A real-time drawing study on solution-crystallized UHMW-polyethylene — comparison with conventional x-ray results

Solution-crystallized ultra-high molecular weight polyethylene (UHMW-PE) can be drawn in the solid state to very high draw ratios, leading to materials with excellent mechanical properties. Very recently, the drawing process has been studied via different x-ray techniques, on the basis of which a deformation mechanism was proposed which could satisfactorily explain all observations. However, like most deformation studies performed in the past, the measuring conditions were quite different from the actual drawing conditions. Cooling drawn samples to room temperature as well as relieving the stretching force may give rise to the introduction of artefacts, leading to misinterpretation of the results. In order to exclude this possibility an x-ray study was performed on solution-crystallized UHMW-PE in real time, i.e.,during the deformation process, using the benefits of synchrotron facilities. Comparison of these results with x-ray results obtained via the conventional method shows that the latter method can be used without any problems for a qualitative study on the solid state drawing of ultradrawable UHMW-PE. One of the major advantages of the real-time method is the possibility to study the initial elastic deformation region.Presented in part at the Rolduc Polymer Meeting-2, April 1987, Kerkrade, The Netherlands.     

A Raman spectroscopic study of the morphological structure of the polyethylenes

The method described by Strobl and Hagedorn to analyze the Raman spectrum internal modes of semi-crystalline polyethylene has been applied to a set of selected polyethylene samples crystallized under controlled conditions. The crystallite structure can be described in terms of the relative amounts of the crystalline orthorhombic phase, the liquid-like amorphous phase and the interfacial region. The dependence of the level of crystallinity on molecular weight and crystallization conditions is very similar to that found by other methods. However, this method allows for the quantitative determination of the interfacial content which becomes significant for molecular weights greater than about 1×10⁵ for linear polyethylene fractions, and for all the branched samples and copolymers. The degree of crystallinity determined from density measurements is equal to the sum of the crystallinity and interfacial content obtained from the Raman analysis while enthalpy of fusion measurements yield values which are equal to just the crystallinity content. The difference between the level of crystallinity obtained from density and enthalpy of fusion is thus found to be primarily due to interfacial contributions.Dedicated to Prof. Dr. F. H. Müller     

A dielectric study of molecular relaxation in oxidized and chlorinated polyethylenes

A study was made of the dielectric relaxation in polyethylenes rendered dielectrically active through oxidation (0.5–1.7 carbonyls/1000 CH₂) and chlorination (14–22 Cl/1000 CH₂). Both linear and branched polymers were studied. All of the relaxations between the melt and ?196° were studied in the frequency range 10 Hz to 10kHz (100 kHz in the chlorinated samples). In the linear samples a wide range of crystallinities was studied (55% in quenched specimens to 95% in extended-chain specimens obtained by crystallization at 5 kbar). As is consistent with its being a crystalline process, the α peak was found to discontinously disappear on melting of the samples and reappear on recrystallizing on cooling. The disappearance of the smaller crystals before the larger ones appeared to be evident in the isothermal loss versus frequency curves. The relaxation strength of the α process increases with crystallinity. The measured relaxation strength is less than that expected on the basis of direct proportionality to the crystalline fraction with full contribution of all dipoles in the crystalline material. However, the intensity is not sufficiently low for the process to be interpreted in terms of reorientation of localized conformational defects in the crystal. The variation of intensity with crystallinity is best interpreted in terms of full participation of crystalline dipoles but with selective partitioning of both carbonyls and chlorines favoring the amorphous domains. A strong correlation of the α loss peak location (T_max at constant frequency or log f_max at constant T) with crystallinity for both carbonyl and chlorine containing polymers was found. This variation is interpreted in terms of chain rotations in the crystal where the activation free energy depends on crystal thickness. The dependence of log f_max and T_max on lamellar thickness as well as a comparison with the loss peaks of ketones dissolved in parafins indicates that the chain rotation is not rigid and is accompanied by twisting as the rotation propagates through the crystal. In agreement with previous studies the β process is found to be strong only in the branched polymers but can be detected in the chlorinated linear polymer. The β process was resolved from the α in the branched samples by curve fitting and its activation parameters determined. The γ relaxation peak in oxidized polymers including its high asymmetry (low-temperature tail) and increasing ε_max with increasing frequency and temperature when plotted isochronally can be interpreted in terms of a simple nearly symmetrical relaxation time spectrum that narrows with increasing temperature. No increase in relaxation strength with temperature was found. The chlorinated polymers behave similarly but appear to have some Boltzmann enhancement (450–750 cal/mole) of relaxation strength with temperature. The dependence of relaxation strength on crystallinity indicates that the process is an amorphous one. Further, no evidence of relaxation peak shape changes with crystallinity that could be interpreted in terms of a crystalline component in addition to the amorphous one was found. The comparison of the γ relaxation strength with that expected on the basis of full participation of amorphous dipoles indicates that only a small fraction (～10% in oxidized linear polymers) of them are involved in the relaxation. Thus it would seem that a glass–rubber transition interpretation is not indicated but rather a localized chain motion. It is suggested that the γ process, including its intensity, width, and activation parameters, can be interpreted in terms of an (unspecified) localized conformational (bond rotation) motion that is perturbed by differing local packing environments. The thermal expansion lessens the effects of variations in packing and leads to narrowing with increasing temperature. The conformational motion itself leads to increase in thermal expansion and hence a transition in the latter property. Some previously proposed localized amorphous phase conformational motions appear to be suitable candidates for the bond rotation motion. A weak relaxation peak found at temperatures below the γ and at 10 kHz may possibly be the dielectric analog of the δ cryogenic peak found previously mechanically at lower frequencies.     

A study of gamma-irradiated polyethylenes by temperature modulated differential scanning calorimetry

Various polyethylenes (PEs) and the effects of high-energy radiation on their structures were widely studied in the past using conventional Differential Scanning Calorimetry (DSC) measurements. In this work, we used the Temperature Modulated Differential Scanning Calorimetry (TMDSC) technique in order to obtain more information about the influence of the initial structural differences and gamma radiation on the evolution in structure and thermal properties of different polyethylenes. For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) samples were exposed to gamma radiation, in air, to a wide range of absorbed doses (up to 2400 kGy). The separation of the total heat flow TMDSC signal into a reversing and non-reversing part enabled us to observe the low-temperature enthalpy relaxation (related to the existence of the “rigid amorphous phase”) and recrystallisation processes, as well as to follow their radiation-induced evolution and/or that of melting in a more revealing manner compared to the case of the conventional DSC. Consequently, our results indicate that TMDSC could improve the understanding of radiation-induced effects in polymers.     

Dielectric study of post-irradiation effects in gamma-irradiated polyethylenes

The post-irradiation dielectric behaviour of different polyethylenes (PEs) has been studied by means of dielectric loss (tan δ) analysis over the wide temperature (25–325 K) and frequency (1 kHz–1 MHz) ranges. For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) samples were previously gamma irradiated in air to absorbed dose of 300 kGy. The irradiated samples were divided into two groups, and for the first one annealing treatment which can substantially reduce the concentration of free radicals were employed. For the second group, e.g. samples stored in air at room temperature after irradiation, post-irradiation evolution in free radical concentration, dielectric relaxation spectra and carbonyl content was investigated as a function of storage time, up to 90 days. Dielectric relaxation behaviour is related to differences in the initial structures of PEs (such as branching, crystallinity, etc.) and to the radiation-induced effects; carbonyl groups that were introduced by irradiation and/or delayed (post-irradiation) oxidation were regarded as tracer groups. Electron spin resonance (ESR), differential scanning calorimetry (DSC), infrared (IR) spectroscopy and gel measurements were used to determine the changes in free radical concentration, crystal fraction, oxidation and degree of network formation, respectively.     

Unit-cell dimensions of bulk- and solution-crystallized linear polyethylene

The unit-cell dimensions and density, at room temperature, of bulk- and solution-crystallized linear polyethylene have been determined. The macroscopic measured densities for the bulk-crystallized samples ranged from 0.917 to 0.993 g/cc, and the lattice parameters were found to be independent of the sample density. In contrast, for solution-formed crystals, despite the limited range in macroscopic densities that can be attained, there is a systematic variation in the a and b dimensions with the measured density and the crystallite thickness. The implication of these results for the calculation of the degree of crystallinity and the interpretation of certain infrared bands are discussed.     

Effect of solvent and temperature on solution-crystallized terfenadine

The aim of this work was to understand the crystallization process of terfenadine in solution.Cooling of saturated solutions prepared at 50 °C at different temperatures, evaporating the solvent from nearly saturated solutions at a certain temperature, and exposing ethanol solutions of terfenadine to water vapour atmosphere were the techniques used for obtaining terfenadine specimens. The characterization of these specimens was carried out by thermal microscopy, differential thermal analysis, thermogravimetry and powder X-ray diffraction. Crystalline phases, amorphous solids, and solvates were identified. For the solvents used in the present study, the crystallinity degree of terfenadine decreases from ethanol-water to ethanol and from this to methanol. Decreasing the temperature promotes the formation of amorphous solid material; at low temperatures, methanol and ethanol solvates are also formed.Desolvation, following the terfenadine aggregation process in solution accounts for the different behaviour found for the solvents and for the effect of temperature on the structure. The role of the solvent as structure-mediator is explained on the grounds of the values previously published for the enthalpy of solution of terfenadine in the solvents under study.     

Phase transition and paracrystalline order in solution-crystallized solid n-paraffins

Solution-crystallized single crystals of various paraffins were investigated at room temperature by nuclear magnetic resonance and by small-angle and wide-angle x-ray scattering. The samples were crystallized from various solvents and annealed 2, 5, 6, and 12°C below the melting point. The NMR spectra are separated into three components (α, β₁ and γ) of different chain-segment mobility. On combining these results with x-ray measurements and with results on polyethylene, enough information is obtained to propose a model of the paracrystalline superlattice built up by at least 30 paraffin lamellae and to find where the chains of various conformation are located in the structure. The phase transition of C₄₄H₉₀ in the solid state gives further hints for this allocation. For instance, the β₁ component of intermediate mobility increases anomalously from 3% before to 10% after the phase transition. The paracrystalline g value of the macrolattice of the orthorhombic phase is 1.5% and the gap between the lamellae is 2.2 Å. At the beginning of the phase transition, the chains incline stepwise to the lamella surface retaining the orthorhombic macrolattice distance P₀ = 58 A and enlarging the gap to 8.8 Å without changing the g value of 1.5%. The growing monoclinic phase, on the other hand, has a constant g value of 3.5% from the beginning with P_m = 52 Å and has gaps of only 3 Å between adjacent lamellae. This explains the large β₁ (ca. 10%) of these two new phases, because the mobile chain ends consist of approxiamately 1 CH₃ and 1 CH₂ group on the average. The γ component of highest micro-Brownian mobility corresponds to the γ component in polyethylene with a line width of ca. 0.07 gauss. Unlike the case of polyethylene it is produced by only a small amount (0.02–0.13) of free CH₃ groups per chain. Another fraction of the CH₃ groups belongs to the rigid component α of the crystalline phase. They are located where adjacent lamellae touch each other in crystalline-like order. Because of these contacts, stacks of lamellae about 1000 Å thick scatter coherently, and the long period P_o of the orthorhombic phase remains undestroyed by annealing until the monoclinic domains collapse to the smaller period P_m of the monoclinic phase.     

Refined NMR analysis of the phase structure of solution-crystallized linear polyethylene

Nuclear magnetic resonance (NMR) spectroscopy reveals that solution-grown polyethylene samples have a unique phase structure independent of molecular weight. The lamellar crystallites are composed of about 85% crystalline material with the noncrystalline overlayer as large as 15%. The molecular motion in the overlayer is comparatively hindered and the liquid-like component, which is generally recognized in melt-grown crystals, cannot be produced appreciably, even at 60°C. Such hindered molecular mobility can be understood in terms of a rather restricted conformation of the molecular chains in the noncrystalline overlayer, arising from the special mode of crystallization from dilute solution.     

A pulsed field gradient NMR study of diffusion in semicrystalline polymers: self-diffusion of alkanes in polyethylenes

By means of the pulsed field gradient NMR technique the self-diffusion of six alkanes (from n-butane to n-pentadecane) in three low density polyethylenes and one high density polyethylene differently thermally treated was examined. The concentration dependence could be described very satisfactorily with the free volume theory in the form of Fujita (Adv. Polymer Sci. 3(1961) 1). The parameter B of the diffusants and the fractional free volumef ₂ of the polyethylenes were determined from the experimental data. The fractional free volumesf ₂ show a strong dependence on the type of polyethylene, the main influence results from the different content of CH₃ groups or short chain branches. The diffusion coefficient extrapolated to zero diffusant concentration is proportional to the eighth power of the amorphous content. This strong dependence shows that the free volumes of the amorphous parts of the polyethylenes are intimately connected with crystallinity, both determined by the different degrees of short chain branching. The pre-exponential factor in the free volume expression decreases with increasing amorphous content of the polyethylenes and increases with increasing length of the diffusants. It was found that the spherulite boundaries in the polyethylenes do not act as diffusion barriers.     

Rubber elasticity of branched polyethylenes

Two grades of ethylene/1-hexene copolymer, containing about 0.4 and 1.3 butyl branches per 1000 carbons, were subjected to electron beam irradiation in vacuum and in an acetylene atmosphere. The resulting networks were characterized by gel fraction determination and melt elasticity behaviour. The rubber elastic force-extension data were analysed in terms of the Edwards-Vilgis slip-link model. This theory provided good fits to the experimental data, and the calculated parameters agreed well with the gel fraction determinations. The results indicate that an increase in branch concentration causes an increased susceptibility to chain scission. Irradiation in acetylene is shown to enhance greatly the crosslinking process, without affecting the chain scission, leading to a more perfect network.     

Post-irradiation oxidation of different polyethylenes

The radiation-induced oxidative degradation of polyethylenes (PEs) with different degrees of crystallinity was characterized after electron-beam irradiation and during storage at room temperature.UHMWPE, HDPE, LDPE, LLDPE and an ethylene-octene copolymer (Engage) were e-beam irradiated to 30 or 60 kGy in vacuum or in air and stored at room temperature in air. EPR spectroscopy was used to investigate macro-radicals produced during irradiation and their post-irradiation changes. FTIR spectroscopy was used to monitor changes in the polymer structure, induced by irradiation, and to follow post-irradiation oxidation.We found that the crystallinity and the size of the crystalline lamellae, in particular, play a major role on the post-irradiation effects. The low-crystallinity polyethylenes showed no oxidation or oxidation only to a small extent, even when irradiated and stored in air. On the contrary, development of post-irradiation oxidation was observed in HDPE and UHMWPE. We attribute these results to a different reactivity of the macro-alkyl radicals formed upon irradiation in the amorphous or in the crystalline phase. While the radicals formed in the amorphous phase decay in short time, the migration time of the radicals trapped in the crystalline phase to the amorphous one is a key factor, governing the oxidation process.     

Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes

Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln.atm ethylene.h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process.     

Morphology of CaCO3-filled polyethylenes

The morphology of one novel “homogeneous composite” and some conventional CaCO₃-particulate-filled polyethylenes (PEs) has been investigated by transmission and scanning electron microscopy. It is found that for three different linear polyethylenes (M _w = 37,000, 200,000, and 1.5 × 10⁶) studied, ordering on the scale of spherulites was absent in the CaCO₃-filled polymer. However, PE lamallae were observed growing normal to the filler interface. Changes in molecular weight of the polyethylene result in easily observed differences in morphology, while DSC studies indicate that crystallinity decreases in the presence of filler for the two lower-molecular-weight polyethylenes.     

Formation of ringed spherulites in polyethylenes

The effects of molecular weight, molecular weight distribution, crystallization temperature, quenching medium, and sample preparation on the formation of ringed spherulites in linear polyethylenes were studied by polarized light microscopy and small-angle light scattering. When the samples were crystallized at a predetermined temperature, ringed spherulites were formed over a narrow range of temperature and molecular weight with both fractionated and unfractionated polymer samples. Quenching the samples in air at room temperature considerably extended the range of molecular weights for the formation of ringed spherulites. Minor modification of an airquench method further extended the range and yielded better-defined structures. The results are interpreted in terms of the anisotropy of the melt, the thermal conductivity of the quenching medium, and the shear stress applied during the crystallization process. That highly specific conditions are necessary for spherulite formation, of both the conventional and ringed type, is a major conclusion of this study.     

Differential scanning calorimetry of chlorinated polyethylenes

The heats of fusion of low-density polyethylene and chlorinated polyethylenes of varying chlorine content have been investigated by differential scanning colorimetry (DSC). Linear correlations are found between the chlorine content and the apparent heat of fusion, crystallinity, and the maximum specific heat measured in the temperature range 90–120°C. The effect of heat treatment on crystallinity is shown to be strongly dependent on the chlorine content of the polymers.     

Immobilization of a protease on grafted polyethylenes

It has been shown that when the protease ofBacillus mesentericus is immobilized on polyethylene with grafted-on polyacrylic acid by the carbodiimide method there is a considerable retention of its activity and an increase in its thermal stability, and the immobilized preparations are active on repeated use.Institute of Physical Chemistry, Academy of Sciences of the Ukrainian SSR, Odessa. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 512–516, July–August, 1983.     

Acquired biodegradability of polyethylenes containing pro-oxidant additives

Biodegrability of high density polyethylene film (HDPE) and low density polyethylene film (LDPE) both containing a balance of antioxidants and pro-oxidants was studied with defined microbial strains particularly with Rhodococcus rhodochrous and Nocardia asteroides in mineral medium. After an abiotic pre-treatment consisting of photooxidation and thermo-oxidation corresponding to about 3 years of outdoor weathering the samples were inoculated, incubated up to 200 days and during the period their metabolic activities were followed by measuring adenosine triphosphate content. Simultaneously the cultures were also monitored by optical microscopy and FTIR spectroscopy. The first initial phase of fast growth caused by the presence of low molecular extractable compounds was followed by a long period of stabilized metabolic activity suggesting that microorganisms continued to gain energy from the substrate but evidently at a much slower rate. Complementary analysis performed at the end of incubation revealed that during the experiment time biodegradation processes probably affected surface layer of materials only.