Melting behavior of linear polyethylene crystallized by solution stirring

Calorimetric and dilatometric studies have been made of the fusion process of linear polyethylene crystals precipitated by high speed stirring from solution. It is shown that long-time annealing at elevated temperatures alleviates the superheating observed when rapid heating rates are employed. By the annealing procedures that have been adopted, a small but demonstrable fraction of high melting material can be produced whose melting temperature depends on the crystallization temperature. For crystallization at 105°C, followed by annealing at 142°C, a melting temperature of 146.0 ± 0.5°C is observed. The dissolution temperature in xylene, determined for the same sample, is consistent with the high melting temperature observed for the pure polymer. It is recognized that a state of high axial orientation need not necessarily be identified with extended chain crystals. Consequently, the increased melting temperature can result from either an increase in the crystallite size or a reduced interfacial free energy relative to crystallites produced by the more conventional mode of crystallization.     

Effect of molecular weight on the radial growth rates of polymer spherulites

Data existing in the literature for the spherulitic growth rate of molecular weight fractions of linear polyethylene, poly-(tetramethyl-p-silphenylene)siloxane, and trans-1,4-polyisoprene have been analyzed according to nucleation theory on taking into account the influence of chain length on the free energy of fusion. All three polymers display very similar behavior in that the interfacial free energy reaches an asymptotic value at high molecular weights, decreases as the molecular weight is lowered, and appears to also reach an asymptotic value at low molecular weights. Although the changes in the interfacial energy with molecular weight are quite distinct, the relative change is much less than has been previously reported when a molecular crystal analysis is used. The same general behavior observed points out the dominating influence of the chain-like character of the molecules in governing the growth rate.     

Electron microscope study of low molecular weight fractions of linear polyethylene

Electron microscope studies are reported for crystals of linear polyethylene formed in dilute solution from very sharp low molecular weight fractions. Emphasis is placed on molecular weights in the range of 1.1 × 10³ to 15.1 × 10³. The dependence of the crystal habit on the crystallization temperature is very similar to that which has been found for the higher molecular weight species. However, the demarcation temperature for the crystallization of the different morphological forms is very molecular weight-dependent. The conditions under which interfacial dislocation networks form can be clearly defined. The molecular weight must be less than 3000, so that these structures are restricted to very small chain lengths. However, not all crystallization conditions within this allowable molecular weight range yield such dislocations. The formation of interfacial dislocation networks are shown to occur only under very special circumstances. Their occurrence clearly cannot be offered as evidence, as has been done in the past, for a regular, chain-folded interfacial structure.     

Supermolecular structure of poly(ethylene oxide) fractions

The crystalline morphology, or supermolecular structure, of poly(ethylene oxide) has been studied as a function of molecular weight and crystallization conditions. Molecular weight fractions, covering the range 6 × 10³ to 1 × 10⁷ are used over the range of accessible temperatures for isothermal crystallization as well as for a large set of controlled nonisothermal crystallization conditions. A morphological map is constructed from these studies and compared with the literature results. Prior reports were primarily confined to low molecular weights, which restricted the generalization of the findings. In the present work, as a consequence of the extended molecular weight range, conditions are established for the systematic development of several different, well-defined, organized super-molecular structures as well as for highly crystalline but disorganized systems. Strong similarities are found between the results for poly(ethylene oxide) and previous reports for linear polyethylene. A generalization for all chain molecules is suggested.     

A quantitative electron microscopic study of the crystallite structure of molecular weight fractions of linear polyethylene

Utilizing thin-section techniques, transmission electron microscope studies were performed on a series of bulk-crystalized fractions of linear polyethylene covering the range M = 5 × 10³?6 × 10⁶. The crystallization conditions were varied from long-time isothermal to rapid quenching. Quantitative analysis could be carried out on such samples crystallized under controlled conditions. The crystallite thickness distributions and long periods are presented in terms of histograms. From these data the degree of crystallinity can be calculated and was found to compare favorably with that from other methods. The amorphous thickness increases significantly with molecular weight for all modes of crystallization. On the other hand, the crystallite thickness is essentially independent of molecular weight for very rapid crystallization, and shows a complex dependence on chain length for isothermal crystallization. The tilt angle, the angle of inclination of the chain axis with the lamellar basal plane, has also been determined. There is a tendency for this angle to increase with decreasing crystallization temperature. This observation can be related to the crystallization mechanisms.     

Effect of molecular weight on the crystalline structure of polytetrafluoroethylene as-polymerized

Melting and crystallization behavior of polytetrafluoroethylene as polymerized in emulsion and suspension is shown to depend on molecular weight. DSC heating curves for virgin PTFE with low molecular weight below 3 × 10⁵ have a single peak, whereas curves for higher molecular weight samples have double peaks. With increasing heating rate the areas of higher melting peaks become larger than the lower melting peaks. The morphology of polymer exhibiting double melting peaks is mainly folded ribbons or granular particles. The phenomenon of double melting is explained on the basis of two different crystalline states which correspond to the “fold regions” and the “linear segments” in a folded ribbon. The melting temperature of virgin PTFE is almost constant at ca. 330°C for molecular weights below 1 × 10⁶, and rises as the molecular weight increases above 1 × 10⁶. The heat of melting of virgin PTFE is nearly independent of molecular weight. On the basis of these results, we propose a model for melting and crystallization of low and high molecular weight PTFE and for the crystal structure.     

Initial lamellar thickness dependency of recrystallization behavior of poly(4‐methyl‐1‐pentene)

The isothermal crystallization and subsequent melting process in semicrystalline poly(4‐methyl‐1‐pentene) were investigated via temperature‐dependent small‐ and wide‐angle X‐ray scattering and Flash DSC techniques. In a phase diagram of inversed crystalline lamellar thickness and temperature, the crystallization and melting lines can be described by two linear dependencies of different slopes and different limiting temperatures at infinite lamellar thickness. Upon subsequent heating, recrystallization lines with different slopes were observed for samples with different lamellar thickness, indicating changes in surface free energy difference between stabilized crystallites and mesomorphic phase. The surface free energy of native crystallites with extended‐chain conformation decreased with increasing lamellar thickness due to a more ordered surface region and less chain ends which changes cooperatively with mesomorphic phase. The surface free energy of stabilized crystallites remained unchanged for all lamellar thickness. Therefore, the recrystallization lines with different slopes are consequences of changes in surface free energy of mesomorphic phase. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 219–224     

Origins of endothermic peaks in differential scanning calorimetry

The origins of multiple peaks observed by differential scanning calorimetry have been examined in detail for a linear polyethylene fraction crystallized from dilute solution and for bulk-crystallized copolymers of ethylene. At least two major bases are demonstrated. One is melting–recrystallization; the other a consequence of the distribution of crystallite sizes. The melting–recrystallization process, however, often only yields one endothermic peak. This peak is therefore not characteristic of the original crystallites present. In these situations complementary methods need to be used to determine the melting temperature. We have complemented the calorimetric studies with measurement of the crystallite size distribution as determined from the Raman low frequency acoustical mode spectra. A major increase occurs cooperatively in the crystallite size distribution during the initial melting. Most importantly, we have also been able to make a direct comparison between the interfacial free energies of thin crystallites formed from dilute solution and from bulk-crystallized linear polyethylene.     

Transition of nylon 6 γ-phase crystals by stretching in the chain direction

A crystal transition was found in nylon 6 fibers from the γ-phase to α-phase on stretching in the chain direction. The γ-phase fiber prepared by iodine treatment was stretched under constant load and the crystal deformation was observed by an x-ray method. The critical stress for the transition was estimated as 4 × 10³ kg./cm.² at room temperature. For this crystal transition the following conditions must be satisfied: (1) extension of the γ-phase chain to untwist the chain around the amide groups, (2) translational mobility of the chain to change the stacking in the crystallite. At the critical stress, the chain in the crystal is extended to nearly the same length as that of α-phase. The translational movement occurs under stress higher than about 3 × 10³ kg./cm.², and the pseudohexagonal cell is deformed into a monoclinic form. However, the monoclinic crystallites present at a stress lower than the critical value estimated above are unstable and may be brought back to the original form by head treatment at 100°C. No crystal transition occurs at low temperature.     

Effect of molecular weight on the growth rates of low melting spherulites of trans-1,4-polyisoprene

Growth rates of G of low-melting spherulites in fractions of trans-1,4-polyisoprene have been measured. The data were analyzed by use of an equation, ln G = ln G₀ ? ΔF^*/RT_c, valid at temperatures close to the equilibrium melting point. Plots of ln G against a function of the critical free energy of nucleation ΔF^* result in a family of straight lines having a common intercept, ln G₀, which is independent of molecular weight. The slope of these lines is a measure of the interfacial free energy of the crystallites and increases with the molecular weight, reflecting increasing irregularity in the structure of the semicrystalline mass. Comparison of growth rates of low-melting and high-melting trans-1,4-polyisoprene indicates that G₀ does not, to a first approximation, depend on the nature of the crystals growing from the melt. The temperature at which spherulites of the two crystalline forms grow at equal rates has been calculated.     

Crystallization, glass transition and morphology of (R)-3-hydroxybutyrate oligomers

The study focuses on the effect of the molecular length of isotactic hydroxybutyrate oligomers on the crystal morphology, crystallinity, and spherulitic superstructure. Furthermore, the process of solidification of the quiescent melt is evaluated by the analysis of the crystallization kinetics and of the glass transition. Melt-crystallization is strongly controlled by the chain length, and the regime of cooling. Crystallization can completely be avoided by rapid cooling. Slow cooling allows at best incomplete crystallization, with the crystallinity increasing with chain length. Typically, the maximum crystallinity is between 50% and 80% for OHB of molecular weights of 500 and 5000 g mol⁻¹, respectively. The temperatures of the glass transition and of crystallization/melting increase with molecular length, and are discussed in terms of the Fox-Flory and Gibbs-Thomson equations, respectively. For all samples, regardless of the chain length, spherulitic crystallization is observed, with the perfection of spherulites increasing with decreasing crystallization temperature. The transition of formation of extended-chain crystals to formation of folded-chain crystals occurs at a molecular weight of about 2000 g mol⁻¹, which corresponds to chain length of about 7 nm. Analysis of the heat-capacity increment at the glass transition temperature reveals the existence of a rigid amorphous fraction.     

Synthesis of side‐chain liquid‐crystalline homopolymers and triblock copolymers with p‐methoxyazobenzene moieties and poly(ethylene glycol) as coil segments by atom transfer radical polymerization and their thermotropic phase behavior

A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 10³ to 20.6 × 10³ with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 10³ to 1.7 × 10⁴ and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with ¹H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003     

The Effect of Molecular Weight on the Thermal Properties of Polystyrene-Based Sidechain Liquid-Crystalline Polymers

Abstract

Sidechain liquid-crystalline polymers were prepared by the derivatization of three poly(4-hydroxystyrene) fractions of different molecular weights (M_w = 1.0 × 10⁴, 2.2 × 10⁴ and 3.0 × 10⁴). 4-Cyanoazobenzene and 4-cyanobiphenyl were incorporated as mesogenic groups with ether-linked methylene spacers of varying length. The polymers all exhibited a smectic A phase, with the exception of the propyl member of the cyanobiphenyl series for which no liquid-crystalline behavior was observed. For short spacers the thermal properties were insensitive to molecular weight changes in the backbone, whereas small but consistent differences in the transition temperatures and entropies were observed as the number of methylene groups in the spacer increased.     

Toughening of in situ polymerized cyclic butylene terephthalate by chain extension with a bifunctional epoxy resin

Cyclic butylene terephthalate (CBT) was polymerized in the presence of a low molecular weight bifunctional epoxy resin. The resultant chain extended polymerized CBT (pCBT) showed an increased ductility compared to that of conventionally polymerized pCBT for all analyzed epoxy concentrations (1–4 wt.%). The best results were obtained with 2 wt.% of epoxy resin. Other mechanical properties remained relatively unaffected by the epoxy resin. ¹H NMR analysis suggested an esterification reaction of the carboxyl end groups of pCBT and the glycidyl functional groups of the diepoxide. With increasing epoxy content, the chain extended pCBT showed an increasing molecular weight and a decreasing glass transition. Crystallization and melting temperatures as well as crystallinity also decreased with increasing epoxy concentration.     

Effect of molecular weight on conformation of poly(β-benzyl L-aspartate) in films

In order to study the effect of the molecular weight on the crystallinity and conformational changes of poly(β-benzyl L aspartate) in films, a previous study on high molecular weight samples has been extended to included polymers of low molecular weight, about 3.3 × 10³. Films were prepared from chloroform solution by quick or slow evaporation at room temperature. The conformation and the thermal behavior were studied by means of infrared spectroscopy and differential scanning calorimetry. All films dried quickly are composed of polymer in the left-handed α-helical form. All samples studied which have molecular weights above 2.3 × 10⁴ are similar in crystallinity and the left-handed α-helices in them crystallize to ω-helices during slow evaporation. In the low molecular weight region, however, the left-handed α-helices reverse to right-handed α-helices during slow evaporation, and the right-handed α-helices, in turn, reverse and crystallize to highly ordered ω-helices upon heat treatment, although there is some simultaneous conversion to the β-form. The transition temperatures of the quick-dried films for conversion from the left-handed α-helix to the ω-helix and from the ω-helix to the β-form increase linearly with increasing molecular weight up to about 2 × 10⁴, but no large molecular weight dependence is observed beyond that region.     

Relaxation characteristics and intrinsic birefringence and viscosity of polystyrene solutions for a wide range of molecular weights

A comparison is made between measurements on polystyrene solutions and the relaxation characteristics and intrinsic birefringence and viscosity given by the theory for the flexible Gaussian chain of variable number of segments and with internal viscosity and internal hydrodynamic interaction. This is done in order to determine the applicability of the theory to polymers over a wide range of molecular weights, including the low molecular weight range in which there may be conflict with the theoretical assumption of chains having a large number of segments. The longest, terminal relaxation time and the number of chain segments are determined from measurements of the frequency dependence of oscillatory flow birefringence while the intrinsic birefringence and viscosity are determined from steady flow measurements. The range of molecular weights studied is from approximately 900 at 10⁶. It is found that the segment weight is approximately 1000 and the number of segments is in direct proportion to the molecular weight for the range from 1 to 1000 segments. The terminal relaxation time has a molecular weight dependence of the type given by the theory but with better agreement for higher molecular weights. While the measured dependences of the intrinsic viscosity and birefringence are in agreement with theory for molecular weights greater than 5 × 10⁴, they deviate significantly for molecular weights below 1 × 10⁴. The ratio of the intrinsic birefringence to intrinsic viscosity, which in theory is a constant independent of molecular weight, is found to change at the lower molecular weights.     

Melting behavior and morphology of drawn nylon 6

Thermal analysis has been carried out on drawn nylon 6 filaments annealed at various temperatures between 150 and 210°C and then methoxymethylated to various degrees. It is shown that the melting point inherent to the morphology of drawn nylon 6 can be obtained from samples in which the reorganization of defect crystallites in the course of thermal analysis is prevented by a proper degree of methoxymethylation of amorphous regions. The melting point thus obtained is in linear relation with the reciprocal crystallite size in the direction of fiber axis which has been obtained from small-angle x-ray data and crystallinity. The extrapolation and the slope of this linear relation give the equilibrium melting point of nylon 6 as 245°C and an end-surface free energy of 42 erg/cm². The results seem to provide strong support for the presence of chain-fold surfaces in the drawn and annealed polymers.     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

Multiple melting behavior in isothermally crystallized poly(trimethylene terephthalate)

Melting behavior of poly(trimethylene terephthalate) (PTT) after isothermal crystallization from the melt state was studied using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) techniques. The subsequent melting thermograms for PTT isothermally crystallized within the temperature range of 182-215 °C exhibited triple (for crystallization temperatures lower than ≈192 °C), double (for crystallization temperatures greater than ≈192 °C but lower than ≈210 °C), or single (for crystallization temperatures greater than ≈210 °C) endothermic melting phenomenon. These peaks were denoted peaks I, II, and III for low-, middle-, and high-temperature melting endotherms, respectively. For the triple melting phenomenon, it was postulated that the occurrence of peak I was a result of the melting of the primary crystallites, peak II was a result of the melting of recrystallized crystallites, and peak III was a result of the melting of the recrystallized crystallites of different stabilities. In addition, determination of the equilibrium melting temperature T_m⁰ for this PTT resin according to the linear and non-linear Hoffmann-Weeks extrapolation provided values of 243.6 and 277.6 °C, respectively.     

Molecular weight dependent structure and charge transport in MAPLE‐deposited poly(3‐hexylthiophene) thin films

In this work, poly(3‐hexylthiophene) (P3HT) films prepared using the matrix‐assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE‐deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side‐chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin‐cast films, though the MAPLE‐deposited films are more disordered. In‐plane carrier mobilities in the MAPLE‐deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE‐deposited simples are consistently lower than those in the solvent‐cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 652–662