Plastic deformation kinetics for glassy polymers and blends

Measurements of the plastic deformation kinetics for several glassy (PS, PC, PI-polyimide, PET, epoxy-amine network), semi crystalline polymers (PBT, PET) and blends (ABS, PC:ABS, PC: PBT) were performed for the unidirectional compression loading conditions by using constant temperature deformation calorimetry. The experiments have permitted us to follow the changes of the mechanical work (A), the heat of deformation (Q) and differences between these quantities, i.e., internal energy (U) stored in samples during their loading and unloading. Experiments have shown that the large portion (45–85%) of the mechanical work of deformation (A) is converted to heat (Q). The rest ofA is converted to internal energy (U) stored in deformed samples. U is quite high as compared with metals [1,2]. After complete unloading of plastically deformed samples, i.e., samples carrying irreversible atT _def plastic deformation ( _irr ), some amount (U) of stored energy disappeared. The amount of (U and (U) are different for different polymers. All data are analyzed in the framework of the model proposed in [3,4]. The experiments support the deformation model where the plasticity of glassy polymers is the process of nucleation and development of so-called PDs-plastic local shear defects of nonconformational and nondilatational nature.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday     

Plastic deformation and performance of engineering polymer materials

The plastic deformation mechanism operating in polymer glasses is analyzed. The whole process consists of two main stages: nucleation of special shear defects, called PSTs (plastic shear transformations), and their disappearance. The important feature of plastic deformation of glasses is the storage of a large amount of internal energy ΔU_def upon straining. Such energy storage is the critical issue for mechanical performance of polymeric material: if the amount of stored energy is high, the appearance of macroscopic failure is very probable while glassy materials collecting a small amount of stored deformation energy are quite ductile. It is proposed that the rate of disappearance of PSTs is a key factor in dissipation of stored deformation energy. A parameter describing the dissipation ability of material upon deformation is introduced.     

Drop deformation in polymer blends during uniaxial elongational flow

The deformation in uniaxial elongational flow of dispersed droplets in immiscible molten polymer blends was studied for negligible interfacial tension and for viscosity ratio p = η(drop)/η(matrix) between 0.005 and 13, with an original method based on quenching elongated specimens. Although drop deformation (drop major axis over initial diameter) was in the range 1 < λ_d < 5, a good overall agreement was found with the small deformation Newtonian theory, which predicts that the drop versus matrix deformation ranges from 5/3 to 0 when p increases from 0 to infinity. The theoretical prediction that for p lower than 1, the droplet should deform more than the faraway surrounding matrix, with a limiting ratio of 5/3 at vanishing droplet viscosity, was experimentally verified.     

ABA triblock copolymer containing two crystallizable components

A triblock copolymer of the ABA type in which both components were crystallizable was synthesized. The A block was poly(ethylene oxide), PEO, and the B block, poly(dimethyl siloxane), PDMS. Upon cooling from the melt to liquid nitrogen temperature, the PEO block crystallized at around 40°C. When the copolymer was heated from ?170°C after quenching, glass transition, crystallization and melting of the PDMS middle block were identified in the thermogram at ?117°C, ?74°C and ?42°C, respectively. The degree of crystallinity of the PDMS block was estimated from the heat of fusion to be about 27%. The growth rates of the PEO spherulites were reduced by the presence of the middle block.     

Thermostimulated currents in low-density polyethylene and its blends with various components after high-pressure plastic deformation

It is established that the plastic deformation of low-density polyethylene (LDPE) under a pressure 0.5–2.0 GPa on a high-pressure apparatus of the Bridgman anvil type leads to the appearance of thermostimulated currents in samples, indicating that the samples contain trapped electrons. It is shown that two peaks are present on the temperature dependences of the currents; one of these is most probably related to the cold crystallization of the polymer, its structure being destroyed upon high-pressure deformation, while the other is related to the melting of the polymer. It is noted that the peaks were absent on temperature dependences of the currents for LDPE blends with some components; this could be due to the formation of a conducting state at interfaces. It is found that the electroconductivity of some blends after processing under pressure was higher than that in LDPE itself by a factor of 25.     

Linear viscoelastic characteristics of in situ compatiblized binary polymer blends with viscoelastic properties of components variable

By Friedel‐Crafts alkylation reaction, catalyzed by a Lewis acid of anhydrous aluminum chloride (AlCl₃), binary polymer blends of polypropylene (PP)/polystyrene (PS) with volume proportion of 80/20 were in situ compatiblized and prepared in an XSS‐30 melt mixer at 210 °C. The linear viscoelastic characteristics of the blends were investigated by checking the variations of storage modulus, loss modulus, complex modulus, and complex viscosity of the in situ compatiblized blends, which were dependent on AlCl₃ content. In addition, Han plots of the in situ compatiblized blends with different AlCl₃ content were also used to characterize the linear viscoelastic properties of the blends. The results showed that both the dynamic rheological parameters and the Han plots were obviously influenced by the rheological properties of the matrix and slightly influenced by the rheological properties of the dispersed phase. Further investigations revealed that phase geometry contributions to the dynamic rheological parameters of the blends could be ignored in comparison with the contributions of the components and the interfacial modification, which were defined and obtained according to log‐linear‐additivity rule. The linear viscoelastic characteristics of the blends were mainly controlled by the combination of the effects of interfacial modification between phases and the rheological properties of the matrix. Storage modulus is the most sensitive dynamic rheological parameter to characterize the interfacial compatiblization effects in the in situ compatiblized binary polymer blends with rheological properties of components variable. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1349–1362, 2010     

Reactive polymer blends with thermoplastic polyurethan

The paper presents the concept of reactive coupling of thermoplastics and describes the technological preconditions and the present state of development. The examples of developments of blends of thermoplastic polyurethan (TPU), and polyethylene terephthalate (PET) serve to show that different mechanisms of reactive coupling of the blend components permit to produce high-quality blends.     

Structured polymer blends

Various morphologies can be realized via processing of incompatible polymer blends such as droplets or fibers in a matrix and stratified or cocontinuous structures as is shown for the model system polyethylene/polystyrene The structures induced are usually intrinsically unstable. Modelling of extrusion processes and continuous mixers yields expressions for the shear rate and shear stress but also for the limited residence time and the number of reorientations. These results could be combined with detailed knowledge of respectively distributive and dispersive mixing processes to predict the development of various morphologies as a function of time. Control of morphology is of utmost importance. In the case of droplets in a matrix, usually encountered in toughening of glassy polymers, the use of compatibilizers and/or reactions at the interphases is utilized. However, in designing specific morphologies i.e. structured polymer blends, fixation of intermediate morphologies before final processing is a prerequisite. Some preliminary results will be presented.     

Plastic deformation of polyamide 6/polypropylene‐g‐acrylic acid blends

Two means of plastic deformation were applied to the poly amide 6/polypropylene‐g‐acrylic acid blends (in two composition 8:2 and 2:8): drawing and plane strain compression in a channel die. X‐ray diffraction pole figures, density measurements, SEM, DMTA were applied for studying the structure and properties of oriented blends. It is concluded that interfaces between blends components are weak elements of the blends even in presence of compatibilizing action of PP‐g‐AA.     

Rheology of concentrated blends with immiscible components

The rheology and morphology evolution of nondilute and concentrated immiscible blends were investigated in this paper. A theoretical model was established by a Hamiltonian formalism. The interactions between droplets were integrated in the morphology‐dependent drag coefficient. The phenomenological parameters in the model were determined by the comparisons with the dilute emulsion model and the Krieger–Dougherty model. The model showed better predictions in the shear viscosity and first normal stress difference than that of the dilute emulsion model. The effects of volume fraction on droplet deformation were also predicted and compared with the numerical simulations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2534–2540, 2005     

Structure formation in polymer blends as a result of phase separation and deformation processes

Polymeric blends, which are materials consisting of two or more polymers, are gaining in practical importance and scientific interest. The properties of these materials are greatly affected by their state of miscibility. This paper reviews selected thermodynamic and rheological considerations regarding the phase behavior and the morphological control of polymer blends. Major emphasis is placed on the phase behavior of poly-blends comprising random copolymers. - The majority of polymer blends are microheterogeneous systems. There is consequently, a great need for control of the phase morphology during processing of immiscible polymers to achieve the desired property combinations. The key to this are both the microrheology of the phases and the macrorheology of the dispersion itself. In a qualitative way, one can establish that the ratio of the viscosities and the difference in the elasticities of the components determine sizes and shapes, respectively, of the phases indicating that the variety of morphologies observed in polymer-polymer systems subjected to shearing has to be attributed to the viscoelasticity of each component. Furthermore, particular compositions are associated with changes in the morphology. This fact supports the particular compositions as an inherent feature of the melt rheology of polyblends.     

Phase behaviour of blends with mesophase components

Temperature transitions and structural transformations were studied for blends of two thermotropic mesophase cyclolinear polymethylsiloxanes with linear PDMS of various molecular weights by means of DSC, optical polarizing microscopy, and optical interferometry. Compatibility of the components which depends on the chemical structure of cyclolinear polymethylsiloxanes, molecular weight of PDMS, composition, and temperature affect formation of mesophase in cyclolinear polymethylsiloxanes. The most interesting aspect of the phase behaviour consists in the fact that it is possible to reach compatibility of the components in the mesomorphic state for the blends of two cyclolinear polymethylsiloxanens due to various annealing regimes in one‐phase molten state.     

Thermodynamics of polymer blends

The general principles of thermodynamic equilibrium in binary liquid systems are reviewed briefly, and extended to quasi-binary mixtures of polydisperse polymers. Molecular models allowing actual phase behaviour to be discussed in terms of molecular parameters are exposed to data on the system polystyrene/polyvinylmethylether. Disparity in size and share between the repeating units must be introduced to obtain reasonable agreement between theory and experiment. The neccessary introduction of the molar-mass distribution detracts from this agreement which makes clear that other aspects exist that must be taken into account. For example, cross association between repeating units has a marked effect on phase behaviour. Blends are subject to two kinds of thermodynamic aging which lead either to considerable mutual solubility in supposedly immiscible blends, or to metastable equilibria transforming into states of lower Gibbs energy. In both cases physical proerties of the blend will change with time.     

A microcalorimetric study of crystallizable polymers subjected to severe plastic deformation

Differential scanning calorimetry has been used to investigate the evolution of the structural and thermophysical parameters of a number of semicrystalline polymers (high-density polyethylene, polyamide-6, polyoxymethylene) that is initiated by severe plastic deformation imposed through equal-channel multiple-angle extrusion. Thermograms of the deformed polymers have been found to exhibit an additional high-temperature melting peak. It has been shown that the onset, maximum, and end temperatures for both melting peaks increase with the strain buildup. The degrees of crystallinity and the thicknesses of crystallites increase as well. The magnitude of the effects is determined by the deformation route selected. It has been revealed that conformational transitions due to the formation of “double-triple” folds in macromolecular chains can occur during the course of equal-channel multiple-angle extrusion.     

Plastic deformation of polyethylene

Summary The deformation behaviour during rolling is studied by small-angle X-ray scattering, density measurement, and investigation of the debris after fuming nitric acid treatment. Crystallinity and mechanical properties are compared with corresponding results on drawn material. Results obtained on quenched and annealed films of two polyethylene brands, Fortiflex and ACX, show many similarities in properties between rolled and drawn samples of similar draw ratio, i. e., a progressive lattice orientation, the appearance of a new long period different from that of the original film at =2 in Fortiflex and at =1.5 at ACX, decrease in crystallinity of annealed films, and constancy in quenched material during rolling. Therefore, it is concluded that, as in the case of drawing, the basic structure transformation during rolling is the destruction of lamellae with pulling out of microfibrils. Significant differences exist, however, between the two cases in ultimate tensile strength and in ultimate elongation.

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Zusammenfassung Das Deformationsverhalten während des Walzens wurde mit Kleinwinkelstreuung, Dichtemessung, Unter-suchung nach Behandlung mit rauchender Salpetersäure betrachtet. Kristallinität und mechanische Eigenschaften wurden mit entsprechenden Ergebnissen an verstrecktem Material verglichen.Die Ergebnisse, die man an abgeschreckten und getemperten Filmen von 2 Polyäthylenarten, Fortiflex und ACX erhielt, zeigen viele Ähnlichkeiten zu gewalzten und getemperten Proben vom gleichen Streckverhältnis, d. h. eine gleiche Gitterorientierung, das Auftreten neuer Langperioden verschieden von derjenigen des ursprünglichen Films, d. h. =2 bei Fortiflex und =1,5 bei ACX, Abnehmen der Kristallinität von getemperten Filmen und Konstanz des abgeschreckten Materials während des Walzens. Daraus wird geschlossen, daß wie im Fall des Verstreckens die Strukturänderung während des Walzens die Zerstörung der Lamellen unter Herausziehen von Mikrofibrillen verursacht. Entscheidender Unterschied zwischen beiden Deformationsarten existiert jedoch in der maximalen Zerreißfestigkeit und der maximalen Dehnung.

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With 13 figures in 18 details and 2 tables     

Miscibility and deformation behavior in some thermoplastic polymer blends containing poly(styrene-co-acrylonitrile)

Miscibility in blends of poly(styrene-co-acrylonitrile) (PSAN) with several other polymeric components has been investigated over a range of compositions by means of thermal analysis and transmission electron microscopy. Systems in vestigated were (i) PSAN/polycarbonate (PC), (ii) PSAN/styrene-maleic anhydride-methyl methacrylate terpolymer (S/MA/MM), (iii) PSAN/polynorbornene nitrile (PNN), and (iv) PSAN//S/MA/MM//PC. PSAN/PC was demonstrated to be partially miscible in all proportions over the PSAN copolymer composition range 23–70 wt % AN, while the miscibility or lack thereof of PSAN//S/MA/MM depended on the relative AN and MA contents of the PSAN and S/MA/MM, respectively. In contrast, PSAN/PNN was found to be immiscible in all proporations, while the system PSAN//S/MA/MM//PC was shown to be partially miscible. Deformation studies performed on rubber-modified versions of these blends defined deformation mode and microstructural deformation behavior. Dual extensometer tensile testing yielded relative contributions of crazing and of plastic flow, which correlated both with blend composition and with toughness. TEM observations of deformed specimens indicated a deformation process in the multiphase matrix blends consisting of craze initiation and propagation in the rubber-containing phase, craze arresting in the ductile second matrix phase, and coordinated extensive deformation of the matrix phases and of the rubber particles, where the ability to support the latter coordinated forms of deformation were observed to increase with increasing proportion of plastically deforming phase.     

Comparison of glass transition and interpretation on miscibility in blends of amorphous poly(vinyl methyl ether) with highly crystallizable versus less‐crystallizable polyesters

Various phase behavior of blends of poly(vinyl ether)s with polyesters of two types (highly crystalline and less crystalline with different main‐chains) were examined using differential scanning calorimetry (DSC) and optical microscopy (OM). Effects of varying the main‐chain polarity of the constituent polyesters on the phase behavior of the blends were analyzed. Miscibility in PVME/polyester blends was found only in polyesters with backbone CH₂/CO ratio = 3.5 to 7.0). T_g‐composition relationships for blends of PVME with highly crystalline polyesters (PBA, PHS) were found to differ significantly from those for PVME blends with less‐crystalline polyesters (PTA, PEAz). Crystallinity of highly crystalline polyester constituents in blends caused significant asymmetry in the T_g‐composition relationships, and induced positive deviation of blends' T_g above linearity; on the other hand, blends of PVME with less crystalline polyesters exhibit typical Fox or Gordon‐Taylor types of relationships. The χ parameters for the miscible blends were found to range from ?0.17 to ?0.33, reflecting generally weak interactions. Phase behavior was analyzed and compared among blends of PVME with rapidly crystallizing vs. less‐crystallizing polyesters, respectively. Effects of polyesters' crystallinity and structures on phase behavior of PVME/polyester blends are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2899–2911, 2007