An investigation of the viscoelastic properties of molten polypropylene

Two series of polypropylene samples of different molecular weight, the first obtained directly from polymerization reactions and the second from controlled thermal degradation, were studied by dynamic testing in the melt state. Several viscoelastic parameters were determined, and correlated with weight-average molecular weightM _w . It is found that theM _w -dependence of the two series is rather different.     

A study of swelling and collapse in polyelectrolyte gels

Swelling and collapse of a polyelectrolyte are shown to be the result of a delicate balance of three thermodynamic forces, viz. osmotic pressure, polymer elasticity, and van der Waals attraction. The behaviour of the polyelectrolyte gel is studied under isotropic pressure and under uniaxial and biaxial loading.     

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.     

Prediction of stress in a linear viscoelastic solid strained while cooling

A simplethermoelastic method is proposed, and justified, for predicting stresses arising during cooling of a linearviscoelastic solid. It is equivalent to representing the material by an array of spring-switch thermoelastic elements. The final stress resulting from an increment of strain is calculated using isochronal modulus data applying to the temperature at which the strain was applied, modified to accommodate temperature dependence of the limiting moduli. The method is exact for a material whose relaxation times and limiting moduli scale uniformly with change in temperature, with time-temperature shift factora _T obeying the Arrhenius equation, cooled such that reciprocal absolute temperature is linear in time. For other cooling sequences it is useful as an approximation. In particular, it assists the computational prediction of stresses arising during cooling in polymer processes.     

Evolution of the rheological properties during the reactive processing of thermoplastic/thermoset epoxy

The melt state reaction, or fusion process of bisphenol-A and the diglycidyl ether of bisphenol-A can produce both linear phenoxy backbone chains and crosslinked network structures. The linear chains can be thought of as thermoplastic polymer, while the crosslinked molecular matrix is a thermoset; therefore, this resin system can be termed a thermoplastic/thermoset epoxy.Rheological analysis has been performed on this system to determine the occurrence of the crossover of the storage and loss moduli during the reaction using three techniques: isothermal cure, interval frequency sweep, and interval stress relaxation.Determination of the activation energy of the reaction by consideration of the conventional gel-point determination prove unsatisfactory as compared to that which is determined by FTIR. An alternative technique is presented which yields a value in good agreement with that obtained by following epoxide consumption. The thermoplastic/thermoset nature of this material leads to the deviation from traditional thermoset cure behavior.     

Instabilities in multi-hole converging flow of viscoelastic fluids

Studies of the onset of instabilities were conducted on single hole and multi-hole contractions using laser speckle visualization. A well characterized elastic fluid was used with constant viscosity of 13.1 Pa · s and elasticity characterized by a longest relaxation time constant of 2.233 s. The onset of instabilities was characterized in terms of the Deborah number and the contraction ratio. Three types of instabilities were observed: pulsing vortices, azimuthally rotating vortices, and swirling vortices. For the single hole contractions the critical Deborah number for instability increased from 4.4 to 5.07 to 5.25 as the contraction ratio increased from 4: 1 to 8: 1 to 12: 1. The magnitude of the instabilities was much greater for the 4: 1 contraction than for the other two contraction ratios. For the multi-hole contraction a square array of nine holes was used and the ratio of the hole diameter to hole spacing was varied. The height of the vortices is very similar for the single hole and multi-hole contractions at low Deborah numbers. At high Deborah numbers the effect of adjacent holes is to reduce the height of the vortices by a factor of three. For the 4: 1 spacing no secondary vortex was observed below a Deborah number of De = 3.7. Secondary vortices occurred for the 8:1 and 10:1 spacing at all Deborah numbers. Unstable pulsing vortices appeared for all spacings at a critical Deborah number around 5.5. Adjacent holes decreased the strength of the unsteady vortex motions. The centerline velocities were measured for the multi-hole contraction at shear rates of 5, 30, and 300 s^–1. The elongational strain rates are similar at a low shear rate of 5 s^–1. As shear rate is increased the onset of stretching occurs closer to the plane of the contraction for the smaller contraction ratios.     

Quantitative evaluation of extrudate swell from viscoelastic properties of polystyrene

A theory of extrudate swell for short, intermediate or long dies is presented. In our experiment, we consider that the swelling phenomenon is mainly due to the recoverable elongational strain induced by the converging flow at the die entrance, as well as by recoverable shear strain originating within the die. From these concepts, an equation has been derived for the quantitative prediction of extrudate swell from the elastic material properties such as the entrance pressure drop, the relaxation modulus and the recoverable shear strain. Excellent agreement is found between predicted and measured values of extrudate swell obtained on commercial polystyrene melt, using capillaries of length-to-diameter ratios ranging from 1 to 20 and in a wide range of shear rates.     

Consistency tests for start-up and cessation deformations of viscoelastic fluids

The time-dependent shear stress and first normal stress difference were measured for a polystyrene solution for start-up and cessation-flow experiments over a relatively wide range of shear rate. Consistency tests for the K-BKZ model were applied to the data, and it was concluded that the K-BKZ equation generally does not satisfactorily describe the start-up and cessation data. Modified consistency tests were developed using a strain-coupling constitutive equation, and the evidence suggests that most of the differences between the predictions of the K-BKZ theory and experiment can be explained by including a strain-coupling effect in the rheological constitutive equation.     

Evaluation of the dynamic-mechanical properties of solids from a cooperative model for stress relaxation

For many solid materials the stress relaxation process obeys the universal relationF = – (d/d lnt)_max = (0.1 ± 0.01) ( ₀ — _i ), regardless of the structure of the material. Here denotes the stress,t the time, ₀ the initial stress of the experiment and _i the internal stress. A cooperative model accounting for the similarity in relaxation behaviour between different materials was developed earlier. Since this model has a spectral character, the concepts of linear viscoelasticity are used here to evaluate the corresponding prediction of the dynamic mechanical properties, i.e. the frequency dependence of the storageE () and lossE () moduli. Useful numerical approximations ofE () andE () are also evaluated. It is noted that the universal relation in stress relaxation had a counterpart in the frequency dependence ofE (). The theoretical prediction of the loss factor for high-density polyethylene is compared with experimental results. The agreement is good.     

Temperature and concentration dependent viscosity and gelation temperature of ABA triblock copolymer solutions

In solutions of ABA-triblock copolymers in a poor solvent for A thermoreversible gelation can occur. A three-dimensional dynamic network may form and, given the polymer and the solvent, its structure will depend on temperature and polymer mass fraction. The zero-shear rate viscosity of solutions of the triblock-copolymer polystyrene-polyisoprene-polystyrene in n-tetradecane was measured as a function of temperature and polymer mass fraction, and analyzed; the polystyrene blocks contained about 100 monomers, the polyisoprene blocks about 2000 monomers. Empirically, in the viscosity at constant mass fraction plotted versus inverse temperature, two contributions could be discerned; one contribution dominating at high and the other one dominating at low temperatures. In a comparison with theory, the contribution dominating at low temperatures was identified with the Lodge transient network viscosity; some questions remain to be answered, however. An earlier proposal for defining the gelation temperature T _gel is specified for the systems considered, and leads to a gelation curve; T _gel as a function of polymer mass fraction.Mathematical symbols {} functional dependence; e.g., f{x} means f is a function of x - p _log logarithm to the base number p; e.g., ¹⁰log is the common logarithm - exp exponential function with base number e - sin trigonometric sine function - lim limit operation - – in integral sign: Cauchy Principal Value of integral, e.g., - derivative to x - partial derivative to x Latin symbols dimensionless constant - b constant with dimension of absolute temperature - constant with dimension of absolute temperature - B dimensionless constant - c mass fraction - dimensionless constant - constant with dimension of absolute temperature - d ^* dimensionless constant - D{0} constant with dimension of absolute temperature - e base number of natural (or Naperian) logarithm - g distribution function of inverse relaxation times - G relaxation strength relaxation function - h distribution function of relaxation times reaction constant enthalpy of a molecule - H Heaviside unit step function - i complex number defined by i ² = –1 - j{0} constant with dimension of viscosity - j index number - k Boltzmann's constant - k _H Huggins' coefficient - m mass of a molecule - n number - N number - p index number - s entropy of a molecule - t time - T absolute temperature Greek symbols as index: type of polymer molecule - as index: type of polymer molecule - shear as index: type of polymer molecule - shear rate - small variation; e.g. T is a small variation in T relative deviation Dirac delta distribution as index: type of polymer molecule - difference; e.g. is a difference in chemical potential - constant with dimension of absolute temperature - (complex) viscosity - constant with dimension of viscosity - [] intrinsic viscosity number - inverse of relaxation time - chemical potential - number pi; circle circumference divided by its diameter - mass per unit volume - relaxation time shear stress - angular frequency     

Comparison of linear viscoelastic constitutive equations for non-uniform polymer melts

Linear-viscoelastic properties of polydisperse and randomly-branched polymer melts were fit with several proposed relaxation functions by non-linear regression. Three polymer systems were investigated, including 1) crosslinked polyethylenes, 2) polydisperse linear poly(dimethylsiloxane)s, and 3) Marlex polyethylenes, which are polydisperse and probably contain long-chain branching. Four relaxation functions were evaluated, including the Rouse, reptation, stretched-exponential, and stretched-exponential-power-law (SEPL) relaxation functions. The SEPL best described each series of polymers, and therefore may be a general relaxation function for non-uniform polymer melts. The flow activation energy for crosslinked polyethylene may be coupled to a breadth-of-relaxation index, indicating that a coupling between a characteristic short relaxation time and longest relaxation time, as suggested by Ngai and Plazek (J. Polym. Sci. Polym. Phys. Ed. 1985, 23:2159–2180), may hold for some non-uniform polymers.     

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].     

The rheology of a smectic main-chain polymer

The rheology of a smectic main-chain polymer shows that the activation energy is high (275 kJ mol^–1) and that the viscosity is more than two orders of magnitude higher than in the isotropic phase. The recoverable strain in the smectic phase is largely due to the reformation of the smectic layers after cessation of shear.     

On the relaxation of shear and normal stresses of viscoelastic fluids following constant shear rate experiments

By means of a cone and plate rheometer the relaxation of the shear stress and the first normal stress difference in polymer liquids upon cessation of a constant shear rate were examined. The experiments were conducted mostly in a high shear rate region of relevance for the processing of these materials. The relaxation behavior at these shear rates can only be measured accurately under extremely precise specifications of the rheometer. To determine under which conditions the integral normal thrust is a convenient measure for the relaxing local first normal stress difference the radial distribution of the pressure in the shear gap was measured. The shape of relaxation of both the shear stress and the first normal stress difference could be closely approximated for the entire measured shear rate and time range by a two parameter statistical function. In the range of measured shear rates, one of the parameters, the standard deviationS, is equal for the shear and the normal stress, and is independent of the shear rate within the limit of experimental error. The second parameter, the mean relaxation timet _50, of the shear stress andt _50, of the first normal stress difference, can be calculated approximately from the viscosity function and only a single relaxation experiment.     

Oscillatory convection in a viscoelastic fluid through a porous layer heated from below

The stability of a viscoelastic fluid in a densely packed horizontal porous layer heated from below is considered using an Oldroyd model. Critical Rayleigh number, wave number, and frequency for overstability are determined by applying the linear stability theory. It is shown that the critical Rayleigh number is invariant under all relevant boundary combinations. Also, it is found that the effect of elasticity of the fluid is to destabilize the system and that of porosity is to stabilize the same. The limiting case of very high Prandtl number and the degenerate case corresponding to the Maxwell model are analyzed in some detail.     

Dynamic-mechanical properties of interfacially modified glass sphere filled polyethylene

Model composites of spherical glass particles dispersed in a matrix of high density polyethylene were prepared both with and without interfacial modification by an azidofunctional trialkoxysilane. Dynamic mechanical measurements of the composites in the melt state were recorded. The unmodified composites behave as theoretically predicted and the effect of particle—particle interaction at high volume fractions can be measured. The composites with a modified interfacial region have greater shear moduli due to the effect of a region surrounding the particle modified by the silane. The material in this region is largely bound to the glass surface and was examined by Fourier transform infrared spectroscopy after extraction of the bulk matrix. Theoretical calculations are shown to be useful in calculating the mechanical properties and volume fraction of the interfacial region.     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Ultrasonic investigation of interpenetrating networks of poly(methyl methacrylate) and polyurethane

Interpenetrating networks are the most recent development in polymeric blend materials. Due to the crosslinking of both the continuous and dispersed phases, a high degree of molecular mixing is achieved in these materials. Notwith-standing that poly(methyl methacrylate)-polyurethane (PMMA-PUR) interpene-trating and semi-interpenetrating networks have been extensively investigated by Meyer et al., ultrasonic relaxation technique has been applied here for the first time. These materials were found to be highly ultrasound absorbing.It is observed that ultrasonic absorption has a peak at a particular composition of PMMA-PUR interpenetrating network. The absorption coefficient increases with frequencyf. The absorption is of relaxational nature and is not due to the scattering of ultrasonic waves by the domains of the dispersed phase. At every composition of the interpenetrating network, the/f ² vs.f curve indicates the presence of a relaxation frequency below 2 MHz and that the absorption increases with the temperature at some compositions which indicates the presence of thermal relaxation. An attempt is made to relate the absorption with the relaxation of pendent groups of polyurethane in the continuous phase.     

The time-dependent stress-optical behavior of polycarbonate in the glass transition region

The mechanical and stress-optical behavior of Bisphenol-A polycarbonate was investigated in the glass-transition region. For this purpose, optical creep experiments were carried out in shear and elongation on a tensile tester specially designed for use on a microscope state. A Kohlrausch Williams Watts equation (KWW) with a temperature-independent parameter could successfully be applied to the curves describing the time-dependent values of the stress-optical coefficient for several temperatures. The temperature dependence of the corresponding retardation time could be established and described by the WLF equation. For variable stresses the time-dependent birefringence is obtained from a generalized linear stress-optical rule as modeled according to linear superposition. The time-temperature superposition principle was applied to all measurements. With the dynamic moduli some deviations were observed at the transition from the rubbery plateau to the relaxation. The strain-optical coefficient was found to decrease with increasing time and strain. The strain dependence was found to be independent of temperature at constant stress.