Stress relaxation,creep, and internal stresses in high density polyethylene filled with calcium carbonate

The effect of filling high density polyethylene (HDPE) with calcium carbonate (up to 50% by weight) on the stress relaxation and the creep in uniaxial extension at room temperature was investigated. The addition of CaCO₃ was found to have a strong influence on the flow behaviour of HDPE. In particular, it was observed that the internal stress level, calculated from relaxation data, increased markedly with the filler content. The reduction in creep rate of the filled samples suggested that the CaCO₃-particles induce a change in the structure of the HDPE-interphase close to the filler surface. This was supported by dynamic mechanical measurements performed at low temperatures on swollen HDPE-CaCO₃ samples.     

The effect of a coupling agent on the viscoelastic properties and internal stresses in high density polyethylene filled with glass spheres

It is shown that covalent bonding between high density polyethylene (HDPE) and glass spheres can have a significant influence on the stress relaxation behaviour and the creep properties of the corresponding composites at room temperature. The bonding is obtained by reacting the glass spheres with an azide functional alkoxysilane which is capable of bonding to the HDPE-chain. The internal stress, evaluated from relaxation experiments, increased markedly as a result of this treatment, and it is suggested that the internal stress level reflects the properties of the interphase region between the filler and the bulk matrix and its effect on the viscoelastic properties.     

A model for the effect of physical ageing on the stress relaxation behavior of high density polyethylene

The stress relaxation behavior of high density polyethylene (HDPE) can be affected by ageing processes; e.g., with increasing storage time at a low temperature following a quench from a high temperature (close to the melting point) the relaxation curves change shape. More specifically, the stress level approached after very long loading times in a stress relaxation experiment increases with the ageing time. Here this stress level is denoted the internal stress _i. Struik has pointed out that physical ageing may also occur in semicrystalline polymers like HDPE. The physical ageing should then be associated with that part of the amorphous phase which is closest to the surfaces of the crystallites. This part of the amorphous phase of HDPE can be assumed to have a restricted mobility at room temperature and may have a partially glassy character. In this paper a model for explaining the increase in _i for HDPE with increasing ageing time is proposed and discussed. It is based on the separation of the amorphous phase into two parts as suggested by Struik. The glassy part of the amorphous phase ages in a way similar to that of an entirely amorphous polymer quenched to a temperature below its glass transition, while the more rubbery phase is assumed not to undergo any physical ageing.     

A theoretical model for the prediction of thermal expansion behaviour of particulate composites

The thermal expansion coefficient of particle-reinforced polymers was evaluated using a theoretical model which takes into account the adhesion efficiency between the inclusions and the matrix — an important factor affecting the thermomechanical properties of a composite. To measure the adhesion efficiency a boundary interphase, i.e. a layer between the matrix and the fillers having a structure and properties different from those of the constituent phases, was considered. This layer is assumed to have varying properties.To obtain information concerning the properties and extent of the interphase, an experimental study of the thermal behaviour of aluminium-epoxy composites was undertaken. Differential Scanning Calorimetry (DSC) measurements were performed to evaluate heat capacity with respect to temperature. In addition, the effects of different factors, such as heating rate and filler concentration on the glass transition temperature of the composite, were examined. The sudden changes in heat capacity values in the glass transition region were used to estimate the extent of the boundary interphase according to an existing theory.Finally, the values of the thermal expansion coefficient, predicted by this model, were compared with theoretical results obtained by other authors and with experimental results.     

Small deformation viscoelastic response of gum and highly filled elastomers

Small deformation viscoelastic response has been investigated in a series of five elastomeric binders, both with and without nonreinforcing filler. The filled systems were found to be both nonlinear viscoelastic and thermorheologically complex. These behaviors suggest the existence of a secondary relaxation process. The origin of this secondary process was modeled as an interphase of polymer weakly adsorbed on the filler surface. Decomposition of timetemperature shift factors for filled vs unfilled properties showed that the mechanical response of this interphase followed Arrhenius behavior. Measured activation energies ranged from 24 to 76kJ/mole, depending on the cohesiveenergy density of the elastomeric binder. Finally, these activation energies were related to the strain amplitude dependent nonlinear factors for the polymeric systems which contained no polar groups in their backbone, suggesting that in these systems both the nonlinear and thermorheologically complex nature of the filled materials' viscoelastic response originate from relaxations within this interphase.     

Zum Einfluß von Füllstoffen auf das rheologische Verhalten von hochmolekularen Polyethylenschmelzen I. Das Fließverhalten in Scher- und Dehnströmungen

Zusammenfassung Das Fließverhalten von Polymersuspensionen in verschiedenen Strömungsformen wird anhand von mit isotropen und anisotropen Partikeln (Glaskugeln bzw. Glasfasern) gefüllten hochmolekularen Schmelzen untersucht. Zur Anwendung kommen dabei sowohl lineare als auch verzweigte Polymere, nämlich Polyethylene mit hoher Dichte (HDPE) und mit niedriger Dichte (LDPE).Alle untersuchten Systeme zeigen in der Scherströmung im Rotationsrheometer bei Zugabe von Füllstoff eine Verringerung der elastischen Eigenschaften. Solches Verhalten ist für Suspensionen isotroper Teilchen zu erwarten, bei Fasersuspensionen wird jedoch gewöhnlich ein verstärktes Anwachsen der ersten Normalspannungsdifferenz mit zunehmender Füllung gefunden. Bei höheren Schergeschwindigkeiten (Messungen im Kapillarviskosimeter) wird die durch die Füllstoffe bewirkte Viskositätserhöhung zunehmend geringer, die Suspensionen verhalten sich also mit zunehmendem Füllgrad stärker scherentzähend. Das Einsetzen der für das lineare HDPE typischen Instabilitäten (stick-slip, Wandgleiten) läßt sich durch den Ersatz von (elastischem) Polymer durch (starre) Kugeln nicht beeinflussen, diese Form des Schmelzenbruchs setzt bei gleichen Schubspannungen ein und ist so wegen der höheren Viskosität der Suspension sogar zu niedrigeren Durchsätzen hin verschoben.Um die Lücke zwischen den Messungen im Rotations- und im Kapillarviskosimeter (niedrige bzw. hohe Schergeschwindigkeiten) zu schließen, wurden Experimente bei oszillatorischer Scherbeanspruchung durchgeführt. Die bekannte Cox-Merz-Beziehung vermag das Verhalten der ungefüllten Schmelzen zwar recht gut zu beschreiben, versagt jedoch bei den Suspensionen gerade im Bereich niedriger Schergeschwindigkeiten, ebenso wie andere vorgeschlagene Korrelationen zwischen dynamischen und stationären Kenngrößen.Zur Bestimmung des Materialverhaltens bei uniaxialer Dehnbeanspruchung wurde ein Rotationsrheometer in geeigneter Weise modifiziert, so daß für die verwendeten sehr hochviskosen Stoffsysteme eine Messung möglich wurde. Die verschiedenen reinen Schmelzen zeigen ein wenig unterschiedliches Dehnverhalten mit ausgeprägten Verfestigungserscheinungen. Eine stationäre Dehnviskosität konnte in keinem Fall gemessen werden. Die Zugabe von Glaskugeln ändert die Dehnviskosität nicht wesentlich, der Zusatz von Glasfasern jedoch bewirkt eine merkliche Erhöhung der instationären Dehnviskosität im Anlaufbereich.

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The flow behaviour of suspensions is examined in different flow geometries using linear and branched high-molecular-weight polyethylene melts as suspension media containing isotropic (glass beads) and anisotropic (glass fibre) particles.In shear flow in a rotational rheometer, all suspensions show a decrease of the elastic properties with increasing filler content. While this behaviour has to be expected with suspensions of isotropic particles, fibre-filled polymer fluids usually show increasing normal stress differences with increasing fibre content. At higher shear rates (in a capillary viscometer) the particle-induced viscosity increase deminishes, hence the suspensions tend to be more shear thinning with increased filler content.The onset point of instabilities typically found with the linear HDPE is not shifted towards higher volumetric flow rates by replacement of elastic polymer by inelastic fillers as might be expected; on the contrary, the so-called stick-slip behaviour is initiated at constant values of shear stress and hence — because of the higher viscosity of the suspensions — at lower flow rates.Additionally, experiments were carried out with oscillating shear strain. Neither the well-known Cox-Merz relation nor similar relations, discussed in the literature, could properly correlate oscillatory and steady-state fluid behaviour of the suspensions, especially in the low shear rate range, whereas the former worked rather well for the unfilled melts.To allow for measurements of extensional properties, a rotational rheometer was slightly modified, thus being capable of determining the extensional viscosity of highly viscous polymeric materials. The pure melts showed only a slightly different behaviour with pronounced strain hardening. No stationary values of the Trouton viscosity could be obtained. While addition of glass beads was of little influence on material behaviour, addition of glass fibres showed remarkable increase of the extensional viscosity in the start-up region.

Erster Teil einer vom Fachbereich Chemietechnik der Universität Dortmund genehmigten Dissertation     

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.     

界面特性对短纤维金属基复合材料蠕变行为的影响

基于短纤维增强金属基复合材料(MMC)的单纤维三维模型(三相)，利用粘弹性有限元分析方法对影响金属基复合材料的蠕变行为的因素进行了较为系统的分析。研究中主要讨论了界面特性和纤维取向角对金属基复合材料的蠕变性能的影响。研究结果发现，界面特性诸如厚度、模量和应力指数都对纤维最大轴应力和稳定蠕变率产生影响：稳态蠕变率随界面模量的增大而逐渐减小，当高于基体模量时基本保持不变；纤维轴应力的变化与蠕变率正好相反。稳态蠕变率随界面厚度、应力指数的增加而增大；而轴应力则随之减小。同时不同的纤维取向也影响金属基复合材料蠕变时的轴应力分布和稳态蠕变率。     

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.     

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.     

Mechanical properties of propellant composite materials reinforced with ammonium perchlorate particles

The purpose of this article is the theoretical interpretation of the experimental data on a continuum Neoprene binder, a glass bead-filled polyurethane binder, and unbound micropulverized ammonium perchlorate particles. After conducting stress relaxation and creep experiments, it is concluded that the large deformation behavior of the filled binder can be described in part in terms of the large deformation behavior of the continuum binder. The time scale of relaxation of stress in the filled binder is much longer than that of the unfilled binder. This has been determined by frictional processes which took place between the filler and the binder as well as among the filler particles. As a result of relaxation and creep studies on ammonium perchlorate (AP) particles, it has been found that the time scale of relaxation is of the same order of magnitude as that of the filler binder. In addition, it is believed that the static indeterminacy of the unbound particles helps to explain much of the strain variation at given stress level that is observed in tensile experiments of composite propellants.     

Prediction of the creep behaviour of polyethylene and molybdenum from stress relaxation experiments

In many applications it is useful to be able to convert observed creep data of a material to corresponding stress relaxation data or vice versa. If the material exhibits non-linear viscoelasticity such a conversion can be rather difficult. In this paper two semi-empirical flow equations, the power law and the exponential law, are used to convert stress relaxation data into corresponding creep behaviour data. These two flow equations are often used to describe non-linear viscoelastic behaviour. The procedure adopted here is based on the assumption that the creep data during the experiment decrease due to an increase in the internal stress level, thus decreasing the effective stress for flow. The conversion method is applied to high density polyethylene and polycrystalline molybdenum at room temperature. In general predictions using the power law are in better agreement with the experimental results than predictions using the exponential formula. The concepts of secondary and ceasing creep are discussed in terms of build-up of internal stress during the creep process.     

Generalized Cole-Cole behavior and its rheological relevance

Starting from an analysis of the rheological behavior of the complex modulus predicted by the Cole-Cole formalism, a generalized Cole-Cole ansatz is suggested in order to overcome the related difficulties. The corresponding rheological constitutive equation with fractional derivatives belonging to the generalized Cole-Cole respondance is stated and the characteristic material functions of the linear viscoelasticity theory (like the dynamic modulus and compliance, the relaxation and ratardation functions, the spectra, etc.) are derived. Model predictions of these functions will be compared with experimental results from dynamical measurements and creep data on different polymer systems which show cooperative phenomena (polymeric glasses and gelling systems). One can see that the modified ansatz fits the data very well, in spite of its relative simplicity.     

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.     

Some inverse problems in rheology leading to integral equations

Two inverse problems of the integral type, which are of the general importance to rheology, are discussed. The first of them is the possibility of calculating the molecular weight distribution (MWD) from the flow curve and the second one is the interrelation between creep and relaxation functions. It was shown that the first problem is incorrect and any solution is unstable in respect to minor experimental errors. It means that the general solution of this problem is impossible in principle and only estimations of the width of unimodal MWD can be received from the curvature of the flow curve. The possibility of the correct calculation of the creep function exists in case the relaxation curve being approximated by the sum of exponential members. But the approximation of the relaxation curve within the experimental accuracy is the necessary, but not sufficient condition for the correct solution of this integral inverse problem, because not every mode of approximation leads to the satisfactory prediction of creep function.Delivered as the Courtaulds Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Interfacial effects on the melt state behavior of polyethylene-EPDM-calcium carbonate composites

Dynamic mechanical spectra of various composites of high density polyethylene (PE), ethylene propylene diene rubber (EPDM), and calcium carbonate were obtained at 190°C with a parallel plate instrument. Interfacial effects were found to have a significant influence on the dynamic mechanical behavior of these composites.Composites of calcium carbonate in PE displayed prominent particle—particle interaction effects. This resulted in a greatly enhanced dynamic shear modulusG _d due to the filler addition. Treatment of the calcium carbonate with gamma-aminopropyltriethoxysilane (-APS) or gamma-methacryloxypropyltrimethoxysilane (-MPS) significantly reduced the particle—particle interactions. Solution deposition of EPDM or EPDM grafted with maleic anhydride (EPDM-MA) on the calcium carbonate, before incorporation into a PE composite, also had a significant effect on the composite properties. Comparison of data from composites treated with EPDM vs. EPDM-MA suggested the presence of an interaction between the calcium carbonate surface and the maleic anhydride modification. This conclusion was further supported by solid state proton NMR relaxation model experiments which showed significant immobilization of the EPDM-MA chains on the filler surface. The treatment of calcium carbonate with-APS or-MPS before incorporation into multicomponent polyethylene-rubber-filler composites also had a significant influence on the dynamic mechanical properties of the resultant composites. There is evidence for a reaction between-APS and EPDM-MA during processing on the roll mill.     

Finite shear strain behavior of a crosslinking polydimethylsiloxane near its gel point

A power law distribution of relaxation times, large normal stress differences, and physical rupture of molecular network strands dominate the shear behavior of polymers at the gel point (critical gels). This is shown in a series of well-defined experiments with increasing magnitude of shear on a model-network polymer system consisting of a linear, telechelic, vinyl-terminated poly-dimethylsiloxane (PDMS) and a four-functional siloxane crosslinker. Stable samples were prepared by stopping the crosslinking reaction at different extents of reaction in the vicinity of the gel point (GP). The Gel Equation has been shown to be valid up to strains of about 2 when using a finite strain tensor. Larger strains have been found to disrupt the network structure of the crosslinking polymer, and introduce a mechanical delay to the gel point. A sample that was crosslinked beyond the gel point (p>p _c ) can be reduced from the solid state to a critical gel, or even to a viscoelastic liquid, depending on the magnitude of shear strain. As a consequence, the relaxation exponent of a critical gel created under the influence of shear is less than that of a quiescently crosslinked critical gel.     

Thermodynamics of relaxation processes in the glass transition region

Relaxation processes in the glass transition region, especially the recovery of the volume and the physical ageing of polymers, do not follow the common (linear) theory of relaxation. On the contrary, they show a development which depends on the previous history, may be non-monotonous and requires a relaxation time that may have negative values and a pole. These phenomena can be explained if the single relaxation time is replaced by a spectrum of relaxation times and the relaxation times are supposed to be subjected to a feedback via certain structure- and temperature-parameters (as, for instance, in the KAHR-theory).However, the feedback and a pole of the relaxation time arise already for a single internal degree of freedom by themselves, if, in the non-equilibrium thermodynamics, a dynamic and a static temperature are strictly differentiated. In the case of the relaxation of the diffusive translational motion of the molecules in the glass transition region the dynamic temperature is identical with the socalled fictive temperature introduced by Tool.With regard to the relaxation of the volume three different temperature regions must be distinguished: A fluid region at high temperatures where the relaxation is controlled by the free volume and complies with the linear theory at least approximately; a glass-like region at low temperatures where the relaxation is controlled by the thermal expansivity of the free volume and where, under certain conditions, the statements set up by Davies and Jones are valid; an intermediate region (the glass transition region) where the free volume as well as its coefficient of expansivity are decisive. In that region the effective relaxation time of the volume may have a pole and the dynamic temperature may approach its equilibrium value by discontinuous jumps or in a chaotic manner.Dedicated to Professor Dr. J. Meissner (ETH Zürich) on the occasion of his 60th birthday     

Shear creep and recovery of a technical polystyrene

The torsional creep and recoverable bahaviour of a technical polystyrene is reported over seven orders of magnitude of the value of the compliance from 10^–8 to 10^–1 Pa^–1 and over more than seven decades in time. The results for the recoverable compliance J_R (t) reveal a dispersion region seen between the glass transition and the steady-state recoverable compliance J_e. The limiting value of the final dispersion J_e = 4.7 · 10^–4 Pa^–1 indicates a broad molecular-weight distribution. The steady-state recoverable compliance J_e is independent of the temperature. The temperature dependence of the final dispersion was found to be indistinguishable from that of viscous flow. However, this temperature dependence differs significantly from that of the glass-rubber transition. A proposal has been made for the construction of creep compliance and recoverable compliance over an extended time scale.     

Failure criteria for transtropic,pressure dependent materials

A convenient criterion in the 3D-principal stress space for describing the yielding and failure behaviour of transversely isotropic (transtropic) materials, presenting also the strength differential effect (SDE) along the three principal stress axes, is the elliptic-paraboloid failure criterion (EPFC). The general properties of the EPFC were examined previously for the general anisotropic material with SDE and its validity was established by comparing it with other criteria and the real behaviour of various anisotropic materials. In this paper the particular properties of materials showing a transverse isotropy were studied and important results were established which simplify considerably the complicated expressions established in the case of total anisotropy. The particular properties of the EPFC for transtropic materials were also compared with experimental evidence and were found to be in agreement with it.