Using oscillatory squeezing flow to measure the viscoelastic properties of dental composite resin cements during curing

We have investigated the rheological changes in two particulate-filled dental composite resin cements during the curing process using a Micro-Fourier Rheometer (MFR). In the MFR, the sample was sandwiched between two parallel plates, and pseudorandom small amplitude squeezing was applied by oscillating the upper plate over a range of frequencies. Fourier transforms of the displacement signal and the resulting time dependent force signal enabled the rapid determination of the dynamic properties G′ and G′′ over the frequency range 2π–200π rad/s . This technique permitted us to follow changes in the rheological properties of the resin cements through the setting period. A typical result was that G′ increased from 2×10³ Pa to 2×10⁵ Pa after about 120 s, and that G′′ changed from 4×10³ Pa to 4×10⁴ Pa over the same period at frequency 40π rad/s. We also found that the dental composite resin cements show linear viscoelastic behaviour over a range of strain amplitudes before curing, but the response becomes distinctly non-linear at the later stages of curing for strain amplitudes γ>0.067%.     

The rheological properties of solder and solar pastes and the effect on stencil printing

Solar and solder pastes are widely used in the electronics industry. Solder paste is the principal joining medium in the assembly of surface mount components, whilst solar paste is used in the manufacture of semiconductor solar cells in the photo-voltaic industry. The stencil printing of both solder and solar pastes is a very important and critical stage in the assembly process. With miniaturisation of components, this is likely to continue. The challenge in stencil printing at such dimensions is in achieving repeatable deposition of both solar and solder pastes from print to print. To meet this challenge requires an understanding of the flow behaviour of both solar and solder pastes. The rheological properties of solar and solder pastes have been evaluated through three different types of experiments. Existing models were applied to compare their rheological behaviour under these schemes. One striking difference was that solar paste showed a higher viscosity than solder paste. Both solar and solder pastes were found to be non-Newtonian materials, showing a decrease in viscosity with increasing shear rates. In this paper we investigate the rheological properties of both solder and solar paste under steady shear and creep-recovery tests. Received: 12 October 1999 Accepted: 11 July 2000     

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.     

Investigation of the band texture occurring in hydroxypropylcellulose solutions using rheo-optical, rheological and small angle light scattering techniques

The band texture occurs in lyotropic and thermotropic main-chain polymers after cessation of flow. This paper begins with a review of work concerned with band texture formation following shear and is followed by the presentation of original results obtained during a recent investigation. The evolution of band texture formation in a Klucel EF, 50% hydroxypropylcellulose (HPC) water solution, has been observed using polarized optical microscopy. The relationship determined between the primary shear rate and the rate of evolution of the band texture is complex and three different behaviours have been observed corresponding to three shear rate regions. Both steady flow and dynamic rheological investigations have been conducted on the HPC solution, the results of which have been related to the optical behaviour of the band texture. Data from steady flow investigations suggest that the viscosity of the solution when the band texture is present, decreases following increasing primary shear rates, is shear thinning and increases linearly with the time following its formation. Dynamic investigations suggest a definite link between the band texture evolution and the evolution of both G′ and G′′. In addition, the perfection of the band texture versus the primary shear rate has been quantified by studying the evolution of tan(δ) following the cessation of the primary shear. Dynamic experiments show that the structure of the band texture remains longer than suggested by the optical aspect of the texture. Small angle light scattering patterns have been correlated with the development of the band texture and confirm the continuing presence of the band texture structure following its optical disappearance. Received: 2 March 1999/Accepted: 26 July 1999     

About the influence of hexamethylene tetramine content on the dynamic-mechanical properties of the polymeric system: Phenolic novolac resin (PF) and nitrile rubber (NBR-29)

Summary On mixtures of phenolic novolac resin (PF) and nitrile rubber with 29% ACN-content (NBR-29) the effect of hexamethylene tetramine content was investigated by torsional pendulum measurements. The shear modulusG and the loss modulusG were registered within a temperature region from –180°C up to 200°C for different hexa-contents.The mechanical damping tests show, that with increasing hexa-content the glass transition range of the mixture is shifted to lower temperature, whereas the absorption maximum becomes smaller. This means, that the hexamethylene tetramine counteracts against the separation of the copolymer which is due to the not completely crosslinked resin and that with increasing hexa-content the mixtures become more compatible.

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Zusammenfassung Mit Hilfe des Torsionsschwingungsversuches wurde an Mischungen aus Phenolnovolakharz (PF) und Nitrilkautschuk mit 29% ACN-Gehalt (NBR-29) der Einfluß des Hexamethylentetramin-Gehalts auf den SpeichermodulG und den VerlustmodulG im Temperaturbereich von –180°C bis + 200°C in Abhängigkeit vom Hexa-Gehalt untersucht.Dabei zeigt sich, daß mit zunehmendem Hexa-Gehalt der Glasübergangsbereich der Mischung zu einer tieferen Temperaturlage hin verschoben wird, wobei der Glasübergangsbereich gleichzeitig schmaler wird. Dies bedeutet, daß das Hexamethylentetramin der Entmischung des Copolymerisats durch das nicht vollständig vernetzte Harz entgegenwirkt und mit wachsendem Hexa-Anteil die Mischung verträglicher wird.

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With 7 figures and 3 tables     

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].     

On the relationship between swelling of myofibrils and their suspension rheology

The swelling of myofibrils extracted from white bovine muscle was followed by measuring their suspension rheology. Swelling of the myofibril with increasing pH and ionic strength was accompanied by an increase in both the steady shear viscosity of the suspension and the dynamic viscoelastic properties. Swelling was continuously monitored by measuringG while the ionic strength of the suspension was being changed by dialysis. The relationship between the degree of swelling and the rheological parameters is complicated because myofibrils are rodshaped and swell radially and therefore swelling results in a change in shape. To allow for this an attempt was made to generalize the data by plotting viscosity andG againstcS/ø _m , wherec is the protein concentration in the suspension,S is the swollen volume of the myofibrils per weight of protein, and ø _m is the maximum packing fraction.The best fit to the data was represented by the equations _sp = 1.05 (cS/ _m – 0.84)^1.23 Pa · sG = 8.78 (cS/ _m – 0.67)^2.22 N m^–2. The scatter was greatest forG, possibly because at low degrees of shear the myofibrils were associated and this was confirmed by optical microscopy. Pronounced non-Newtonian behavior was observed and it was suggested that this was due to the disruption of aggregate structures, although at low concentration, orientation of the rods in the shear field may also be important.     

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     

Improvements of an oscillatory squeezing flow rheometer for small elasticity measurements of liquids

Dilute dispersions and polymer solutions used as functional fluids or operation fluids are required to be controlled in an extremely high quality level in the semiconductor industry or MEMS (Micro Mechanical Electric System) devices, such as inkjet print heads and micro pumps. Many of the quality items depend on microscopic state of dispersion or solution stem from mutual interactions among the dispersed particles and solved polymers; hence, close investigations of these complex interactions are of great concern for developments of highly functional fluids and micro fluidic devices. Here, some great improvements are presented on a random oscillatory squeezing flow rheometer to detect subtle rheological properties arise as results of interactions between micro solid particles dispersed in liquids. To detect subtle elasticity within fundamentally viscous liquids, very small phase difference from the viscous response has to be measured, and for this reason effects from three major sources (sensor nonlinearity, nonlinear squeeze flow response, and instrument compliance) that give phase errors and noises as well as fluid inertia are completely compensated by data processing, achieving sensitivity for subtle dynamic modulus G to the extent of G/G 0.001. As examples of the dilute dispersions, water dispersions of monodisperse acrylic latex were measured and detections of dynamic modulus G of 10^–3 Pa at 100 Hz were demonstrated.     

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.     

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.     

Linear and non linear rheology of a wormlike micellar system in presence of sodium tosylate

In this experimental work, we investigate the influence of an organic counterion, sodium tosylate, on the rheological properties of an aqueous solution of CTAB at the concentration of 0.05M. With this system we can clearly see shear thickening for small salt concentrations C _s and only shear thinning behavior at higher C _s characterized by a linear evolution of η=f(γ) in a log-log representation. In these evolutions it is only in a very small domain of concentrations of the salt (near C _s =0.035M) that we can observe a nearly constant plateau of the shear stress against shear rate. The values of σ₀ (characterizing the stress plateau), G ₀ (the plateau modulus) and τ_R (the relaxation time) obtained by dynamical rheological measurements, allow to compare experimental results obtained to predicted values of the theory of Cates corresponding to the occurrence of shear induced banding structures. Received: 22 July 1997 Accepted: 3 February 1998     

In situ monitoring the sol–gel transition for polyacrylamide gel

The effects of heating rate and shear stress on the sol–gel transition for a polyacrylamide gel during in situ preparation were investigated by dynamic rheology. The gelation evolution was also studied through monitoring of the static gelation process by means of temperature, pH, and conductivity variation. The gels were prepared by polymerization of acrylamide crosslinked with N,N′-methylenebisacrylamide using a redox initiation based on potassium persulfate/ascorbic acid. In situ gelation process was studied using oscillatory deformation tests at constant frequency of 0.1 Hz for different heating rate (from 0.5 to 5 °C/min) and shear stress (in the range of 0.1 to 10 Pa). The paper was presented at the third annual rheology conference, AERC 2006, Crete, Greece, 27–29 April 2006.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

Molecular orientation in sheared molten thermotropic random copolyester

The macromolecular alignment and texture orientation in sheared thermotropic copolyester were investigated using in situ wide-angle X-ray scattering (WAXS) and polarizing optical microscopy (POM). The molecular behavior was correlated with viscoelastic properties. The polymer is a random copolyester based on 60 mol% 1,4-hydroxybenzoic acid (B) and 40 mol% ethylene terephthalate (ET) units. X-ray scattering showed that the molecular chains were aligned along the flow direction. The degree of molecular orientation, , is an increasing function of the applied shear rate. However, rheo-optics showed that shear flow could not orient the polydomain texture, i.e., neither defect stretching nor elimination of defects was observed. Instead, shear compressed the microdomains and gave rise to long-range orientation correlations. Rheology showed that the nematic melt is viscoelastic, the loss modulus G″ dominates the elastic modulus G′, and the dynamic viscosity η* is shear thinning. Moreover, the steady shear viscosity, η, also behaved shear thinning, while the first normal stress difference N ₁ remained positive. The empirical Cox–Merz rule did not hold, , within the shear rate range studied. The microscopic and rheological properties suggest that B–ET is a flow-aligning nematic polymer.     

Viscoelastic properties of dibenzylidene sorbitol (DBS) physical gels at high frequencies

The rheological behavior of Dibenzylidene D-Sorbitol (DBS) gels formed in ethylene glycol, glycerol, mineral oil, ethanol, and chlorobenzene was studied using oscillatory squeezing flow viscometry. The storage (G ^′) and loss (G ^″) moduli were measured as a function of gellant concentration (0.5–2 w/w) and type of solvent. As expected greater values of gel strength (G ^′) were observed for gels containing higher concentrations of DBS. In addition, both storage and loss moduli of 2% systems were mostly frequency independent over the studied range, whereas 0.5% gels did exhibit some degree of dependence. We also found that the solvent plays an important role in the properties of the gels. Among the parameters that affect the viscoelastic properties of DBS gels, the solvent polarity and its ability to form hydrogen bonding may have significant effects on the gel rheology.     

Rheometry on magnetorheological (MR) fluids

Test fixtures of a commercial concentric cylinder rheometer (Physica Rheolab MC 20) were modified to enable measurements under magnetic inductions up to 0.5 Tesla in a shear rate range of 0.1 up to 1000 s ^–1 and temperatures 0° to 150°C. In the 2 x90°-cups only two 90° sectors of the stationary part of the double concentric cylinder arrangement are submitted to the magnetic field which is created outside the test tools by an electromagnet. A prototype of a 360°-cup contains the electromagnet within the cup and avoids the correction necessary for the sector geometry. Measurements are shown for a carbonyl iron MR fluid and two nano MR fluids. An encouraging comparison of the viscosity function and MR effect (shear stress changes due to the field) measured by using the various cups is presented. The detailed investigation of the magnetic field distribution in the tools yields a distinct radial field gradient and also stray fields that make the quantification of the effective field in the gap difficult. The change of the field when the gap is filled with MR fluid is addressed. MR effects up to 13 000 Pa have been found, the limited torque range of the rheometer making it necessary to use relatively small gap dimensions which introduce errors due to edge effects. Shear rates up to 40000 s^–1 as typical for the application in dampers were investigated by a piston-driven capillary rheometer making use of a thermostated rectangular slit with superimposed magnetic field. A satisfactory agreement of the magnetorheological data with the concentric cylinder results is found in the overlapping shear rate range.     

An empirical constitutive law for concentrated colloidal suspensions in the approach of the glass transition

Concentrated, non-crystallizing colloidal suspensions in their approach of the glass state exhibit distinct dynamics patterns. These patterns suggest a powerlaw rheological constitutive model for near-glass viscoelasticity, as presented here. The rheological parameters used for this model originate in the mode-coupling theory. The proposed constitutive model provides explicit expressions for the steady shear viscosity, the steady normal stress coefficient, the modulus-compliance relation, and the α peak of G″. The relaxation pattern distinctly differs from gelation.     

Rheological properties of white soft paraffin

Rheological properties of a sample of white soft paraffin B. P., determined using continuous shear and creep viscometry, are reported for temperatures from 5 °C to 50 °C. The material is linear viscoelastic up to 45 °C but non linear viscoelastic at 50 °C. Activation energies are derived fromArrhenius type curves of both continuous shear and creep viscosity data. A discontinuity in rheological properties between 25 °C and 30 °C is due to a structural transition within the material.

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Zusammenfassung Obwohl weiße Vaseline seit fast einem Jahrhundert in der Pharmazie verwendet worden ist, sind ihre rheologischen Eigenschaften immer noch nicht vollständig geklärt. Eine Probe mit Arzneibuchqualität (B. P.) ist unter kontinuierlichen Scherbedingungen mit einem Konus- und Plattenviskosimeter und unter geringen Beanspruchungen mit einem Kriechviskosimeter mit konzentrischen Zylindern über einen Temperaturbereich von 5–50 °C untersucht worden. Für kontinuierlich veränderliche Schubspannungen ergab sich eine Hysteresisschleife; Aktivierungsenergien für laminares Fließen sind berechnet worden. Unter Kriechbedingungen verhielt sich das Material viskoelastisch, wobei die temperaturbedingten Grenzbereiche für lineares Verhalten bestimmt worden sind. Aus den analysierten Kriechdiagrammen wurden mechanische Modelle abgeleitet, die aus einerMaxwell-Einheit verbunden mit einigenVoigt-Einheiten bestanden. Die Aktivierungsenergien sind hergeleitet worden, und die Veränderungen im rheologischen Verhalten bei etwa 30 °C sind mit den Strukturveränderungen der Bestandteile des Materials korreliert worden.

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Paper presented to the British Society of Rheology Conference on Rheology in Medicine and Pharmacy, London, April 14–15, 1970.     

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.