Microstructure and Thermal Properties of Polylactides with Different L‐ and D‐Unit Sequences: Importance of the Helical Nature of the L‐Sequenced Segments

A series of polylactides (PLA) with different stereo sequences are prepared by the copolymerization of L ‐lactide and DL ‐lactide. It is confirmed that the glass transition temperature (T_g) of the PLA decreases with decreasing optical purity of the lactate units (%ee) according to the Fox's equation. Analysis of the FT‐IR spectra of these PLA samples reveals that the absorbance at 1 265 cm^?1 (δCH + νCOC) decreases with increasing L ‐content while the absorbance at 1 210 cm^?1 (ν_asCOC + r_asCH₃) increases with increasing L ‐content. These changes in absorbance are reasonably correlated with the randomness and helical nature of the L ‐sequenced segments involved in PLA. Namely, the PLA chains with higher L ‐content comprise a higher number of short helical blocks that are made of several L ‐lactate units. This difference in helical nature causes the opposite dependences of T_g and density on the L ‐content of PLA; i.e., the increased T_g and decreased density with increasing L ‐content.

FT‐IR spectra of a PDLLA film, NO‐PLLA, and BO‐PLLA.     

Biocomposites Made from Short Abaca Fiber and Biodegradable Polyesters

Natural fiber‐reinforced biodegradable polyester composites were prepared from biodegradable polyesters and surface‐untreated or ‐treated abaca fibers (length ca. 5 mm) by melt mixing and subsequent injection molding. Poly(butylene succinate)(PBS), polyestercarbonate (PEC)/poly(lactic acid)(PLA) blend, and PLA were used as biodegradable polyesters. Esterifications using acetic anhydride and butyric anhydride, alkali treatment, and cyanoethylation were performed as surface treatments on the fiber. The flexural moduli of all the fiber‐reinforced composites increased with fiber content. The effect of the surface treatment on the flexural modulus of the fiber‐reinforced composites was not so pronounced. The flexural strength of PBS composites increased with fiber content, and esterification of the fiber by butyric anhydride gave the best result. For the PEC/PLA composites, flexural strength increased slightly with increased fiber content (0–20 wt.‐%) in the case of using untreated fiber, while it increased considerably in the case of using the fiber esterified by butyric anhydride. For the PLA composite, flexural strength did not increase with the fiber reinforcement. The result of soil‐burial tests showed that the composites using untreated fiber have a higher weight loss than both the neat resin and the composites made using acetylated fiber.

Flexural modulus of PBS composites as a function of fiber content.     

Study of the Fire Performance of Magnesium Hydroxide Sulfate Hydrate Whisker Flame Retardant Polyethylene

Summary: Halogen‐free, flame retardant low density polyethylene (LDPE) composites, using magnesium hydroxide sulfate hydrate (MHSH) whiskers as a flame retardant, combined with microencapsulated red phosphorous (MRP) as a synergist, have been prepared using a two‐roll mill. Their fire properties were determined by using the limiting oxygen index (LOI), the UL‐94 test and cone calorimetry. The results showed that MRP was a good synergist in improving the flame retardance of the LDPE/MHSH whisker system. Poly[ethylene‐co‐(vinyl acetate)] (EVA), used as a compatibilizer, increased the fire performance of LDPE/MHSH whisker composites.

HRR curves for LDPE/MHSH whisker composites.     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Structural Properties and Enzymatic Degradation Behavior of PLLA and Stereocomplexed PLA Nanofibers

PLLA and stereocomplexed polylactide (sc‐PLA) nanofibers were formed by electrospinning solutions of the polymers in HFIP. A highly semi‐crystalline sc‐PLA nanofiber having only sc crystallites was confirmed by WAXD analysis. The diameters of the nanofibers of both polymers decreased slightly when they were annealed at 60 °C, which was near T_g. Enzyme degradation of both as‐spun PLLA and sc‐PLA nanofibers by proteinase K from Tritirachium album was carried out. The rate of degradation of the nanofibers can be controlled by varying annealing conditions, hence the extent of crystallinity.

     

One‐Step Synthesis of Hybrid Composites of Poly(6‐hexanelactam) Combining Solid Tribological Additives and Reinforcing Components

Four types of composites of polyamide 6 with hybrid tribological additives were synthesized via anionic adiabatic “in situ” polymerization of 6‐hexanelactam (ε‐caprolactam) initiated with metallic sodium and activated with cyclic trimer of phenyl isocyanate or diphenylmethane 4,4′‐diisocyanate. The optimization of the initiator/activator systems in the range of 0.3 to 1.2 mol‐% and of the initial polymerization temperatures from 125 to 150 °C preceded the composite preparation. Combinations of fillers and their maximum applied concentrations (in wt.‐%) were the following: MoS₂/graphite/oil (5/16/9), carbon fibers/graphite/oil (5/20/10), copper phthalocyanine (7), and B₂O₃ (11). Analysis of selected composites encompassed water extraction, DSC, and DMTA measurements. All tested fillers decreased the polymerization rate, polymer yield, melting temperature and crystalline fraction. Polymerization rate constants of the neat polyamide 6 obtained for various initial temperatures obeyed the Arrhenius plot giving an average activation energy value of 78.6 kJ · mol^?1.

Rate of polymerization as a function of the total fillers content in adiabatic anionic polymerization of 6‐hexanelactam (A: MoS₂ + G/O, Na/PIC, B: CPC, Na/MDI, C: MoS₂ + G/O, Na/MDI, D: CF + G/O Na/MDI).     

Effect of High‐Energy Vibromilling on Interfacial Interaction and Mechanical Properties of PVC/Nano‐CaCO3 Composites

Summary: The effects of interfacial interaction between nano‐CaCO₃ and PVC on mechanical properties and morphology of PVC/nano‐CaCO₃ composites were studied. Nano‐CaCO₃ was treated with vibromilling in the presence of PVC and coupling agents. The mechanical properties of PVC/treated nano‐CaCO₃ are remarkably improved. Transmission electron microscopy results revealed that vibromilled nano‐CaCO₃ particles are well dispersed in PVC matrix with good homogeneity and well adhered to PVC matrix. Molau test indicated that chemical reaction between newly formed surface of nano‐CaCO₃ and PVC or coupling agent took place. Theoretical calculation results show that the interfacial interaction between PVC and nano‐CaCO₃ are substantially improved through vibromilling treatment of nano‐CaCO₃ in the presence of PVC and coupling agent.

Molau test results of the samples in THF.     

Improvement of Flexural Strengths of Poly(L‐lactic acid) by Solid‐State Extrusion, 2. Extrusion Through Rectangular Die

Solid‐state extrusion of poly (L ‐lactic acid) (PLLA) through rectangular die was performed to produce high flexural strength plates that can be used as internal fixation devices. A single‐angle wedge‐shaped rectangular die was utilized having the die exit dimension of 4 mm × 1 mm. Billets were machined out from vacuum compression molded PLLA having different crystallinities to have various thicknesses and thus various imposed draw ratios. Solid‐state extrusion of billets was performed at various drawing rates at 130 °C, above glass transition and below melting temperature. Extruded plates had the width and thickness smaller than the die due to the further drawing outside the die. The decrease in width was larger than the decrease in thickness, and this became more prominent with increasing draw ratio and drawing rate, resulting in a significantly smaller aspect ratio. Contributions of die drawing and further drawing outside the die were estimated from the extruded plate dimensions, by which the drawing rate effect was attributed to the further drawing outside the die. As actual draw ratio increased, crystallinity, melting temperature, crystalline orientation factor, and birefringence increased. Throughout the whole process the decrease in molecular weight was largely suppressed to be about 10%. As billet crystallinity, draw ratio, and drawing rate increased, both flexural strength and flexural modulus increased up to the maxima of 202 MPa and 9.7 GPa, respectively. This enhancement in mechanical properties was correlated with structural developments.

Changes in flexural strength of solid‐state extruded PLLA plates as a function of draw ratio (the effect of drawing rate is co‐plotted by hollow symbols at corresponding draw ratio.).     

High Temperature Thermosets With a Low Coefficient of Thermal Expansion

Summary: Polymeric thermosetting composites can be used as metal substitutes for certain applications if they possess high temperature stability in air, low coefficient of thermal expansion (CTE), and sufficient flexural strength, in combination with competitive costs. Commercial bismaleimide, bisnadimide, and cyanate ester thermosetting materials were selected due to their excellent thermal stability. Low CTEs were achieved by adding high loading levels of fused silica or silicon nitride fillers. Several optimized composites were fabricated by varying the materials, composition, and cure conditions. Characteristic composite properties, such as CTE, thermal stability, glass transition temperature (T_g), flexural strength, and filler distribution were investigated. The best system developed consists of Matrimide 5292, a commercial two‐component bismaleimide resin, filled with 75% Silbond FW100EST, and additionally reinforced with 0.5% Twaron short fibers. This composite is distinguished by a CTE around 15 ppm · K⁻¹, a T_g around 340 °C, flexural strength above 100 MPa, and attractive material costs.

Matrimid 5292 (75%)/Silbond FW100AST (24.5%), and Twaron 2 mm short fibers (0.5%). Three fibers are visible, embedded and well dispersed in the matrix.     

Photodegradation of Poly(L‐lactic acid): Effects of Photosensitizer

Summary: Amorphous and crystallized poly(L ‐lactic acid) (PLLA‐A and PLLA‐C, respectively) films with different contents of N,N,N′,N′‐tetramethyl‐1,4‐phenylenediamine (TMPD) as a photosensitizer were prepared, and the effects of the addition of TMPD on the photodegradation of PLLA films were investigated. It was found that the addition of TMPD effectively enhanced the photodegradation of PLLA films and thereby decreased their molecular weight of PLLA films regardless of their crystallinity, and that PLLA films with different molecular weights can be prepared by the addition of different amounts of TMPD and subsequent UV irradiation. Too high contents of TMPD however caused the brittleness of PLLA films due to a large decrease in molecular weight. The PLLA chains in crystalline regions as well as those in amorphous regions are photodegradable even at an early stage, in marked contrast to their hydrolytic degradation, where the chains in the amorphous regions are selectively degraded. The basic changes in glass transition, cold crystallization, and melting temperatures (T_g, T_cc, and T_m, respectively) of PLLA films during UV irradiation can be ascribed to low‐temperature annealing effects; i.e., annealing‐induced stabilization in chain packing should have elevated T_g, and annealing‐induced formation of crystallite nuclei should have lowered T_cc and increased T_m. The exceptional large decreases in T_cc and T_m of UV‐irradiated PLLA‐A films and in T_g of UV‐irradiated PLLA‐C films at high TMPD contents are attributable to the large decrease in molecular weight, whereas the exceptional decrease in T_m of PLLA‐C films at high TMPD contents can be due to the folding surface structural change of crystalline regions or to the lattice disorder caused by molecular structural changes.

of PLLA‐A films before UV irradiation and after UV irradiation for 60 h as a function of TMPD content.     

Structure and Properties of Cellulose Films Reinforced by Chitin Whiskers

Cytocompatible nanocomposite films are prepared by blending α‐chitin whiskers and cellulose solution in NaOH/urea. Structure and properties of the chitin/cellulose composite films are characterized by FT‐IR, XRD, ¹³C NMR, SEM, UV‐Vis, TGA, and tensile tests. The results reveal that the chitin whiskers are dispersed homogeneously, leading to good miscibility and properties of the chitin/cellulose composite films. By varying the chitin whisker content, the tensile strength and elastic modulus of the films can be controlled. HeLa and T293 cells are seeded onto the surfaces of the nanocomposite films, showing that the composite films were nontoxic to both cell types and that the addition of chitin whiskers promotes cell adhesion and proliferation.

     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

Non‐Isothermal Crystallization Behavior of Poly(L‐lactic acid) in the Presence of Various Additives

Summary: The effects of various additives: poly(D ‐lactic acid) (PDLA), talc, fullerene C₆₀, montmorillonite, and various polysaccharides, on the non‐isothermal crystallization behavior of poly(L ‐lactic acid) (PLLA), during both the heating of melt‐quenched films from room temperature, and the cooling of as‐cast films from the melt, was investigated. When the melt‐quenched PLLA films were heated from room temperature, the overall PLLA crystallization was accelerated upon addition of PDLA or the stereocomplex crystallites formed between PDLA and PLLA, the mixtures containing PDLA, and the mixture of talc and montmorillonite. No significant effects on the overall PLLA crystallization were observed for talc, C₆₀, montmorillonite, and the mixtures containing C₆₀. Such rapid completion of the overall PLLA crystallization upon addition of the aforementioned additives can be ascribed to the increased density (number per unit volume or area) of PLLA spherulites. When the as‐cast PLLA films were cooled from the melt, the overall PLLA crystallization completed rapidly, upon addition of PDLA, talc, C₆₀, montmorillonite, and their mixtures. Such rapid overall PLLA crystallization is attributable to the increased density of the PLLA spherulites and the higher nucleation temperature for PLLA crystallization. In contrast, the addition of various polysaccharides has no significant effect, or only a very small effect, on the overall PLLA crystallization during heating from room temperature or during cooling from the melt. This finding means that the polysaccharides can be utilized as low‐cost fillers for PLLA‐based materials, without disturbing the crystallization of the PLLA. The effect of additives in accelerating the overall PLLA crystallization during cooling from the melt, decreased in the following order: PDLA > talc > C₆₀ > montmorillonite > polysaccharides.

Polarization optical photomicrographs of pure PLLA, and the PLLA‐F film, with the fullerene additive, during cooling from the melt (Process IIB). Both of the photomicrographs were taken at 120 °C.     

Poly(lactic acid)/Aluminum Oxide Composites Fabricated by Sol‐Gel and Melt Compounding Processes

Aluminum‐oxide‐coated PLA pellets, particles derived from aluminum oxide sol‐gel, and calcinated α‐Al₂O₃ powders were used to fabricate PLA/AlO_x composites. The formation of aluminum oxide was confirmed by FTIR and EDS. SEM images suggested the melt compounding system provided a fairly homogeneous dispersion of AlO_x particles in the PLA matrix. XRD analysis showed PLA and PLA/AlO_x composites were both amorphous. The incorporation of AlO_x particles did not alter the melting temperature of PLA. However, the shape and intensity of the melting endotherms was significantly changed, suggesting bimodal melting behavior. UV‐Vis transmission spectra suggested that PLA/AlO_x composites may act as a better UV barrier than neat PLA.

     

Nylon 6‐Polyesteramide Block Copolymers (NBC) and NBC/Phenolic Resin Composites, 1

Summary: A series of NBC/phenolic resin composites, containing 0, 1, 3, 5 or 7 wt.‐% of a powdered phenolic resin of different particle diameter, was prepared by the reaction injection molding (RIM) process. It was determined by SEM analysis that there exists a strong interaction between particles and matrix and that such interaction occurs through hydrogen‐type bonds as determined by FTIR analysis. According to the results it is thought that the glass transition temperature of the NBC/phenolic resin composites depends on two competing factors: the rigidity promoted by the hard solid filler and the flexibility imparted by the nylon 6 amorphous phase, whose proportion becomes more important with increasing amounts of phenolic resin particles. The elastic and flexural moduli of the NBC were improved by the addition of phenolic resin confirming the reinforcing effect of this filler. On the contrary, the impact strength diminishes with increasing amounts of phenolic resin, although this property is strongly dependent on the particle diameter.

SEM micrograph of the nylon 6‐polyesteramide block copolymer (80/20).     

Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

Colloidal Crystalline Arrays of β‐Polymorphic Poly(vinylidene fluoride)

Stable layers of nearly monodisperse spheres of β‐polymorphic poly(vinylidene fluoride) with iridescent properties are prepared. The colloidal crystalline arrays (CCAs) were characterized by optical microscopy, differential scanning calorimetry (DSC), and FT‐IR spectroscopy. FT‐IR spectroscopic and wide‐angle X‐ray scattering (WAXS) studies revealed a β‐polymorphic PVF₂ structure, the DSC study showed that the level of crystallinity in the CCA was much higher than that in the melt‐crystallized sample, and UV‐visible spectroscopy showed extinction peaks at 323 and 510 nm in the CCAs. The β‐polymorphic PVF₂ structure, along with the optical extinction properties of these CCAs, raises the prospect of their application in optical filters and/or piezoelectric sensors.

Optical micrograph of PVF₂ CCA films cast on glass substrates.     

Polyglycolide as a Biodegradable Nucleating Agent for Poly(L‐lactide)

DSC indicated that the nucleation of PLLA is enhanced in the presence of PGA even at a PGA content as low as 0.1 wt.‐%. However, the enhancing behavior of PGA was different to that of other nucleating agents for PLLA. Polarized optical microscopy revealed that the presence of PGA increased the number of PLLA spherulites per unit area. WAXD showed that in the PLLA/PGA films, PLLA and PGA crystallize separately to form their respective crystallites and PGA crystallites were formed at a PGA content at above 3 wt.‐% (at least). FTIR spectroscopy indicated that that there are significant interactions between PLLA and PGA chains in amorphous regions. Such interactions should have enhanced the growth of PLLA crystallites from the surface of PGA crystallites.

     

Effect of Maleated Compatibilizer on Performance of PLA/Wheat Straw‐Based Green Composites

In this study, the use of PLA‐g‐MA is investigated as a potential method for improving interfacial adhesion between agricultural residues and PLA, with the goal of enhancing mechanical properties. Compatibilization was achieved by using PLA‐g‐MA prepared via reactive extrusion. Green renewable and compatibilized PLA/wheat straw composites were extruded and injection‐molded. Addition of 3 and 5 phr PLA‐g‐MA to the composites resulted in significant improvements in tensile strength (20%) and flexural strength (14%) of the composites, matching that of the neat polymer. The observed improvement in strength was attributed to the good interfacial adhesion between the fiber and matrix.

     

Segmented Block Copolymers with Monodisperse Hard Segments: The Influence of H‐Bonding on Various Properties

The properties of segmented‐copolymer‐based H‐bonding and non‐H‐bonding crystallisable segments and poly(tetramethylene oxide) segments were studied. The crystallisable segments were monodisperse in length and the non‐hydrogen‐bonding segments were made of tetraamidepiperazineterephthalamide (TPTPT). The polymers were characterised by DSC, FT‐IR, SAXS and DMTA. The mechanical properties were studied by tensile, compression set and tensile set measurements. The TPTPT segmented copolymers displayed low glass transition temperatures (T_g, ?70 °C), good low‐temperature properties, moderate moduli (G′ ≈ 10–33 MPa) and high melting temperatures (185–220 °C). However, as compared to H‐bonded segments, both the modulus and the yield stress were relatively low.