Rheology of liquid crystalline phases of alkyloxybenzylidene toluidines

A unique viscometer of the CS rheometer viscometer class designed at the Kazan State University of Technology is used to measure viscosities of two p-n-alkyloxybenzylidene-p-toluidines in the entire temperature range of the liquid crystalline state and transition into an isotropic liquid. The measured shear stresses and flow rates are used to calculate shear rates and plot flow and viscosity curves. The liquid crystalline phase and isotropic liquid are demonstrated to possess Newtonian viscosity, whose viscous flow activation parameters are calculated in the temperature range under study. The results are discussed from the standpoint of intermolecular interactions and structural details of the liquid crystalline phase.     

Electrorheological properties of polyaniline suspensions: field-induced liquid to solid transition and residual gel structure

Polyaniline (PANI) was synthesized via oxidative coupling polymerization in acid conditions and de-doped in solution of ammonia. The electrorheological (ER) properties of the PANI/silicone oil suspensions were investigated in oscillatory shear as functions of electric field strength, particle concentration, and host fluid viscosity. Consistent with literature, the PANI ER fluid exhibits viscoelastic behavior under the applied electric field and the ER response is strongly enhanced with increasing electric field strength and particle concentration. The dynamic moduli, G' and G' increase dramatically, by 5 orders of magnitude, as the electric field strength is increased to 2 kV/mm. A viscoelastic liquid to solid transition occurs at a critical electric field strength, in the range Ec = 50-200 V/mm, whose value depends on particle concentration and host fluid viscosity. The fibrillar structure formed in the presence of the applied field has a static yield strength tau(y), whose value scales with electric field strength as tau(y) approximately E(1.88). When the field is switched off a residual structure remains, whose yield stress increases with the strength of the applied field and particle concentration. When the applied stress exceeds the yield stress of the residual structure, fast, fully reversible switching of the ER response is obtained.     

Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.     

Effect of high electric fields on the isotropic phase of a lyotropic liquid‐crystalline system

The effect of high (>1000 V/mm) electric fields on solutions of a lyotropic liquid‐crystalline polymer, poly(n‐hexyl isocyanate) in p‐xylene, is presented. The concentrations are adjusted such that the solutions are strictly within the isotropic phase domain region, thus exhibiting no spontaneous liquid crystallinity. The effects of field strength, frequency, and concentration are varied and the morphological changes are noted. The results are analyzed with birefringence measurements via comparison with the optical Kerr effect. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4116–4125, 2004     

Electrorheological effect in hybrid fluids with liquid crystalline additives

Conventional electrorheological (ER) fluids consist of electrically polarizable particles dispersed in an inert insulating liquid. They are characterized by a development of a yield stress upon application of an external electric field. They resemble Bingham fluids with yield stress value depending on electric field. A viscosity increase in the presence of an electric field has been also found in homogeneous solutions of liquid crystalline polymers with no yield stress observed. In this study these two types of fluids and combined dispersions of the solid particles in the liquid crystalline matrix were investigated. A lyotropic liquid crystalline polymer—poly(n‐hexyl isocyanate) (PHIC)—dissolved in xylene was chosen as the active matrix. The dispersed solid phase was comprised of two kinds of polymers: pyrolyzed polyacrylonitryle (PAN) showing electron conductivity, and PAN doped with two salts (KSCN, NaSCN), resulting in ionic conductivity. The rheological measurements under an electric field were performed. The pristine xylene solution of PHIC was characterized first as well as the 15% m/m dispersions of PAN powders in silicone oil. Then the dispersions in the liquid crystalline matrix were investigated showing a strong ER effect whose magnitude was considerably enhanced in comparison to both ER active components measured separately. Copyright © 2006 John Wiley & Sons, Ltd.     

Response of a biphasic poly(n‐hexyl isocyanate)/p‐xylene solution to applied high electric fields

The effect of a high electric field on a solution of a lyotropic liquid‐crystalline polymer, poly(n‐hexyl isocyanate) in p‐xylene, was studied. The application of a high‐voltage alternating‐current electric field to the biphasic solution resulted in an elongation of the nematic domains in the field direction, the degree of elongation varying approximately with the square of the electric field. At a constant field, the extent of elongation decreased, varying inversely with the frequency in an exponential fashion. The domain structure and thus the molecular orientation were examined to explain these electric field effects. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1124–1133, 2005     

Ionic strength effects on the microstructure and shear rheology of cellulose nanocrystal suspensions

The effect of ionic strength on the rheology and microstructure of Cellulose nanocrystals (CNC) aqueous suspensions are studied over a broad range of CNC (3–15 wt%) and NaCl concentrations (0–15 mM), using polarized optical microscopy combined with rheometry. The CNC suspensions are isotropic at low concentration and form chiral nematic liquid crystalline structure above a first critical concentration and gel above a second critical one. It has been shown that for isotropic CNC suspensions, increasing the ionic strength of the system up to 5 mM NaCl concentration weakens the electro-viscous effects and thus reduces the viscosity of these suspensions. For biphasic samples, which contain chiral nematic liquid crystal domains, increasing the ionic strength up to 5 mM NaCl concentration decreases the size of the chiral nematic domains, and leads the viscosity of the samples at low shear rates to increase. On the other hand, at high shear rates, where all the ordered domains are broken, the viscosity decreases with NaCl addition. For gels, the addition of NaCl up to 5 mM weakens the gel structure and decreases the viscosity. Further addition of NaCl (10 and 15 mM NaCl concentrations) results in extensive aggregation and de-stabilizes the CNC suspensions.     

Influence of an electric field on the non-Newtonian response of a hybrid-aligned nematic cell under shear flow

The authors study shear flow in hybrid-aligned nematic cells under the action of an applied electric field by solving numerically a hydrodynamic model. The authors apply this model to a flow-aligning nematic liquid crystal (4'-n-pentyl-4-cyanobiphenyl) and obtain the director's configuration and the velocity profile at the stationary state. The authors calculate the local and apparent viscosities of the system and found that the competition between the shear flow and the electric field gives rise to an interesting non-Newtonian response with regions of shear thickening and thinning. The results also show an important electrorheological effect ranging from a value a bit larger than the Miesowicz viscosity etab [Nature (London) 17, 261 (1935)] for small electric fields and large shear flows to etac for large electric fields and small shear flows. The analysis of the first normal stress difference shows that for small negative shear rates, the force between the plates of the cell is attractive, while it is repulsive for all other values of shear rates. However, under the application of the electric field, one can modify the extent of the region of attraction. Finally, the authors have calculated the dragging forces on the plates of the cell and found that it is easier to shear in one direction than in the other.     

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     

Rheology of concentrated solutions of helical polypeptides

Rheological studies were carried out on concentrated m-cresol solutions of two helical synthetic polypeptides; poly-γ-benzyl-L -glutamate (PBLG; molecular weight, 150,000) and poly-?-carbobenzyloxy-L -lysine (PCBZL; molecular weight, 200,000). Steady shear measurements were made over a range of 0.01–16,000 sec^?1 to obtain steady shear viscosity and first normal stress difference. Dynamic viscosity and dynamic storage modulus were measured both by oscillatory shear between cone and plate and also by an eccentric rotating disk device over frequency ranges of 0.1–400 and 0.1–63 rad/sec, respectively. The concentration ranges were such that both liquid crystalline and isotropic solutions were investigated. The previously reported observations of an apparent negative first normal stress difference within a defined range of shear rate for liquid crystalline solutions were confirmed for the PBLG and PCBZL solutions. At high shear rates the peaks in plots of steady shear viscosity against concentration were profoundly suppressed but peaks in first normal stress difference versus concentration were not. The observation of liquid crystalline order in PCBZL/m-cresol solutions at room temperature constitutes evidence that the inverse coil-helix transition temperature is lower in concentrated solutions than in dilute solutions. The critical concentration for formation of the liquid crystalline phase was higher for PCBZL than for PBLG, despite a higher axial ratio, due to helix flexibility.     

聚苯胺类电流变体的稳态剪切流动分析

对聚苯胺、及聚苯胺/聚丙烯酸盐复合粒子的稳态剪切流动行为进行了综合考察.结果表明, 在交流电场下,电流变体的剪切应力和剪切速率的关系符合Bingham流体形为.并对此现象进行了分析,提出用非理想塑性体的新模型来描述交流电场下聚苯胺类电流变体的稳态剪切流动.     

Electrorheological properties and microstructure of silica suspensions

We present experimental and theoretical results on the electrorheological response and microstructure of colloidal suspensions composed of silica nanoparticles dispersed in a silicon oil, as a function of electric field strength and silica water content. Using small-angle neutrons scattering experiments, we determined the evolution of the static structure factor of the suspensions when an electric field is applied. Experimental data were fitted with model calculations using the Percus-Yevick solution for Baxter's hard-sphere adhesive potential. The obtained stickiness parameter is directly related to the polarization interactions that depend on the water content of silica particles. The influence of the polarization interparticle potential on the rheology of the silica dispersions was investigated in a second time. A microscopic theory for the shear viscosity of adhesive hard-sphere suspensions was successfully used which describes the steady shear viscosity of suspension in terms of the fractal concept.     

Effect of polydimethylsiloxane viscosity on the electrorheological activity of dispersions based on it

The effect the viscosity of a dispersion medium of a polymethylsiloxane fluid (PMS) with a kinematic viscosity over a wide range of values from 5 to 300 cSt has on the electrorheological properties of suspensions based on nanosized titanium dioxide obtained via the sol-gel method is investigated. The investigations are conducted in a wide range of concentrations of suspensions: from 30 to 60 wt % (from 15 to 38 vol %) of the dispersed phase. The role the dispersion medium in two-phase disperse systems plays in the formation of structures of dispersed phase in the presence of an electric field is determined from the dependence of yield points of TiO₂ in PMS with different viscosities on the applied electric field strength.     

Dielectric study on the flow alignment in 4-n-pentyl-4'-cyanobiphenyl

Dielectric permittivity and loss are measured under steady shear flow as functions of temperature, shear rate, electric field frequency, and electric field strength in the nematic (N) and the isotropic (I) phases of 4-n-pentyl-4'-cyanobiphenyl. In the N phase, the dielectric permittivity in the quiescent state is largely modified if the steady shear flow is applied. These behaviors are discussed based on the Leslie-Ericksen theory [Q. J. Mech. Appl. Math. 19, 357 (1966); Arch. Ration. Mech. Anal. 4, 231 (1960)], showing that the dielectric properties under the shear flow are consistently interpreted in terms of the flow alignment of the director, a unit vector specifying the orientation of the liquid crystals. It is also suggested that the behaviors of dielectric permittivities are similar to those of the viscosities.     

An investigation of electrorheological properties of calcium carbonate suspensions in silicone oil

In this study, electrorheological behavior of suspensions prepared from 0.9 and 5.0 µm calcium carbonate particulates, dispersed in insulating silicone oil medium was investigated. Sedimentation stabilities of suspensions (c = 5 wt %) prepared using these calcium carbonate powders were determined to be 6 and 4 days, respectively. Electrorheological activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. Shear stress of calcium carbonate suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions was decreased sharply with increasing shear rate and particle size, showing a typical shear thinning non-Newtonian visco-elastic behavior. Effects of elevated temperature and polar promoter onto electrorheological activity of calcium carbonate/silicone oil system were also investigated.__________From Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 268–273.Original English Text Copyright © 2005 by Yilmaz, Ünal, Yavuz.This article was submitted by the authors in English.     

Rheological properties in cholesteric and blue phases of cholesteryl isostearyl carbonate: viscosity and effect of electric field on the rheology

Rheological property (shear stress versus shear rate) of cholesteryl isostearyl carbonate (CISC) is measured as a function of temperature, finding that, like some other cholesteryl derivatives, CISC has blue phases (BPs) between the cholesteric (Ch) and the isotropic (I) phases. In the Ch and the BP phases, measurements of the electrorheological (ER) effect, of the electric field on the rheology, are made; a slight increase of the viscosity is observed in the BPs and no ER effect in the Ch phase, which is contrasted to the distinct ER effect in the nematic (N) and the smectic A (SmA) phases.     

ELECTRORHEOLOGICAL PROPERTIES OF TALC POWDER/SILICONE OIL SUSPENSIONS UNDER DC FIELDS

In this study, the electrorheological （ER） behavior of suspensions prepared from d50 = 2.4 lam talc powder, dispersed in insulating silicone oil （SO） medium was investigated. Sedimentation stabilities of suspensions （c = 5 wt%） prepared using these talc powder powders were determined to be 78 days. The ER activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. The shear stress of talc powder suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions decreased sharply with increasing shear rate and showed a typical shear thinning non-Newtonian visco-elastic behavior. Effects of frequency on the ER activity of talc powder/SO system were also investigated.     

Effects of medium oil on electroresponsive characteristics of chitosan suspensions

Biocompatible chitosan particle suspensions in host oils of corn, soybean, and silicone were prepared and their electrorheological (ER) characteristics were examined under the imposition of electric fields. The effects of the weight concentration of particulate chitosan and the strength of the applied electric field on ER response in the various chitosan particle suspensions were investigated via measurements of rheological properties including flow curve, shear viscosity, and yield stress. The yield stresses of the three different chitosan–oil systems showed different values of slope in the electric field, but all data were found to fit well with our previously proposed universal scaling function.     

Electrorheological Effect and Electro‐Optical Properties of Side‐on Liquid Crystalline Polysiloxane in a Nematic Solvent

The electrorheological (ER) effect and the electro‐optical properties of a ′′side‐on′′ liquid crystalline polysiloxane (PS) are investigated. A large ER effect is observed and the response to the shear stress of neat PS in the nematic phase is shown to be affected by the shear rate. PS is also mixed with a low‐molar nematic liquid crystal (5CB) in order to improve the response behavior to the applied electric field. The rheological properties of such mixtures are highly dependent on the concentration of 5CB. The composites respond faster to the applied electric field and have improved electro‐optical properties. This study offers a new perspective on the development of liquid crystal materials for the ER effect.     

ELECTRORHEOLOGICAL PROPERTIES OF DIATOMITE/SILICONE OIL SUSPENSIONS UNDER DC FIELDS

In this study, electrorheological （ER） behavior of suspensions prepared from 3.0 and 9.0 μm diatomite particulate, dispersed in insulating silicone oil （SO） medium was investigated. Sedimentation stabilities of suspensions （c = 5 wt%） prepared using these diatomite powders were determined to be 32 days （d = 3 μm） and 24 days （d = 9 μm）, respectively. ER activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. Shear stress of diatomite suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions decreased sharply with increasing shear rate and particle size, showing a typical shear thinning non-Newtonian visco-elastic behavior. Effects of high temperature and polar promoter onto ER activity ofdiatomite/SO system were also investigated.