Rheological properties of polymer blends with sphere-in-sphere morphology

The linear viscoelastic behavior of polystyrene (PS) and poly(methylmethacrylate) (PMMA) blends with PS as the matrix and amounts of PMMA in the range 10–30 wt% was investigated. Transmission electron microscopy (TEM) revealed a complex morphology which was characterized by the existence of composite particles; the PMMA particles which are enclosed in the PS matrix themselves carry PS inclusions. In order to explain the G* data of these blends a model is presented which consists of a Palierne model for the composite particles and a Palierne model for the whole blend, taking into account composite and neat particles. Simulations show the principal relevance of the assumptions made. Moreover, it is shown that the measurements agree well with the model for the whole measured frequency region and that the fit parameters, the size of the composite particles and the concentration and size of interior particles are in reasonable agreement with data available from TEM. Received: 1 November 1998 Accepted: 5 April 1999     

Stress relaxation behavior of PMMA/PS polymer blends

In this work, the stress relaxation behavior of PMMA/PS blends, with or without random copolymer addition, submitted to step shear strain experiments in the linear and nonlinear regime was studied. The effect of blend composition (ranging from 10 to 30 wt.% of dispersed phase), viscosity ratio (ranging from 0.1 to 7.5), and random copolymer addition (for concentrations up to 8 wt.% with respect to the dispersed phase) was evaluated and correlated to the evolution of the morphology of the blends. All blends presented three relaxation stages: a first fast relaxation which was attributed to the relaxation of the pure phases, a second one which was characterized by the presence of a plateau, and a third fast one. The relaxation was shown to be faster for less extended and smaller droplets and to be influenced by coalescence for blends with a dispersed phase concentration larger than 20 wt.%. The relaxation of the blend was strongly influenced by the matrix viscosity. The addition of random copolymer resulted in a slower relaxation of the droplets.     

Temperature dependence of the interfacial tension of PS/PMMA, PS/PE, and PMMA/PE blends

The effect of temperature on the interfacial tension for PS/PMMA, PS/PE, and PMMA/PE was measured using the imbedded fiber retraction method. Interfacial tensions for PS/PMMA, PS/PE, and PMMA/PE were measured over temperature ranges of 160–250 °C, 140–220 °C, and 140–220 °C, respectively. The interfacial tension was found to follow a dependence of 3.6–0.013 T dyn/cm, 7.6–0.051 T dyn/cm and 11.8–0.017 T dyn/cm for PS/PMMA, PS/PE, and PMMA/PE, respectively. Comparison of the data with the mean field theory of Helfand and Sapse were made; however, a simple linear fit to the data described the temperature dependence in the experimental window as well as the predictions of the mean field theory. Received: 6 July 1999 Accepted: 23 March 2000     

Recoverable deformation and morphology after uniaxial elongation of a polystyrene/linear low density polyethylene blend

The transient recoverable deformation ratio after melt elongation at various elongational rates and maximum elongations was investigated for pure polystyrene and for a 85 wt.% polystyrene/15 wt.% linear low density polyethylene (PS/LLDPE 85:15) blend at a temperature of 170 ^oC. The ratio p of the zero shear rate viscosity of LLDPE to that of PS is p = 0.059 ≈ 1:17. Retraction of the elongated LLDPE droplets back to spheres and end-pinching is observed during recovery. A simple additive rule is applied in order to extract the contribution of the recovery of the elongated droplets from the total recovery of the blend. In that way, the recoverable portion of the PS/LLDPE blend induced by the interfacial tension is determined and compared with the results of a theory based on an effective medium approximation. The effective medium approximation reproduces well the time scale of the experimental data. In addition, the trends that the recoverable deformation increases with elongational rate and maximum elongation are captured by the theoretical approach.     

Rheological behavior of PS-melts containing surface modified PMMA-particles

The rheological properties of polystyrene (PS) compounds containing cross-linked PMMA particles are characterized by oscillatory shear experiments, while the amount of covalently grafted carboxylic-acid terminated polystyrene (CT-PS) on their surface is varied. All samples show an additional relaxation process with a long relaxation time in the frequency range where the matrix flows. The strength of this process depends strongly on the amount of particles, i.e., on the degree of filling and, to the same extent, on the different “coverage” of the particles surface, i.e., the degree of grafting. For the highest degrees of filling and in dependence on the degree of grafting a particle network is formed which is characterized by an evolving equilibrium modulus. Moreover, compatibilization by grafting CT-PS onto the PMMA particles' surface reduces the strength of the additional relaxation process remarkably. This surprising effect is related qualitatively to the balance of the interaction between particles and the interaction between the particles and the matrix due to PS grafts. Some of these results can be understood quantitatively on the basis of the sticky hard-sphere model. Received: 3 January 2000 Accepted: 14 August 2000     

Viscoelastic behavior of PMMA/grafted PBA nanoparticle systems in the molten state

The viscoelastic properties of poly(methyl methacrylate) (PMMA)/grafted poly(butyl acrylate) (PBA) nanoparticle systems were investigated. The rubber particles consist of PBA core (60 nm in diameter) and grafted PMMA shell. The grafting degree, defined as the weight ratio of grafted PMMA to PBA particles, ranges from 0.8 to 1.5. Two series of samples, A series with 7.5 wt.% of PBA content and B series with 12 wt.% of PBA content, were used. The systems exhibited fast and slow relaxation process, the former reflecting the relaxation of the matrix PMMA chains and the latter being attributed to grafted PBA particles. For A series samples, time-temperature superposition (TTS) was held well over the frequency (ω) and temperature (T) ranges measured. However, for B series samples, TTS was not satisfied at low ω due to the particle-particle interaction of grafted PBA particles, although the samples obeyed TTS at high ω associated with the relaxation with entanglement of matrix PMMA. At high T and low ω region, the B series samples showed a sol-gel transition at elevating T and the critical gel behavior characterized with a power-law relationship, G′ = G″/tan(nπ/2) ∝ ωⁿ, was observed. This behavior suggested formation of a self-similar, fractal structure of grafted PBA particles. The critical gel temperature (T _gel) and the critical exponent (n) were determined for the B series samples. TEM observations revealed that as-prepared A and B samples had well-dispersed particles but the B samples after viscoelastic measurements had fragmented networks of the PBA particles, confirming that the sol-gel transition occurred for the PMMA/grafted PBA systems at elevating T.     

Viscoelastic properties of semidilute poly(methyl methacrylate) solutions

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

Stress relaxation behavior of co-continuous PS/PMMA blends after step shear strain

Stress relaxation probing on the immiscible blends is an attractive route to reveal the time-dependent morphology–viscoelasticity correlations under/after flow. However, a comprehensive understanding on the stress relaxation of co-continuous blends, especially after subjected to a shear strain, is still lacking. In this work, the stress relaxation behavior of co-continuous polystyrene/poly(methyl methacrylate) (50/50) blends with different annealing times, strain levels, and temperatures was examined under step shear strain and was correlated with the development of their morphologies. It was found that co-continuous blends display a fast relaxation process which corresponded to the relaxation of bulk polymer and a second slower relaxation process due to the recovery of co-continuous morphology. The stress relaxation rates of co-continuous blends tend to decrease due to the coarsening of instable co-continuous structure during annealing. Furthermore, the stress relaxation of the co-continuous blends is strongly affected by the change of viscosity and interfacial tension caused by the temperature. The contribution of morphological coarsening, viscosity, and interfacial tension variation on the stress relaxation behavior of co-continuous blends was discussed based on the Lee–Park model and time–temperature superposition principle, respectively.     

Manifestation of phase separation processes in oscillatory shear: droplet-matrix systems versus co-continuous morphologies

Phase separation processes in mixtures of poly-α-methylstyrene-co-acrylonitrile (PαMSAN) and poly-methylmethacrylate (PMMA) with lower critical solution temperature (LCST) behavior have been studied, focusing on the manifestation of the interface in oscillatory shear measurements. By using blends of different composition, systems with a droplet-matrix morphology or a co-continuous structure are generated during the phase separation process. The feasibility of probing this morphology development by rheological measurements has been investigated. The development of a disperse droplet phase leads to an increase in the elasticity of the blend at low frequency, showing up as a shoulder in the plot of storage modulus versus frequency. Here, the droplet growth is unaffected by the shear amplitude up to strains of 0.2; therefore the resulting dynamic data are suitable for quantitative analysis. In contrast, for blends in which phase separation leads to a co-continuous structure, the storage modulus shows a power law behavior at low frequency and its value decreases as time proceeds. For the latter systems, effects of the dynamic measurement on the morphology development have been observed, even for strain amplitudes as low as 0.01. To probe the kinetics of morphology evolution in droplet-matrix systems, measurements of the time dependence of the dynamic moduli at fixed frequency should be performed (for a whole series of frequencies). Only from such measurements, curves of the frequency dependence of the moduli at a well defined residence time can be constructed. From fitting these curves to the emulsion model of Palierne, the droplet diameter distribution at that particular stage in the phase separation and growth process can be obtained. It is not appropriate to use a simplified version of the Palierne model containing only the average droplet size, because a morphology with too broad a size distribution is generated. Received: 15 February 1999 Accepted: 20 May 1999     

Thermal contraction and volume relaxation of amorphous polymers

Two experimental techniques are described for the determination of the change of specific volume of polymers with temperature and aging time, which allow measurements between – 160 °C and + 200 °C. Four technical amorphous polymers, PS, PVC, PMMA and PC have been investigated. Volume-temperature curves under constant rate of cooling are presented and interpreted with respect to relaxation processes known from other physical investigations. The rate dependence of dilatometric glass transition temperatures is compared with the time dependence of rheometric glass transition temperatures from shear creep data. Volume relaxation data at constant aging temperature are presented. Aging is found to proceed until very low temperatures in the glassy state for e.g. PMMA.For polystyrene, a comparison is made between the predictions of a very simple theory of volume relaxation due to Kovacs with experimental data, using additional information from volume temperature curves and the time temperature shift of the shear creep transition. The theory predicts a rate of volume relaxation which is much lower than that found by experiment.     

Impact of material processing and deformation on cell morphology and mechanical behavior of polyurethane and nickel foams

The cell morphology and mechanical behavior of open-cell polyurethane and nickel foams are investigated by means of combined 3D X-ray micro-tomography and large scale finite element simulations. Our quantitative 3D image analysis and finite element simulations demonstrate that the strongly anisotropic tensile behavior of nickel foams is due to the cell anisotropy induced by the deformation of PU precursor during the electroplating and heat treatment stages of nickel foam processing. In situ tensile tests on PU foams reveal that the initial main elongation axis of the cells evolves from the foam sheet normal direction to the rolling direction of the coils. Finite element simulations of the hyperelastic behavior of PU foams based on real cell morphology confirm the observation that cell struts do not experience significant elongation after 0.15 tensile straining, thus pointing out alternative deformation mechanisms like complex strut junctions deformation. The plastic behavior and the anisotropy of nickel foams are then satisfactorily retrieved from finite element simulations on a volume element containing eight cells with a detailed mesh of all the hollow struts and junctions. The experimental and computational strategy is considered as a first step toward optimization of process parameters to tailor anisotropy of cell shape and mechanical behavior for applications in batteries or Diesel particulate filtering.     

Re-examination of terminal relaxation behavior of high-molecular-weight ring polystyrene melts

For high-molecular-weight (M) ring polymers with low contamination of linear chains, recent viscoelastic tests revealed broad terminal relaxation associated with no clear entanglement plateau. This relaxation behavior is qualitatively similar to that deduced from molecular models (double-folded lattice-animal model and the fractal loopy globule model) for entangled ring polymers, but quantitatively important differences are also noted: For example, the full terminal relaxation of those polymers is slower than the model prediction. This study re-examined the viscoelastic data of entangled high-M ring polystyrene (PS) samples (coded as R-240; M = 244×10³) specifically for two points: the purity of the ring samples after the viscoelastic tests and the molecular origin of the stress. For the first point, the R-240 samples contaminated with linear chains at low but different levels were prepared by tuning either the purification efficiency or the retention time of the sample at high temperature (T) before/during the viscoelastic test. The fraction w _L of the linear contaminant, determined after the viscoelastic measurement, was ranging from 0.7 to 4.9%, and the extrapolation of the modulus data to w _L = 0 gave the data for the ideally pure ring melt. This pure ring melt exhibited broad terminal relaxation that started faster but completed slower compared to the model prediction, indicating that the ring relaxation is not well described by the current model(s) even in the absence of linear contaminant. For the second point, dynamic birefringence measurements were conducted for the R-240 samples with w _L = 4.6 and 1.0%. These samples obeyed the stress-optical rule, and their stress-optical coefficient was indistinguishable from that for linear PS samples, revealing that the stress of the ring PS chains reflects the orientational anisotropy of the chains (as is the case also for linear chains). The relaxation behavior of pure ring PS melt is discussed on the basis of these findings, with the focus being placed on the ring-ring threading not considered in the models.     

Phase morphology and rheological behavior of polymer/layered silicate nanocomposites

Rheological behavior of polymer/layered silicate nanocomposites are strongly dependent not only upon their microstructure but also upon the interfacial characteristics. Different phase morphology (intercalated or exfoliated) of polymer/clay is obtained according to interfacial characteristics between polymer chains and clay. In intercalated structure, the presence of randomly oriented anisotropic stacks of silicate layers is responsible for the enhancement of both moduli. The PS/clay nanocomposites exhibit a slight enhancement at low frequency because of its simple intercalated structure and little interaction. On the other hand, the PS-co-ma/clay nanocomposites have a similar intercalated structure but exhibit a distinct plateau-like behavior at low frequency since the PS-co-ma has a strong attractive interaction with the silicate layers. Finally, PE-g-ma/clay nanocomposites display an exfoliated structure, which exhibit both a distinct plateau-like behavior at low frequency and enhanced moduli at high frequency. Percolation structure as well as large interfacial area between polymer chains and clay are responsible for the rheological behavior. Received: 20 March 2000   Accepted: 11 September 2000     

Rheology/morphology/flow conditions relationships for polymethylmethacrylate/rubber blend

Viscoelastic behavior, phase morphology and flow conditions relationships in polymer/rubber blends have been investigated. The importance of such correlations is illustrated on polymethylmethacrylate (PMMA)/rubber blends subjected to different flow conditions both under small and large deformations. In small-amplitude oscillatory shear (the morphology does not change during the flow) the elastic modulus G of the concentrated blends shows a secondary plateau, G _p , in the low frequency region. This solid-like behavior appears for rubber particle contents beyond the percolation threshold concentration (15%). Morphological observations revealed that for concentrations higher than 15%, the particles are dispersed in a three-dimensional network-type structure.In capillary flow it was found that the network-type structure was destroyed and replaced by an alignment of particles in the flow direction. This morphological modification resulted in a decrease in both viscosity and post-extrusion swell of the blends. Morphological observations revealed that the ordered structure in the flow direction was concentrated only in the skin region of the extrudate, where the shear stress is higher than the secondary plateau, G _p . A simple kinetic mechanism is proposed to explain the observed morphology.Similarly, steady shear measurements performed in the cone-and-plate geometry revealed alignment of particles in the flow direction for shear stress values higher than G_p.Presented in part at the Symposium Recent Developments in Structured Continua Montréal (Canada) 26–28 May 1993 and at the 45th Canadian Chemical Engineering Conference, Quebec, October 15–18 (1995)     

Transient behaviour of the mechanical loss factor of high density polyethylene during creep and relaxation

The mechanical loss factor of high density polyethylene has been measured during creep and stress relaxation experiments. The application of a constant stress (creep) or strain (relaxation) resulted in an instantaneous increase in tan above the value obtained in absence of the creep or relaxation process. During the flow the tan-value decreased and approached an apparent equilibrium value slightly above the value obtained without the static load or deformation. This behaviour was observed both at 1 and 10 Hz and at 23 and 60 °C. It is suggested that this time dependence of the mechanical loss factor is associated with the basic mechanisms responsible for the creep or relaxation process itself.     

Effect of cooling rate on fracture behavior of polypropylene

The purpose of this work is to investigate the influence of morphology, induced by cooling rate during molding, on the time–temperature dependence of fracture behavior of polypropylene (PP). Fractures tests were performed over a range of loading rates from 0.2 mm/min to 2.5 m/s, using the single edge notched bending specimen. The results show that the transition temperature from brittle to ductile behavior increases with decreasing cooling rate. However, at very low loading speed (0.2 mm/min), an opposite effect is observed, the brittle–ductile transition temperature diminishes with lower cooling rate. At low test speeds, the fracture performance is reduced with a decreasing cooling rate. Conversely, under impact, the fracture toughness of PP is enhanced with a decrease in cooling rate. This is explained by the mechanism of blunting of the crack tip due to adiabatic heating under high loading rates. The blunting effect results in a more significant plastic deformation of the crystalline region that requires a higher energy. The brittle–ductile transition was characterized by an energy activation process expressed by the Arrhenius equation. Decreasing the cooling rate results in a decrease of both the pre-exponential factor and the energy barrier controlling the time–temperature dependence of fracture behavior. The reduction of the pre-exponential factor corresponds to a more ordered morphology due to a reduction in the entropy and is consistent with a higher crystallinity. The reduction of activation energy with higher crystalline level suggests that the brittle–ductile transition also involves the primary relaxation process that is known to occur mostly in an amorphous structure. A higher crystallinity would restrain the primary relaxation processes and the brittle–ductile transition becomes more dependent on the secondary movements of the chain segments. The results demonstrate that the relationship between deformation rate, temperature, and mechanical performance of PP is not only controlled by molecular relaxation processes, but also strongly dependent on its morphology.     

Rheology and morphology of polystyrene/polypropylene blends with in situ compatibilization

Rheology and flow-induced morphology were studied in immiscible polypropylene (PP)/polystyrene (PS) blends with a droplet–matrix microstructure. Two reactive precursors, maleic anhydride grafted PP and amino terminated PS, were added during the melt-mixing process to form a graft copolymer. The effects of both the amount of compatibilizer and the shear history on the rheological and morphological behavior were investigated systematically. Small amplitude oscillatory experiments and scanning electron microscopy were used to study the phase morphology. Shear history has an important effect on the morphology of the uncompatibilized blends. The droplet size refines with increasing shear rate. The decrease of this effect with increasing degrees of in situ compatibilization is mapped out. The results are discussed in terms of interfacial tension and the interfacial coverage. It turns out that most of the conclusions that were previously obtained on physically compatibilized blends are also valid for chemically compatibilized ones.     

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.     

Finite viscoelasticity of filled rubber: experiments and numerical simulation

Summary  Constitutive equations are derived for the viscoelastic behavior of particle-re-inforced elastomers at isothermal deformation with finite strain. A filled rubber is thought of as a composite medium where inclusions with high and low concentrations of junctions between chains are randomly distributed in the bulk material. The characteristic length of the inhomogeneities is assumed to be small compared to the size of the specimen and substantially exceed the radius of gyration for macromolecules. Inclusions with high concentration of junctions are associated with regions of suppressed mobility of chains that surround isolated clusters and/or the secondary network of filler. Regions with low concentration of junctions arise during the preparation process due to a heterogeneity in the spatial distribution of the cross-linker and the filler. With reference to the concept of transient networks, the time-dependent response of an elastomer is attribute d to thermally activated rearrangement of strands in the domains with low concentration of junctions. Stress–strain relations for particle-reinforced rubber are developed by using the laws of thermodynamics. Adjustable parameters in the constitutive equations are found by fitting experimental data in tensile relaxation tests for several grades of unfilled and carbon black-filled rubber. It is demonstrated that even at moderate finite deformations (with axial elongations up to 100%), the characteristic rate of relaxation is noticeably affected by strain. Unlike glassy polymers, where the rate of relaxation increases with longitudinal strain, the growth of the elongation ratio results in a decrease in the relaxation rate for natural rubber (unfilled or particle-reinforced). The latter may be explained by (partial) crystallization of chains in the regions with low concentration of junctions. Received 16 October 2001; accepted for publication 25 June 2002 Present address: A. D. Drozdov Department of Production, Aalborg University, Fibigerstraede 16, DK-9220 Aalborg, Denmark We would like to express our gratitude to Dr. K. Fuller (TARRC, UK) for providing us with rubber specimens and to Prof. P. Haupt and Dr. S. Hartmann (University of Kassel, Germany) for sending their experimental data. We are indebted to Mr. G. Seifritz for his assistance in performing mechanical tests. ADD acknowledges stimulating discussions with Prof. N. Aksel (University of Bayreuth, Germany).