Poly (lactic acid) blends: Processing, properties and applications.

Poly (lactic acid) or polylactide (PLA) is a commercial biobased, biodegradable, biocompatible, compostable and non-toxic polymer that has competitive material and processing costs and desirable mechanical properties. Thereby, it can be considered favorably for biomedical applications and as the most promising substitute for petroleum-based polymers in a wide range of commodity and engineering applications. However, PLA has some significant shortcomings such as low melt strength, slow crystallization rate, poor processability, high brittleness, low toughness, and low service temperature, which limit its applications. To overcome these limitations, blending PLA with other polymers is an inexpensive approach that could also tailor the final properties of PLA-based products. During the last two decades, researchers investigated the synthesis, processing, properties, and development of various PLA-based blend systems including miscible blends of poly l-lactide (PLLA) and poly d-lactide (PDLA), which generate stereocomplex crystals, binary immiscible/miscible blends of PLA with other thermoplastics, multifunctional ternary blends using a third polymer or fillers such as nanoparticles, as well as PLA-based blend foam systems. This article reviews all these investigations and compares the syntheses/processing-morphology-properties interrelationships in PLA-based blends developed so far for various applications.

Influence of Nanoparticle Pretreatment on the Thermal, Rheological and Mechanical Properties of PLA-PBSA Nanocomposites Incorporating Cellulose Nanocrystals or Montmorillonite.

Nanoparticles based on cellulose nanocrystals (CNC) and montmorillonite clay (MMT) were prepared using spray freeze-drying. The nanoparticles were then used as reinforcement to prepare nanocomposites with poly(lactic acid) (PLA) as the polymer matrix. The effect of spray freeze-dried CNC (SFD-CNC) and spray freeze-dried MMT (SFD-MMT) on the rheological and mechanical properties of PLA and its blends with poly[(butylene succinate)-co-adipate)] (PBSA) were investigated. An epoxy chain extender was used during preparation of the blends and nanocomposites to enhance the mechanical properties of the products. Different methods such as scanning electron microscopy, X-ray diffraction and adsorption/desorption analyses were used to characterize the prepared nanoparticles and their localization in the blends. Dynamic oscillatory shear behavior, elongational viscosity and mechanical characteristics of the nanocomposites of PLA and the blends were evaluated. The results obtained for nanocomposites filled with unmodified SFD-MMT were compared with those obtained when the filler was a commercial organically modified montmorillonite nanoclay (methyl-tallow-bis(2-hydroxyeethyl) quaternary ammonium chloride) (C30B), which was not spray freeze-dried.

Effect of Hybrid Carbon Fillers on the Electrical and Morphological Properties of Polystyrene Nanocomposites in Microinjection Molding.

The effect of hybrid carbon fillers of multi-walled carbon nanotubes (CNT) and carbon black (CB) on the electrical and morphological properties of polystyrene (PS) nanocomposites were systematically investigated in microinjection molding (µIM). The polymer nanocomposites with three different filler concentrations (i.e., 3, 5 and 10 wt %) at various weight ratios of CNT/CB (100/0, 30/70, 50/50, 70/30, 0/100) were prepared by melt blending, then followed by µIM under a defined set of processing conditions. A rectangular mold insert which has three consecutive zones with decreasing thickness along the flow direction was adopted to study abrupt changes in mold geometry on the properties of resultant microparts. The distribution of carbon fillers within microparts was observed by scanning electron microscopy, which was correlated with electrical conductivity measurements. Results indicated that there is a flow-induced orientation of incorporated carbon fillers and this orientation increased with increasing shearing effect along the flow direction. High structure CB is found to be more effective than CNT in terms of enhancing the electrical conductivity, which was attributed to the good dispersion of CB in PS and their ability to form conductive networks via self-assembly. Morphology observations indicated that there is a shear-induced depletion of CB particles in the shear layer, which is due to the marked difference of shear rates between the shear and core layers of the molded microparts. Moreover, an annealing treatment is beneficial to enhance the electrical conductivity of CNT-containing microparts.

Effect of cellulose nanocrystals (CNC) on rheological and mechanical properties and crystallization behavior of PLA/CNC nanocomposites.

In earlier work, we reported that spray freeze drying of cellulose nanocrystals (CNC) yields porous agglomerate structures. On the other hand, the conventional spray dried CNC (CNCSD) and the freeze dried CNC (CNCFD) produce compact solid structures with very low porosity. As it is rather difficult to obtain direct microscopic evidence of the quality of dispersion of CNC in polymer nanocomposites, it was shown that supporting evidence of the quality and influence of dispersion in a polypropylene (PP)/CNC nanocomposite could be obtained by studying the rheological behavior, mechanical properties and crystallization characteristics of PP/CNC nanocomposites. In an effort to produce a sustainable, fully biosourced, biodegradable nanocomposite, this manuscript presents the results of a study of the rheological, mechanical and crystallization behavior of PLA/CNCSFD nanocomposites obtained by melt processing. The results are analyzed to determine CNC network formation, rheological percolation threshold concentrations, mechanical properties in the rubbery and glassy states, and the effect of CNCSFD on crystalline nucleation and crystallization rates of PLA. These results suggest that the porosity and network structure of CNCSFD agglomerates contribute significantly to good dispersion of CNC in the PLA matrix.

Effect of cellulose nanocrystals (CNC) particle morphology on dispersion and rheological and mechanical properties of polypropylene/CNC nanocomposites.

Polypropylene (PP) nanocomposites containing spray-dried cellulose nanocrystals (CNC), freeze-dried CNC, and spray-freeze-dried CNC (CNCSFD) were prepared via melt mixing in an internal batch mixer. Polarized light, scanning electron, and atomic force microscopy showed significantly better dispersion of CNCSFD in PP/CNC nanocomposites compared with the spray-dried and freeze-dried CNCs. Rheological measurements, including linear and nonlinear viscoelastic tests, were performed on PP/CNC samples. The microscopy results were supported by small-amplitude oscillatory shear tests, which showed substantial rises in the magnitudes of key rheological parameters of PP samples containing CNCSFD. Steady-shear results revealed a strong shear thinning behavior of PP samples containing CNCSFD. Moreover, PP melts containing CNCSFD exhibited a yield stress. The magnitude of the yield stress and the degree of shear thinning behavior increased with CNCSFD concentration. It was found that CNCSFD agglomerates with a weblike structure were more effective in modifying the rheological properties. This effect was attributed to better dispersion of the agglomerates with the weblike structure. Dynamic mechanical analysis showed considerable improvement in the modulus of samples containing CNCSFD agglomerates. The percolation mechanical model with modified volume percolation threshold and filler network strength values and the Halpin-Kardos model were used to fit the experimental results.

Mechanical and barrier properties of nanocrystalline cellulose reinforced chitosan based nanocomposite films.

Nanocrystalline cellulose (NCC) reinforced chitosan-based biodegradable films were prepared by solution casting. The NCC content in the films was varied from 1 to 10% (dry wt. basis). It was found that the tensile strength (TS) of the nanocomposite films with 5% (w/w) NCC content was optimum with an improvement of 26% compared to the control chitosan films. Incorporation of NCC also significantly improved barrier properties. Water vapor permeability (WVP) of the chitosan/NCC films was decreased by 27% for the optimum 5% (w/w) NCC content. Swelling studies revealed a decrease in water uptake of the NCC-reinforced chitosan films. Analyses of thermal properties showed no significant effect of NCC whereas X-ray diffraction studies confirmed the appearance of crystalline peaks in the nanocomposite films. Surface morphology of the films was investigated by scanning electron microscopy and it was found that NCC was dispersed homogenously into chitosan matrix.

Nanocrystalline cellulose (NCC) reinforced alginate based biodegradable nanocomposite film.

Nanocrystalline cellulose (NCC) reinforced alginate-based nanocomposite film was prepared by solution casting. The NCC content in the matrix was varied from 1 to 8% ((w/w) % dry matrix). It was found that the nanocomposite reinforced with 5 wt% NCC content exhibits the highest tensile strength which was increased by 37% compared to the control. Incorporation of NCC also significantly improved water vapor permeability (WVP) of the nanocomposite showing a 31% decrease due to 5 wt% NCC loading. Molecular interactions between alginate and NCC were supported by Fourier Transform Infrared Spectroscopy. The X-ray diffraction studies also confirmed the appearance of crystalline peaks due to the presence of NCC inside the films. Thermal stability of alginate-based nanocomposite films was improved after incorporation of NCC.

Production and properties of nanocellulose-reinforced methylcellulose-based biodegradable films.

Methylcellulose (MC)-based films were prepared by casting from its 1% aqueous solution containing 0.5% vegetable oil, 0.25% glycerol, and 0.025% Tween 80. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient, and water vapor permeability (WVP) were found to be 147 N/mm, 3.46 mm, 41%, and 6.34 g.mm/m(2).day.kPa, respectively. Aqueous nanocellulose (NC) solution (0.1-1%) was incorporated into the MC-based formulation, and it was found that PS was improved (117%) and WVP was decreased (26%) significantly. Films containing 0.25% NC were found to be the optimum. Then films were exposed to gamma radiation (0.5-50 kGy), and it was revealed that mechanical properties of the films were slightly decreased after irradiation, whereas barrier properties were further improved with a decrease of WVP to 28.8% at 50 kGy. Molecular interactions due to incorporation of NC were supported by FTIR spectroscopy. Thermal properties of the NC-containing films were improved, confirmed by TGA and DSC. Crystalline peaks appeared due to NC addition, found by XRD. Micrographs of films containing NC were investigated by SEM.