Optical anisotropy of a thermotropic liquid-crystalline polymer in transient shear

A rheo-optical apparatus, based on a linear shear rheometer, has been constructed to study the deformation of liquid–crystalline polymers. This apparatus uses optical techniques such as flow birefringence, small-angle light scattering, and optical microscopic image analysis. The rheological responses were simultaneously measured under varying temperatures and deformation conditions. The modified Debye-Bueche equation for scattering, in the nonspherically symmetrical form, was adapted to analyze small-angle light-scattering data. The orientation correlation lengths, determined by this method, reveal the deformation mechanism in nematic melts. Flow birefringence results are in agreement with the proposed mechanism.     

Fluorescence study on a thermotropic liquid-crystalline polyester at high temperatures

A thermotropic liquid-crystalline (LC) polyester, poly[(ethylene terephthalate)-co-(p-oxybenzoate)] (PET40/OBA60) (OBA content: 60 mol %), is investigated by fluorescence technique using two model compounds: dimethyl terephthalate (DMT) and methyl methoxybenzoate (MMB) and is demonstrated to form an intermolecular ground-state complex between the terephthalate and OBA moieties. The change in fluorescence of PET40/OBA60 film is studied from 25°C to 450°C. The peak wavelength change for fluorescence of the intermolecular ground-state complex from 394 to 430 nm was observed in the temperature range between T_g and the LC transition temperature (115～ 250°C). This is attributed to the electronic distribution change between terephthalate and OBA moieties in the excited state, which play roles of acceptor and donor, respectively. The increase in the fluorescence intensity from the temperature near the annealing temperature to the temperature near the isotropic temperature (287～370°C) is suggested to be the increase in LC configuration and the formation of a more stable excited state due to the electronic distribution change between terephthalate and OBA moieties. The lifetime of PET40/OBA60 film quenched from LC temperature (300°C) to room temperature is in agreement with that of the nonannealed one, which is due to the fact that the deactivation process of the sample quenched from LC temperature is in accord with that of the nonannealed one. © 1995 John Wiley & Sons, Inc.     

Measurement of the interfacial tension between polyethersulfone and a thermotropic liquid-crystalline copolyester

Due to the increasing interest in forming blends of liquid-crystalline polymers with conventional thermoplastics, it becomes important to determine the interfacial tension between two such polymers. A method for evaluating the interfacial tension between a thermotropic copolyester based on hydroxybenzoic and hydroxynaphthoic acid residues, and polyethersulfone is presented, based on the Fort and Patterson method. It is found that the value of the interfacial tension in the melt is much higher than is the case between conventional polymer pairs. It is suggested that this high value reflects an entropic effect due to the strong exclusion of the flexible coil polymer from the nematic melt. © 1993 John Wiley & Sons, Inc.     

Studies on thermotropic liquid crystalline polymer. XI. Effect of amide group on thermotropic liquid crystalline polymer properties

A series of poly(azomethine)s containing amide, ether, or ester groups was prepared by the condensation of dialdehydes with various diamines. The thermotropic liquid crystalline properties were examined by DSC and microscopic observations. The effects of the number and position of amide groups, which are attached to the rigid segment, on the thermotropic liquid crystalline properties of the homo-and copoly(amide-azomethine-ether)s were also investigated in this study. The copolymerization took place by changing the amount of amide group to obtain copoly(amide-azomethine) ( P13 and P14 ) which exhibit thermotropic liquid crystalline properties. The poly(azomethine)s containing ether or ester groups also exhibited thermotropic liquid crystalline properties. © 1993 John Wiley & Sons, Inc.     

Studies on the thermotropic liquid-crystalline polymer. IX. Synthesis and properties of crosslinkable copoly(amide-ester)s containing conjugated double bonds

Four series of copoly(amide-ester)s containing conjugated double bonds were prepared by using direct polycondensation in the presence of diphenylchlorophosphate (DPCP) and pyridine. Series I–III were prepared from para, meta-aminophenol, or their mixture with p-phenylene bis(acrylic acid) (PPBA), p-carboxylic cinnamic acid (PCCA), and stilbenedicarboxylic acid (SDBA), respectively. Series IV was prepared from a mixture of aminophenols [2-methyl 4-aminophenol (MePAP) and m-aminophenol (MAP)] with a mixture of diacids (PPBA and SDBA). Thermotropic liquid-crystalline behavior of these polymers was studied by differential scanning calorimetry (DSC), and optical polarizing microscopy equipped with a heating stage. Series I , series II , and P40–P100 of series IV could undergo crosslinking reaction by heating. However, series III could undergo crosslinking reaction only by photoirradiation upon heating. After crosslinking reaction occurred, the properties of these polymers were also examined by DSC, TGA, WAXD, and IR. The synthesized polymers could be crosslinked in the liquid-crystalline phase with retention of the order in the final crosslinked solid. © 1993 John Wiley & Sons, Inc.     

Flow-induced structure in a thermotropic liquid crystalline polymer as studied by SANS

Small-angle neutron scattering is utilized to determine the flow induced alignment of a model thermotropic liquid crystalline polymer (LCP) as a function of shear rate and temperature. The results demonstrate that the flow-induced structures in thermotropic liquid crystalline polymers have similarities and differences to those in lyotropic liquid crystalline polymer solutions. The shear rate dependence of the alignment shows that the flow-induced alignment correlates very well to the viscosity behavior of the LCP in the shear thinning regime, while temperature variation results in a change in the extent of alignment within the nematic phase. Relaxation results also demonstrate that the flow-induced alignment remains essentially unchanged for up to an hour after the shear field has been removed. Last, there exists a regime at low shear rate and low temperature where alignment of the LCP molecule perpendicular to the applied shear flow is stable. These results provide important experimental evidence of the molecular level changes that occur in a thermotropic liquid crystalline polymer during flow, which can be utilized to develop theoretical models and more efficiently process thermotropic polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3017–3023, 1998     

Effect of the vibration shear flow field in capillary dynamic rheometer on the crystallization behavior of polypropylene

The self-made capillary dynamic rheometer was adopted to study the relationship between the crystallization behavior of isotactic polypropylene (iPP) and the vibration shear conditions, namely, vibration amplitude and vibration frequency. The crystalline structure of iPP under different vibration conditions was characterized by using differential scanning calorimeter (DSC) and wide-angle X-ray diffractometer (WAXD) techniques. The samples extruded under vibration shear conditions had a higher melting temperature (from DSC). A new shoulder-shape peak appeared at ca. 162 °C under low frequency or low amplitude conditions, which was engulfed by the main melting peak with the increase of the vibration amplitude or frequency. This was probably an indication that more perfect crystals had formed [Polym Eng Sci 38 (1998) 1-20]. The WAXD demonstrated that crystalline form of iPP extruded was not changed but the average crystalline size decreased, according to the Scherrer formula [Analytical methods of polymer materials, China Petrochemical Press, Beijing, 1997]. This proved a large increase in the number of small crystals.     

Nonlinear rheology of highly entangled polymer solutions in start‐up and steady shear flow

Orientation angle and stress‐relaxation dynamics of entangled polystyrene (PS)/diethyl phthalate solutions were investigated in steady and step shear flows. Concentrated (19 vol %) solutions of 0.995, 1.81, and 3.84 million molecular weight (MW) PS and a semidilute (6.4 vol %) solution of 20.6 million MW PS were used to study the effects of entanglement loss on dynamics. A phase‐modulated flow birefringence apparatus was developed to facilitate measurements of time‐dependent changes in optical equivalents of shear stress (n₁₂ ≈ Cσ) and first normal stress differences (n₁ = n₁₁ ? n₂₂ ≈ CN₁) in a planar‐Couette shear‐flow geometry. Flow birefringence results were supplemented with cone‐and‐plate mechanical rheometry measurements to extend the range of shear rates over which entangled polymer dynamics are studied. In slow (τ > ) steady shear‐flow experiments using the ultrahigh MW polymer sample (20.6 × 10⁶ MW PS), steady‐state n₁₂ and n₁ results manifest unusual power‐law dependencies on shear rate [n_12,ss ～ ^0.4 and n_1,ss ～ ^0.8]. At shear rates in the range τ < < τ, steady‐state orientation angles χ_SS are found to be nearly independent of shear rate for all but the most weakly entangled materials investigated. For solutions containing the highest MW PS, an approximate plateau orientation angle χ_p in the range 20–24° is observed; χ_p values ranging from 14 to 16° are found for the other materials. In the start‐up of fast steady shear flow (γ˙ ≥ τ), transient undershoots in orientation angle are also reported. The molecular origins of these observations were examined with the help of a tube model theory that accommodates changes in polymer entanglement density during flow. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2275–2289, 2001     

Structure and dynamics of concentration fluctuations in a polymer blend solution under shear flow

The technique of small-angle light scattering (SALS) has been employed to investigate the time-dependent behavior of a single-phase, semidilute solution of polystyrene and polybutadiene in dioctyl phthalate under shear flow. Concentration fluctuations in the polymer blend solution are found to grow with time in the direction of flow, and their orientation angles evolve from 45° from the flow direction toward 0°, with the steady-state value being dependent on shear rate. SALS patterns are simulated using a modified Cahn-Hilliard-Cook model, with an additional collective restoring force to account for polymer elasticity. Predictions from this modified model for the orientation angles of the concentration fluctuations are in excellent agreement with the experimental results. Our model also predicts that the quiescent structure factor has a Gaussian form and that the steady-state orientation of the scattering patterns is dependent on shear rate. These predictions are also in good agreement with our experimental observations. © 1994 John Wiley & Sons, Inc.     

Studies on the thermotropic liquid-crystalline polymer. VIII. Synthesis and properties of fully aromatic poly(ester)s and poly(amide-ester)s containing p-phenylene diacrylic group

Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc.     

Effects of flexibility on liquid crystalline polymer behavior: The nematic broken rod

A new theory for liquid crystalline polymers is developed, and its behavior in simple shear flow is analyzed. The theory accounts for molecular flexibility by employing a microstructure consisting of two rigid rods linked by a joint with a tunable stiffness. The probability distribution function equation for the orientation of the arms of the broken rod is derived. The adaptation of the smoothed particle hydrodynamics (SPH) technique for obtaining numerical solutions to this theory is detailed. The behavior of the theory at equilibrium is derived analytically and compared with numerical results; the SPH technique is then used to obtain results in flow. It is found that in the limit of a nearly stiff joint, the model gives behavior that is very similar to that of rigid rod polymers, the only difference being a lesser tendency to tumble due to greater variation in the order parameter. For nearly free joints, the shear flow induces interesting dynamics for the transition between states with the arms outstretched and those where they are folded up (so‐called “hairpins” of main‐chain LCPs). © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 281–300, 1999     

Interfacial slip at the thermotropic liquid‐crystalline polymer/poly (ethylene naphthalate) interface

The unique rheological properties of a thermotropic liquid‐crystalline polymer (TLCP) were first studied. The thermal and shear history of the TLCP was found to play a critical role in its rheological properties. Crystallites were observed in the TLCP melt even above the melting temperature detected by differential scanning calorimetry. Because interfacial slip had long been suggested as an important reason for viscosity reduction in TLCP/thermoplastic blends, for the first time, interfacial slip at the TLCP/poly(ethylene naphthalate) (PEN) interface was investigated with an energy model. The model quantified the degree of interfacial slip at the TLCP/PEN interface by an energy factor. The calculated energy factors revealed a high degree of interfacial slip at the TLCP/PEN interface. It was proposed that the high rigidity of rodlike TLCP chains and their alignment parallel to the interface prevented mutual entanglements at the TLCP/PEN interface. The lack of mutual entanglements promoted the interfacial slip. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 302–315, 2004     

Effect of shear flow on the phase‐separation behavior in a blend of polystyrene and polyvinyl methyl ether

The phase behavior and phase‐separation dynamics of polystyrene/polyvinyl methyl ether (PS/PVME) blend with a critical composition of 70 vol % PVME were examined with a light scattering technique under a shear‐rate range of 0.1–40 s^?1. If the shear rates were less than 8 s^?1 and the starting temperatures of the measurement were 343 and 383 K, respectively, two cloud points were observed, whereas after the shear rate was higher than 8 s^?1, only one cloud point existed, 20 K higher than that of the static state of the blend. Investigation of the phase‐separation dynamics at 443 K suggested that in the vorticity direction the phase‐separation behavior at the early stage and the later stage can be explained by Cahn–Hilliard linearized theory and the exponent growth law, respectively. Phase separation occurs after a shearing time, which was called a delay time τ_d. The delayed time τ_d, the apparent diffusion coefficient, and the exponent term of the blend show strong dependence on shear rates. A theoretical prediction of the phase behavior of PS/PVME under a shear flow field by introducing an elastic energy term into Flory's equation‐of‐state theory was made, and the prediction was consistent with the experimental results. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 661–669, 2003     

Effect of pyridazine structure on thin‐film polymerization and phase behavior of thermotropic liquid crystalline copolyesters

An intensive study has been conducted to compare the effects of malei hydrazine (MH) and hydroquinone (HQ) on the liquid crystallinity and phase transition behavior in the ABA/HQ/TFTA and ABA/MH/TFTA copolyesters (p‐acetoxybenzoic acid (ABA) and tetrafluoroterephthalic acid (TFTA)). These two copolyesters were prepared by thin‐film polymerization and characterized by differential scanning calorimetry (DSC), polarizing light microscope (PLM), wide‐angle X‐ray diffraction (WAXD), as well as Cerius² computational simulation. Characterization and comparison of the liquid crystalline (LC) evolution and morphology changes of HQ moiety with corresponding MH moiety suggest that ABA/MH/TFTA system is energetically favorable to mesophase formation than ABA/HQ/TFTA system. When the films are quenched, a surface microcrack decoration is observed in both systems. Both systems, which have the persistence ratio larger than 6.42, satisfy the minimum requirement for the LC formation by molecular science software. The ABA/MH/TFTA film exhibits only one single peak transition. However, two distinct transitions have been observed in the ABA/HQ/TFTA system. The average Avrami exponent, n, is ～1.2, and PLM and WAXD results suggest mesophase transition in ABA/MH/TFTA film. As reflected by the results obtained from PLM, WAXD, and DSC studies, the phase transition is confirmed as crystal → nematic → isotropic in ABA/HQ/TFTA copolyester. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2230–2242, 2005     

A new proposal for polymer dynamics in steady shearing flows

Beginning with a recently proposed expression for the drag force on a single macromolecule pulled with constant velocity through a fluid of long‐entangled molecules (V. R. Mhetar and L. A. Archer, Macromolecules 1998, 31, 6639), we investigate the effect of entanglement loss on polymer dynamics in steady shearing flows. At steady‐state, a balance between the elastic restoring force and viscous drag acting on entangled polymer segments reveals a critical molecular strain γ_m,c beyond which the drag force exerted on polymer molecules by their neighbors is insufficient to support arbitrarily small orientation angles. Specifically, we find that in fast steady shear flows τ < γ˙ < τ, polymer orientation in the shear plane approaches a limiting angle χ_c ≈ atau(1/(1 + γ_m,c)) beyond which flow becomes incapable of producing further molecular alignment. Shear flow experiments using a series of concentrated polystyrene/diethyl phthalate solutions with fixed entanglement spacing, but variable polymer molecular weight 0.94 × 10⁶ ≤ M_w ≤ 5.48 × 10⁶, reveal a limiting steady‐state orientation angle between 6° and 9° over a range of shear rates; confirming the theoretical result. Orientation angle undershoots observed during start‐up of fast steady shearing flows are also explained in terms of a transient imbalance of elastic restoring force and viscous drag on oriented polymer molecules. Our findings suggest that the Doi–Edwards affine orientation tensor (Q) is not universal, but rather depends on deformation type and deformation history through a balance of elastic force and viscous drag on polymer molecules. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 222–233, 2000     

Effect of internal viscosity on Brownian dynamics of DNA molecules in shear flow

The results of Brownian dynamics simulations of a single DNA molecule in shear flow are presented taking into account the effect of internal viscosity. The dissipative mechanism of internal viscosity is proved necessary in the research of DNA dynamics. A stochastic model is derived on the basis of the balance equation for forces acting on the chain. The Euler method is applied to the solution of the model. The extensions of DNA molecules for different Weissenberg numbers are analyzed. Comparison with the experimental results available in the literature is carried out to estimate the contribution of the effect of internal viscosity.     

Effect of the thermal history on the phase transition and the liquid crystalline structure of thermotropic polyesters

A series of triad type thermotropic polyesters based on phenylsulfonyl hydroquinone and α,ω-bis(4-carboxyphenoxy)alkane was prepared, and the effect of the thermal history on the phase transition and the liquid crystalline structure of the polyesters was studied. The phase transition was significantly affected by the thermal history. When annealed at various temperatures, multiple endotherms were observed for all polyesters in DSC thermograms. A phase stability concept was employed to explain the complicated phase transitions. The time evolution of the liquid crystalline structure was investigated by optical microscopy and transmitted light intensity measurement under crossed polars during annealing. The steady decrease in the density of disclinations with accompanying increase of transmitted light intensity was observed. Depending on the surface conditions of the liquid crystal polymer film, two markedly different domain growth patterns and different textures were found on isothermal annealing; the continuous wormlike texture and the discontinuous droplet texture. The structural relaxation of the deformed texture during annealing was also studied. When shear was applied, the characteristic banded texture was formed in all polyesters.     

Effect of pressure on the flow behavior of polybutene

The rheology of submicron thick polymer melt is examined under high normal pressure conditions by a recently developed photobleached‐fluorescence imaging velocimetry technique. In particular, the validity and limitation of Reynold equation solution, which suggests a linear through‐thickness velocity profile, is investigated. Polybutene (PB) is sheared between two surfaces in a point contact. The results presented in this work suggest the existence of a critical pressure below which the through‐thickness velocity profile is close to linear. At higher pressures however, the profile assumes a sigmoidal shape resembling partial plug flow. The departure of the sigmoidal profile from the linear profile increases with pressure, which is indicative of a second‐order phase/glass transition. The nature of the transition is confirmed independently by examining the pressure‐dependent dynamics of PB squeeze films. The critical pressure for flow profile transition varies with molecular weight, which is consistent with the pressure‐induced glass transition of polymer melt. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 708–715