Rheological properties of poly(vinyl chloride)/plasticizer systems—relation between sol–gel transition and elongational viscosity

Poly(vinyl chloride) (PVC)/di-isononyl phthalate systems with PVC content of 45.5 (PVC8) and 70.4 wt% (PVC6) were prepared by a hot roller at 150 °C and press molded at 180 °C. The dynamic viscoelasticity and elongational viscosity of PVC8 and PVC6 were measured in the temperature range from 150 to 220 °C. We have found that the storage and loss shear moduli, G′ and G″, of PVC8 and PVC6 exhibited the power-law dependence on the angular frequency ω at 190 and 210 °C, respectively. Correspondingly, the tan δ values did not depend on ω. These temperatures indicate the critical gel temperature T _gel of each system. The critical relaxation exponent n obtained from these data was 0.75 irrespective of PVC content, which was in agreement with the n values reported previously for the low PVC concentration samples. These results suggest that the PVC gels of different plasticizer content have a similar fractal structure. Below T _gel, the gradual melting of the PVC crystallites takes place with elevating temperature, and above T _gel, a densely connected network throughout the whole system disappears. Correspondingly, the elongational viscosity behavior of PVC8 and PVC6 exhibited strong strain hardening below T _gel, although it did not show any strain hardening above T _gel. These changes in rheological behavior are attributed to the gradual melting of the PVC crystallites worked as the cross-linking domains in this physical gel, thereby inapplicability of the of time–temperature superposition for PVC/plasticizer systems.     

聚乙烯醇水凝胶的生物摩擦学研究进展

介绍了聚乙烯醇水凝胶的制备方法及其物理化学性能,评述了润滑介质、摩擦配副、摩擦运动方式、水凝胶自身特性及载荷和基体材料性质等对聚乙烯醇水凝胶生物摩擦磨损性能的影响,指出今后应加强对多因素协同作用下水凝胶磨损机理、关节运动模拟系统、关节滑液的主要组分润滑协同效应及其润滑机理的研究.     

Rheological properties of liver actin solutions

G-actin prepared from pork liver and purified to give a product of 95–98% purity was polymerized to F-actin in a rotational dynamic viscometer. The rheological properties were investigated during the course of polymerisation and after polymerisation. G andG measured at frequencies around 0.1 Hz increased strongly during the first 3 hours of the reaction and then slowly approached a constant value in the range of 10–50 mPa. The rise during polymerisation was more than two orders of magnitude. When a solution of F-actin was subjected to steady shear at a high shear rate for a short period of time and subsequently dynamic measurements were performed, then a considerably smallerG (about 70% smaller) was observed immediately after cessation of the steady shear.G then increased with time and approached its initial value.When measuring the viscosity of F-actin solutions as a function of shear rate, a strong shear thinning effect was seen which did not vanish even at shear rates as low as 0.001 s^–1. Even at this low shear rates, a pronounced yield maximum was observed before reaching the steady state. Oscillatory experiments showed a remarkably weak frequency dependence ofG. The results imply that F-actin solutions are largely structured forming a weak temporary network which can be easily destroyed by application of high shear rates. It seems most likely that the destruction occurs by a reversible, shear induced depolymerisation process.     

Rheological behaviour of poly(ethylene terephthalate) and poly(butylene terephthalate) blends

The presence of up to 4% Poly(butylene terephthalate) (PBT) in blends of Poly(ethylene terephthalate) (PET) with PBT results in an increase in viscosity and a decrease in activation energy, which has been related to the entanglement density. However, further increases in the amount of PBT up to 10% result in decreases in the viscosity, which may be due to partial phase segregation. Various blending rules have been applied to correlate the experimental results and predict the viscosities of the blends.     

Viscoelastic properties of semidilute poly(methyl methacrylate) solutions

Viscoelastic properties were examined for semidilute solutions of poly(methyl methacrylate) (PMMA) and polystyrene (PS) in chlorinated biphenyl. The number of entanglement per molecule, N, was evaluated from the plateau modulus, G _N . Two time constants, _s and ₁, respectively, characterizing the glass-to-rubber transition and terminal flow regions, were evaluated from the complex modulus and the relaxation modulus. A time constant _k supposedly characterizing the shrink of an extended chain, was evaluated from the relaxation modulus at finite strains. The ratios ₁/ _s and _k / _s were determined solely by N for each polymer species. The ratio ₁/ _s was proportional to N ^4.5 and N ^3.5 for PMMA and PS solutions, respectively. The ratio _k / _s was approximately proportional to N ^2.0 in accord with the prediction of the tube model theory, for either of the polymers. However, the values for PMMA were about four times as large as those for PS. The result is contrary to the expectation from the tube model theory that the viscoelasticity of a polymeric system, with given molecular weight and concentration, is determined if two material constants _s and G _N are known.     

Longitudinal volume viscosity of poly (vinyl chloride)

The volume flow of poly (vinyl chloride) ( = 45,000,T _g = 350 K) has been measured in an Instron Capillary Rheometer.The elastic modulus in longitudinal compression, the longitudinal volume viscosity and initial longitudinal volume viscosity, and retardation times were determined at temperatures both below (324 – 343 K) and above (403 – 453 K) the glass transition temperatureT _g , and at compression rates between approximately 10^–5 and 200 · 10^–5 s^–1.An increase in the longitudinal volume viscosity was observed for decreases in the volume deformation, increases in the compression rate and increases in temperature.T _g decreased at 0.16 K/MPa. The volume flow activation energy was found to be equal to that for shear flow with a constant value of 91.37 kJ/mol.     

Rheo-optical measurements of the first and third normal stresses of homopolymer poly(vinyl methyl ether) melt

Normal stresses play a key role in polymer processing, yet accurate measurements are still challenging. Simultaneous rheo-optical measurements are conducted on a poly(vinyl methyl ether) homopolymer melt over a wide range of temperatures and oscillatory shear frequencies, in an effort to measure the normal stresses, by using quantitative flow birefringence measurements. The stress optical rule holds well for this polymer as expected, with the value of the stress optic coefficient of (6.38±0.19)×10⁻¹¹ cm²/dyn at 30°C. The first and third normal stress difference coefficients, calculated using a single memory constitutive equation applied to the stress and birefringence data, are in excellent agreement. The ratio of the measured third and first normal stress difference coefficients, (1−β)=0.71±0.05, agrees well with the result of the Doi–Edwards model with independent alignment approximation (β=0.28). The measurement of normal stress difference coefficients with such small deviations proves the robust nature of the improved rheo-optical instrument and its ability to measure complete stress tensor.     

Rheological properties of lightly crosslinked carboxy copolymers in aqueous solutions

The rheological properties of a series of lightly crosslinked carboxy copolymers in aqueous solutions have been evaluated in steady shear and dynamic oscillatory modes. Viscosity profiles and the behavior of storage modulus are related to the chemical composition of the copolymers and their crosslinking density. A maximum in viscosity and in storage modulus which depends on the type of crosslinking agent used is explained by a combination of a chain entanglement mechanism and a closely-packed spheres model. The recovery of viscosity and storage modulus after shearing is very fast and is related to the very fast rearrangement of the microgel structure as a function of time.     

Nonlinear rheological properties and stability of dibenzylidene sorbitol fiber networks in poly(propylene oxide)

Dibenzylidene sorbitol (DBS) is known to gel organic liquids and polymers such as poly(propylene oxide) (PPO) by forming long fibers and fiber networks. Potential applications of these networks depend on their ability to withstand large deformations without significant morphological changes. Therefore, we studied the nonlinear rheological properties of the DBS fiber network in PPO for different DBS concentrations. We found that the concentration dependence of critical deformation (transition from linear to nonlinear viscoelastic region) and gel strength (G′ plateau in the linear region) can be explained on the basis of a model for densely cross-linked fiber gels (MacKintosh et al., Phys Rev Lett 75:4425–4428, 1995). Performing periodic strain sweeps, we found that the decrease in gel strength during the deformation cycles can be ascribed to reversible fiber coarsening. Additionally, start-up experiments showed a strong shear thinning behavior, which is in quantitative agreement with the SGM model (Sollich, Phys Rev E 58:738–759, 1998).     

Rheological characterization of highly branched poly(ethyleneterephthalate)

Linear and highly branched poly(ethyleneterephthalate) samples were synthesized and characterized in terms of intrinsic viscosity, molecular weight and melt viscosity over a wide range of shear rates at several temperatures, in the range from 265° to 295 °C. Linear samples exhibited Newtonian behavior over a wide range of shear rates, while the branched ones became shear thinning at relatively low shear rates. Our experimental data, as well as data previously reported, were found to be described by a proposed correlation between the melt viscosity ratio and a branching index. Moreover, the activation energy for melt flow was found for the highly branched samples to be a little higher than that of the linear samples.     

A study on the melt viscosity of linear and branched poly(butyleneterephthalate)

Linear and branched PBTP samples were synthesized and characterized in terms of the intrinsic viscosity, the melt-flow-index and, for some, the melt viscosity over a range of shear rates at 250 °C.An exponent of 3.2 in the equation relating to was found for linear samples. Both linear and branched samples exhibited Newtonian behaviour over a wide range of shear rates, but for any given melt-viscosity the branched samples became shear thinning at lower shear rates than the linear ones. Correlation between a branching index,, and melt-visocity ratio (0,b/0,l) was in agreement with a previous theoretical study.     

Effect of maleic anhydride content on the rheology and phase behavior of poly(styrene-co -maleic anhydride)/ poly(methyl methacrylate) blends

 We investigated the thermo- rheological behavior of high glass transition, high molecular weight and small dynamic asymmetry blends of poly(styrene-co-maleic anhydride) (SMA) and poly (methyl methacrylate) (PMMA) with varying amounts of maleic anhydride (MA) content, namely 8 wt%, 14 wt% and 32 wt%, in the SMA component. The phase separation (binodal) temperature of each blend was determined rheologically using a combination of dynamic frequency and temperature sweeps in parallel plate geometry; it was marked by a change in slope of the elastic modulus and the occurrence of a peak in tan δ in temperature sweeps. Failure of the time-temperature superposition principle and observation of two peaks in the Cole-Cole plots corroborated these findings. The blends displayed lower critical solution temperature (LCST) behavior with the critical temperatures exhibiting a non-monotonic dependence on the MA content. From rheological and thermal measurements it was concluded that SMA/PMMA blends containing 14% MA were more miscible than those containing 8% or 32% MA, a finding attributed to the compositional dependence of the interplay between SMA-SMA and SMA-PMMA interactions in the different samples. MA also influenced the dynamic asymmetry and pretransitional concentration fluctuations. The phase diagrams corresponding to each blend were modeled using a two-parameter temperature dependent interaction parameter, based on the concept of generalized Gibbs free energy of mixing. The fitted values of interaction parameter were in good agreement with values calculated explicitly using the Flory-Huggins theory. Received: 16 February 2001 Accepted: 11 July 2001     

Rheological properties of concentrated latex suspensions of poly(styrene-butadiene)

Concentrated suspensions of charged latex particles of poly(styrene-butadiene) have been used as model systems to investigate the influence of surface charges on the rheology of colloidal suspensions. The suspensions were found to behave as elastic solids at small strains and to require a finite stress to flow. This was related to an ordered structure of the suspensions at rest, resulting from electrostatic and van der Waals forces. Important shear-thinning effects were observed as a consequence of structure rearrangements under shear. At a fixed shear rate, the steady-shear viscosity as a function of the ionic strength exhibits a minimum. Under oscillatory shear flow, the behavior of the concentrated suspensions was found to be non-linear above a very small strain amplitude. The non-linear output signal from dynamic experiments was analyzed using a fast Fourier transform algorithm. A maximum in the third harmonic intensity as a function of the strain amplitude was observed and the intensity of higher harmonics decreased with increasing ionic strength. The behavior of the suspensions could be adequately described using the structural model of Yziquel et al. (Yziquel F, Carreau PJ, Moan M, Tanguy PA (1999) Rheological modeling of concentrated colloidal suspensions. J Non-Newtonian Fluid Mech 86:133–155).     

Linear and branched poly(butyleneterephthalate): Activation energy for melt flow

Poly(butyleneterephthalate) (PBTP) samples of different molecular weights, both linear and branched, were synthetized by mass polymerization and studied in the molten state with a melt-flow-index apparatus at different temperatures in the range 245–270 °C. In our experimental conditions ( 20 s^–1) the behaviour of PBTP samples was Newtonian, as reported previously. The flow activation energyE _a,0 was found to increase with degree of branching: typicallyE _a,0 was about 47 and 63–79 kJ/mol for linear and branched polymers respectively.Presented in part at the IX. International Congress on Rheology, Acapulco, Mexico, October 8–13, 1984     

Rheology and structure of precipitated silica and poly(dimethyl siloxane) system

The reinforcing capability of precipitated silica in poly(dimethyl siloxane: PDMS) was characterized by means of bound rubber formation, solvent swelling, yield stress, rheological and dynamic properties. Volume concentration of precipitated silica in PDMS was varied from 0 to 0.16. The homogeneity of the compounds after mixing was confirmed by studying a uniformity of dispersion of silica particles in PDMS via SEM morphology of vulcanizates. Bound rubber measurements of the compounds and solvent swelling studies of vulcanizates showed that the precipitated silica exhibited much stronger interaction with PDMS than that of typical carbon black with rubbers but less than that of fumed silica with PDMS. At high volume concentrations of silica (0.128 and 0.160), a yield behavior was evident from the storage modulus measurements. The network formation due to an interaction between the precipitated silica and PDMS was visualized via dynamic property measurements.     

Dispersion of multi-walled carbon nanotubes in poly（p-phenylene） thin films and their electrical characteristics

Dispersion of multi-walled carbon nanotubes in poly（p-phenylene） composite exposed to toluene was experimentally investigated. 3 mg of multi-walled carbon nanotubes with nominal size of 20 nm was compounded with 30 mg of poly（p-phenylene） with the presence of terpineol as binding initiator. To investigate an optimal condition for homogenizing all constituents, ultrasonication with an output power of 750W was employed with compounding time of 3, 10, 20 and 30 min. With FTIR analyses, it could be confirmed that homogeneous composite of multi-walled carbon nanotubes and poly（p-phenylene） could be prepared. SEM analyses were also conducted to examine the dispersion of multi-walled carbon nanotubes in the polymer matrix. Then intrinsic electrical resistance of the composites after being exposed to toluene was also investigated. It was found that the composite film prepared with ultrasonication for 20 min could provide sufficiently sensitive response with respect to varied concentration of toluene.