Uniaxial elongational behavior of poly(vinyl chloride) physical gel

A poly(vinyl chloride) (PVC,  M_w = 102×10³)(\mbox{PVC,}\;{\rm M}_{\rm w} =102\times 10^3) di-octyl phthalate (DOP) gel with PVC content of 20 wt.% was prepared by a solvent evaporation method. The dynamic viscoelsticity and elongational viscosity of the PVC/DOP gel were measured at various temperatures. The gel exhibited a typical sol–gel transition behavior with elevating temperature. The critical gel temperature (T_gel) characterized with a power–law relationship between the storage and loss moduli, G^′ and G^″, and frequency ω, G￠=G^￠￠/tan  ( np/2 ) μ wⁿ{G}^\prime={G}^{\prime\prime}{\rm /tan}\;\left( {{n}\pi {\rm /2}} \right)\propto \omega ^{n}, was observed to be 152°C. The elongational viscosity of the gel was measured below the T_gel. The gel exhibited strong strain hardening. Elongational viscosity against strain plot was independent of strain rate. This finding is different from the elongational viscosity behavior of linear polymer solutions and melts. The stress–strain relations were expressed by the neo-Hookean model at high temperature (135°C) near the T_gel. However, the stress–strain curves were deviated from the neo-Hookean model at smaller strain with decreasing temperature. These results indicated that this physical gel behaves as the neo-Hookean model at low cross-linking point, and is deviated from the neo-Hookean model with increasing of the PVC crystallites worked as the cross-linking junctions.     

Rheology of SiO2/(acrylic polymer/epoxy) suspensions. I. Linear viscoelasticity

Linear viscoelastic properties of SiO₂/(AP/EP) suspension with various SiO₂ volume fractions (ϕ) in a blend of acrylic polymer (AP) and epoxy (EP) were investigated at various temperatures (T). The AP/EP contained 70 vol.% of EP. The SiO₂ particles were treated with epoxy silane coupling agent. The effects of the SiO₂ particles are more pronounced in the terminal zone: a transition from viscoelastic liquid (ϕ ≤ 30 vol.%) to viscoelastic solid (ϕ ≥ 40 vol.%) was observed which can be interpreted as a critical gelation occurring at a critical particle content and critical gel temperature. The SiO₂/(AP/EP) systems exhibited a critical gel behavior at ϕ ≅ 35 vol.% and T ≅ 100°C characterized with a power–law relationship between the storage and loss moduli (G ^′ and G ^″) and frequency (ω); G ^′ = G ^″/tan(nπ/2) ∝ ω ⁿ . The critical gel exponent (n) was estimated to be about 0.45. The gelation occurred with increasing T.     

High-frequency viscoelasticity of crosslinked actin filament networks measured by diffusing wave spectroscopy

We study the short-time relaxation dynamics of crosslinked and uncrosslinked networks of semi-flexible polymers using diffusing wave spectroscopy (DWS). The networks consist of concentrated solutions of actin filaments, crosslinked with increasing amounts of α-actinin. Actin filaments (F-actin) are long semi-flexible polymers with a contour length 1–100μm and a persistence length of 5–15μm; α-actinin is a small 200kDa homodimer with two actin-binding sites. Using the large bandwidth of DWS, we measure the mean-square-displacement of 0.96μm diameter microspheres imbedded in the polymer network, from which we extract the frequency-dependent viscoelastic moduli via a generalized Langevin equation. DWS measurements yield, in a single measurement, viscoelastic moduli at frequencies up to 10⁵Hz, almost three decades higher in frequency than probed by conventional mechanical rheology. Our measurements show that the magnitude of the small-frequency plateau modulus of F-actin is greatly enhanced in the presence of α-actinin, and that the frequency dependence of the viscoelastic moduli is much stronger at intermediate frequencies. However, the frequency-dependence of loss and storage moduli become similar for both crosslinked and uncrosslinked networks at large frequencies, G′(ω)∝G′′(ω)∝ω^0.75±0.08. This high-frequency behavior is due to the small-amplitude, large-frequency lateral fluctuations of actin filaments between entanglements. Received: 20 January 1998 Accepted: 12 February 1998     

Effect of nanofillers on the phase separation and rheological properties of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The viscoelastic characteristics of the blends of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) (PMMA/SAN) were investigated at various temperatures below, near, and above the phase separation temperature. The investigated polymer system is characterized by a lower critical solution temperature. Rheological behavior of the blends in the region of a phase separation was compared with change of the light scattering intensity. The presence of nanofillers in the blend results in that the phase separation occurs at a higher temperature. At the isothermal conditions, the phase separation begins earlier and proceeds with a higher rate as compared with the same blend without filler. The results of the study show the considerable change of the viscoelastic characteristics of PMMA/SAN when the polymer system passes from the homogeneous state to the heterogeneous one. Such characteristics as the dependence of the storage modulus (G ^′) on the loss modulus (G ^″), the dependence of the loss viscosity (η ^″) on the dynamic viscosity (η ^′), the dependences of the complex viscosity (η*), and the free volume fraction (f) on the blend composition are the most sensitive to the phase separation. The phase separation affects the characteristics G ^′(ω), where ω is the frequency only in a low-frequency range. Temperatures of phase separation were estimated using dependence G ^′(T) at ω, which is the constant in the range of low frequencies.     

A newly designed coaxial cylinder-type dynamic rheometer

A newly designed dynamic rheometer is described. This apparatus is designed for the purpose of the investigation of the physical ageing process of gels and for the determination of the viscoelastic properties of polymer melts. With this instrument the dynamic moduli can be determined very accurately in a range of about 8 decades (– 2 < logG < 5.3 and – 3 < logG < 5.4;G andG in N/m²) and in a frequency range of more than 6 decades (5 10^–5 – 100 Hz) with an accuracy and stability of 0.025%. Results are shown of measurements on a silicon oil (with loss angles deviating only little from 90°), on a gel of polyvinyl chloride in Reomol (with loss angles deviating only little from 0°) and on a polystyrene melt for which, at low frequencies, the dependencies of the storage and loss moduli on the frequency are quadratic and linear, respectively.Dedicated to the Sixtieth birthday of Prof. Dr. H. R. K. N. Janeschitz-Kriegl, Johannes Kepler University, Linz, Austria.     

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).     

Viscoelastic properties of phosphoric and oxalic acid-based chitosan hydrogels

In a previous work, we have shown that chitosan true physical gelation occurs in some organic and inorganic acids (Hamdine et al. 2004). Two systems presenting similar gelation mechanisms were characterized furthermore in order to investigate the sol–gel transition: the chitosan–phosphoric acid and the chitosan–oxalic acid systems. By performing rheological measurements in the framework of linear viscoelasticity, we have investigated the effect of time, temperature, and polymer concentration on the gelation evolution. For both acid-based systems, gelation occurred above a critical polymer concentration around 5% w/v (g/100 ml) of chitosan. Isothermal time sweep experiments showed that the gelation occurs in three stages: (i) incubation; (ii) rapid increase of G′; and (iii) a last stage where G′ slowly reached its equilibrium value due to slow molecular diffusion. At the gel point, G′ and G′′ scaled with ω ⁿ , with n=0.55 for both acid-based systems and a fractal dimension d _f of 1.9. Cooling–heating cycles revealed that the gels showed thermoreversibility after one sequence, but became permanent during subsequent cycles.This revised version was published online in October 2005 with corrections to the author's name.     

Gelation behavior of polysaccharide-based interpenetrating polymer network (IPN) hydrogels

We report the preparation and rheological characterization of interpenetrating polymer network (IPN) hydrogels made from alginate and hydrophobically modified ethyl hydroxyl ethyl cellulose (HMEHEC). To our knowledge, there have been no studies of the gelation behavior of IPNs. We found that the rheology of these systems can be easily tuned, with the elastic modulus of the IPN strongly dependent on the relative ratio of HMEHEC to alginate. The sol–gel transition of these systems was found to satisfy the Winter–Chambon criterion for gelation at various crosslinker densities. From the power law relationship of the dynamic moduli (G ^′ ~G ^″ ~ω ⁿ), the exponent n appears to be dependent on both the crosslinker density and relative amount of two polymers. The value of n was found to be ~0.5 for all samples for stoichiometric amounts of crosslinker. The effect of molecular weight of HMEHEC on the gel point and viscoelastic exponent has also been reported. Alginate seems to dominate the kinetics of the process but the effect of high molecular weight HMEHEC on the gel point, especially at lower proportion was also evident.     

Viscoelastic behavior of polymerizing systems

Experimental data of the dynamic viscoelastic properties, storage modulus (G′), loss modulus (G′′), and phase shift (δ) as well as of the viscosity, η, are reported for the polymerization of a free radical polymerization system (methyl methacrylate) which exhibits the Trommsdorff effect. A rheometer-reactor assembly developed in our laboratory is used for this purpose. It is observed that in the early stages of reaction, data lie in the terminal zone. As the polymerization progresses, the Trommsdorff effect leads to a sharp increase in both the polymer concentration and the weight average molecular weight, and the viscoelastic properties then lie in the entanglement zone. A modulus crossover point (when G′ = G′′) is identified that could be used as an identification of the point where the Trommsdorff effect starts assuming significance. Received: 17 September 1998 Accepted: 9 December 1998     

Heat-induced gelation of globular proteins. Part 5. Creep behaviour of β-lactoglobulin gels

 Creep and recovery experiments have been used to investigate the behaviour of heat set protein gels exemplified by those prepared from β-lactoglobulin (β-Lg). Some initial experiments were also performed on heat set BSA gels to establish appropriate experimental conditions. The latter illustrated the importance of a well-controlled thermal regime and the use of an appropriate solvent trap. Results from the concentration dependence of compliance for β-Lg were in good agreement with previously published results for the long time extrapolated storage modulus, G ^′ _∞ we introduced previously, especially considering the necessarily different experimental conditions. The exponent of creep and recovery phase viscosity vs concentration was extremely high, ∼30, but reflects the nature of such gelling systems close to their critical concentration. In this respect, the behaviour of the creep phase viscosity was in qualitative agreement with our recently postulated viscosity vs concentration state diagram for a gelling system. Received: 12 July 2001 Accepted: 29 October 2001     

Rheological properties of skim milk gels at various temperatures; interrelation between the dynamic moduli and the relaxation modulus

The rheological properties of rennet-induced skim milk gels were determined by two methods, i.e., via stress relaxation and dynamic tests. The stress relaxation modulusG _c (t) was calculated from the dynamic moduliG andG by using a simple approximation formula and by means of a more complex procedure, via calculation of the relaxation spectrum. Either calculation method gave the same results forG _c (t). The magnitude of the relaxation modulus obtained from the stress relaxation experiments was 10% to 20% lower than that calculated from the dynamic tests.Rennet-induced skim milk gels did not show an equilibrium modulus. An increase in temperature in the range from 20° to 35 °C resulted in lower moduli at a given time scale and faster relaxation. Dynamic measurements were also performed on acid-induced skim milk gels at various temperatures andG _c (t) was calculated. The moduli of the acid-induced gels were higher than those of the rennet-induced gels and a kind of permanent network seemed to exist, also at higher temperatures. G storage shear modulus,N·m^–2; - G loss shear modulus,N·m^–2; - G _c calculated storage shear modulus,N·m^–2; - G _c calculated loss shear modulus,N·m^–2; - G _e equilibrium shear modulus,N·m^–2; - G _ec calculated equilibrium shear modulus,N·m^–2; - G(t) relaxation shear modulus,N·m^–2; - G _c (t) calculated relaxation shear modulus,N·m^–2; - G ^*(t) pseudo relaxation shear modulus,N·m^–2; - H relaxation spectrum,N·m^–2; - t time,s; - relaxation time,s; - angular frequency, rad·s^–1. Partly presented at the Conference on Rheology of Food, Pharmaceutical and Biological Materials, Warwick, UK, September 13–15, 1989 [33].     

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.     

Large amplitude oscillatory shear behavior of PEO-PPO-PEO triblock copolymer solutions

Rheological properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer solution in both linear and nonlinear regions have been investigated. PEO-PPO-PEO triblock copolymer solution shows a dramatic change in mechanical properties as temperature changes. PEO-PPO-PEO triblock copolymer undergoes a transition from sol to gel with increase of temperature. During this transition the copolymer solution passes through three different stages, namely sol, soft gel, and hard gel. In our previous research (Hyun et al. in J Non-Newtonian Fluid Mech 55:51–65, 2002), large amplitude oscillatory shear (LAOS) behavior was found to be very sensitive to the generated microstructures. In this study, we investigated the relationship between the LAOS type and the microdomain structure. Newtonian behavior is observed in sol region, while there appear two kinds of LAOS types in the soft gel region. One is type I (G′, G′′ decreasing) and the other is a combination of type I and type IV (G′, G′′ increasing followed by decreasing). Type III (G′ decreasing, G′′ increasing followed by decreasing) is observed in the hard gel region. We compared the shape of stress curves, Lissajous pattern, and Fourier transform (FT) rheology of hard gel and soft gel under LAOS, and tried to relate the complex LAOS behavior with the microstructural change. From these investigations, it was found that the LAOS behavior and the stress pattern at large strain are closely related to the microdomain structure of PEO-PPO-PEO triblock copolymer, and provide a lot of useful information on the microstructures induced by large deformation.     

Relaxation patterns of long,linear, flexible,monodisperse polymers: BSW spectrum revisited

Theoretical predictions for the dynamic moduli of long, linear, flexible, monodisperse polymers are summarized and compared with experimental observations. Surprisingly, the predicted 1/2 power scaling of the long-time modes of the relaxation spectrum is not found in the experiments. Instead, scaling with a power of about 1/4 extends all the way up to the longest relaxation times near τ/τ _max = 1. This is expressed in the empirical relaxation time spectrum of Baumgaertel-Schausberger-Winter, denoted as “BSW spectrum,” and justifies a closer look at the properties of the BSW spectrum. Working with the BSW spectrum, however, is made difficult by the fact that hypergeometric functions occur naturally in BSW-based rheological material functions. BSW provides no explicit solutions for the dynamic moduli, G ^′(ω), G ^″(ω), or the relaxation modulus G(t). To overcome this problem, close approximations of simple analytical form are shown for these moduli. With these approximations, analysis of linear viscoelastic data allows the direct determination of BSW parameters.     

Elasticity and dynamics of particle gels in non-Newtonian melts

We investigate the relation between the structure and the viscoelastic behavior of a model polymer nanocomposite system based on a mixture of titanium dioxide (TiO₂) nanoparticles and polypropylene. Above a critical volume fraction, Φ _c, the elasticity of the hybrids dramatically increases, and the frequency dependence of the elastic and viscous moduli reflects the superposition of the independent responses of the suspending polymer melt and of an elastic particle network. In addition, the elasticity of the hybrids shows critical behavior around Φ _c. We interpret these observations by hypothesizing the formation of a transient network, which forms due to crowding of particle clusters. Consistent with this interpretation, we find a long-time, Φ-dependent, structural relaxation, which emphasizes the transient character of the structure formed by the particle clusters. For times below this characteristic relaxation time, the elasticity of the network is Φ-independent and reminiscent of glassy behavior, with the elastic modulus, G^′, scaling with frequency, ω, as G^′∼ω ^0.3. We expect that our analysis will be useful for understanding the behavior of other complex fluids where the elasticity of the components could be superimposed.     

Unsteady free convection on a vertical cylinder with variable heat and mass flux

The unsteady natural convection boundary layer flow over a semi-infinite vertical cylinder is considered with combined buoyancy force effects, for the situation in which the surface temperature T ^′ _w(x) and C ^′ _w(x) are subjected to the power-law surface heat and mass flux as K(T ^′/r) = −ax ⁿ and D(C ^′/r) = −bx ^m . The governing equations are solved by an implicit finite difference scheme of Crank-Nicolson method. Numerical results are obtained for different values of Prandtl number, Schmidt number ‘n’ and ‘m’. The velocity, temperature and concentration profiles, local and average skin-friction, Nusselt and Sherwood numbers are shown graphically. The local Nusselt and Sherwood number of the present study are compared with the available result and a good agreement is found to exist. Received on 7 July 1998     

Exact Connections of Warping Fields and Torsional Rigidities of Symmetric Composite Bars

Saint-Venant's torsion of symmetric cylindrical bars consisting of two or four homogeneous phases is studied. A symmetric section is meant that the cross section of the cylindrical bar possesses reflectional symmetry with respect to one or more axes. Each constituent region may have different shear modulus. The idea of the analysis is to superimpose suitably reflected potentials to obtain the torsion solution of the same composite section but with different moduli. For two-phase sections, we show that, if the warping fields for a given symmetric section with phase shear moduli μ₁ and μ₂ are known a priori, then the warping fields for the same configuration but with a different set of constituent moduli μ₁ ^′ and μ₂ ^′ are readily found through simple linear superpositions. Further, suppose that the torsional rigidities T(μ₁,μ₂) and T(μ₁ ^′,μ₂ ^′) for any two sets of phase moduli can be measured by some experimental tests or evaluated through numerical procedures, then the torsional rigidity for any other combinations of constituent moduli T(μ₁ ^′′,μ₂ ^′′) can be exactly determined without any recourse to the field solutions of governing differential equations. Similar procedures can be applied to a 4-phase symmetric section. But the coefficients of superposition are only found for a few branches. Specifically, we find that depending on the conditions of μ and μ^′, admissible solutions can be divided into three categories. When the correspondence between the warping field is known to exist, a link between the torsional rigidities can be established as well. This revised version was published online in June 2006 with corrections to the Cover Date.     

Time- and temperature-dependent crosslinking behaviour of a silicone resin

The crosslinking behaviour of a silicone resin which is interesting from a technical point of view was investigated by means of rheology. In order to accelerate the crosslinking process, zinc acetylacetonate and aluminium acetylacetonate were applied as latent catalysts. The effect of the type of catalyst, its concentration, and the temperature on crosslinking was determined by isothermal dynamic-mechanical measurements. A radial gradient in crosslinking causes the gel point to be reached earlier at the outer edge of the sample in the rheometer. This radial gradient is averaged when measuring G′ and G″. Therefore, since the physically well-defined state of critical gelation (gel point) could not be obtained from the data, the time at which a distinct crosslinking state is reached was determined by the crossover of the moduli G′ and G″. For this distinguished point, the denotation gelation index GI is introduced. The gelation indices measured at different temperatures follow an Arrhenius-type relationship. Activation energies between 89 and 126 kJ/mol were determined. They were found to be dependent on the type of catalyst used but independent of its concentration. The activation energies of the crosslinking processes enable the calculation of the gelation index at temperatures not measured directly.     

Grafting of polyamide 6 on a styrene–acrylonitrile maleic anhydride terpolymer: melt rheology at the critical gel state

In this work, we studied the melt rheology of multigraft copolymers with a styrene–acrylonitrile maleic anhydride (SANMA) terpolymer backbone and randomly grafted polyamide 6 (PA 6) chains. The multi-grafted chains were formed by interfacial reactions between the maleic anhydride groups of SANMA and the amino end groups of PA 6 during melt blending. Because of the phase separation of SANMA and PA 6, the grafted SANMA backbones formed nearly circular domains which were embedded in the PA 6 melt with a diameter in the order of 20 to 40 nm. The linear viscoelastic behaviour of PA 6/SANMA blends at a sufficiently large SANMA concentration displayed the characteristics of the critical gel state, i.e. the power relations G′ ∝ G′′ ∝ ω ^0.5. In elongation, the PA 6/SANMA blend at the critical gel state showed a non-linear strain hardening behaviour already at a very small Hencky strain. In contrast to neat PA 6, the elasticity of the PA 6/SANMA blends was strongly pronounced, which was demonstrated by recovery experiments. Rheotens tests agreed with the linear viscoelastic shear oscillations and the measurements using the elongational rheometer RME. Increasing the SANMA concentration led to a larger melt strength and a reduced drawability. The occurrence of the critical gel state can be interpreted by the cooperative motion of molecules which develops between the grafted PA 6 chains of neighbouring micelle-like SANMA domains.     

Field-induced gelation, yield stress, and fragility of an electro-rheological suspension

 Electro-rheological suspensions (ERS) are known to undergo liquid-to-solid transition under the application of an electric field. Long-range interaction between neighboring particles results in sample-spanning particulate structures which behave as soft solids. Here, we studied the rheological expression of this field-induced transition which has many similarities with chemical gelation. This similarity shows in mechanical spectroscopy on a suspension of monodisperse silica in PDMS as model ERS. Upon application of the electric field, dynamic moduli G′, G′′ grow by orders of magnitude and evolve in a pattern which is otherwise typical for gelation of network polymers (random chemical or physical gelation). At the gel point, the slow dynamics is governed by power-law relaxation behavior (frequency-independent tan δ). A low field strength is sufficient to reach the gel point and, correspondingly, the percolating particle structure at the gel point is still very fragile. It can be broken by the imposition of low stress. For inducing a finite yield stress, the field strength needs to be increased further until the long-range electrostatic interaction generates string-like particle alignments which become clearly visible under the optical microscope. The onset of fragile connectivity was defined experimentally by the tan δ method. The ERS was probed dynamically at low frequencies where the transition is most pronounced, and also in steady shear where the rate of structure formation equals the rate of internal breaking. Received: 1 May 2001 Accepted: 11 August 2001