New polylactide/layered silicate nanocomposites. 5. Designing of materials with desired properties

Understanding the structure/property relationship in polymer/layered silicate nanocomposites is of great importance in designing materials with desired properties. In order to understand these relations, a series of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites have been prepared using a simple melt extrusion technique. Four different types of OMLS have been used for the preparation of nanocomposites, three were modified with functionalized ammonium salts while fourth one was a phosphonium salt modified OMLS. The structure of the nanocomposites in the nanometer scale was characterized by using wide-angle X-ray diffraction and transmission electron microscopic observations. Using four different types of layered silicates modified with four different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, thermal properties and spherulite morphology, materials properties, and biodegradability. Finally, we draw conclusions about the structure/property relationship in the case of PLA/OMLS nanocomposites.     

Enhanced thermal stability of poly(lactide)s in the melt by enantiomeric polymer blending

Poly(l-lactide) (i.e. poly(l-lactic acid) (PLLA)) and poly(d-lactide) (i.e. poly(d-lactic acid) (PDLA)) and their equimolar enantiomeric blend (PLLA/PDLA) films were prepared and the effects of enantiomeric polymer blending on the thermal stability and degradation of the films were investigated isothermally and non-isothermally under nitrogen gas using thermogravimetry (TG). The enantiomeric polymer blending was found to successfully enhance the thermal stability of the PLLA/PDLA film compared with those of the pure PLLA and PDLA films. The activation energies for thermal degradation (ΔE_td) were evaluated at different weight loss values from TG data using the procedure recommended by MacCallum et al. The ΔE_td values of the PLLA/PDLA, PLLA, and PDLA films were in the range of 205-297, 77-132, and 155-242 kJ mol⁻¹ when they were evaluated at weight loss values of 25-90% and the ΔE_td value of the PLLA/PDLA film was higher by 82-110 kJ mol⁻¹ than the averaged ΔE_td value of the PLLA and PDLA films. The mechanism for the enhanced thermal stability of the PLLA/PDLA film is discussed.     

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.     

Grafting polymerization of l-lactide on the surface of hydroxyapatite nano-crystals

A novel method of grafting ring-opening polymerization of l-lactide (LLA) onto the surface of hydroxyapatite nano-particles (n-HAP) was developed. PLLA was directly connected onto the HAP surface through a chemical linkage. The PLLA-g-HAP particles could be stably dispersed in organic solvent such as chloroform for several weeks. The n-HAP particles still retained the original dimension and shape after the grafting of PLLA. Compared with the ³¹P MAS-NMR spectrum of pure HAP powders, there appeared a downfield displacement of 1.2 ppm in the spectrum of PLLA-g-HAP. Fourier transformation infrared (FT-IR) spectra further confirmed the existence of PLLA on the surface of PLLA-g-HAP. The amount of grafted polymer determined by thermal gravimetric analysis (TGA) was about 6% in weight. The tensile strength and elongation at break of the PLLA/PLLA-g-HAP composite containing 8 wt% of PLLA-g-HAP were 55 MPa and about 10-13%, respectively, while those of the PLLA/n-HAP composites were 40 MPa and 3-5%, respectively.     

Miscibility and properties of linear poly(l-lactide)/branched poly(l-lactide) copolyester blends

Polymer blends consisting of linear poly(l-lactide) (PLLA) and different proportions of dendritic PLLA-based copolyesters (hb-PLLA) characterized by different degrees of branching (DB) were obtained in melt. The solid-state properties of poly(l-lactide)s and their blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), atomic force microscopy (AFM) and stress-strain measurements. DSC and DMA methods proved miscibility of PLLA/hb-PLLA blends for the studied composition range. AFM indicated that no phase separation occurs in PLLA/hb-PLLA blends and that PLLA and hb-PLLA cocrystallize in one single lamellae type. The mechanical characteristics of PLLA/hb-PLLA blends deteriorated with an increase of the DB and with changing blend composition. Susceptibility of the blends to biodegradation was studied by measuring the weight loss in two different biodegradation media. PLLA/hb-PLLA blends showed more pronounced hydrophilic character and higher susceptibility to biodegradation with an increase in the degree of branching.     

Poly (lactic acid) foaming

Poly (lactic acid) or polylactide (PLA) is an aliphatic thermoplastic polyester produced from renewable resources and is compostable in the environment. Because of the massive use of foamed products of petroleum-based polymers, PLA foams have been considered as substitutes for some of these products. Specifically, because of PLA's competitive material and processing costs, and its comparable mechanical properties, PLA foams could potentially replace polystyrene (PS) foam products in a wide array of applications such as packaging, cushioning, construction, thermal and sound insulation, and plastic utensils. Due to their biocompatibility, PLA foams can also be used in such biomedical applications as scaffolding and tissue engineering. But PLA has several inherent drawbacks, which inhibit the production of low-density foams with uniform cell morphology. These drawbacks are mainly the PLA's low melt strength and its slow crystallization kinetics. During the last two decades, researchers have investigated the fundamentals of PLA/gas mixtures, PLA foaming mechanisms, and the effects of material modification on PLA's foaming behavior through various manufacturing technologies. This article reviews these investigations and compares the developments made thus far in PLA foaming.     

Blends of amorphous and crystalline polylactides with poly(methyl methacrylate) and poly(methyl acrylate): a miscibility study

Blends of amorphous and crystalline polylactides (PDLA and PLLA) with poly(methyl methacrylate) (PMMA) and poly(methyl acrylate) (PMA) have been prepared. Thermal behaviour and miscibility of these blends along the entire composition interval were studied by differential scanning calorimetry (d.s.c.). The results were compared with those obtained by dynamic mechanical analysis (DMTA). Only one T_g was found in PDLA/PMA and PDLA/PMMA blends, indicating a high degree of miscibility in both systems. Nevertheless, the PDLA/PMMA blend presented enlargements of the T_g width at high PMMA contents. In this case, additional evidence of complete miscibility was obtained by studying the evolution of the enthalpic recovery peaks which appear after different thermal annealing treatments. When the polylactide used was semicrystalline (PLLA), once the thermal history of the blends had been destroyed, crystallization of PLLA was disturbed in both blends PLLA/PMMA and PLLA/PMA, but in a rather different fashion: in the first case crystallization was almost prevented while in the second one it was favoured. This behaviour was explained in terms of the effect of the higher stiffness as indicated by the value of T_g for PMMA compared to that for PMA.     

Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films

Plasticized poly(l-lactide) (PLA) montmorillonite layered silicate (MLS) nanocomposites were compounded and blown-film processed using a co-rotating twin screw extruder. PLA was mixed with 10 wt% acetyltriethyl citrate ester plasticizer and 5 wt% of an organically modified montmorillonite at various screw speeds. Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) determined that the compounded pellets and the blown film PLA/MLS nanocomposites were intercalated. The effect of processing screw speeds on the barrier, thermal, mechanical, and biodegradation properties of the nanocomposites were analyzed and compared to the neat polymer. Nanocomposite films show a 48% improvement in oxygen barrier and a 50% improvement in water vapor barrier in comparison to the neat PLA. The thermogravimetric analysis (TGA) showed an overall 9 °C increase in the decomposition temperature for all of the nanocomposites. Differential scanning calorimetry (DSC) has determined that the glass transition, cold crystallization and melting point temperatures were not significantly influenced by the presence of MLS. Mechanical properties of the nanocomposites showed that the Young's modulus increased by 20% and the ultimate elongation of the nanocomposites were not sacrificed in comparison to the neat samples. Biodegradation rates in soil were slightly greater for the PLA/MLS nanocomposite than the pure PLA. However, none of the PLA pure and nanocomposites achieved significant biodegradation levels after 180 days.     

Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes

Functionalized multiwalled carbon nanotubes (F-MWNTs) were prepared by covalent grafting of five-armed star polylactide (fa-PLA), and were characterized by thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR) spectroscopy and Raman spectroscopy. A series of polylactide (PLA)/F-MWNTs composites was prepared via coagulation method. Several techniques were applied to investigate the effects of F-MWNTs on the morphology, melt rheology, and crystallization and melting behaviors of the PLA composites. The optical microscope (OM), field-emission scanning electron microscope (FE-SEM) and transmission electron microscopy (TEM) observations demonstrated that, in comparison with the case of PLA filled with pristine MWNTs, F-MWNTs case showed improved dispersion and interfacial adhesion. Oscillatory frequency sweep measurements showed that addition of about 2.0 wt% F-MWNTs led to a solidlike response where a percolated network structure formed, and the composites exhibited remarkable improvement of rheological properties in the melt state as compared with that of neat PLA. DSC measurements showed that F-MWNTs acted as a nucleating agent to enhance crystallization when below the percolation concentration, while also acted as a hindrance to retard crystallization above the percolation concentration. The double melting peaks on the DSC curves were attributed to melting of the crystals formed in the cold crystallization stage and the melting-recrystallization-remelting (mrr) event during heating, respectively.     

Surprising shape-memory effect of polylactide resulted from toughening by polyamide elastomer

Melt blending of polylactide (PLA) and biodegradable polyamide elastomer (PAE) has been performed in an effort to toughen the PLA. DMA tests showed good compatibility between PAE and PLA blends, and the PAE were dispersed in PLA matrix uniformly shown in SEM photos. Mechanical properties of blends with different PAE concentrations were observed. With the PAE contents increasing, the elongation at break of blends increased and the brittle break became ductile break. When the PAE content is 10%, the tensile strength of blend is similar to neat PLA, and the elongation increased to 194.6% significantly. Remarkably, the blends showed wonderful shape-memory effect. PAE domains act as stress concentrators in system with the stress release locally and lead to energy-dissipation process. These will prevent PLA matrix from breaking under high deformation, and lead to the PLA molecular orientation. Consequently, the blends occurred to deformation upon tensile load, and heating up the material will reform the shape back to the original shape.