Starch/polylactide sustainable composites: Interface tailoring with graphene oxide

The high production cost of polylactide (PLA) can be effectively reduced by simply mixing with starch, unfortunately a trade-off of its mechanical properties. In this paper, we reported a new strategy in which graphene oxide (GO) was used as a compatibilizer to bridge PLA and starch. The native starch was first cationized and then encapsulated with GO by electrostatic force between the negatively charged GO and the positively charged cationic starch. The encapsulating GO was reduced by the quaternary ammonium ions on the cationic starch, which converted the surface of the starch from hydrophilic to hydrophobic. Due to the amphipathicity approximation between PLA and starch, a good dispersion as well as a strong interfacial adhesion was achieved. The PLA composite reinforced with GO encapsulated starch exhibited much higher yield strength than that of pure PLA, increasing from 36.64 MPa up to 41.40 MPa.     

Improvement on the properties of polylactic acid (PLA) using bamboo charcoal particles

Bamboo charcoal (BC) derived from bamboo plants is one kind of well recognized multi-functional materials which has been used in various applications such as medical, cosmetic, food processing and health-related products. In this paper, BC particle is used as reinforcement for polylactic acid (PLA) to enhance its mechanical, thermal and optical properties. The comparison on tensile, flexural and impact properties of BC particle reinforced PLA composites (BC/PLA composites) with the content ranging from 2.5 to 10 wt.% is conducted. Experimental results indicated that the maximum tensile strength, flexural strength and ductility index (DI) of BC/PLA composites increased by 43%, 99% and 52%, respectively as compared with those of neat PLA. This phenomenon was attributed to the uniform distribution of high aspect ratio and surface area of BC particles. Further increasing the BC content to 7.5 wt.% would decrease the glass transition temperature of BC/PLA composites. The mechanical properties of BC/PLA composites were reduced as compared with a neat PLA sample when they were exposed to compost degradation. However, less reduction in these properties was found when they were subject to UV irradiation. UV–Vis spectrometer analysis supported the results of UV irradiation. Fracture surfaces of tensile test samples with and without compost degradation or UV irradiation were analysed by using scanning electron microscopy (SEM). SEM images revealed that there was a good BC particle dispersion in the composites through extrusion and injection moulding processes if the particle content was below 7.5 wt.%.     

Polylactide (PLA)-clay nanocomposites prepared by melt compounding in the presence of a chain extender

Polylactide-layered silicate nanocomposites with and without a chain extender were prepared by melt mixing using a twin-screw extruder. An organo-modified clay, Cloisite® 30B, and a chain extender Joncryl®-ADR 4368F were employed in this study. The effect of the chain extender and processing conditions on the properties of the PLA-clay nanocomposites were investigated for different strategies of mixing. The resulting nanocomposites were characterized by X-ray diffraction (XRD), while their morphology was observed by SEM and TEM. The incorporation of the chain extender could enhance the degree of clay dispersion provided that it is judiciously added to the nanocomposite. The corresponding results revealed that the Joncryl-based nanocomposites, where nanoclay platelets were well-dispersed, exhibited a significantly reduced permeability as compared to others. The mechanical properties of the neat PLA, the PLA and Joncryl-based nanocomposites were also examined. The increased molecular weight in Joncryl-based nanocomposites caused a significant increase in the modulus, drawability and toughness of the samples.     

Experimental and theoretical analyses of mechanical properties of PP/PLA/clay nanocomposites

Compatibilized and non-compatibilized blends of polypropylene (PP) and poly(lactic acid) (PLA) with various compositions containing nanoclay particles were prepared by one step melt compounding in a twin screw extruder. Two nanocomposite systems with different matrices i.e. PP-rich (75/25 composition) containing Cloisite 15A and PLA-rich (25/75 composition) containing Cloisite 30B were selected for investigation of effect of nanoclays and n-butyl acrylate glycidyl methacrylate ethylene terpolymers (PTW) as compatibilizer on mechanical properties of PP/PLA/clay nanocomposites. Tensile and impact properties of the nanocomposite systems were investigated and correlated with their microstructures. Tensile modulus and strength of the blends were increased while elongation at break decreased by increasing PLA content. There was an irregular relationship between impact strength of the blends and PLA content. Several proposed models for blends and nanocomposites were used for prediction of tensile modulus of the samples. Most of the proposed models for blends could predict the tensile modulus of the blends successfully at low content of PLA. Another notable point was that most of the micromechanical models for nanocomposites fitted well to experimental values at low content of the clays and showed deviations at high clay loadings.     

The relationship between microstructure and mechanical properties of carbon nanotubes/polylactic acid nanocomposites prepared by twin-screw extrusion

Twin-screw extrusion was applied to prepare the carbon nanotubes/polylactic acid (CNT/PLA) nanocomposites. Five different extruded plates were produced under variation of CNT concentrations. The internal microstructures were also observed by optical microscope to examine the distribution and dispersion of CNT in the PLA. Besides, the crystallinity of the CNT/PLA nanocomposites was investigated by differential scanning calorimetry (DSC) and density method. The effects of the CNT concentrations on the mechanical and electrical properties of the nanocomposites were investigated. Scanning electron microscope (SEM) was performed to observe the CNT dispersion in the nano-scale. These results suggested that the crystallinity was increased with the increase of CNT concentrations, demonstrating that CNT played a role as a nucleating agent in PLA. Moreover, the mechanical and electrical properties of PLA have been improved by a proper incorporation of CNTs due to a good distribution and dispersion of the CNTs.     

Effect of diisocyanates as compatibilizer on the properties of ramie/poly(lactic acid) (PLA) composites

Ramie/PLA composites with the diisocyanates as compatibilizer were fabricated by extrusion and injection molding. The influence of different diisocyanates and various diisocyanate content on the mechanical properties and thermal properties of the composites was investigated. The presence of the diisocyanates in the composites lead to the improvements in mechanical properties and thermal properties of the composites. The morphologies of fracture surface using scanning electron microscopy (SEM) provided evidence of improved interfacial adhesion between ramie and PLA from the addition of the diisocyanates. The composites containing isophorone diisocyanate (IPDI) showed the best mechanical properties. The comparison of various IPDI content showed that the composites with 1.5% IPDI could get the optimum mechanical properties, and the excess diisocyanate content resulted in the decrease in the mechanical properties of the composites. However, IPDI content had almost no effect on the crystallization and melting behavior of the ramie/PLA composites.     

Electron beam irradiation enhanced of Hibiscus cannabinus fiber strengthen polylactic acid composites

This paper reported the effects of increasing Hibiscus cannabinus fiber (also known as kenaf fiber) loading level on properties of electron beam irradiated polylactic acid/low density polyethylene (PLA/LDPE). PLA and LDPE were compounded with 5–20 parts per hundred resins (phr) of kenaf respectively to enhance mechanical properties. The compounded kenaf added PLA/LDPE samples were electron beam irradiated from 15 to 60 kGy. The physical properties of kenaf added PLA/LDPE samples were characterized using gel content, X-Ray diffraction and scanning electron microscopy analysis. The results showed that the increasing of irradiation dosages in PLA/LDPE have gradually increased the gel content and tensile strength due to the formation of crosslinking networks in polymer matrix. However, the higher loading level of kenaf and irradiation dosages could decrease the elongation at break of PLA/LDPE samples. This is due to the restriction of polymer chains mobility as resulted by the poor interfacial adhesion between polymer matrix and kenaf particles as well as the formation of crosslinking networks in polymer matrix limits the sliding of polymer chains. Meanwhile, the increasing of kenaf loading level also has gradually increased the crystallinity of PLA/LDPE matrix. It is concluded that the electron beam irradiation dosages and amount of kenaf fiber in PLA/LDPE matrix should be kept at maximum 45 kGy and 15 phr, respectively for better combination to enhance the properties of the composites.     

Thermo-mechanical characterization of Manicaria Saccifera natural fabric reinforced poly-lactic acid composite lamina

The development and thermo-mechanical characterization of a novel green composite lamina, made of PolyLactic Acid (PLA) reinforced with a natural fabric extracted from Manicaria Saccifera palm, are presented. The composite was characterized by thermal-analysis (TGA), tensile, flexural, and izod impact tests, and scanning electronic microscopy (SEM). TGA analysis showed that the degradation process of the composite started earlier than that of neat PLA due to the lower thermal stability of the fabric. The mechanical tests showed that PLA properties were improved. The tensile strength, elastic modulus and impact resistance were improved by 26%, 51% and 56% respectively. Good dispersion and mechanical interlocking of PLA into the fabric were seen by SEM explaining the improvements of the mechanical properties of the composite. In summary, the good tensile properties and the excellent energy absorption capabilities of the MF/PLA composite lamina show great potential of Manicaria fabric as reinforcement in green composites.     

Characterisation of polylactic acid biocomposites made from prepregs composed of woven polylactic acid/hemp–Lyocell hybrid yarn fabrics

This paper describes the mechanical properties and water absorption characteristics for biocomposites made from woven PLA/hemp/Lyocell prepregs. The aim was to improve the properties with the addition of Lyocell fibre into a hybrid yarn. Well-aligned hybrid yarns composed of hemp/PLA, hemp–Lyocell/PLA, respective, Lyocell/PLA were made by wrap spinning. Unidirectional satin fabrics were made by weaving with PLA (warp) and the hybrid yarns (weft). Uniaxial composites were fabricated with 30 fibre mass% using compression moulding. The composites were investigated for tensile, flexural and impact properties. Combining hemp with Lyocell in a PLA matrix improves the mechanical properties, compared to hemp/PLA composites. The composite made from the satin Lyocell/PLA fabric gave the best mechanical properties. The type of fibre reinforcement compositions did not significantly affect the water absorption of the biocomposites. Scanning electron microscopy showed that fibre pull-outs appear more often in hemp/PLA composites than in composites also including Lyocell fibre.     

Strength improvement in injection-molded jute-fiber-reinforced polylactide green-composites

The mechanical properties of green-composites based on polylactic acid (PLA) with jute fibers were investigated. A long fiber pellet was developed to obtain a high aspect ratio of residual fiber after injection molding. Comparative studies were carried out, where shorter fiber pellets were compounded by different screw configurations using a twin-screw extruder. To interpret the results of our mechanical tests, the fiber geometry, dispersion state, and fiber fracture surfaces after tensile testing were analyzed. We found that the composites made of short fiber pellet (which suffer high compound intensity), exhibited optimal mechanical performance. Although, compounding with a twin-screw extruder decreased the overall aspect ratio of residual fibers, we observed that it significantly facilitated both the dispersion of the jute yarn to jute bundle and the decohesion of jute bundle to elementary fibers. This fiber separation caused by high intensity mixing led to efficient load transfer from matrix to fiber, and improvement of interfacial strength. These findings provide us with an insight into the critical parameters required to develop a high performing jute/PLA composite.     

Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes

We herein report the effects of interfacial reinforcement on mechanical and electrical properties of nanocomposites based on polylactide (PLA) and multi-walled carbon nanotube (MWCNT). For this purpose, a series of MWCNTs grafted with PLA chains of various lengths (MWCNT-g-PLAs) were prepared by ring-opening polymerization of l-lactide with carboxylic acid-functionalized MWCNT (MWCNT-COOH). MWCNT-g-PLAs were then mixed with commercial PLA to obtain PLA/MWCNT-g-PLA nanocomposites with 1.0 wt.% MWCNT content. It was revealed that morphological, mechanical, and electrical properties of PLA/MWCNT-g-PLA nanocomposites were strongly dependent on the PLA chain length of MWCNT-g-PLAs. FE-SEM images exhibited that the nanocomposites containing MWCNT-g-PLA with longer PLA chain length exhibited better dispersion of MWCNTs in the PLA matrix. Initial moduli and tensile strengths of PLA/MWCNT-g-PLA composites increased with the increment of chain length of PLA grafted on MWCNTs, which attributes to the improved interfacial adhesion between the grafted PLA chains of MWCNT-g-PLA and the PLA matrix. As a result, the experimental initial modulus (2775 ± 193 MPa) of the nanocomposite including MWCNT-g-PLA with PLA chains of average molecular weight of 530 g/mol was quite close to the theoretical value (2911 MPa) predicted for the nanocomposite with perfect interfacial adhesion. Unexpectedly, electrical resistivities of PLA/MWCNT-g-PLA nanocomposites were found to increase from ∼10⁴ to ∼10¹² Ω/sq with increasing the PLA chain length of MWCNT-g-PLA, which is due to the fact that the PLA chains grafted on MWCNTs prevent the formation of the electrical conduction path of MWCNTs in the PLA matrix.     

Preparation,optical and thermal properties of CdSe–ZnS/poly(lactic acid) (PLA) nanocomposites

In this study, CdSe–ZnS/poly(lactic acid) (PLA) nanocomposite films, containing different concentrations of surface-modified CdSe–ZnS quantum dots (QDs), were prepared via a solution casting method. The optical microstructural and thermal properties of the as-prepared QDs/PLA films were investigated. The QDs/PLA films exhibited strong and stable photoluminescence (PL) intensity with concentration dependent amplitudes. The transmission electron microscopy (TEM) pictures revealed that QDs of ∼5 nm diameter were uniformly dispersed in the PLA matrix. According to the results of thermogravimetric analysis, the weight-loss onset temperature of PLA clearly decreased with the QD content. A combination of Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) results suggested that the QDs exhibit obvious nucleation activity on the crystallization behavior of the PLA matrix. This research provides useful information to the foundations of practical applications of QDs/PLA nanocomposites as fluorescent and biodegradable functionalized materials.     

Plasticized polylactic acid nanocomposite films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: Effects on mechanical,thermal and optical properties

Triacetate citrate plasticized poly lactic acid and its nanocomposites based on cellulose nanocrystals (CNC) and chitin nanocrystals (ChNC) were prepared using a twin-screw extruder. The materials were compression molded to films using two different cooling rates. The cooling rates and the addition of nanocrystals (1 wt%) had an impact on the crystallinity as well as the optical, thermal and mechanical properties of the films. The fast cooling resulted in more amorphous materials, increased transparency and elongation to break, (approx. 300%) when compared with slow cooling. Chitin nanocomposites were more transparent than cellulose nanocomposites; however, microscopy study showed presence of agglomerations in both materials. The mechanical properties of the plasticized PLA were improved with the addition of a small amount of nanocrystals resulting in PLA nanocomposites, which will be further evaluated for film blowing and thus packaging applications.     

The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion

The main aims of this work were to study the effect of surface modifications on sisal fiber properties as well as on fiber/poly (lactic acid) (PLA) interface adhesion. For this purpose, alkali, silane and combination of both treatments were applied to sisal fiber. The effects of treatments on fiber thermal stability, fiber wettability, morphology, tensile properties and on fiber/PLA interfacial shear strength (IFSS) were studied. After treatments IFSS values improved at least 120%, however, tensile strength of sisal fibers decreased. Alkali treatment removed some non-cellulosic components (hemicelluloses, lignin) as confirmed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The removal of non-cellulosic materials led to fibrillated and rough morphology as observed by optical microscopy (OM). FTIR spectrum of silane treated fibers showed a band related to silane amino group and contact angle measurements confirmed that fibers became more hydrophobic. All treatments used improved fiber/PLA adhesion.     

Processing and characterization of solid and microcellular poly(lactic acid)/polyhydroxybutyrate-valerate (PLA/PHBV) blends and PLA/PHBV/Clay nanocomposites

The morphology, microstructure, tensile properties, and dynamic mechanical properties of solid and microcellular poly(lactic acid) (PLA)/polyhydroxybutyrate-valerate (PHBV) blends, as well as PLA/PHBV/clay nanocomposites, together with the thermal and rheological properties of solid PLA/PHBV blends and PLA/PHBV/clay nanocomposites, were investigated. Conventional and microcellular injection-molding processes were used to produce solid and microcellular specimens in the form of ASTM tensile test bars. Nitrogen in the supercritical state was used as the physical blowing agent in the microcellular injection molding experiments. In terms of rheology, the PLA/PHBV blends exhibited a Newtonian fluid behavior, and their nanocomposite counterparts showed a strong shear-thinning behavior, over the full frequency range. An obvious pseudo-solid-like behavior over a wide range of frequencies in the PLA/PHBV/clay nanocomposites suggested a strong interaction between the PLA/PHBV blend and the nanoclay that restricted the relaxation of the polymer chains. PLA/PHBV/clay nanocomposites possess a higher modulus and greater melt strength than PLA/PHBV blends. The addition of nanoclay also decreased the average cell size and increased the cell density of microcellular PLA/PHBV specimens. As a crystalline nucleating agent, nanoclay significantly improved the crystallinity of PHBV in the blend, thus leading to a relatively high modulus for both solid and microcellular specimens. However, the addition of nanoclay had less of an effect on the tensile strength and strain-at-break.     

Mechanical and thermal properties of chicken feather fiber/PLA green composites

Chicken feather fiber (CFF)/reinforced poly(lactic acid) (PLA) composites were processed using a twin-screw extruder and an injection molder. The tensile moduli of CFF/PLA composites with different CFF content (2, 5, 8 and 10 wt%) were found to be higher than that of pure PLA, and a maximum value of 4.2 GPa (16%↑) was attained with 5 wt% of CFF without causing any substantial weight increment. The morphology, evaluated by scanning electron microscopy (SEM), indicated that an uniform dispersion of CFF in the PLA matrix existed. The mechanical and thermal properties of pure PLA and CFF/PLA composites were compared using dynamic mechanical analysis (DMA), thermomechanical analysis (TMA) and thermogravimetric analysis (TGA). DMA results revealed that the storage modulus of the composites increased with respect to the pure polymer, whereas the mechanical loss factor (tan δ) decreased. The results of TGA experiments indicated that the addition of CFF enhanced the thermal stability of the composites as compared to pure PLA. The outcome obtained from this study is believed to assist the development of environmentally-friendly composites from biodegradable polymers, especially for converting agricultural waste – chicken feather into useful products.     

Influence of glass microspheres on selected properties of polylactide composites

Comparison of some changes occurring in polylactide (PLA) due to its modification by glass filler being in the form of microspheres (GM) was the objective of the present study. Mechanical and thermal properties, density, mass flow rate, and were determined. In addition, there were examined surface free energy and changes in the surface geometrical structure of sample fractures. It was found that PLA as modified with GM exhibited the enhanced longitudinal modulus of elasticity, flexural modulus, and mass flow rate. The impact strength and flexural strength did not change. The tensile strength and tensile strain at break decreased. The used glass filler did not affect essentially the thermal properties of PLA. The prepared composites exhibited uniform distribution of the dispersed phase in the polymer matrix and adequate adhesion at the interface between the two components. Substantial changes in the properties of the surface layer were observed, mainly in surface free energy.     

PLA/algae composites: Morphology and mechanical properties

Bio-composites with poly(lactic) acid as matrix and various algae (red, brown and green) as filler were prepared via melt mixing. Algae initial size (below 50 μm and between 200 and 400 μm) and concentration (from 2 to 40 wt%) were varied. First, algae morphology, composition and surface properties are analysed for each algae type. Second, an example of algae particle size decrease during processing is given. Finally, tensile properties of composites are analysed. The surface of algae flakes was covered with inorganic salts affecting filler–matrix interactions. The Young’s modulus of composites increased at 40 wt% load of algae as compared with neat PLA although the strain at break and tensile strength decreased. In most cases the influence of algae type was minor. Larger flakes led to better mechanical properties compared to the smaller ones.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Morphology and degradation properties of PCL/HYAFF11® composite scaffolds with multi-scale degradation rate

The analysis of scaffold degradation is a promising strategy for understanding the dynamic changes in texture and pore morphology which accompany polymer resorption, and for collecting same fundamental indicators regarding the potential fate of the scaffold in the biological environment. In this study, we investigate the morphology and degradation properties of three composite scaffolds based on poly(ε-caprolactone) (PCL) embedded with benzyl ester of hyaluronic acid (HYAFF11®) phases, and, in turn, different reinforcement systems – i.e., calcium phosphate particles or continuous poly(lactic acid) (PLA) fibres. Scanning electron microscopy (SEM) and μ-tomography supported by digital image analysis enabled a not invasive investigation of the scaffold morphology, providing a quantitative assessment of porosity (which ranged from 63.1 to 82.8), pore sizes (which varied from 170.5 to 230.4 μm) and pore interconnectivity. Thermal analyses (DSC and TGA) and Raman spectroscopy demonstrated the multi-scale degradation of the composite with highly tailoring degradation kinetics depending on the component material phases and scaffold architecture changes, due to their conditioning in simulated in vivo environment (i.e., SBF solution). These results demonstrate that the judicious mixing of materials with faster (i.e., HYAFF11) and slower (i.e., PLA and PCL) degradation kinetics, different size and shape (i.e., domains, particles or long fibres), certainly concurs to design a smart composite scaffold with time-controlled degradation which can support the regeneration of a large variety of tissues, from the cartilage to the bone.