Micro-Raman study of the transition front in uniaxially stretched semicrystalline polymers

The transition front of the neck between the isotropic and oriented region in uniaxially stretched polyvinylidene fluoride (PVDF) and polypropylene (PP) is analyzed with a high spatial resolution by micro-Raman spectroscopy. The variation of the microstructure, i.e. change in the degree of crystalline modification in the case of PVDF and in the orientation of the PP chains in function of the strain rate, is correlated with other parameters associated with the drawing response of these polymers and the temperature rise during deformation. The results here described can be understood through the clear increase of temperature that was detected in the neck due to the heat generated by the deformation work of the drawing process.     

A latent entanglement model for the draw of semicrystalline polymers

A novel molecular model, the latent entanglement, is proposed to explain the relationships between ductilities of polyethylene reactor powders and different conditions of synthesis. According to Hoffman's variable cluster model, irregularities in the crystallite fold surface increase as the synthesis temperature is decreased. The concept of latent entanglement stems from the potentiality of these defects to convert into active entanglements when the involved chain segments are drawn out of the crystals.     

Micromechanical modeling of the elastic properties of semicrystalline polymers: A three‐phase approach

The mechanical performance of semicrystalline polymers is strongly dependent on their underlying microstructure, consisting of crystallographic lamellae and amorphous layers. In line with that, semicrystalline polymers have previously been modeled as two and three‐phase composites, consisting of a crystalline and an amorphous phase and, in case of the three‐phase composite, a rigid‐amorphous phase between the other two, having a somewhat ordered structure and a constant thickness. In this work, the ability of two‐phase and three‐phase composite models to predict the elastic modulus of semicrystalline polymers is investigated. The three‐phase model incorporates an internal length scale through crystalline lamellar and interphase thicknesses, whereas no length scales are included in the two‐phase model. Using linear elastic behavior for the constituent phases, a closed form solution for the average stiffness of the inclusion is obtained. A hybrid inclusion interaction model has been used to compute the effective elastic properties of polyethylene. The model results are compared with experimental data to assess the capabilities of the two‐ or three‐phase composite inclusion model. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Determination of molecular orientation distribution of stable paramagnetic probes in stretched polymers

The possibility of determination of the orientation distribution functions of paramagnetic probes in stretched polymers by analyzing the angular dependence of EPR spectra was demonstrated taking two stable radicals, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 2-septadecyl-2,3,4,5,5-pentamethylimidazolidine, as examples. The method employed permits establishment of the preferred orientation of the probe molecules relative to the polymer macromolecules. The technique is responsive to changes in the orientation distribution of impurity particles on annealing of the matrix. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1120–1126, May, 2005.     

On the predictability of the high-frequency elastic modulus of semicrystalline polymers as function of crystallinity

The relation of the high-frequency elastic moduli of semicrystalline polymers to volume fraction crystallinity is correctly described by the Hashin-Shtrikman theory, without any disposable constants, as a function of the ratio of the modulus of the amorphous to that of the crystalline phase. Hence the (high-frequency) reduced modulus of semicrystalline polymers is largely a function of the temperature T/T_g. The importance of T/T_m for the modulus of the crystalline phase precludes the existence of a single universal reduced modulus versus temperature curve.     

Observation of textures of nematic polymers and estimation of the elastic constants

The texture of a copolyesteramide, Vectra® B950, has been studied by optical microscopy. At rest, the defects are typical of a biaxial nematic phase, but under the influence of a magnetic field or under shear, the nematic transforms into a uniaxial phase. The Freedericksz geometry yields a K₁ elastic constant of the order of 10^-8 N. The diffusivities K_III/_n and K_II/_n are obtained by measuring the light intensity transmitted through a sample during shear start-up and relaxation, and from this we estimate K_III ≅ 10 ^-9N and K_II ≅ 10 ^-10N. Since the biaxiality is small, these uniaxial constants adequately describe the phase at rest.     

Nanoindentation of high performance semicrystalline polymers: A case study on PEEK

Semicrystalline high performance polymers (HPPs) exhibit desirable thermomechanical properties which make them suitable materials in several industries. However, when their mechanical characteristics are investigated at nanoscale, the inhomogeneous nature of semicrystalline HPPs results in measurement of localized properties which might not represent the overall material response. In this paper, the nanomechanics of poly(ether-ether-ketone) (PEEK) as a tough HPP is scrutinized using the nanoindentation technique. It is demonstrated how surface properties of this polymer can affect the nanoindentation measurements and reveal significant anomalies compared to the nanoindentation of fully crystalline or amorphous solids. In addition, polishing and annealing procedures are introduced as simple techniques that can be used for eliminating the inhomogeneity of the mechanical response of PEEK. Lastly, the capability of depth sensing indentation for determining the distribution of crystalline and amorphous sub-regions within semicrystalline solids is scrutinized and critically discussed.     

Understanding the effect of skin formation on the removal of solvents from semicrystalline polymers

The effect of glassy skin formation on the drying of semicrystalline polymers was investigated with a comprehensive mathematical model developed for multicomponent systems. Polymers with high glass‐transition temperatures can become rubbery at room temperature under the influence of solvents. As the solvents are removed from the polymer, a glassy skin can form and continue to develop. The model takes into account the effects of diffusion‐induced polymer crystallization as well as glassy–rubbery transitions on the overall solvent content and polymer crystallinity. A Vrentas–Duda free‐volume‐based diffusion scheme and crystallization kinetics were used in our model. The polymer–solvent system chosen was a poly(vinyl alcohol) (PVA)–water–methanol system. The drying kinetics of PVA films were obtained by gravimetric methods with swollen films with known water/methanol concentrations. The overall drying behaviors of the polymer system determined by our model and experimental methods were compared and found to match well. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3191–3204, 2005     

Comparison of micromechanical models for the prediction of the effective elastic properties of semicrystalline polymers: Application to polyethylene

In this paper, we discuss the application of different micromechanical composite models to compute the effective elastic properties of semicrystalline polymers. The morphology of these two-phase materials consists of crystalline lamellae and amorphous domains which may form a spherulitic microstructure. The selected models are the Mori-Tanaka type models, the Double-Inclusion models, and the Self-Consistent models. We applied these composite estimates to both fully isotropic and transverse isotropic transcrystalline polyethylene. The results from these different models are compared to the experimental results for different crystallinities. The Generalized Mori-Tanaka (GMT) model and the Self-Consistent Composite-Inclusion (SCCI) model give the best predictions of the effective elastic constants compared to the other models. Published in Russian In Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 5, pp. 809–820. This article was submitted by the authors in English.     

Crystallization-driven self-assembly of semicrystalline block copolymers and end-functionalized polymers: A minireview

Self-assembly has been a powerful method to fabricate the polymer materials with well-defined structures and morphologies. Such assembled materials have shown wide potential applications in many fields such as nanomaterial, nanomedicine, lithography, and microelectronic. Crystallization has been a general behavior of stereoregular polymers. Besides the various noncovalent interactions, crystallization of polymer blocks or end groups can be an efficient way to manipulate the self-assembly pathway and assembled structures of polymers in both solid and solution. Crystallization-driven self-assembly has been widely implemented for the semicrystalline block copolymers (BCPs) and end-functionalized polymers. This minireview briefly presents the recent progresses in the crystallization-driven self-assembly of BCPs and end-functionalized polymers in both solid and solution states. Formation process, mechanism, and hierarchical structure of the crystallization-induced assemblies for BCPs and end-functionalized polymers are highlighted.     

ESR studies of the orientational and reorientational properties of mesomorphic polymers

Abstract

The orientational properties of two mesomorphic azobenzene-containing polyacrylates are investigated by ESR spectroscopy using the spin probe technique. Procedures to achieve a uniform alignment of the director in the presence of a static magnetic field are described in detail. The recovery of the alignment after the creation of controlled non-equilibrium states in the presence of a magnetic field is studied. It is found that the recovery time is proportional to the reciprocal square of the static magnetic field, analogous to that which occurs in low molar mass liquid crystals.     

Measurement of the orientational elastic constants and the twist viscosity of nematic side chain polymers

Abstract

The temperature dependence of the three elastic constants k _ii (i = 1, 2, 3) and the twist viscosity γ₁ of two nematic side chain polyacrylates and one comparable low molecular weight compound have been measured by means of the Freedericksz effect. The change from the low to the high molecular liquid crystal causes a change of the ratio k ₃₃/k ₁₁ from greater to less than unity, but the order of magnitude of the elastic constants remains the same. In contrast, the twist viscosity of the polymeric liquid crystal is about 1000 times greater in magnitude than that of a comparable low molecular weight liquid crystal. The activation energy for the viscosity of the polymer differs by a factor 3–4 from that of the low molecular weight liquid crystal. The elastic constants as well as the twist viscosity show a quadratic dependence on the order parameter S over a wide temperature range.     

The effect of pressure on gas permeation through semicrystalline polymers above the glass transition temperature

A method is proposed to analyze the effect of pressure on permeation of gases through semicrystalline polymers above the glass transition temperature. The method utilizes similarities in molecular diameters of the gases and differences in their solubilities. Two polymers, polyethylene and polypropylene, and a series of gases are chosen for an application of the method, and the effect of pressure on the permeabilities for 10 gases is measured in the pressure range 1–130 atm at 25°C. For polymers, the logarithm of the permeability coefficient is linear in the pressure for each gas, with negative slope for slightly soluble gases (He, Ne, H₂, N₂, O₂, and Ar) and positive slope for highly soluble gases (CH₄, Kr, CO₂, and N₂O). Analyzing these slopes by the method proposed permits contributions of hydrostatic pressure and concentration to the pressure dependence of permeation to be evaluated. On the basis of the results, the mechanism of gas permeation in rubbery films under high pressures is discussed.     

Hydration in semicrystalline polymers: Small-angle neutron scattering studies of the effect of drawing in nylon-6 fibers

Water absorbed by nylons appears to be partitioned into interlamellar and interfibrillar spaces. The amount of water in the interfibrillar region remains essentially unchanged with increasing draw ratio, whereas that in the interlamellar regions decreases with draw ratio; the latter accounts for the decrease in the water uptake in the drawn fibers. These results suggest that the amount of the amorphous material in the interfibrillar regions remains unchanged during drawing, and the increase in the crystallinity during drawing results from the incorporation of the amorphous chain segments in the interlamellar regions into the crystalline lamellae. Further, the interfibrillar water is more tightly bound than the interlamellar water. The length of the longitudinal channels into which water diffuses is about the same as that of the fibrils, and increases from ca. 1500 to 2000 Å upon drawing. The longitudinal channels are highly oriented even in undrawn fibers, and their misorientation increases from 5° to 15° upon drawing. These channels can be described as surface fractals of dimension 3.4–3.6. © 1994 John Wiley & Sons, Inc.     

Micromechanics of semicrystalline polymers: Yield kinetics and long-term failure

The process of plastic deformation in semicrystalline polymers is complicated due to the operation of a variety of mechanisms at different levels and is strongly dependent on their underlying microstructure. The objective of this work is to establish a quantitative relation between the microstructure and the mechanical performance of semicrystalline polymers, as characterized by elasto-viscoplastic deformation. To do that, a micromechanically based constitutive model is used. The model describes the material as an aggregate of two-phase layered composite inclusions, consisting of crystalline lamellae and amorphous layers. The starting point for adding quantitative abilities to the model, in particular for the yield kinetics, is formed by experimental observations on both the yield kinetics and the time-to-failure of polyethylene at different temperatures, which reveal the contribution of two relaxation processes. To predict the thermo-rheologically complex short-term and long-term failure behavior, the crystallographic slip kinetics and the amorphous yield kinetics are re-evaluated, and the Eyring flow rule is modified by adding a temperature shift function. To enable the prediction of both tension and compression, a non-Schmid effect is added to the constitutive relation of each slip system. The creep behavior of polyethylene is then simulated directly using the multiscale, micromechanical model, predicting the time-to-failure, controlled by plastic deformation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The effect of orientation on the mechanism of deformation of polymers

The mechanical behavior of HDPE, medium-density PE, and amorphous and amorphous-crystalline PET after their preliminary orientation is studied. The polymers are oriented by rolling at room temperature on lab-scale rolls, tensile drawing at temperatures somewhat higher than their glass-transition temperatures, and extrusion at room temperature. At low degrees of rolling (below 1.5), the tensile yield stress does not actually increase. (In amorphous-crystalline PET, this parameter even decreases.) It seems that the absence of strain hardening at low draw ratios is a common feature of the behavior of polymers below their glass-transition temperatures. In contrast to the tensile yield stress, the engineering strength increases in proportion to the degree of rolling. A new procedure for construction of the dependence of true tensile yield stress on tensile strain is advanced. At low strains, the true tensile yield stress shows practically no increase. This conclusion is verified by theoretical calculations.     

The effect of orientation on the radiation induced degradation of polymers

A study has been made of the effect of orientation on the oxidative degradation of poly(vinylchloride) (PVC), low density polyethylene (LDPE) and high density polyethylene (HDPE) under the influence of γ- and u.v.-radiation. The effect of drawing in PVC is to increase the rate of oxidative degradation; in LDPE and HDPE, this rate decreases (especially for HDPE) both under u.v. and γ-radiation.     

Influence of tacticity on orientation and relaxation in uniaxially stretched polymethylmethacrylates

Orientation and relaxation behavior in uniaxially stretched stereoregular polymethyl-methacrylate (PMMA) was investigated. When compared at a reference temperature T = T_g + constant, isotactic PMMA orients more readily and relaxes slightly faster than the conventional or syndiotactic polymers. Orientation relaxation of the different PMMAs can be reduced to a unique master curve, whatever the tacticity, when the results are compared at same monomeric friction coefficient. © 1996 John Wiley & Sons, Inc.