Rheological studies on the phase separation of hydroxypropylcellulose solution systems

Phase behavior of hydroxypropylcellulose (HPC) in a mixed solvent of glycerol and water was investigated by two different rheological methods: rheooptical birefringence measurement in an elongational flow field and viscometric measurement in a shear flow field. The association process of the HPC chain during phase separation observed by the elongational flow birefringence method was also investigated by the shear viscometric method. The temperature dependence of chain rigidity was determined by measuring the intrinsic viscosity, and change in the conformation was investigated by observing elongational flow birefringence over the temperature range from the one‐phase to inside a phase boundary. The results focus on the molecular process of phase separation. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1976–1986, 2001     

Highly sensitive optical humidity probe

A highly sensitive optical humidity probe based on reflectance measurements has been developed using Nafion^®-crystal violet (CV) films. This sensor can be used to calibrate relative humidity (RH) in the range 0-0.25% with a detection limit (blank signal + 3σ_b, where σ_b = the standard deviation (S.D.) of the blank signal) of 0.018% RH (∼4.37 ppm) and exhibited low hysteresis. The sensor films were fully reversible in dry nitrogen and reversal times were shown to be dependent on exposure time and % RH. The response to 1% RH was highly reproducible (S.D. = 1.67%, number of samples (n) = 5). Hydrogen chloride gas did not interfere with the response of the sensor to RH but did reduce sensor reversal times. This sensor displayed sufficient sensitivity that it could be used to detect ppm levels of moisture in process gases such as nitrogen and HCl.     

Salting-in behavior of isotropic and anisotropic aqueous hydroxypropylcellulose solutions

 Salts with large polarizable ions are capable of salting-in complex aqueous polymer solutions exhibiting microstructure, thereby inducing changes in the phase behavior and properties of the solutions. In this work, the dynamic rheological properties of isotropic and mesomor-phic hydroxypropylcellulose (HPC) in aqueous media have been investigated in the presence of one such salt, guanidine thiocyanate (GuSCN). Addition of this salt to isotropic aqueous HPC solutions is found to induce an increase in the magnitude of the elastic shear modulus (G′). At HPC concentrations above the isotropic→mesophase transition, however, addition of GuSCN results in a substantial reduction in G′ due to microstructural changes in the chiral nematic HPC mesophase. This reduction in G′ indicates that the microstructure of a water-soluble polymer exhibiting supramolecular organization can be tailored through salting-in, and is likewise expected to facilitate the commercial processing of HPC at high solids concentrations. Received: 4 June 1996 Accepted: 3 September 1996     

The rheology of polymeric liquid crystals

The molecular theory of Doi has been used as a framework to characterize the rheological behavior of polymeric liquid crystals at the low deformation rates for which it was derived, and an appropriate extension for high deformation rates is presented. The essential physics behind the Doi formulation has, however, been retained in its entirety. The resulting four-parameter equation enables prediction of the shearing behavior at low and high deformation rates, of the stress in extensional flows, of the isotropic-anisotropic phase transition and of the molecular orientation. Extensional data over nearly three decades of elongation rate (10^–2–10¹) and shearing data over six decades of shear rate (10^–2–10⁴) have been correlated using this analysis. Experimental data are presented for both homogeneous and inhomogeneous shearing stress fields. For the latter, a 20-fold range of capillary tube diameters has been employed and no effects of system geometry or the inhomogeneity of the flow-field are observed. Such an independence of the rheological properties from these effects does not occur for low molecular weight liquid crystals and this is, perhaps, the first time this has been reported for polymeric lyotropic liquid crystals; the physical basis for this major difference is discussed briefly. A Semi-empirical constant in eq. (18), N/m² - c rod concentration, rods/m³ - c ^* critical rod concentration at which the isotropic phase becomes unstable, rods/m³ - C interaction potential in the Doi theory defined in eq. (3) - d rod diameter, m - D semi-empirical constant in eq. (19), s^–1 - D _r lumped rotational diffusivity defined in eq. (4), s^–1 - rotational diffusivity of rods in a concentrated (liquid crystalline) system, s^–1 - D _ro rotational diffusivity of a dilute solution of rods, s^–1 - f distribution function defining rod orientation - F tensorial term in the Doi theory defined in eq. (7) (or eq. (19)), s^–1 - G tensorial term in the Doi theory defined in eq. (8) - K _B Boltzmann constant, 1.38 × 10^–23 J/K-molecule - L rod length, m - S scalar order parameter - S tensor order parameter defined in eq. (5) - t time, s - T absolute temperature, K - u unit vector describing the orientation of an individual rod - rate of change ofu due to macroscopic flow, s^–1 - v fluid velocity vector, m/s - v velocity gradient tensor defined in eq. (9), s^–1 - V mean field (aligning) potential defined in eq. (2) - x coordinate direction, m - Kronecker delta (= 0 if = 1 if = ) - _r ratio of viscosity of suspension to that of the solvent at the same shear stress - _s solvent viscosity, Pa · s - ^* viscosity at the critical concentrationc ^*, Pa · s - v ₁, v₂ numerical factors in eqs. (3) and (4), respectively - deviatoric stress tensor, N/m² - volume fraction of rods - ⁰ constant in eq. (16) - ^* volume fraction of rods at the critical concentrationc ^* - average over the distribution functionf(u, t) (= d ²u f(u, t)) - gradient operator - d ²u integral over the surface of the sphere (|u| = 1)     

Phase separation effects in the rheology of aqueous solutions of hydroxypropylcellulose

Aqueous solutions of hydroxypropylcellulose (HPC) have been widely used as a model system to study liquid crystalline behavior in polymers. The HPC limiting concentration for mesophase formation in water is about 40% wt, quite independent of molecular weight. Most rheo-optical investigations have been carried out in the concentration range from 50% to 65% wt, on the assumption that only the liquid crystalline phase was present. In this study, by using video-enhanced contrast light microscopy, we show that an isotropic phase in form of tiny droplets is also present at concentrations up to 60% wt, both in quiescent and in sheared samples at room temperature. The isotropic phase can be made to disappear by lowering the temperature. The effects of phase separation on the rheology of the HPC/water system are studied by measuring viscosity as a function of temperature and concentration. A slope of Region I of the viscosity curve close to –0.5 is found only at low temperatures, when the sample is fully anisotropic, whereas an anomalous dependence of the viscosity on temperature is observed when phase separation is significant. This study shows that special care is needed when interpreting experimental results from the HPC/water system in terms of theories for liquid crystalline polymers.     

Viscosity of a liquid crystalline polymer solution with a polydomain or a band texture

The viscosity of a main-chain liquid crystalline polymer (anisotropic aqueous solution of hydroxypropylcellulose) is measured in the case where the liquid crystalline polymer presents a band texture and is compared to the case of a polydomain texture.     

On the time-dependency of the flow-induced dynamic moduli of a liquid crystalline hydroxypropylcellulose solution

Some unusual rheological features of a liquid crystalline solution of hydroxypropylcellulose (HPC) in water have been investigated. Measurements have been performed by using a variety of different apparatuses with cone and plate geometries. Particular attention has been devoted to the experimental procedures, including the use of different sealing techniques, which are necessary to avoid solvent evaporation during the very long transients. Shear fracture effects, and their dependence on the type of sealing agents have also been studied. In steady shear, the HPC solution shows some rheological features which are common to other lyotropic systems, such as a three-region viscosity curve, and a double sign change in the first normal stress difference vs shear rate curve. The structural changes which take place after cessation of shear flow have been investigated by following the evolution of the dynamic moduli as a function of the time elapsed after the shear flow is stopped. It was found that the rate of the previously applied shear strongly affects both the kinetics and the asymptotic, long time values of the dynamic properties. Possible explanations for such behavior in terms of microstructure evolution are presented and discussed.     

Rheo-optics of hydroxypropylcellulose solutions in Poiseuille flow

The behavior of an aqueous solution of hydroxypropylcellulose in the liquid crystalline phase is investigated when it is flowing in a rectangular channel. Rheological characterization shows that the viscosity vs. shear rate curve follows the typical three region pattern, with the intermediate plateau of region II extending over a relative large range of shear rates (more than one decade). Two complementary rheo-optical determinations are performed. Velocity profiles across the channel thickness are measured by a hydrogen bubble visualization technique. Texture evolution is monitored by in situ optical microscopy. Accurate focusing inside the sample thickness allows observation in real time of the texture at various shear rates, as generated in the Poiseuille type of flow in the channel. It is shown that the velocity profiles can be accurately predicted by assuming that the flow in the channel is purely viscous, and using only the viscosity data described above. It is also shown that the morphology of the texture generated inside the flowing system is a function of the local shear rate. In particular, an elongated structure is observed when the shear rate exceeds the critical value corresponding to the onset of region II in the viscosity curve.     

Nanofiber formation of hydroxylpropylcellulose (HPC)

The aggregative behaviors of hydroxypropylcellulose (HPC) molecules in aqueous solution and on substrates have been observed by employing laser light scattering (LLS) and, after deposition on a mica surface, atomic force microscopy (AFM). LLS studies showed that the HPC molecules formed large aggregates through self-association when the concentration of the solution was above the critical concentration c(t). AFM measurements revealed that when a dilute aqueous solution of HPC molecules was deposited onto a mica substrate at a temperature below its lower critical solution temperature (LCST) thin nanofibers were formed with a height of 0.9 nm, whereas thick nanofibers were formed when an aqueous solution of HPC molecules was deposited onto a substrate above its LCST. Furthermore, the growth of nanofibers led to the formation of fan structures.     

A novel orientation technique for semi-rigid polymers. 2. Mechanical properties of cellulose acetate and hydroxypropylcellulose films

The networks of cellulose acetate and hydroxypropylcellulose prepared in the first part of this investigation were studied with regard to their mechanical properties. The quantities of particular interest were increases in tensile modulus and tensile strength obtained by drying the swollen films under strain, both uniaxial and equi-biaxial. These increases or improvements in mechanical properties were determined as a function of polymer concentration during cross-linking, polymer molecular weight, degree of cross-linking, and elongation during drying. In all cases, the improvements increased with increase in elongation during drying, and the largest increases were obtained in the case of the highest molecular weight polymer which had been lightly cross-linked in dilute (isotropic) solutions. The extent of ordering in these systems was gauged approximately by measurements of birefringence, which were correlated with their tensile moduli and tensile strengths.