Multiple Melting Behavior of High-Speed Melt Spun Polylactide Fibers

High-speed melt spinning of polylactide (PLA) was conducted and the structure and multiple melting behavior of the as-spun fibers were investigated. In the analysis of temperature modulated differential scanning calorimetry (TMDSC) thermograms for the as-spun PLA fibers taken-up at 1 and 6 km/min, the peaks around the melting temperature region in the reversing heat flow (RHF) and nonreversing heat flow (NRHF) curves were mainly separated into (1) a pair of an endothermic peak (Peak L) in RHF and an exothermic peak (Peak R) in NRHF in a low temperature region, (2) an endothermic peak (Peak M) both in RHF and NRHF (only in RHF for PLA fiber spun at the low-speed) in an intermediate temperature region, and (3) an endothermic peak (Peak H) both in RHF and NRHF in a higher temperature region. Wide-angle X-ray diffraction (WAXD) measurements were conducted during the heating process of the as-spun fibers cut into powders. In the case of fibers obtained at 1 km/min, disordered crystals, i.e. α′-form crystals, were formed through cold crystallization followed by a disorder-to-order phase transition, i.e. α′ to α crystalline modification, with partial melting of the α′ crystals around 148.5°C in the temperature range of Peaks R and L. Finally, the α form crystals melted above 169.4°C, in the temperature range of Peak H. On the other hand, the PLA crystals generated by the orientation-induced crystallization during the spinning process at a spinning velocity of 6 km/min did not show a WAXD profile of perfect α form crystals but showed an intermediate structure having lattice spacings between the α′ and α forms. Such intermediate crystals did not transformed into α form crystals during the heating process.     

Unexpected Reorganization Effects of Cold-Crystallized Polylactide Stereocomplex

Cold crystallization of poly (l-lactide)/poly (d-lactide) blends at low temperatures results in the formation of a stereocomplex with loose intermolecular packing. Upon heating, it undergoes significant reorganization into a compact one with an extremely high melting point via a solid–solid transition. In contrast, the stereocomplex crystallized at high temperatures exhibits little reorganization and thus a relatively low melting point.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.     

Analysis of Multiple Melting of High-Speed Melt Spun Polylactide Fibers Based on Kinetic Modeling

Multiple melting behavior of high-speed melt-spun polylactide (PLA) fibers was investigated by temperature modulated differential scanning calorimetry (TMDSC) in the heating process with various modulation periods in the calorimeter. In the case of the as-spun PLA fibers taken-up at 1 km/min, a melting endothermic peak and a recrystallization exothermic peak appeared at the same peak temperature of 151°C in the reversing and non-reversing heat flows (RHF and NRHF), respectively, whereas at 168°C, an endothermic peak was observed in both the RHF and NRHF. On the other hand, the as-spun PLA fibers taken-up at a high-speed of 6 km/min showed the melting in both the RHF and NRHF, but the recrystallization behavior was not obvious in the NRHF at the shorter modulation period conditions. The obtained data were analyzed based on the kinetic modeling of melting proposed by Toda et al. The real and imaginary parts of the complex apparent heat capacity in the melting region showed a strong modulation period dependence for both the low- and high-speed spun fibers. The endothermic heat flow of melting was separated by extrapolating the frequency to zero. For the PLA fibers spun at 1 km/min, a set of melting and recrystallization peaks in the RHF and NRHF appeared even for the melting at 168°C. In other words, the simultaneous occurrence of melting and recrystallization was confirmed through this extrapolation. For the 6 km/min PLA fibers, the presence of an exothermic heat of recrystallization was clearly confirmed at a peak temperature of 164°C.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Crystal structure of stereocomplex of poly(L-lactide) and poly(D-lactide)

An equimolar mixture of poly(L-lactide) and poly(D-lactide) was crystallized into a stereocomplex whose crystal system is triclinic (P1) with cell dimensions: a = 0.916 nm, b = 0.916 nra, c (chain axis) = 0.870 nm, α = 109.2°, β - 109.2°, and γ = 109.8°. In the unit cell, a poly(L-lactide) segment and a poly (D-lactide) segment are contained as a pair and packed laterally in parallel fashion. The L- and D-poly(lactides) in the complex take a 3₁ helical conformation, which is a little extended from a 10₃ helix in the homopolymer crystal with the α-form. Homopolymers are also able to take the 3₁ helical conformation and form the β-form crystal. The 3₁ helix in the homopolymer crystal is less stable than the 10₃ one, and hence the β-form is easily transformed to the α-form by annealing.     

CO2-induced Crystallization of Isotactic Polypropylene by Annealing Near Its Melting Temperature

CO₂-induced crystallization of isotactic polypropylene (iPP) by annealing had been studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). The iPP before annealed was in α-form and amorphous states. At lower temperatures by CO₂ isothermal treatments, iPP chains crystallized from the amorphous phase and only one crystal form, i.e., α-form, was observed. At higher temperatures by CO₂ isothermal treatments, both crystallization from the amorphous phase and thickening of existing crystal lamellae were observed. Moreover, light γ-form crystal appeared in the treated iPP. The crystalline lamellar thickness of iPP annealed at different CO₂ pressures had been determined. Using the Gibbs–Thomson plot method, the equilibrium melting temperature was found to be 187.6°C.     

The Preparation and Study on Ultrahigh Molecular Weight Polypropylene Gel‐spun Fibers

A novel polypropylene (PP) fiber was prepared by using gel spinning/crystallization from dilute solutions of ultrahigh molecular weight isotactic polypropylene (i‐UHMWPP), and subsequently drawing at various temperatures. The influence of drawing temperature on the properties of the resulted fibers was investigated. We found that the draw‐ability and mechanical as well as crystallization properties of the fibers obtained were dramatically improved with increasing drawing temperature. When the drawing temperature is below the α‐crystal relaxation temperature of PP, which was measured by wide‐angle X‐ray diffraction (WAXD) analysis as 100–120°C, the fibers are characterized by lower crystallinity and smaller crystals with less perfection, resulting in brittle fracture and subsequently poor mechanical durability. With drawing at temperatures above the α‐crystal relaxation temperature of PP, a novel UHMWPP fiber with Young's modulus of 27 GPa and tensile strength of 1.3 GPa was obtained. Higher crystallinity and larger crystals with better perfection and orientation were observed in this fiber.     

High pressure: a tool to improve the enzymatic production of glycosides

Naringinase, an enzyme complex that expresses α -l-rhamnosidase and β -d-glucosidase activities in native state, can be used to deglycosylate natural glycosides. The selective inactivation of one of these activities will allow the biosynthesis of different bioactive compounds in a simple, effective and cheap way. In this work, pressure and temperature were the tools used to selectively inactivate the activities expressed by naringinase. The main goal was the identification of pressure–temperature conditions to acquire conditions for the maximization of enzymatic hydrolysis of substrates with different numbers of glycosidic residues. α -l-Rhamnosidase was 32-fold more resistant against inactivation at 250 MPa than at atmospheric pressure. The best pressure condition to reduce β -d-glucosidase inactivation at 75°C was 173 MPa, while in the case of α -l-rhamnosidase inactivation at 85°C, it was above 250 MPa. Moreover, a selective inactivation of β -d-glucosidase activity of naringinase was attained, allowing an easy and cheap method with which to produce prunin and other expensive glycosides. The present work highlights the effect of high pressure on enzyme protection against thermal inactivation, demonstrating its potential as a powerful tool in biosynthesis.     

Melting Point Elevation of Isotactic Polypropylene

The melting point of a conventional isotactic polypropylene (PP) was enhanced by a rapid annealing procedure of an extruded sheet composed of β trigonal form crystals having thick lamellae, which was prepared by T-die processing with a specific β-nucleating agent, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide. Although the melting point of PP with α monoclinic form, prepared by a conventional processing method, is known to be located around at 165°C, the sample obtained by the present technique showed a higher melting point, 170°C. The phase transformation from β-to α-form crystals, retaining the lamellar thickness, was responsible for the melting point elevation.     

Melting behavior of the oriented β-phase polypropylene texture crystallized by the temperature slope method

Isotactic polypropylene consisting of uniaxially oriented P-phase lamellae was crystallized in a temperature gradient. The β → α transition was investigated by simultaneous measurements with differential scanning calorimetry (DSC) and X-ray diffraction using synchrotron radiation (SR). To compare the transition mechanism, the β-phase sample was deformed by rolling it along the direction of the crystallization. During rolling, the β-crystal is deformed by interlamellar and interchain slip, which induces c-axis-oriented molecules along the rolling direction. The melting behavior is changed by the rolling deformation. For the as-grown β-crystal, the DSC thermogram has three peaks: the β-melting endotherm at 150°C, an exotherm by recrystallization into the °-form, and the endotherm at 167°C caused by melting of the recrystallized α-form. After the rolling deformation, the β-endotherm is extinguished by the successive exotherm. Simultaneous X-ray measurements reveal that the β → α transition is shifted to a lower temperature and that the recrystallized α-form has a c-axis-orientation caused by the rolling deformation. In the process of the β→ α transition, higher-order lamellar structure is developed earlier than formation of the crystalline structure. In this study, the heating phenomena, such as the β α transition and thickening of the β- and α-lamellae, are consistently explained by a mechanism involving melting and subsequent recrystallization.     

Spectrophotometric Studies of the Energy Consumed During Oxidative Degradation of D-Fructose

ABSTRACT

Mechanistic investigation of the oxidative degradation of d-fructose (D-Fruc) has been studied by spectrophotometric technique. Molecular mechanics (MM +) calculations suggest that the potential energy (PE/kcal mol^?1) of the d-fruc (opening structure) is at least three (3.71) times more stable than the PE of the cycling structure of the same matrix. The oxidation constant (K _ox) of the anionic form of the d-Fruc (Fruc-NaOH) is about seven times greater than that of the protonated form (Fruc-H₂SO₄). Therefore, the anionic form is more highly oxidizable than is the cationic form of this matrix. The limit of detection can be as low as 18 ppm (mg L^?1) of d-Fruc. This is about 60 times lower than the blood sugar level (BSL) or 100 times lower than that reported previously. The proposed procedure was applied successfully for the oxidation of D-Fruc in uni-fructose powder. The anionic form of D-Fruc (Fruc-NaOH) has the ability to store energy about 744.72 kJ g^?1 h at 608 nm in a condensed lightweight form. Kinetic parameters of the oxidative degradation of the anionic form of D-Fruc at different concentration were deduced. A number of models were used to evaluate the kinetic parameters. The mechanism of the degradation of D-Fruc is explained on the basis of kinetic parameters.     

Synthesis of Co(II) Complex with Hexamethylenetetramine Using Jet Milling and Its Influence on the Thermal Performance of Poly(l-lactic acid)

Cobalt(II)-hexamethylenetetramine (Co(II)-HMTA) complex was prepared using jet milling. Elemental analysis and thermogravimetric analysis confirmed that the structure of the Co(II)-HMTA complex was Co(HMTA)₂Cl₂·6H₂O (LG). The influence of LG on the thermal performance of poly(l-lactic acid) (PLLA) was investigated. Isothermal crystallization behavior and X-ray diffraction analysis (XRD) results of PLLA/LG showed that LG could improve the crystallization performance of PLLA; 1% LG caused the half time of overall crystallization (t_1/2) of PLLA to decrease from 96.5 min to a minimum value 3.8 min at 100°C. However, the isothermal crystallization kinetics of PLLA/LG described using the Avrami equation and XRD analysis indicated that the isothermal crystallization temperature and the LG concentration significantly affected the isothermal crystallization process of PLLA. In particular, 0.3% LG caused the intensity of the X-ray crystal diffraction peaks of PLLA to decrease with an increase of isothermal crystallization time after increasing for the first 5 min. The thermal decomposition analysis of PLLA/LG showed that the onset decomposition temperature of PLLA with a small amount of LG was higher than that of the neat PLLA and PLLA with a high concentration LG.     

Higher-Order Structure of Poly(Ethylene 2,6-Naphthalene Dicarboxylate) Fibers Produced by Direct High-Speed Spin-Drawing

In order to efficiently produce poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) fibers comprising α-phase crystallites with a high melting temperature, a direct high-speed spin-drawing (HSSD) system was implemented. The higher-order structure of the HSSD PEN fibers was investigated by focusing on the radial anisotropy of the fibers. A nucleating agent was added to the PEN fibers, and its effect on the formation of the higher-order structure was also studied. Highly crystalline PEN fibers predominantly composed of α-phase crystallites were produced by operating the HSSD system at 4?km/min. The PEN fibers exhibited a melting temperature of 288.8?°C and a storage modulus of 31.4?GPa. The excellent thermal stability of the HSSD PEN fibers was presumably brought about by the formation of a shish-kebab-like structure. The generation of the shish-kebab-like structure and radial anisotropy seemed to be more dependent on the effect of tensile stress during the drawing process rather than from the nucleating additive. The nucleating agent used in this study effectively increased both the α- and β-phase crystallite sizes. Such structural modification, however, did not appear to contribute to the thermal stability enhancement of the PEN fibers.     

A COMPARISON OF THE HOT-COMPACTION BEHAVIOR OF ORIENTED,HIGH-MODULUS,POLYETHYLENE FIBERS AND TAPES*

The purpose of this article is twofold. First, there is an account of the hot-compaction behavior of a new, highly oriented, high-modulus polyethylene (PE) tape with the trade name of Tensylon® (manufactured by Synthetic Industries, USA). This tape, produced by a melt spinning route, has mechanical properties comparable to those of commercially available gel-spun fibers. Unidirectional samples were produced for a range of compaction temperatures to determine the optimum compaction conditions to obtain the best mechanical properties of the resulting compacted sheets. Second, the mechanical properties of the best Tensylon sample, manufactured at a compaction temperature of 153°C, was compared with three other hot-compacted, highly oriented PE materials, based on Certran®, Dyneema®, and Spectra® commercial PE fibers. The results showed that the optimum compaction temperature was in most cases about 1°C below the point at which substantial crystalline melting occurred. At this optimum temperature, differential scanning calorimetry (DSC) melting studies showed that approximately 30% of the original oriented phase had been lost to bond the structure together. In the case of Dyneema, the properties of the fiber were not translated into the properties of a compacted sheet, and morphological studies showed that this was because melting did not occur on the fiber surfaces, but rather in the interior of the fiber due to a skin structure. The properties of the compacted Tensylon tapes were found to be exceptional, combining very high modulus and strength with interlayer bonding and good creep resistance. Moreover, the optimum temperature appeared to be about 2°C below the point at which complete melting occurred, giving a wider processing window for this material.

     

Reflections on Ernest Roy Davidson: the UW years 1962–1984

In the following research acetylation as an unexplored factor in the anomeric effect in carbohydrate chemistry has been examined. Crystallographic data for methyl glycosides and their acetates have been compared and discussed. Some of the methyl glycosides form hydrogen bonding with the participation of acetal oxygen atoms. This seems to have the most significant influence on the structural diagnostic parameters for anomeric effect.

Abbreviations: Me-α-Glc: methyl α-D-glucopyranoside; Me-β-Glc: methyl β-D-glucopyranoside; Me-α-Gal: methyl α-D-galactopyranoside; Me-β-Gal: methyl β-D-galactopyranoside; Me-α-Man: methyl α-D-mannopyranoside; Me-β-Man: methyl β-D-mannopyranoside; Ac-Me-α-Glc: methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside; Ac-Me-β-Glc: methyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside; Ac-Me-α-Gal: methyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside; Ac-Me-β-Gal: methyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside; Ac-Me-α-Man: methyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside; Ac-Me-β-Man: methyl 2,3,4,6-tetra-O-acetyl-β-D-mannopyranoside; GIPAW (Gauge Including Projector Augmented Waves) calculations: a DFT based method used for calculating nuclear magnetic resonance parameters; CP/MAS NMR: cross-polarisation (CP) magic angle spinning (MAS) NMR spectroscopy; δ_ss: chemical shift in ¹³C CP/MAS NMR spectrum; δ_t: theoretical chemical shift: as derived from GIPAW DFT; dis: distorted multiplet in ¹H NMR spectrum.     

Improvement of the Mechanical Properties of Poly(Glycolic Acid) Fibers Through Control of Molecular Entanglements in the Melt Spinning Process

Abstract

To improve the mechanical properties of poly(glycolic acid) (PGA) fibers prepared by the direct spin-drawing process, the concept of “melt structure control” was introduced. A heating chamber was installed in the vicinity of the spinning head and a low take-up velocity in the melt spinning process was adopted to reduce the Deborah number in the spin-line. As a result, improvement of the toughness of as-spun fibers prepared by the melt-spinning process was accomplished, and the drawn fibers of high-strength and high-toughness were obtained by applying an additional in-line drawing process. Entanglement density reduction in the melt spinning process was found to be suppressed by installing a heating chamber as well as by lowering the take-up velocity. Through the matching of the true stress versus true strain curves of in-line drawn fibers by shifting the curves along the true-strain axis, the network draw ratio of the drawn fibers was estimated and the master curves for individual spinning conditions were prepared. The master curves were found to show steeper increases from lower true-strains for the lower Deborah number conditions, whereas the increases in birefringence and strength of the drawn fibers proceeded from the lower network draw ratios.     

The polarized reflection and absorption spectra of perylene crystals in monomeric and dimeric forms

The electronic absorption spectra of perylene crystals in the α- and β-forms were measured by the normal incidence reflection method in the spectral region from 20 000 to 60 000 cm^?1. From the absorption spectrum polarized perpendicular to [1$\text{1}$0] axis of the α-form crystal, the bands around 24 000 cm^?1 were determined to be polarized along the long molecular axis. Two strong bands with different polarizations were observed around 50 000 cm^?1 for each of the α- and β-perylene crystals and were assigned to the transitions to the ¹B_2u and ¹B_3u states. The observed polarized absorption spectra as a whole were consistent with the theoretical results by Hummel and Ruedenberg and the reflection method was found to be suitable to the polarized absorption measurement of strong bands of crystals. The observed factor-group splittings were compared with the theoretical values, the oriented gas model being found to be applicable to the β-form crystal.     

Elastic-plastic deformation and fracture of shock-compressed single-crystal and polycrystalline copper near melting

The Hugoniot elastic limit, the yield strength, and the spall strength of polycrystalline M1 copper and single-crystal (110) and (111) copper are determined during shock compression up to 8 GPa in the temperature range 20–1080°C from an analysis of the free-surface velocity profiles recorded with VISAR laser velocimeter. The measurements show that all copper samples exhibit strong athermal hardening (increase in the Hugoniot elastic limit) near the melting temperature. Copper single crystals have a very low elastic limit in the temperature range up to 600°C, this limit increases sharply as the temperature increases to 1000°C, and it depends on the crystallographic orientation of a single crystal. The temperature dependence of the spall strength has a threshold character for all copper samples. Copper single crystals demonstrate higher resistance to spall fracture; however, near the melting temperature, the difference between the spall strengths of the copper single crystals and M1 copper becomes insignificant, 50% of the initial level.     

Melting and Recrystallization of Nylon-6,10 Thin Films

The melting and recrystallization of nylon-6,10 thin films immersed in an aqueous solution of calcium chloride were investigated by DSC measurements. The crystal length, ζ, was determined as a function of the melting peak temperature, T _m . The end surface free energy of nylon-6,10 crystals used for the ζ–T _m conversion was derived thermodynamically. For films of 0.01 mm thickness, the original length of ζ (=7.6 structural units) at T _m decreased step by step with increasing immersion time by the length near the structural unit (2.24 nm) per step. However, the suppression of the recrystallization after melting of the original crystals formed during the first cooling by the adsorbed calcium ions did not occur completely, even for films immersed for 30～60 min at 50°C.