Transition regions and surface melting in partially crystalline polyethylene: A raman spectroscopic study

Structures of semi crystalline high-molecular weight polyethylene and their changes with temperature were studied by analysis of Raman spectra. Decomposition of spectra into contributions of an orthorhombic crystalline phase, a meltlike phase, and two kinds of transition regions yields the respective mass fractions. The results of temperature dependent measurements is indicative of a largely reversible surface melting process, the transition regions being located at the crystal surfaces. As-polymerized samples show a large fraction of the intermediate phase. Annealing leads to a reduction of this phase. © 1993 John Wiley & Sons, Inc.     

Specific reversible melting of polyethylene

The specific reversibility of the crystallization and melting of linear and branched polyethylene has been determined as function of temperature by temperature‐modulated differential scanning calorimetry. The specific reversibility of crystallization and melting is defined as the ratio of the reversible enthalpy to the total enthalpy of the transition, both measured at the same temperature. This definition emphasizes a close connection between the reversible and irreversible parts of the transition. As one would expect, the crystal‐to‐melt transition of a given portion of a sample can only be reversible at a temperature close to its own temperature of irreversible melting. Reversible melting is absent at temperatures far from irreversible melting, and this is usually seen by experimentation as its zero‐entropy production melting temperature. The reversible change in the fold length, in contrast, is observed far from the melting temperature of the crystal involved. The specific reversibility of the crystallization and melting of polyethylene crystals may exceed 50% outside the temperature range of the main crystallization and melting. The specific reversibility seems rather independent of the branch concentration, and this points to similar mechanisms of the reversible transition in linear polyethylene of high crystallinity and in branched polyethylene of low crystallinity. The reversible transition is due to a local equilibrium at the crystal surface and is, therefore, largely independent of the overall morphology of the sample. In this study, a model is developed that is based on partial molecular melting, which avoids the need of molecular nucleation and permits, therefore, reversible melting as seen for small molecules in the presence of crystal nuclei. It provides an explanation of the rather large number of the crystals that may participate in reversible melting and allows a connection to the fully reversible crystallization of paraffins and the fully irreversible crystallization of extended‐chain crystals of high crystallinity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2157–2173, 2003     

Exact topological twistons in crystalline polyethylene

We investigate the presence of topological twistons in crystalline polyethylene. We describe crystalline polyethylene with a model that couples the torsional and longitudinal degrees of freedom of the polymeric chain by means of a system of two real scalar fields. This model supports topological twistons, which are described by exact and stable topological solutions that appear when the interaction between torsional and longitudinal fields is polynomial, containing up to the sixth power in the fields. We calculate the energy of the topological twiston, and the result is in good agreement with values obtained using numerical simulation methods.     

Crystallization and melting of fractions of branched polyethylene

Effects of the molecular weight on the crystallization behaviour of branched polyethylene become observable if isothermal crystallization is studied at temperatures near to the melting end. Crystallinities decrease with decreasing molecular weight. Thicknesses of lamellae grown during isothermal crystallization are independent of the molecular weight. They depend only on temperature. Compared to the effect of the branches polydispersity gives only a minor contribution to the broadening of the crystallization and melting range of low density polyethylene.     

Crystallite orientation during melting of oriented ultra-high-molecular-weight polyethylene

The changes in crystallite orientation during melting of oriented ultra-high-molecular-weight polyethylene (UHMW PE) were investigated by means of wide-angle X-ray scattering. The orientation distribution of crystallites in drawn UHMW PE is composed of two components differing in width. The narrow and broad components revealed in this study indicate the existence of two classes of crystallites with different orientability. Some of the crystallites are oriented almost perfectly even at low-draw ratios, while the others do not orient so effectively. The analysis of melting behaviour of such a texture composed of orthorhombic crystals indicates that highly oriented crystallites are formed by taut molecules and transform first to the hexagonal phase, while the molecules constituting low-oriented crystallites melt directly to the typical amorphous phase. The increase in orientation of highly oriented crystallites during their partial melting, observed in the samples kept at constant length and even those allowed to shrink under constant load, can be explained by the kinetic factor proposed by Ziabicki. Received: 11 September 1998 Accepted in revised form: 18 February 1999     

Frequency dependence of dielectric crystalline dispersion in oxidized polyethylene

Summary Observed results of the frequency dependence of the dielectric crystalline dispersion in oxidized polyethylene are shown at various temperatures. The value ofɛ(0)—ɛ (∞) increases with the increase of the amount of the carbonyl groups and also the degree of crystallinity. The shape of the absorption curve is nearly the same for various temperatures and also for various samples, including a single-crystallites one. It is also noticeable that the absorption curve has a nearly symmetric shape when it is plotted against the logarithm of frequency. The estimated value of activation enthalpy lies between 24 and 29 Kcal/mol, and the value for a single-crystallites sample is smaller than that for a melt-grown sample. All the experimental results can be explained quantitatively by using a modified theory of our general theory for the dielectric crystalline dispersion. The modification was necessary because the inserted carbonyl groups made the properties of the dielectric crystalline dispersion in oxidized polyethylene to be different from that in other pure polymers. The agreement between the theory and the observed data seems to be satisfactory, except the shape of the absorption curve. The theoretical curve is slightly narrower than the observed shape because of, presumably, too idealized calculations in the present paper.

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Zusammenfassung Die beobachteten Ergebnisse für die Frequenzabh?ngigkeit der Dielektrizit?tskonstante im Kristallinen für oxydierte Poly?thylene werden für verschiedene Temperaturen gezeigt. Die Werte vonɛ(0) —ɛ(∞) steigen mit wachsendem Anteil an Carbonylgruppen und auch mit dem Kristallmit?tsgrad. Die Form der Absorptionskurve ist nahezu für verschiedene Temperaturen und auch für verschiedene Proben dieselbe, einschlie?lich für Einkristallite. Es ist auch bemerkenswert, da? die Absorptionskurve eine beinahe symmetrische Form besitzt, wenn man sie gegen den Logarithmus der Frequenz auftr?gt. Der gesch?tzte Wert der Aktivierungs-Enthalpie liegt zwischen 24 und 29 kcal/mol, und der Wert für die Probe aus Einkristallen ist kleiner als für die aus der Schmelze kristallisierten. Alle experimentellen Ergebnisse k?nnen quantitativ erkl?rt werden unter Benutzung einer modifizierten Theorie aus unserer allgemeinen, für die dielektrische kristalline Dispersion aufgestellten Theorie. Die Modifikation ist notwendig, weil die Zahl der Carbonylgruppen zu klein ist, um die allgemeine Theorie anzuwenden. Die übereinstimmung zwischen Theorie und Experiment scheint zufriedenstellend, au?er hinsichtlich der Gestalt der Absorptionskurve. Die theoretische Kurve ist etwas schmaler als die beobachtete, vermutlich weil die Errechnungen im vorliegenden Fall zu sehr idealisiert sind.

     

Dynamic mechanical properties of crystalline,linear polyethylene

Two sets of dynamic mechanical property data and some stress relaxation data for semicrystalline, linear polyethylene are treated by data reduction methods previously described. These data can be represented by a master plot of reduced modulus versus reduced frequency and two sets of temperature-dependent shift factors. The first of these factors reflects the change of viscoelastic relaxation times with temperature. The second represents a separable change of modulus with temperature which applies over the entire time or frequency range of the experiments. This change is larger and in the opposite direction to that found applicable in the behavior of noncrystalline plastics and rubbers. The two sets of dynamic data show the same frequency–temperature dependence which can be represented by an activation energy of 22 kcal./mole. Small differences in the modulus–temperature dependence are attributed to differences in molecular weight or annealing conditions. The stress relaxation data superposes to a curve in good agreement with the dynamic data but with a factor of 20 difference in time scale. This difference is attributed to the finite strains used in the stress relaxation measurements. Such strains might be expected to increase free volume in simple extension deformations and so accelerate the relaxation.     

Hydrogen catalysis of alkyl radical decay in single crystalline polyethylene

Although hydrogen gas is about tenfold more soluble in hot-filtered mats of polyethylene (PE) single crystals (SC) than in bulk linear PE, we found that no hydrogen solubility at all could be measured in freeze-dried SC. Despite this, hydrogen gas still exerts a catalytic effect on alkyl radical decay on both the fast and slow first-order decay reactions in the freeze-dried samples. Above 40°C the first-order decay constants of the slowly decaying component decrease with increasing fold period.     

Polarized Raman studies of crystalline and amorphous orientation in polyethylene

Polarized Raman intensities have been obtained from thin films of oriented low-density polyethylene (PE) immersed in silicone oil to minimize surface scattering. Studies were made using the 1170 cm^?1 crystalline band and the 1081 cm^?1 amorphous band, and from these the orientation averages 〈cos² θ〉 and 〈cos⁴ θ〉 were calculated. These were found to compare favorably with the values of 〈cos² θ〉 for the polymer chain in the crystalline and amorphous phases obtained from measurements of infrared dichroism. Both orientation averages could be theoretically fitted by using reasonable parameters.     

Mixed crystal infrared study of chain folding in crystalline polyethylene

Infrared spectroscopic studies have been made of mixed crystals of linear polyethylene and perdeuteropolyethylene. On the basis of normal vibration analyses by Tasumi and Krimm it had been shown that the study of crystal splittings of internal chain modes in such mixed crystals could provide information on the geometry of chain folding. The present results, which include a study of n-paraffin (C₃₆) mixed crystals, confirm these predictions. They show that (110) folding predominates in dilute solution grown crystals, and that this is transformed to (200) folding in melt-crystallized polymer. Folding with adjacent re-entry is favored, a random re-entry model being clearly eliminated.     

A theoretical study of the conformation of crystalline polyethylene

The conformation of polyethylene chains in crystals has been investigated using the MO SCF method in the CNDO/2 approximation for the isolated chain energy and an empirical method for the packing energy.     

Morphology and melting behavior of nascent ultra-high molecular weight polyethylene

The nascent morphology of UHMW PE exhibits high melting point, high crystallinity, and increased WAXS line breadth relative to samples formed by melt crystallization. Different empirical relationships between crystal size and melting point are observed for nascent and molded samples. This differentiation is removed following nitric acid treatment of the nascent flake. Solid-state annealing behavior is differentiated by several regimes. Regime I is characterized by increasing crystallite dimensions and crystallinity at low annealing temperatures. Regime II[a] and II[b] is identified by double melting in DSC scans of moldings and nascent flake, respectively. The double melting is due to partial melting with incomplete recrystallization. Regime II[a] of moldings is differentiated from Regime II[b] of flake by an increase in melting point of the higher melting endotherm. Within Regime II[b], the partial melting of the nascent structure is sensitive to the distribution of morphological stability. Regime III is initiated at annealing temperatures approaching the zero heating rate melting point, and shows melting kinetics by DSC or time-resolved WAXS using synchrotron x-ray radiation. The superheat, partially associated with Regime III behavior, is sensitive to morphological heterogeneity and annealing history. Morphological models are discussed which highlight the role of noncrystalline regions and melting kinetics on the melting behavior of nascent form crystallinity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 495–517, 1998     

The melting of high-pressure polyethylene subjected to stepwise heat treatment

Silver antimony oxide (Ag₂Sb₂O₆) having a defect pyrochlore structure has been synthesized by solid-state reaction between silver oxide and either Sb₂O₃ and Sb₂O₅. The reaction sequence has been shown by thermogravimetry, interdiffusion measurements on oxide pellets and electrical conductance measurements to involve the reduction of Ag₂O, followed by diffusion of silver and oxygen into the antimony oxide component. When the starting material is Sb₂O₃, initial diffusion of oxygen occurs, forming Sb₂O₄ into which silver and further oxygen subsequently diffuse. Comparison of the activation energies for diffusion and electrical conductance in the various oxide phases suggests that the rate of Ag₂Sb₂O₆ formation is controlled by the diffusion of oxygen rather than that of silver.

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Zusammenfassung Silber-Antimonoxid (Ag₂Sb₂O₆) von defekter Pyrochlorstruktur wurde durch eine Festphasenreaktion zwischen Silberoxid und entweder Sb₂O₃ oder Sb₂O₅ synthetisiert. Durch Thermogravimetrie, Interdiffusionsmessung an Oxidpillen, sowie elektrische Leitfähigkeitsmessungen wurde erwiesen, daß die Reaktionsfolge die Reduktion von Ag₂O mit darauffolgender Diffusion des Silbers und Sauerstoffs in die Antimonoxidkomponente enthält. Bei Sb₂O₃ als Ausgangsmaterial erfolgt eine Diffusion des Sauerstoffs wodurch Sb₂O₄ entsteht, in welches dann Silber und weiterer Sauerstoff diffundiert. Der Vergleich der Aktivierungsenergien der Diffusion und der elektrischen Leitfähigkeit in den verschiedenen Oxidphasen läßt vermuten, daß die Bildungsgeschwindigkeit des Ag₂Sb₂O₆ eher durch die Diffusion des Sauerstoffs als durch die des Silbers bedingt ist.

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Résumé L'oxyde d'argent antimonié (Ag₂Sb₂O₆) à structure pyrochlore imparfaite a été synthétisé par réaction en phase solide entre l'oxyde d'argent et Sb₂O₃ ou Sb₂O₅. La séquence de réaction étudiée par thermogravimétrie, par mesures d'interdiffusion sur pastilles d'oxyde et par mesures de conductibilité électrique consiste en la réduction de Ag₂O suivie par la diffusion de l'argent et de l'oxygène dans le composant d'oxyde antimonié. Quand le matériau de départ est Sb₂O₃, la diffusion initiale d'oxygène a lieu et donne Sb₂O₄ dans lequel l'argent et l'oxygène en excès diffusent ensuite. La comparaison des énergies d'activation pour la diffusion et la conductivité électrique dans les diverses phases d'oxydes suggère que la vitesse de formation de Ag₂Sb₂O₆ est contrôlée par la diffusion de l'oxygène plutôt que par celle de l'argent.

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ë (Ag₂Sb₂O₆), . . , . ë , Sb₂O₄ . , , Ag₂Sb₂O₆ , .

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We are grateful to Mr. M. Ahangarha for assistance with the diffusion experiments and to Mr. A. Nossoni for assistance with the thermogravimetric experiments.     

A study of melting of low density polyethylene by in situ WAXD

Analysis of low density polyethylene using in situ wide-angle X-ray diffraction shows that the melting process takes place over a broad temperature range with continuous destruction of lamellar laterals. This process exhibits decreasing rate as the temperature increases, indicating that in general each lamellae has less order in outer regions than in central ones. The shifts in angular position of the amorphous halo as a function of the temperature show that the amorphous phase in a semicrystalline sample is less disordered compared to that in an overall melted sample. As the temperature increases the unit cell parameter a increases, generating a crystalline phase density reduction.     

Nonisothermal crystallization kinetics and melting behavior of bimodal medium density polyethylene/low density polyethylene blends

Nonisothermal crystallization kinetics and melting behavior of bimodal-medium-density- polyethylene (BMDPE) and the blends of BMDPE/LDPE were studied using differential scanning calorimetry (DSC) at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of BMDPE. The BMDPE DSC data were analyzed by the theory of Ozawa. Kinetic parameters such as the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the peak temperatures (T_p) and the half-time of crystallization (t_1/2) etc. were determined at various scanning rates. The appearance of double melting peaks and the double crystallization peaks in the heating and cooling DSC curves of BMDPE/LDPE blends indicated that the BMDPE and LDPE could crystallize respectively.