains which contain the mesogenic group. © 1997 John Wiley & Sons, Inc.     

Polypropylene modified with elastomeric metallocene‐catalyzed polyolefin blends: Fracture behavior and development of damage mechanisms

The fracture behavior and deformation mechanisms of polypropylene modified by elastomeric metallocene‐catalyzed polyolefin blends were investigated under both static and dynamic loading conditions. The fracture toughness was evaluated with the J integral approach. The development of damage mechanisms was studied by the examination of fracture surfaces with scanning electron microscopy and by the examination of single‐edge, double‐notch, four‐point‐bending or low‐impact‐energy fractured samples with optical microscopy. In addition, tensile dilatometry measurements were carried out to determine the nature of the deformation micromechanisms. The fracture behavior and the size and shape of the damage zones were drastically influenced by the elastomeric particles and the imposed constraint. The role of the elastomeric particles was different, depending on the strain rate. Under impact loading, particle pullout and crazing were responsible for the increased fracture toughness of polypropylene. Under quasistatic loading, stable fracture growth was caused by particle cavitation, which promoted ductile tearing of polypropylene before failure continued in an unstable fashion via crazing. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1075–1089, 2004     

Crystallization,mechanical, and fracture behaviors of spherical alumina‐filled polypropylene nanocomposites

The objectives of this paper are to study the crystallization behavior and fracture characteristics of spherical alumina (Al₂O₃) nanoparticle‐filled polypropylene (PP) composites. Nanocomposites containing 1.5–5.0 wt % of the Al₂O₃ nanoparticles (pretreated with silane coupling agent) were prepared for this investigation. Wide angle X‐ray diffraction (WAXD) results show that a small amount of β‐crystal of PP forms after adding the Al₂O₃ nanoparticles. According to differential scanning calorimetric (DSC) and optical microscopy (OM) measurements, the Al₂O₃ nanoparticles make PP spherulite size reduced and crystallization temperature of PP enhanced, by acting as effective nucleating agents. However, there are no obvious differences in the crystallinity for the virgin PP and the Al₂O₃/PP nanocomposites. Tensile test shows that both the Young's modulus and the yield strength of the Al₂O₃/PP nanocomposites increase with the particle content increasing, suggesting that the interfacial interaction between the nanoparticles and PP matrix is relatively strong. Under quasi‐static loading rate, the fracture toughness (K_IC) of the Al₂O₃/PP nanocomposites was found to be insensitive to nanoparticle content. Under impact loading rate, the Izod impact strength and the impact fracture toughness (G_c) indicate that the impact fracture toughness increases initially with the addition of 1.5 wt % of the Al₂O₃ nanofillers into the PP matrix. However, with the further addition of up to 3.0 and 5.0 wt % nanoparticles, both the Izod impact strength and impact G_c change very little. By observing the single‐edge‐double‐notch (SEDN) specimens with optical microscopy after four point bending (4PB) tests, it was found that numerous crazes and microcracks form around the subcritical crack tip, indicating that crazing and microcracking are the dominant fracture mechanisms. Scanning electron microscopy (SEM) observation confirms this result. In addition, when the strain rate of 4PB tests was increased, some wave‐like branches were formed along the fractured edge for the Al₂O₃/PP nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3652–3664, 2005     

The effect of a semi‐industrial masterbatch process on the carbon nanotube agglomerates and its influence in the properties of thermoplastic carbon nanotube composites

This study details an industrial process to prepare polypropylene (PP) composites reinforced with different loadings (0.5–10wt.%) of carbon nanotubes (CNTs) from a direct dilution of a masterbatch produced by an optimized extrusion compounding process. The work demonstrates how the anisotropy in the distribution of CNTs can have a positive effect on the electrical conductivity and fracture toughness of the resulting composites. The composite with the highest loading of CNTs had an electrical conductivity of 10^?2 S/m comparable with those reported in the available literature. The composites showed anisotropy in their properties that seems to be caused by the non‐homogeneous distribution of the agglomerates produced by the orientation of the flow direction during the injection process. The composites produced in this work exhibited a fracture toughness up to 55% higher than neat PP and failed by polymer ductile tearing. It was found that the CNT agglomerates distributed throughout the matrix increased the toughness of PP by promoting plastic deformation of the matrix during the fracture process and by a slight load transfer between the polymer matrix and the CNTs of the agglomerates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 189–197     

Liquid‐crystalline thermosets from mesogenic dimeric epoxy resins by tertiary amine catalysis

Liquid‐crystalline thermosets (LCTs) were prepared by the curing of difunctional liquid‐crystalline dimeric epoxy monomers with imine moieties in the mesogenic core and central spacers of different lengths. Tertiary amines were used as catalysts in different proportions. The locked mesophases of the LCTs were characterized by polarized optical microscopy and wide‐angle X‐ray scattering and identified as smectic‐C, regardless of their smectic‐A or smectic‐C initial state. The influence of a 7.1‐T magnetic field on the macroscopic orientation of these materials was studied by dynamic mechanical analysis, and the orientation parameter was determined by IR dichroism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3916–3926, 2002     

Deformation mechanisms of nanoclay‐reinforced maleic anhydride‐modified polypropylene

Fracture properties and deformation mechanisms of nanoclay‐reinforced maleic anhydride‐modified polypropylene (MAPP) were investigated. Elastic–plastic fracture mechanics was employed to characterize the toughness in light of substantial postyield deformation for the reinforced MAPP. Upon introduction of 2.5 wt % clay loading in maleated MAPP, it was observed that tensile strength, modulus, and fracture initiation toughness concomitantly increased substantially. Continued increase in clay loading thereafter only led to stiffening and strengthening effects to the detriment of fracture toughness. A plot of the J‐integral initiation fracture toughness versus the plastic zone size demonstrated that toughening arose from plastic deformation in the reinforced matrix. Careful examination of deformed tensile specimens using small angle X‐ray scattering (SAXS) showed 2.5 wt % clay gave rise to the highest equatorial scattering, which indicates the presence of microvoids in the matrix. The SAXS results were consistent with that shown in subcritically loaded crack‐tip deformation zone using transmission electron microscopy. Thus, both macroscale three‐point bend fracture data and SAXS results led us to consistent findings and conclusions. Further increase in clay loading above 2.5 wt % reduced the scattering the matrix plasticity and thus the fracture toughness. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2759–2768, 2004