Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion

The aim of this study was to develop cellulose nanofiber (CNF) reinforced polylactic acid (PLA) by twin screw extrusion. Nanocomposites were prepared by premixing a master batch with high concentration of CNFs in PLA and diluting to final concentrations (1, 3, 5 wt.%) during the extrusion. Morphology, mechanical and dynamic mechanical properties (DMA) were studied theoretically and experimentally to see how different CNF concentrations affected the composites’ properties. The tensile modulus and strength increased from 2.9 GPa to 3.6 GPa and from 58 MPa to 71 MPa, respectively, for nanocomposites with 5 wt.% CNF. The DMA results were also positive; the storage modulus increased for all nanocomposites compared to PLA; being more significant in the high temperature region (70 °C). The addition of nanofibers shifted the tan delta peak towards higher temperatures. The tan delta peak of the PLA shifted from 70 °C to 76 °C for composites with 5 wt.% CNF.     

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.     

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.     

Effect of hydrothermal pretreatment on the properties of moso bamboo particles reinforced polyvinyl chloride composites

Bamboo plastic composites were fabricated from polyvinyl chloride (PVC) and moso bamboo particles (BP). In order to improve the interfacial interaction between BP and PVC, as well as to obtain composites with outstanding mechanical properties, the roles of hydrothermal treating temperatures (120, 140, 160, 180, 200, 220, 240, 260 and 280 °C) on characteristics of BP and properties of the PVC/BP composites were investigated. Results showed that hydrothermal modification improved the surface property of BP and wiped off hemicelluloses and pectin. A uniform dispersion of BP in PVC matrix was observed by SEM with hydrothermal treatment. Tensile strength, tensile modulus and flexural strength of the composites achieved their maximal values of 15.79 MPa, 6702.26 MPa and 39.57 MPa, respectively, with 180 °C hydrothermal treatment. The highest values of elongation at break and flexural deformation were 3.75 ± 0.20% with 200 °C hydrothermal modification and 36.22 ± 2.70% with 140 °C hydrothermal modification, respectively. Due to more decomposition of hemicellulose, the composites expressed lower water absorption and higher thermal stability when the hydrothermal treating temperature exceed 160 °C.     

Development of PLA/cellulosic fiber composite foams using injection molding: Crystallization and foaming behaviors

Poly(lactic acid) (PLA) and northern bleached softwood kraft (NBSK) or black spruce medium density fiberboard (MDF) fibers were melt compounded using a co-rotating twin screw extruder and subsequently microcellular injection molded. Poly(ethlylene glycol) (PEG) was used as a lubricant. The microcellular structure, thermal properties, and crystallization behaviors were characterized using scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, and wide angle X-ray diffraction. Results show that cellulosic fibers, acting as crystal nucleating agents, increased the crystallization temperature and the crystallinity and decreased the crystallization half time. The dissolved N₂, the shear stress, and biaxial stretching during foaming also enhanced the crystallinity of PLA. Compared to PLA/PEG, a finer and more uniform cell structure was achieved in the cellulosic fiber composite foams. The improved foam morphology was attributed to the cell nucleating effects of the fibers and the increased melt strength by the addition of cellulosic fibers and by the gas- and fiber- induced crystallization.     

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.     

A comparison of the mechanical characteristics of kenaf and lyocell fibre reinforced poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) composites

Cellulose fibre-reinforced poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) composites have become increasingly interesting with regard to their biodegradability and mechanical characteristics. The use of different matrices leads to variable composite characteristics. This study provides a comparison of the mechanical characteristics of compression-moulded 30 mass% lyocell and 40 mass% kenaf fibre-reinforced PLA and PHB. The results of the tensile tests showed that 30 mass% lyocell/PLA composites reached the highest tensile and bending strength with 89 and 148 N/mm², respectively. The highest Young’s modulus was also measured for 30 mass% lyocell/PLA with 9.3 GPa, and the highest flexural modulus was measured for 40 mass% kenaf/PHB with 7.1 GPa. By far, the best impact strength was determined for lyocell/PHB with 70 kJ/m², followed by lyocell/PLA with 52 kJ/m². The investigation of the Shore D hardness resulted in a higher value for the PLA matrix with 81.5. PHB achieved a hardness of 67.5. By adding fibres as reinforcement, the Shore D hardness increased up to 83.6 for lyocell/PLA and 73.1 for kenaf/PHB. Density measurements showed lower densities for the composites with higher fibre loads (kenaf/PLA and kenaf/PHB) in comparison to the theoretical density. This speaks for a higher proportion of air inclusion in the composites which could negatively affect the mechanical composite characteristics.     

Influence of the process parameters on the mechanical properties of engineering biocomposites using a twin-screw extruder

The utilization of bio-based engineering polymers as a matrix material for cellulosic fiber reinforced composites has become an important focus in materials research. This is due to a rising demand for sustainable materials from renewable resources. In addition to this aspect, the bio-based materials provide an advantage for lightweight applications with their lower density. In this investigation, the completely bio-based polyamide 10.10, with a melting point above 200 °C, was used as a polymer matrix. Chopped man-made cellulose fibers (Cordenka CR-Type) were investigated as reinforcement for use in injection molded applications. A co-rotating twin-screw extruder with a screw-diameter of 18 mm was used for compounding. It was verified that reinforcing polyamide 10.10 with 20 wt% and 30 wt% cellulosic fibers is possible, resulting in an increase of impact and tensile properties. Furthermore, it was shown that the temperatures and screw-configurations of the twin-screw extruder only result in different fiber length distributions but in minor differences of the morphological structure and mechanical properties of PA 10.10 with 20 wt% fibers. Compounds with 30 wt% cellulose fibers show significant higher impact properties that those with 30 wt% glass fibers.     

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.     

The effects of the injection moulding temperature on the mechanical properties and morphology of polypropylene man-made cellulose fibre composites

Composites made of polypropylene and man-made cellulose fibres that are intended for injection moulding applications show potential for use in sustainable and light weight engineering with high energy absorption capacity. Due to the thermal sensitivity of the cellulose fibres, process parameters play an important role during the injection moulding process. A polypropylene and a man-made cellulose fibre were chosen for this investigation. Effective melt temperatures between 200 °C and 269 °C were used to process the compounds into test specimens. Tensile, impact and colorimetric tests, as well as an SEM analysis, and a measurement of the fibre length distribution were carried out in order to characterise the mechanical and optical properties of the composites. It was observed that the fibre length becomes shorter above 256 °C and elongation at break and Charpy strength (notched) of the composites already decrease at lower temperatures than tensile strength. A direct correlation between mechanical properties and discoloration was not observed. Therefore, melt temperatures up to 250 °C are suitable for these composites.     

Effect of carbon nanofibers (CNFs) content on thermal and mechanical properties of CNFs/SiC nanocomposites

Carbon nanofibers dispersed β-SiC (CNFs/SiC) nanocomposites were prepared by hot-pressing via a transient eutectic phase route at 1900 °C for 1 h under 20 MPa in Ar. The effects of additional CNFs content between 1 and 10 wt.% were investigated, based on densification, microstructure, thermal and mechanical properties. The CNFs/SiC nanocomposites by the CNFs contents below 5 wt.% exhibited excellent relative densities over 98% with well dispersed CNFs. However, the CNFs/SiC nanocomposites containing the CNFs of 10 wt.% possessed a relative density of 92%, accompanying CNFs agglomerates and many pores located inside the agglomerates. The three point bending strength gradually decreased with the increase of CNFs content, but the indentation fracture toughness increased to 5.7 MPa m^1/2 by the CNFs content of 5 wt.%. The thermal conductivity was enchanced with the increase of CNFs content and represented a maximum value of 80 W/mK at the CNFs content of 5 wt.%.     

Nanocomposites based on polystyrene-b-poly(ethylene-r-butylene)-b-polystyrene and exfoliated graphite nanoplates: Effect of nanoplatelet loading on morphology and mechanical properties

Exfoliated graphite nanoplates (xGnPs)/polystyrene-b-poly(ethylene-r-butylene)-b-polystyrene (SEBS) nanocomposites have been prepared by the simple melt-compounding approach. The structural, mechanical and viscoelastic properties of these composites were studied and compared. Wide-angle X-ray diffraction (WAXD) studies indicated that the processing of nanocomposites did not change the original d-spacing of xGnPs. Scanning electron microscopy observation on the fracture surfaces of the composites shows a uniform dispersion of xGnPs throughout SEBS matrix and strong interfacial adhesion between oxidized xGnPs and the matrix, which are responsible for the considerable enhancement of mechanical properties of the composites. It is found that the addition of xGnPs particles improved both the elastic modulus and storage modulus of pure SEBS significantly and the higher the xGnPs content, the higher the modulus of the nanocomposite. Moreover, the effects of dispersed xGnPs on the microphase separation of SEBS have also been investigated using small angle X-ray scattering (SAXS).     

Preparation and bending properties of three dimensional braided single poly (lactic acid) composite

New three dimensional (3D) braided single poly (lactic acid) composites (PLA–SPCs) were obtained by combining 3D and five (5)-direction braiding technique and hot-compression technical process. 3D and 5-direction braided preforms with different braiding angles, thicknesses and fiber volume fractions were prepared. Preforms were preheated in the specially designed die system in order to make all of the fibers partially melted. In the next stage, the preforms were consolidated under a certain pressure (from 7.8 to 10 MPa) at temperatures ranging from 130 up to 150 °C. Under the controlled processing conditions, one part of fiber body formed matrix while the other part retained its fibrous form.At the same consolidation temperature, the maximum bending stress values resulted to be substantially dependent on the fiber volume fraction of PLA–SPCs, while the bending modulus values were largely subjected to the fiber content in the length direction. The increases of consolidation pressure gave rise to better fusion of neighboring fibers with the result that the maximum stress and modulus were increased. As the consolidation temperature increases, the fusion bonding was improved, the bending failure feature was converted from plastic to brittle, both maximum bending stress and modulus values were increased. It is expected that this study could provide a new approach for the manufacture of high-performance single polymer composites (SPCs) by using thermoplastic polymer fibers.     

Physicochemical properties of organoclay filled polylactic acid/natural rubber blend bionanocomposites

A novel toughened polylactic acid (PLA) bionanocomposite with tuneable properties was successfully prepared by melt mixing PLA with natural rubber and several montmorillonites (MMTs). The organoclays were preferentially located at the interface acting as compatibilisers between both polymer phases. This location resulted in a marked improvement of the physical and mechanical properties of the system. Moreover, these properties can be controlled as a function of the nanofiller nature and the mixing procedure used.     

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.     

Structure and properties of hybrid PLA nanocomposites with inorganic nanofillers and cellulose fibers

Polylactide reinforced with 3 wt% of organo-modified montmorillonite, 5 wt% of stearic acid-modified calcium carbonate nanoparticles, 15 wt% of cellulose fibers (PLA/MMT, PLA/NCC, PLA/CF) and hybrid composites containing 15 wt% of fibers in addition to montmorillonite (PLA/MMT/CF) or calcium carbonate (PLA/NCC/CF) were prepared and examined. The nanoparticles were dispersed in polylactide almost homogeneously; montmorillonite was exfoliated during processing. T_g of polylactide remained unaffected but its cold crystallization was enhanced; the cold-crystallization behavior of the hybrid composites was dominated by nanofillers nucleating ability. The fibers and calcium carbonate decreased whereas exfoliated montmorillonite improved the thermal stability of the materials. Polylactide, PLA/NCC and PLA/MMT exhibited ability to plastic deformation, although the latter the weakest. Tensile behavior of the hybrid composites was strongly influenced by the fibers and similar to that of PLA/CF. All the fillers increased the storage modulus below T_g; that of PLA/MMT/CF and PLA/NCC/CF was improved with respect to polylactide by 50% and 45%, respectively.     

Microindentation and differential scanning calorimetry of “liquid wood”

Lignin was used only as a fuel until not so long ago, but the research done in the last few years has shown that it is a substance that confers wood its strength and takes the form of granules that may be melted. Thus, lignin was used to produce a material out of which almost anything can be manufactured, from furniture, accessories, toys, plastic cases for electronic devices, and food containers of any shape, to car bodies, and which is known as “liquid wood”. Its properties recommend “liquid wood” as an alternative to all plastic products in the near future, as it is biodegradable and reusable several times, and its properties remain intact. Three types of “liquid wood” are known: Arbofill, Arboblend and Arboform. Whereas Arboform is 100% biodegradable, the other two materials are only partially biodegradable. The following types of “liquid wood” were used: Arbofill Fitchie, Arboblend V2 Nature and Arboform L, V3 Nature. The research described in this paper focuses on the study of microindentation and differential calorimetry. Also, the software package we used enabled us to read both the microhardness values, and the reduced indentation modulus and Young’s modulus.The studied test samples showed the following mean recovery values: 45.9170 μm for Arbofill Fitchie, 22.2783 μm for Arboblend V2 Nature and 17.7430 μm for Arboform L, V3 Nature. These values are in agreement with the microhardness and modulus of elasticity values. Differential calorimetry research has shown that Arboblend V2 Nature and Arboform L, V3 Nature suffered two transformations each, one endothermal and the other exothermal, during which we measured the transformation onset and completion temperatures, as well as the temperature in the middle of the transformation process. We also measured the amount of absorbed and dissipated heat, respectively. As far as Arbofill Fitchie is concerned, the DSC diagram showed no temperature-dependent heat flow variation that could suggest a solid state transformation. We could safely state that the Arbofill Fitchie sample is thermally stable up to a temperature of 423 K.     

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.     

Effect of surface etching on interphase and elastic properties of a biocomposite reinforced using glass–silica particles

Biopolymer based composites are designed using glass–silica reinforcement. Surface etching of spherical glass–silica particles is performed using chemical and physical treatments. In particular, treatment with hydrofluoric acid proved to be efficient to achieve acceptable anchoring effect. Experimental testing of thermomoulded composites confirms that samples with chemically modified microbeads have improved mechanical properties, irrespective of phase content. A quantitative evaluation of the improvement of the starch/glass–silica interphase properties is achieved using a finite element model. Generation of typical microstructures is used to simulate phase arrangement and interphase properties. Microstructures are meshed taking into account the interphase region. Finite element results indicate that for all samples, interphase Young’s modulus is lower than those of the intrinsic materials. The thickness weighted interface modulus increases for composites where the mechanical adhesion is improved using HF chemical treatment.     

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.