Relation between molecular structure and electrorheological effects in liquid crystalline polymers

The influence of the molecular structure of homogeneous fluids comprised of liquid crystalline polysiloxanes (LCSs) diluted in polydimethylsiloxane (DMS), on the increase in their viscosity upon application of an electric field (electrorheological effect, or the ER effect) was investigated, particularly in relation to the degree of polysiloxane polymerization, the composition of their mesogenic side chains, and the composition of alkyl spacers inserted between these two components. A large ER effect was observed in LCSs having spacer length of 3 carbons (C3) and diluted with DMS, even though little such effect was observed with no DMS dilution. The ER effect generally increased with increasing DMS dilution and with increasing mesogenic group content, main chain length, and spacer length. At the same time, however, the miscibility of the DMS solvent with the LC polymer decreased, resulting in instability and difficulty in measuring the shear stress at temperatures up to 40°C or higher. When spacers containing an ether bond were employed, on the other hand, little or no polymer-solvent phase separation occurred, and the ER effect was strong and stable down to temperatures of 30°C or lower. With all of the LCSs, the ER effect was observed at temperatures above their isotropic phase transition temperature as measured by DSC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 303–310, 1997     

Blends of PBT with rigid thermotropic LCP having flexible side groups: Comparison of their tensile properties with semirigid main-chain TLCP blends

Two new thermotropic liquid crystalline polymers (LCPs) were synthesized. One is a di-mesogenic LCP having a flexible hexamethylene spacer in the main chain, the other is a rigid-type main-chain LCP having alkoxy side groups on the terephthaloyl moiety of the polymer. Blends of LCP with poly(butylene) terephthalate were melt-spun at different LCP contents and different draw ratios to produce a monofilament. Maximum enhancement in the ultimate tensile strength was observed for the blends containing 5% LCP at any draw ratio, and decreased with further increase in LCP content. The initial modulus monotonically increased with increasing LCP content. The tensile properties of the rigid-type LCP blends were higher than those of the flexible main-chain LCP blends. © 1996 John Wiley & Sons, Inc.     

Influence of dilution by polydimethylsiloxane on electrorheological effect of side-chain liquid crystalline polysiloxane

A liquid crystalline polysiloxane (LCP), having an ether bond in the spacer between its siloxane main chain and its mesogenic-group side chains, exhibited a very small electrorheological (ER) effect or increase in shear stress upon application of an electric field, but mixtures of the LCP and polydimethylsiloxane (PDMS) exhibited a sharply increasing ER effect with increasing PDMS content throughout the tested range of up to 0.5 of PDMS weight fraction. When phenyl-substituted PDMS (Ph-PDMS) at a weight fraction of 0.3 was used instead of PDMS, however, the ER effect decreased with increasing phenyl content and became nearly undetectable with Ph-PDMS having a phenyl content (ratio of substituted phenyl groups to initial methyl groups) of approximately 15%. DSC analyses showed that the ER effect of the LCP/PDMS mixtures occurred undiminished throughout a temperature range in which LCP itself is an isotropic liquid in the absence of an applied electric field and suggested that the LC structure of the LCP was maintained even when it was diluted with PDMS in weight fractions of 0.5 or higher, but disrupted when diluted by a 0.3 weight fraction of Ph-PDMS having a 15% phenyl content. Optical microscopic observation of the mixtures of the LCP with a 0.3 weight fraction of PDMS or Ph-PDMS (15% phenyl content) showed that both consisted of uniformly dispersed micron-sized droplets which became elongated in the direction of the applied electric field when it was applied alone but became smaller when both the electric field and shear were applied. These results suggest that the phase separation between the LCP and the dilution oil, as well as the existence and orientation of LC domains, is essential for the generation of a large ER effect. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1319–1328, 1997     

Study on a series of main-chain liquid–crystalline ionomers containing sulfonate groups

A series of main-chain liquid–crystalline ionomers containing sulfonate groups pendant on the polymer backbone were synthesized by an interfacial condensation reaction of 4,4′-dihydroxy-α,α′-dimethyl benzalazine, a mesogenic monomer, with brilliant yellow (BY), a sulfonate-containing monomer, and a 1/9 mixture of terephthaloyl and sebacoyl dichloride. The structures of the polymers were characterized by IR and UV spectroscopies. DSC and thermogravimetric analysis were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by a polarized optical microscope, DSC, and wide-angle X-ray diffraction. The ionomers were thermally stable to about 310 °C. They were thermotropic liquid–crystalline polymers (LCPs) with high mesomorphic-phase transition temperatures and exhibited broad nematic mesogenic regions of 160–170 °C, and they were lyotropic LCPs with willowy leaf-shaped textures in sulfuric acid. However, the thermotropic liquid–crystalline properties were somewhat weakened because the concentration of BY was more than 8%. The inherent viscosity in N-methyl-2-pyrrolidone suggested that intramolecular associations of sulfonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2210–2218, 2001     

Viscosity‐reducing effects of two semiflexible liquid‐crystalline polyesters with different chain rigidities in a matrix of polycarbonate

Two liquid‐crystalline polyesters (LCPs) with different chain rigidities were synthesized and melt‐blended with polycarbonate (PC) at an LCP concentration of 2 wt %. The first LCP (LCP1) was based on hydroxybenzoic acid (HBA), hydroquinone (HQ), sebacic acid (SEA), and suberic acid (SUA) and contained a relatively high concentration of flexible units (SEA and SUA). The other one (LCP2) was based on HBA, hydroxynaphthoic acid, HQ, and SEA and contained a lower concentration of flexible units. LCP2 had a much lower melting point, a higher clearing temperature, and a lower shear viscosity than LCP1. The blending was carried out at 265, 280, and 300°C for both systems. The extent of the viscosity reduction induced by the addition of LCP1 depended on the compounding temperature, and the lowest viscosity was achieved with blending at 280°C. This was attributed to the large interfacial area and interactions between the flexible segments of LCP1 and PC chains at the interface. For PC/LCP2, the viscosity reduction was not significantly dependent on the compounding temperature, and when it was compounded at 280°C, its viscosity was significantly higher than that of PC/LCP1 at high shear rates, even though LCP2 had lower viscosity. A scanning electron microscopy study revealed that, with compounding at 265 and 280°C, LCP2 was poorly dispersed in the PC matrix in comparison with LCP1, and the glass‐transition‐temperature depression caused by the addition of LCP2 was relatively small. This indicated that interfacial interactions in PC/LCP2 were weaker, thereby explaining their different rheological behavior in comparison with PC/LCP1. With compounding at 300°C, the compatibility of both systems improved because of transesterification reactions, but this did not lead to a lower viscosity because of the lack of physical interfacial interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 960–969, 2004     

Preparation and properties of self-reinforced polypropylene/liquid crystalline polymer blends

The mechanical properties of self-reinforced liquid crystalline polymer/polypropylene (LCP/PP) blends strongly depend on the viscosity ratio of the blend components in the melt. This ratio was determined for PP blends with different commercial LCPs (Vectra A950 and Vectra B950), by means of capillary rheometry, under conditions representative for the blending process during extrusion. It was found that optimal mechanical properties were achieved when the LCP/PP viscosity ratio at 285°C ranges between 2 and 4 at a shear rate of 800–1000s⁻¹. The LCP/PP viscosity ratio appears to be shear stress dependent. This creates the option of fine tuning the LCP droplet deformation process by means of the extrusion rate. This shear stress dependence is more pronounced for PP blends with Vectra B950 than for blends with Vectra A950.     

Rheology of blends of a thermotropic liquid crystalline polymer with polyphenylene sulfide

Blends of thermotropic liquid crystalline polymer (LCP) and polyphenylene sulfide (PPS) were studied over the entire composition range using Rheometrics Stress Rheometer, capillary rheometer, and differential scanning calorimeter. There is no molecular scale mixing or chemical reaction between the components, as evidenced by melting and crystallization points in the PPS phase. From the strain scaling transients test at low‐rate, LCP and the blends require approximately 60 strain units to obtain steady stale shearing results. The large recoveries in the strain recovery test, magnitude 3 to 3.3 strain unit, are likely the results of texture present in LCPs. With increasing PPS content in LCP/PPS blends, the total recovery declines. Scaling of the transient strain rate remains, but the magnitude of the transients is reduced. At low‐rate, when the LCP is added to the PPS, the pure melts have similar visosity: 500 Pa · s for LCP and 600 Pa · s for PPS, but the viscosity of the blends goes through a maximum with concentration that is nearly three times the viscosity of the individual melts. At high‐rate, a significant depression of the viscosity is observed in the PPS‐rich compositions and this may be due to the fibrous structure of the LCP at high shear rates.     

Phase behaviour and bistable effect of a mixture comprising a dye side chain liquid crystalline polymer and a low molecular weight liquid crystal

Phase behaviour and bistable effect of dye side chain liquid crystalline polymer (dye LCP)/low molecular weight liquid crystal (LC) mixtures have been investigated. The smectic dye LCP was observed to be miscible with the nematic LC over wide ranges of concentration and temperature. The electro-optical effects of the dye LCP/LC mixtures could be classified into the turbid and the transparent states upon a respective application of electric fields at low and high frequencies. Both transparent and turbid states of the mixture could be maintained stable, despite an electric field having been turned off.     

Electrorheological behavior of two thermotropic and lyotropic liquid crystalline polymers

A thermotropic liquid crystalline (LC) polymer, consisting of an LC silicone having benzoic acid phenylester LC groups as side chains of the siloxane polymer main chain diluted with dimethylsilicone, and a lyotropic LC polymer solution, consisting of poly(γ-benzyl-L -glutamate) in 1,4-dioxane, both showed a large electrorheological (ER) effect, i.e., an instantaneous increase in shear stress upon the application of an electric field. In the electric field, the thermotropic polymer exhibited Newtoman-like flow and a dynamic viscoelasticity similar to that of low molecular weight liquid crystals, while the lyotropic polymer solution exhibited elastic flow and a dynamic viscoelasticity similar to that of particle-dispersion ER fluids. These differences in ER behavior suggest large differences in their ER mechanisms, with that of the thermotropic polymer dominated by interaction between its LC domains and that of the lyotropic polymer solution by the orientation of the dipoles of its LC groups. © 1996 John Wiley & Sons, Inc.     

Rheology and morphology of some thermoplastic blends with a liquid crystalline copolyester

Liquid crystalline polymers (LCPs) are known for their high performance properties. However, owing to their high cost, research efforts are much oriented to their use as reinforcements for different thermoplastics. In this study, we investigated the morphology, mechanical and dynamic rheological properties of blends of a 60/40 para hydroxybenzoic acid–ethylene terephthalate copolyester LCP (PHB/PET) with poly(butylene terephthalate) (PBT), poly(hexamethylene terphthalate) (PHMT), and polycarbonate (PC). Addition of up to 30 wt% of LCP to the different thermoplastics was performed in a Haake Rheomix mixer at 300°C. The dynamic rheological properties of the blends showed significant changes upon the addition of LCP, but no improvement in the mechanical properties was observed. The rheological properties of the blends below the nematic transition temperature of the LCP (210°C) were similar to those of solid filled thermoplastics. At 270°C, at which the LCP is in the nematic phase, the viscosity of LCP blends with PC blends decreased, whereas that obtained with PBT blends was increased. This is interpreted as being due to the differences in viscosity and interfacial tension between the components and to a possible reaction between the LCP and the thermoplastics.     

Shear rate dependence of viscosity and first normal stress difference of LCP/PET blends at solid and molten states of LCP

The liquid crystalline polymer (LCP) and polyethylene terephthalate (PET) were blended in an elastic melt extruder to make samples having 20, 40, 60, 80, and 100 wt % of LCP. Morphology of these samples was studied using scanning electron microscopy. The steady state shear viscosity (η), dynamic complex viscosity (η*) and first normal stress difference (N₁) were evaluated and compared at two temperatures: 265°C, at which LCP was in solid state, and 285°C, at which LCP was in molten state. The PET was in molten state at both the temperatures. The shear viscosity of the studied blends displayed its dependence on composition and shear rate. A maxima was observed in viscosity versus composition plot corresponding to 80/20 LCP/PET blend. The N₁ increased with LCP loading in PET and with the increased asymmetry of LCP droplets. The N₁ also varied with the shear stress in two stages; the first stage demonstrated elastic deformation, whereas second stage displayed dominant plastic deformation of LCP droplets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2212–2218, 2007     

Silicone‐based cholesteric liquid crystalline polymers: Effect of crosslinking agent on phase transition behavior

Silicone‐based cholesteric liquid crystalline polymers (ChLCP) were fabricated with variable clearing temperatures as controlled by their chemical compositions. The chemical structures of the mesogenic monomers and ChLCP were confirmed by FTIR and ¹H‐NMR spectroscopy. The mesogenic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The experimental results demonstrated that the glass transition temperatures and the clearing points of the liquid crystalline polymers decreased with increasing proportion of mesogenic crosslinking agent up to 12.50 mol % (LCP‐3), and at higher proportion of crosslinking agent, the clearing points disappeared, indicating that the network chains have less chance to orient themselves. Thermogravimetric analysis showed that the LCP‐3 was the most stable up to 230°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Blends of thermotropic liquid crystalline polyesters and poly(butylene terephthalate): Thermal,mechanical, and morphological properties

Blends of poly(butylene terephthalate) (PBT) with three different thermotropic liquid crystalline polyesters (TLCPs) were prepared. The first TLCP (HBH-6) consists of diad aromaticester type mesogenic units and the hexamethylene spacers along the main chain, and the second (TB-S6) is a wholly aromatic polyester TLCP having alkoxy side groups on the terephthaloyl moiety. The last (TR-4,6) is an LC copolymer comsisting of triad aromatic ester type mesogenic units and two differents spacers; tetramethylene and hexamethylene units. Blends of TLCP with PBT were melt spum at different LCP contents and differnt draw ratios to produce monofilaments. For the HBH-6/PBT and TB-S6/PBT blends, the ultimate tensile strength showed a maximum value at the 5 wt% level of LCP in the blends, and then it decreased when the LCP content was increased up to 20%. On the other hand, the initial modulus monotonically increased with increasing LCP content in all cases. The blends with TB-S6 showed the highest tensile properties of the three blends systems. This can be ascribed to the highest rigidity of the polymer chain, which still carries relatively long alkoxy substituents that promote sufficient adhesion between the LCP and PBT matrix. When compared with the PBT fiber itself, the fibers obtained from the 5% TB-S6/PBT blends exhibited an improvement in tensile strength by > 25% and in tensile modulus by ～ 200%.     

Synthesis and characterization of new ferroelectric liquid‐crystalline cyclic oligosiloxanes containing methyleneoxymethylene spacers

The synthesis of side‐chain liquid‐crystalline oligocyclosiloxanes containing methyleneoxymethylene spacers, two different mesogenic cores (including biphenyl phenyl carboxylate or biphenyl fluorophenyl carboxylate groups) and chiral tails is presented. Differential scanning calorimetry, optical polarizing microscopy and X‐ray diffraction measurements reveal liquid‐crystalline properties for all of the synthesized monomers and oligomers. All cyclic oligosiloxanes exhibit enantiotropic smectic A and chiral smectic C phases. The mesogenic properties of the cyclic oligomers and side‐chain liquid‐crystalline precursor are discussed. Copyright © 2005 Society of Chemical Industry     

Molecular orientation of extruded PET/LCP blend films. Part I: Polarized infrared spectroscopy

The polarized infrared (IR) spectroscopy technique was used to evaluate the surface uniaxial molecular orientation of films of poly(ethylene terephthalate) (PET), two thermotropic liquid crystalline polymers (LCPs), Vectra®A950 and Rodrun®LC5000, and their blends obtained by extrusion. The molecular orientation of the LCP and of the crystalline and amorphous PET phases in the draw direction was evaluated along the transverse section of the films and as a function of the blend composition. A compatibilizer agent was used to improve the interfacial adhesion between the PET and LCPs. The results showed that the surface molecular orientation of both LCPs was very high along the draw direction. However, when blended, the orientation of the LCP phase decreased drastically, it was dependent of its content and varied along the transverse section of the extruded films. The maximum orientation was observed in the blend with 5 wt % LCP content and at the position where the shear rate was maxima. The LCP Vectra®A950 showed higher orientation than the Rodrun®LC5000, as a pure material and as blended. For the PET phases, an alignment of the amorphous phase in the draw direction due to the presence of LCP and compatibilizer agent was observed. The crystalline phase of PET, however, showed no significant orientation in the draw direction. The compatibilizer agent proved efficient for both PET/LCP systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2241–2248, 2006     

Side-Chain Liquid Crystalline Polymers with [α-terpineol-co-MMA] Main Chain: Synthesis and Characterization of Polymers with Phenyl Benzoate Mesogenic Group

Summary Side chain liquid crystalline (SCLC) [α-terpineol-co-MMA] polymers with a phenyl benzoate mesogenic group with polymethylene spacers have been synthesized and characterized in which the spacer length is taken 9 methylene units. The thermal behavior and liquid crystallinity of the polymer has been characterized using Differential Scanning Calorimetry (DSC) and Polarized Optical Microscopy (POM) techniques . The DSC curve of the LCpolymer shows glass transition at 52 °C followed by nematic phase which undergoes isotropization at 120 °C without undergoing side chain crystallization. Under optical polarized microscope the appearance of characteristic schlieren texture confirms the presence of nematic phase .     

One-pot synthesis of soluble wholly aromatic liquid crystalline copoly(ester amide)s with high thermal and dimensional stability

Abstract

Thermotropic liquid crystalline polymers (LCPs) have been of great interest for electronic packaging. Herein, we introduce a series of wholly aromatic, thermotropic LCPs from copoly(ester amide)s of 6-hydroxy-2-naphthalic acid, isophthalic acid, terephthalic acid, and 4-aminophenol, prepared by a convenient one-pot melt polycondensation. Almost synthesized copoly(ester amide)s exhibited good solubility in common organic solvents at room temperature. Furthermore, they possessed high thermal stability with 2% degradation temperatures (T_id) of 359–368?°C and the char yields (at 600?°C) of 50.3–55.6%. The synthesized copoly(ester amide)s had relatively low coefficient of thermal expansion (CTE) values, which were 35.85–41.21?ppm °C^?1 in the temperature range of 50–200?°C. Furthermore, an annealing process could be employed to improve the thermomechanical properties of synthesized polymers. For instance, the CTE of sample LCP3 in range temperature of 275–315?°C was reduced by more than 90% after annealing at 320?°C for 1?h, implying the feasibility for electronic packaging.     

Self‐reinforcing elastomer composites based on ethylene–propylene–diene monomer rubber and liquid‐crystalline polymer

In this study, the prime factor determining the size, shape, and distribution of liquid‐crystalline polymer (LCP) was the viscosity ratio at the processing conditions. The fiber‐forming capacity of the LCP depended on the viscosity of the ethylene–propylene–diene monomer rubber (EPDM). With increasing LCP content, the tensile and tear strengths did not increase, perhaps because of incompatibility between the EPDM and LCP. The hardness increased because of the hard mesogenic groups in the LCP. The percentage swelling decreased as the LCP content increased. With increasing LCP content, processability became easier because of a lower melt viscosity. The scorch time increased at higher LCP levels. A higher percentage crystallinity was observed with increasing LCP content. Scanning electron microscopy clearly showed the fiber phase formation, which was two‐dimensionally isotropic in nature, confirming fiber formation even in a shear field. The addition of LCP improved the thermal stability. The onset degradation temperatures shifted to higher values with increasing LCP content. Dynamic mechanical thermal analysis revealed that with the addition of LCP, the mechanical damping increased at its lower level. High‐temperature processing increased the effective amorphous zone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 711–718, 2004     

Phase transition behavior and electro‐rheological effect of liquid crystalline cyclic‐siloxanes with fluorine atoms

The phase transition behavior of liquid crystalline cyclic‐siloxanes containing fluorine atoms in the terminal mesogenic groups is reported. The series has different spacer length and the number of fluorine atoms that are included in the terminal mesogenic group. The thermal property of the compounds was investigated by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The influence of the spacer length between cyclic‐siloxane core and the terminal mesogenic groups on the mesomorphic properties was discussed. Moreover, we measured rheological property of these compounds in the presence of electric field. We described their electro‐rheological effect (ER effect) in consideration of the influence of molecular structure. The cyclic compounds exhibited considerably large ER effect of which the response time to an electric field was fast. They were expected to be used as novel ER fluids in engineering field. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Molecular dynamics simulation of liquid crystal formation within semi-flexible main chain LCPs

Molecular dynamics simulations of a semi-flexible main chain LCP (liquid crystalline polymer) have been carried out using a newly developed model named solo-LJ-spring-GB model. The new model represents the molecular chain in the form of GB-spring-LJ-spring-…-LJ-spring-GB sections that simplifies the model and reduces the simulation computation by many times. The new model was evaluated by studying the phase behaviors of semi-flexible main chain LCPs through simulation. The results, such as the spontaneous phase transition from isotropic phase to nematic phase as the system temperature decreases and the odd-even effect of the number of flexible spacers on its thermodynamic properties agree well with other experimental results as well as simulations using the traditional GB/LJ model. The orientational and translational mobilities of mesogenic units in the new model have also been measured and compared with those in the traditional GB/LJ model with very little differences found.