Phase Structure of Compatibilized Poly(Lactic Acid)/Linear Low-Density Polyethylene Blends

Blends of PLA and linear low-density polyethylene (LLDPE) were compatibilized with glycidyl methacrylate (GMA)–grafted poly(ethylene-octene) copolymer (mPOE). Effects of compatilizer on phase structure of compatibilized PLA/LLDPE were studied by spreading coefficient calculation prediction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD) analysis. The spreading coefficient calculations, based on experimental and calculated surface tension data, show that mPOE spreads on LLDPE extensively to encapsulate LLDPE completely, which is in good agreement with the results of DSC, SEM, and WAXD analysis. The chemical reaction between the end carboxyl groups or end hydroxyl groups of PLA and epoxy groups of mPOE, which is suggested as the driving force leading to an ideal interfacial adhesion between PLA and the dispersed phase, was confirmed by Fourier transform infrared ray (FT-IR) spectroscopy analysis.     

On Localization of Clay Nanoparticles in Polypropylene/poly(Lactic Acid) Blend Nanocomposites: Correlation with Mechanical Properties

Two polypropylene (PP)/polylactide (PLA)/clay ternary nanocomposite systems, i.e. PP-rich and PLA-rich ones, each containing various amounts of one of two types of clay, were prepared by one step melt compounding in a twin screw extruder. The microstructures of the developed systems were correlated with tensile and impact properties. A theoretical calculation using wetting coefficients was used for predicting the clay nanoparticles localization in the blends. The nanoparticles were almost completely located within the PLA phase in both the PP-rich and PLA-rich systems, in good agreement with the predictions. Addition of a compatibilizer led to localization of the nanoparticles at the interfaces of the blends. From the wide angle X-ray scattering (WAXS) spectra it was concluded that the incorporation of clay led to intercalated structures in the both systems. The increase in impact toughness of the compatibilized blend nanocomposites, with respect to the uncompatibilized ones, was attributed to the weakened interfacial debonding in the presence of the interfacial-localized nanoparticles.     

Melting and Crystallization Behaviors of Poly(Lactic Acid) Modified with Graphene Acting as a Nucleating Agent

Graphene (GN)-filled polylactic acid (PLA) nanocomposites were prepared through a solution blending method with GN weight percent ranging from 0.5 to 2?wt%. Rheological, melting and crystallization behaviors of the prepared PLA/GN nanocomposites were investigated by means of dynamic rheological measurements and differential scanning calorimetry (DSC). The shear viscosities of the PLA/GN nanocomposites decreased with increasing GN content, which was remarkably different from previous reports on the modifications using traditional nanofillers (e.g., clay, carbon nanotubes, etc.). The nonisothermal melt crystallization kinetic analysis suggested that GN served as a nucleating agent and could considerably promote the PLA’s crystallization through heterogeneous nucleation. Our findings suggested that at relatively low cooling rates (??≤?10?°C/min) even a small amount of GN promoted the nucleation and considerably increased the crystallization rate. However, the crystallinity began to decrease at higher cooling rates (e.g., ??≥?20?°C/min), especially when the GN content was high (e.g., 2?wt%), possibly owing to the GN aggregation effect considering PLA is a slowly crystallizing polymer.     

Improving the Barrier Properties of Poly(Lactic Acid) by Blending with Poly(Ethylene-Co-Vinyl Alcohol)

Poly(lactic acid) (PLA)/poly(ethylene-co-vinyl alcohol) (EVOH) blends were prepared via melt blending to improve the barrier properties of PLA. The phase morphologies and final properties (rheological behavior, thermal and dynamical-mechanical features, barrier properties, and mechanical behaviors) of the blends were investigated as a function of the EVOH content. The results indicated that hydroxyl groups of EVOH promoted the degradation of PLA, and thus affected the viscosities and morphologies of the resulting blends. The intrinsic viscosities of PLA in the blends decreased with the content of EVOH. The PLA and EVOH presented typical phase-separated morphologies, with a relatively small domain size of the EVOH phase. The EVOH enhanced the cold-crystallization behavior of PLA. The barrier properties to water vapor and oxygen increased linearly with increasing EVOH content.     

Compatibilization of Poly(Trimethylene Terephthalate)/Polycarbonate Blends by Epoxy. Part 2. Melting Behavior and Spherulite Morphology

The melting behaviors of poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends, compatibilized by epoxy, and PTT spherulite morphology in the blends were investigated. When epoxy was present during blending, the melting behaviors of PTT/PC blends changed substantially; glass transition temperatures (T_g's) and cold crystallization temperature (T_cc's) of the PTT‐rich phase shifted to higher temperatures, while T_m's shifted slightly to lower temperatures, indicating that epoxy suppressed considerably all processes of dynamic movements pertinent to molecular (or segmental) movements. The cold crystallization process responded sensitively to thermal history. Changes of T_cc's with composition suggested that the epoxy's compatibilization effect was pronounced when PTT and PC were in near equal content.

Recrystallization or reorganization exotherms appeared before melting for isothermally crystallized PTT/PC and PTT/PC epoxy (E) blends. A wide angle X‐ray diffraction (WAXD) analysis showed that, although the perfection of PTT crystallites was influenced either by PC content and the presence of compatibilizer or by the crystallization temperature and crystallization time, PTT's crystal structure was independent of these variables.

The polarized light microscopy (PLM) observations showed that PTT spherulite morphology was very sensitive to blend composition. Epoxy addition interfered severely with the growth of PTT spherulites, causing them to be much less developed. When the spherulites grew under a condition of varied composition, they would exhibit diversified spherulite morphology, though in one spherulite.     

Reactive Compatibilization of Poly(Butylene Terephthalate)/Acrylonitrile-Styrene-Acrylate Blends by Epoxy Resin: Morphology and Mechanical Properties

The effect on the notched Izod impact strength of poly(butylene terephthalate) (PBT) by blending it with acrylonitrile-styrene-acrylate (ASA) was examined. Epoxy resin (ER) was demonstrated to be an efficient compatibilizer for the partially compatible blends of PBT/ASA. It requires only a very small amount of ER to improve the toughness of the PBT/ASA blends drastically. Furthermore, there exists an optimum proportion of ER added to achieve maximum notched Izod impact strength. Transmission electron microscopy (TEM) observation suggests that the ER in the PBT/ASA/ER blends suppressing the tendency of coalescence of ASA, leading to better dispersion of the ASA particles. Field emission scanning electron microscopy (FESEM) shows that ER enhances the phase dispersion and the interfacial adhesion between the PBT and ASA phases, it improves the compatibility between PBT and ASA. The compositions in the interphase was continuous, which results in multiphase composites with a graded interphase. It is suggested that enhanced interphase adhesion was necessary to obtain improved dispersion, fine phase morphology, and better toughness.     

Properties and Morphology of Poly(Lactic Acid)/Calcium Carbonate Whiskers Composites Prepared by a Vane Mixer based on an Extensional Flow Field

Binary composites of poly(lactic acid) (PLA)/calcium carbonate whiskers (CCW) with different weight fractions were prepared with a vane mixer based on extensional rheology. The mechanical properties, thermostability, crystallization behavior, rheology behaviors and micromorphology of the composites were analysed to study the effect of the CCW fibers on the composite's properties; a pure PLA sample was also prepared for comparison. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) revealed that the CCW fibers had excellent compatibility with the PLA matrix and the CCW fibers were dispersed and distributed evenly in the PLA matrix under the action of the extensional flow field produced by the vane mixer. Differential scanning calorimetric (DSC) analysis showed that introducing a vane mixer into the PLA processing could increase the degree of crystallization (χ_c) of the composites significantly, and moderate CCW fibers adding could further increase its χ_c value. Thermogravimetric analysis (TGA) revealed that adding the CCW fibers reduced the thermostability of the composites. The G′, G″, η* and the torque, T_N, of the composites, obtained from rheology analyses, declined obviously, because of the hydrolysis and chains scission induced by residual water and fatty acid when the CCW content less than 4%. Tensile tests proved that filling moderate amounts of CCW fibers into PLA could increase its tensile strength and strain at break, increasing by 5% and 29.6%, respectively.     

Mechanical and Thermal Properties Enhancement of Poly(Lactic Acid)/Halloysite Nanocomposites by Maleic-Anhydride Functionalized Rubber

Poly(lactic acid) (PLA)/halloysite composites were prepared using melt compounding followed by compression molding. Maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) was used to toughen the PLA composites. The mechanical properties of the PLA composites were studied through tensile, flexural, and impact tests. The thermal properties were characterized by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The fracture surfaces of the composites were assessed by using field emission scanning electron microscopy (FESEM). The impact strength and thermal properties of the PLA/halloysite composites were increased by addition of SEBS-g-MAH.     

Assessment of Compatibility in Polypropylene/Poly(lactic acid)/Ethylene Vinyl Alcohol Ternary Blends: Relating Experiments and Molecular Dynamics Simulation Results

Two systems of polypropylene (PP), poly(lactic acid) (PLA) and ethylene vinyl alcohol copolymer (EVOH) ternary blends having different compositions were extruded in a co-rotating twin screw extruder. The first system was PP/PLA (75/25) with various EVOH contents, the second one was PP/EVOH (75/25) having various PLA contents. The effects of composition on the morphology and the tensile and impact properties of the blends were investigated. There were increases in the tensile modulus and tensile strength with an increase in the EVOH and PLA contents in the first and second systems, respectively. A molecular dynamics (MD) simulation was used to investigate the compatibility between the components. Prediction of the miscibility of the blends was carried out by determining the interaction parameters (χ), mixing energies (ΔH_mix), phase diagrams and Gibbs free energies. The MD simulation showed a UCST behavior for the components. Moreover, the simulation results showed a compatibilizer effect for the EVOH component. The experimental values of the dynamic mechanical thermal analysis (DMTA) and mechanical properties were correlated to the MD results. There was a good correlation between the MD and DMTA results. The modulus values using the parallel and Davis models were near to the experimental ones. A good fitting to the mixture law with addition of EVOH confirmed a good compatibilzing effect of it between the PP and PLA components.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.