Influence of type of compatibilizer on the rheological and mechanical behavior of LCP/TP blends under different stationary and nonstationary shear conditions

The addition of small amounts of liquid‐crystalline polymers to thermoplastics leads to the formation of in situ–reinforced materials, with improved processability and mechanical properties. Nevertheless, the lack of adhesion between the thermoplastic and the liquid‐crystalline polymer often occurs, thus requiring the use of compatibilizers. In this case, the results of several previous works show that there is an improvement of strength, usually accompanied by a decrease of toughness and, thus, the interest of LCP/TP blends for industrial applications will certainly increase if both strength and toughness are obtained. Additionally, the emphasis of previous studies has been on the evaluation of the properties of the blend under stationary conditions and not under non‐stationary ones, which are, in fact, those most relevant to processing sequences. Thus, the present work focuses on the influence of type of compatibilizer on the mechanical and rheological properties of polypropylene/LCP blends under nonstationary conditions. In terms of mechanical properties, the traditional increase of tensile strength was obtained for all compatibilizers, which was essentially due to the formation, during processing, of thinner and longer fibrils of LCP dispersed in the matrix than those observed for the noncompatibilized blends. Additionally, an improvement of the impact strength and flexural modulus was also observed for the blend in which a compatibilizer with an elastomeric nature was used. Rheologically, the experiments most sensitive to the structure were those performed in transient shear, with an increase of the transient stress (in the form of an overshoot) of different magnitudes being observed for the different compatibilizers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 694–703, 2005     

Studies on morphology,mechanical, thermal,and rheological behavior of extrusion‐blended polypropylene and thermotropic liquid crystalline polymer

Polypropylene (PP) was melt‐blended in a single‐screw extruder with a thermotropic Vectra B‐950 liquid crystalline polymer (LCP) in different proportions. The mechanical properties of such blends were compared in respect of their Young's moduli, ultimate tensile strength (UTS), percent elongation at break, and toughness to those of pure PP. The thermal properties of these blends were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphology was studied by using a polarizing light microscope (PLM) and a scanning electron microscope (SEM) while the rheological aspects of the blends and the pure PP were studied by a Haake Rheowin equipment. Mechanical analysis (tensile properties) of the blends showed pronounced improvement in the moduli and the UTS of the PP matrix in the presence of 2–10% of LCP incorporation. TGA of all the blends showed an increase in the thermal stability for all the blends with respect to the matrix polymer PP, even at a temperature of 410°C, while PP itself undergoes drastic degradation at this temperature. DSC studies indicated an increase in the softening range of the blends over that of PP. Morphological studies showed limited mixing and elongated fibril formation by the dispersed LCP phase within the base matrix (PP) at the lower ranges of LCP incorporation while exhibiting a tendency to undergo gross phase separation at higher concentrations of LCP, which forms mostly agglomerated fibrils and large droplets. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 767–774, 2003     

Characterization of the skin orientation of thermotropic liquid‐crystalline copolyester moldings with near‐edge X‐ray absorption fine structure

The process of injection‐molding net‐shape parts from thermotropic liquid‐crystalline polymers results in a skin‐core macrostructure. The underlying orientation in the core and the skin may differ both in magnitude and direction. A combination of near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy and two‐dimensional wide‐angle X‐ray scattering (2D WAXS) in transmission was used to characterize the orientation in injection‐molded plaques fabricated from thermotropic liquid‐crystalline copolyesters based on either 4,4′‐dihydroxy‐α‐methylstilbene or 6‐hydroxy‐2‐naphthoic acid/6‐hydroxybenzoic acid. NEXAFS is presented as a noninvasive in situ means of determining surface layer orientation that samples to a depth of as little as 2 nm and does not require slicing or ultramicrotoming of the samples. The effects of various processing conditions on the surface orientation in the region of the centerline of square injection‐molded plaques are presented and discussed. Comparisons are made between orientation parameters obtained by 2D WAXS in transmission, which is dominated by the microstructure in the core, and the NEXAFS technique. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2473–2480, 2005     

Synthesis and thermotropic liquid‐crystalline behavior of novel main‐chain poly(aryl ether ketones)

Novel aromatic poly(ether ketones) containing bulky lateral groups were synthesized via nucleophilic substitution reactions of 4,4′‐biphenol and (4‐chloro‐3‐trifluoromethyl)phenylhydroquinone (CF‐PH) with 1,4‐bis(p‐fluorobenzoyl)benzene. The copolymers were characterized by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, and polarized light microscopy observation. Thermotropic liquid‐crystalline behavior was observed in the copolymers containing 40, 50, 60, and 70 mol % CF‐PH. The crystalline–liquid‐crystalline transition [melting temperature (T_m)] and the liquid‐crystalline–isotropic phase transition appeared in the DSC thermograms, whereas the biphenol‐based homopolymer had only a melting transition. The novel poly(aryl ether ketones) had glass‐transition temperatures that ranged from 143 to 151°C and lower T_m's that ranged from 279 to 291°C, due to the copolymerization. The polymers showed high thermal stability, and some exhibited a large range in mesophase stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1347–1350, 2003     

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     

Influence of the monomer feeding sequence on the structure and properties of thermotropic liquid‐crystalline poly(ester imide)s

A series of poly(ester imide)s mainly derived from N,N′‐hexane‐1,6‐diylbistrimellitimides, 4,4′‐dihydroxybenzophenone, and p‐hydroxybenzoic acid were synthesized by a direct polycondensation method in benzenesulfonyl chloride, N,N′‐dimethylformamide, and pyridine with different monomer feeding sequences. The molecular structures and properties of the resultant poly(ester imide)s were characterized with NMR, IR spectrometry, polarized light microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The results showed that the monomer feeding sequences had a great effect on the sequential structure of the molecular chains of the copolymers and consequently on their liquid‐crystalline (LC) properties, fiber‐forming capability, and other properties. Thus, it is probable that one could obtain an LC poly(ester imide) with given properties by controlling the monomer feeding sequence during the polycondensation process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Barrier properties of a thermotropic liquid‐crystalline polymer

A developmental thermotropic liquid‐crystalline polymer (TLCP) made by Eastman (trade name LN001) was used for barrier property studies. This material is a highly aromatic TLCP with a T_m of 332°C. A permeability study was carried out to determine the chemical resistance of the TLCP. The permeability of methanol and toluene through a membrane of the TLCP was studied using a two‐part cell and a gas chromatograph to monitor the flux. The membranes of the TLCP and LDPE (as control) were made by compression molding. Both solvents had higher permeability through LDPE than TLCP and that of toluene was higher than that of methanol. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2457–2463, 2003     

Miscibility study of polymer blends composed of semirigid thermotropic liquid crystalline polycarbonate,poly(vinyl alcohol), and chitosan

Miscibility of binary and ternary polymer blends composed of thermotropic liquid crystalline polycarbonate (LCPC), poly(vinyl alcohol) (PVA), and chitosan was investigated by viscosity method, FTIR spectrum, and scanning electron microscope techniques. Effect of addition of chitosan as a compatibilizer on miscibility and morphology of binary LCPC/chitosan and PVA/chitosan and ternary LCPC/PVA/chitosan polymer blends was discussed. These measurements indicated that addition of chitosan into the blends of LCPC with PVA leads to an increase of miscibility and a formation of clear fibril structures on fractured surfaces, which are due to intermolecular hydrogen‐bonding interaction between LCPC, PVA, and chitosan chains. It was suggested that side‐chain hydroxy group of PVA and amino and hydroxy groups of chitosan play an important role in the formation of miscible phase and improvement of morphology in binary and ternary blends composed of LCPC, PVA, and chitosan. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1616–1622, 2004     

Blends of liquid crystalline polyester–polyurethane and epoxy: Preparation and properties

A novel liquid crystalline polyester–polyurethane (LCPU) that contains polyester mesogenic units was synthesized in the present work. Through a careful investigation of the structure and morphology of the LCPU, it was found that the home‐synthesized LCPU is a highly birefringent thermotropic nematic liquid crystal. After being blended with bisphenol‐A epoxy, the liquid crystalline polymer can, simultaneously, improve the impact strength and the glass transition temperature as well as the tensile strength and the tensile modulus of the blends. It was proved to be an efficient toughening agent for epoxy without the expense of other properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 783–787, 2003     

Influence of processing conditions on the morphological and mechanical properties of compatibilized PP/LCP blends

The main aim of this work is to study the influence of the application of different processing conditions on the morphological and mechanical properties of thermoplastic/LCP blends, in which the viscosity ratios are inferior to unity and decrease with increasing temperature. The way the microstructure evolves along the extruder determines the final morphology and thus, the mechanical performance of the systems. In the present case, the mechanical properties are related with the degree of fibrillation in the final composites. The best degree of fibrillation was obtained for low screw speeds and temperatures and for intermediate outputs. The use of high screw speeds and processing temperatures results in a decrease of the viscosity ratio, in the former case via an increase in the viscous dissipation, at the regions of higher shear rates (kneading‐elements). The application of a lower processing temperature is advantageous for deformation, break‐up, and fibrillar formation because of the higher viscosity ratios and higher shear stresses involved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Organoclay/thermotropic liquid crystalline polymer nanocomposites. Part VI: Effects of intercalated organoclay on nanocomposite morphology,thermal and rheological properties

A study of a typical intercalated structure of a thermotropic liquid crystalline polymer (TLCP) with organoclay was performed to elucidate the influence of intercalated organoclay on the TLCP molecules, especially on their liquid crystallinity, thermal and rheological properties. The intercalated structures were confirmed in TLCP and organoclay formed molecular interactions with TLCP molecules in the system. Such intercalated structures caused the glass transition temperature of the nanocomposite to become invisible in thermal measurement and also caused loss of liquid crystallinity. The TLCP molecules inside the organoclay galleries showed higher thermal stability and transition temperatures, but the orderly structure of the TLCP molecules outside the galleries was destroyed by the organoclay, causing the TLCP to display lower thermal stability and transition temperatures than pristine TLCP. At 185°C, where TLCP is in the nematic phase, the nanocomposite had three orders of magnitude higher viscosity in the linear viscoelastic region than that of TLCP, with chain mobility and relaxation time slowed due to the intercalated effects in the nanocomposite. Steady shear altered the domain sizes and oriented the highly anisotropic organoclay layers or tactoids along the shear direction.     

Mesomorphic properties of cholesteric side‐chain liquid crystalline polysiloxanes and elastomers

A series of crosslinked liquid crystalline polymers and corresponding uncrosslinked liquid crystalline polymers were prepared by graft copolymerization. Their liquid crystalline properties were characterized by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The results showed that the crosslinking obtained in the isotropic state and the introduction of nonmesogenic crosslinking units into a polymeric structure could cause additional reduction of the clearing point (T_i) of the crosslinked polymers, compared with the corresponding uncrosslinked polymers. The crosslinked polymers (P‐2–P‐4) with a low crosslinking density exhibited cholesteric phases as did the uncrosslinked polymers. In contrast, a high crosslinking density made the crosslinked polymer P‐5 lose its thermotropic liquid crystalline property. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 773–778, 2004     

Interfacial properties of polycarbonate/liquid‐crystal polymer and polystyrene/high‐impact polystyrene polymer pairs under shear deformation

We developed an energy model derived from the first principle for multilayer configurations to enhance our understanding of the interfacial property between two polymers under shear deformation. We carried out specific experiments satisfying the boundary and loading conditions of the model to obtain the energy dissipation factor (β), which characterized and quantified the interfacial property. Two polymer pairs, the miscible system polystyrene (PS)/high‐impact polystyrene (HIPS) and the immiscible system polycarbonate (PC)/liquid‐crystal polymer (LCP), were investigated. As expected, β was zero for PS/HIPS, reflecting the strong interaction at the PS/HIPS interface. For PC/LCP, the value of β could be significant, and its behavior was complex; it reflected the thermal sensitivity and thermal history effect of the PC/LCP interface. A positive value of β also indicated the possibility of slip at the interface and provided an explanation for the negative deviation from the rule of mixture. This complex behavior of the interface was attributed to the changes in the phases and microstructure of LCPs and, therefore, the LCP/PC interface as thermal cycling was carried out in the melting/nematic range of LCPs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 258–269, 2003     

Effects of shear rate,viscosity ratio and liquid crystalline polymer content on morphological and mechanical properties of polycarbonate and LCP blends

Studies were conducted on the effects of shear rate, viscosity ratio and liquid crystalline polymer (LCP) content on the morphological and mechanical properties of polycarbonate (PC) and LCP blends. The LCP (LC5000) used was a thermotropic liquid crystalline polymer consisting of 80/20 of parahydroxybenzoic acid and poly(ethylene terephthalate) (PHB/PET). The viscosity ratio (viscosity of LCP: viscosity of matrix) was varied by using two processing temperatures. Due to the different sensitivity of materials to temperature, variation in the processing temperature will lead to varying viscosity of the components in the blends. Based on this principle, the processing temperature could be manipulated to provide a favourable viscosity ratio of below unity for fibre formation. To study the effect of shear rate, the flow rate of the blend and the mould thickness were varied. The shear rate has a significant effect on the fibrillation of the LCP phase. The effect was more prominent when the viscosity ratio was low and the matrix viscosity was high. At 5 wt% LCP, fibrillation did not occur even at low viscosity ratios and high shear rates. It was also observed that the LCP content must be sufficiently high to allow coalescence of the dispersed phase for subsequent fibrillation to occur. © 2002 Society of Chemical Industry     

Interrogation of “surface,” “skin,” and “core” orientation in thermotropic liquid‐crystalline copolyester moldings by near‐edge X‐ray absorption fine structure and wide‐angle X‐ray scattering

Injection molding thermotropic liquid‐crystalline polymers (TLCPs) usually results in the fabrication of molded articles that possess complex states of orientation that vary greatly as a function of thickness. “Skin‐core” morphologies are often observed in TLCP moldings. Given that both “core” and “skin” orientation states may often differ both in magnitude and direction, deconvolution of these complex orientation states requires a method to separately characterize molecular orientation in the surface region. A combination of two‐dimensional wide‐angle X‐ray scattering (WAXS) in transmission and near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy is used to probe the molecular orientation in injection molded plaques fabricated from a 4,4′‐dihydroxy‐α‐methylstilbene (DHαMS)‐based thermotropic liquid crystalline copolyester. Partial electron yield (PEY) mode NEXAFS is a noninvasive ex situ characterization tool with exquisite surface sensitivity that samples to a depth of 2 nm. The effects of plaque geometry and injection molding processing conditions on surface orientation in the regions on‐ and off‐ axis to the centerline of injection molded plaques are presented and discussed. Quantitative comparisons are made between orientation parameters obtained by NEXAFS and those from 2D WAXS in transmission, which are dominated by the microstructure in the skin and core regions. Some qualitative comparisons are also made with 2D WAXS results from the literature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and mesomorphic properties of side‐chain cholesteric liquid‐crystalline polymers containing menthyl groups

A series of new cholesteric liquid‐crystalline polysiloxanes ( P₁ – P₅ ) derived from menthyl groups were synthesized. The chemical structures of the monomers and polymers were characterized with Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, and elemental analyses. The mesomorphic properties and thermal behavior were investigated with differential scanning calorimetry, polarizing optical microscopy, thermogravimetric analysis, and X‐ray diffraction measurements. The influence of the polymer structure on the thermal behavior was discussed. The monomer diosgeninyl 4‐allyloxybenzoate exhibited a typical cholesteric oily‐streak texture and a focal‐conic texture. Polymers P₁ – P₅ showed thermotropic liquid‐crystalline properties. P₁ displayed a smectic fan‐shaped texture, P₂ – P₅ showed a cholesteric Grandjean texture, and P₆ and P₇ did not show mesomorphic properties. The experimental results demonstrated that the glass‐transition temperature and the clearing temperature decreased, and the mesomorphic properties weakened with an increasing concentration of menthyl units. Moreover, P₁ – P₅ exhibited wide mesophase temperature ranges and high thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5559–5565, 2006     

Thermotropic liquid‐crystalline polymers: Synthesis,characterization, and properties of poly(azomethine esters)

A series of poly(azomethine ester) copolymers were synthesized by the solution polycondensation method with different diamines. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), hot‐stage polarized microscopy, wide‐angle X‐ray diffraction, and solution viscosity. All polymers showed good thermal stability. The thermotropic liquid‐crystalline properties were examined by DSC and by microscopic observations. Except for one, all of the polymers showed nematic liquid‐crystalline behavior. The effects of temperature on crystallinity and the substituent on solubility, thermal stability, melting temperature, and viscosity were also studied. The voluminosity and shape factor were also computed from the viscosity data. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 153–160, 2003     

Mesomomorphism enhancement of modified side‐chain liquid‐crystalline polysiloxanes by copolymerization

The liquid‐crystalline (LC) monomer 4‐allyoxybenzoyloxy‐4′‐buthylbenzoyloxy‐p‐phenyl (M₁), whose LC phase appeared at lower temperatures, from 137 to 227°C, and the modified mesogenic monomer 4‐allyoxybenzoyloxy‐4′‐methyloxybenzoyloxy‐p‐biphenyl (M₂), whose LC phase appeared at higher temperatures, from 185 to 312°C, were prepared. A series of side‐chain LC polysiloxanes containing M₁ and M₂ were prepared by graft copolymerization. Their LC properties were characterized by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. The results show that the introduction of the modified mesogenic monomer M₂ into the polymeric structure caused an additional increase in the clearing point (isotropic transition temperature) of the corresponding polysiloxanes, compared with unmodified polysiloxanes, but did not significantly affect the glass‐transition temperature. Moreover, the modified polysiloxanes exhibited nematic phases as the unmodified polymer did. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1196–1201, 2005     

Synthesis and liquid‐crystalline properties of poly(4‐vinylpyridinium) bromides N‐substituted with dialkyloxyterphenyl groups

Poly(4‐vinylpyridine)s (P4VPs) fully and partially quaternized with dialkyloxyterphenyl groups were synthesized and characterized. These new polymers developed both liquid‐crystalline (LC) properties and a light emission (luminescence) in the blue region. The mesomorphic behavior of the polymers was initially characterized by differential scanning calorimetry and polarizing optical microscopy and was further corroborated by X‐ray diffraction analyses. The X‐ray diffraction patterns showed in the low‐angles region several equidistant diffraction peaks (d₀₀₁, d₀₀₂, d₀₀₃, …) and in the wide‐angles region a broad peak typical of nonordered mesophases. From d₀₀₁ and the length of the monomers, we deduced that the molecular arrangement in the mesophase corresponded to a double‐layered stacking of molecules with mesogens tilted with respect to the smectic plane and the backbones sandwiched between. In this arrangement, the different parts of mesogens are segregated from one another in layered domains. The longer smectic periods observed for copolymers indicated that the nonsubstituted pyridine cycles were sandwiched between two smectic layers. The emission spectra of these polymers were characterized by a broad signal centered at 365 nm. The combination of LC properties with luminescence in the polymers is interesting for the preparation of thin films with aligned emitters, particularly for linearly polarized light emission. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of PP–LCP graft copolymers and their compatibilizing activity for PP/LCP blends

The aim of this work was the synthesis of new graft copolymers consisting of polypropylene (PP) backbones and liquid crystalline polymer (LCP) branches, to be used as compatibilizing agents for PP/LCP blends. The PP-g-LCP copolymers have been prepared by polycondensation of the monomers of a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2), that is, sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the mole ratio of 1 : 1 : 2, carried out in the presence of appropriate amounts of a commercial acrylic-acid-functionalized polypropylene (PPAA). The polycondensation products, referred to as COPP50 and COPP70, having a calculated PPAA concentration of 50 and 70 wt %, respectively, have been fractionated with boiling toluene and xylene, and the soluble and insoluble fractions have been characterized by Fourier transform infrared and nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry, and X-ray diffraction. All analytical characterizations have concordantly shown that the products are formed by intricate mixtures of unreacted PPAA and SBH together with PP-g-SBH copolymers of different composition. Exploratory experiments carried out by adding small amounts of COPP50 or COPP70 into binary mixtures of isotactic polypropylene (iPP) and SBH while blending have demonstrated that this practice leads to an appreciable improvement of the dispersion of the minor LCP phase, as well as to an increase of the crystallization rate of iPP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 391–403, 1998