Thermal and structure properties of biobased cellulose nanowhiskers/poly (lactic acid) nanocomposites

Cellulose nanowhiskers were used to improve the performance of poly (lactic acid) (PLA). The nanocomposites mixed with three different molecular weight of poly (ethylene glycol) (PEG) were characterized by mechanical testing, thermal gravimetry and differential scanning calorimetry. The tensile test showed an increase in tensile strength and elongation at break with the addition of PEG to PLA/CNW nanocomposites, the thermal analysis results showed an increase of crystallization temperature (T _c) and crystallization compatibility (larger crystallization and melting areas), which indicated that the cellulose nanowhiskers (CNW) and PEG or CNW alone should not be considered as nucleating agents for the PLA matrix; The CNW was homo-dispersed which contributed to decreasing mobility of polymer chain segments. The compatibility between hydrophobic PLA matrix and the hydrophilic CNW was improved by the addition of different molecular weight polymeric-PEG. The thermo gravimetric analysis indicated that the thermal stability of the different composites were reflected well in the region between 25 °C and 245 oC. The structure of the PLA/CNW/PEG composites was characterized by AFM, which showed that the CNW dispersed in the PLA matrix evenly.     

Effect of fiber reinforcement on mechanical and thermal properties of poly(ɛ-caprolactone)/poly(lactic acid) blend composites

Optimized palm press fiber composites of poly(?-caprolactone)/poly(lactic acid) were produced and their mechanical and thermal properties were studied. The composites were melt blended using twin screw extruder and test specimens were produced by injection molding. The composites mechanical and thermal performances were tested using standard methods. The incorporation of dicumyl peroxide as compatibilizer significantly increased the tensile strength, flexural modulus and impact strength of the composites as compared to the uncompatibilized composites. Crystallization temperature of the composites initially increased after which it dropped as fiber load increased. The composites melting point and percentage crystallinity slightly decreased as fiber load increased.     

Extraction of cellulose nanowhiskers from natural fibers and agricultural byproducts

In this work the feasibility of extracting cellulose from cotton, sisal and flax fibers, corn stover and rice husk by means of usual chemical procedures such as acid hydrolysis, chlorination, alkaline extraction, and bleaching was analyzed. Cellulose nanowhiskers from these sources, and from commercial cellulose, were produced by the acid hydrolysis of the obtained celluloses. The final products were characterized by means of Thermogravimetric Analysis (TGA), Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electronic Microscopy (SEM) and Atomic Force Microscopy (AFM). The chemical procedure used to obtain cellulose nanowhiskers was effective in all cases but differences on the thermal stability, chemical composition, crystallinity and morphology were found due to the dissimilar nature of the different sources. Thus, this work demonstrates that the morphology and physical properties of cellulose nanowhiskers synthesized by the same conditions are strongly dependent on their source.     

Mechanical,Thermal, and Swelling Properties of Cross-linked Hydrogels Based on Oxidized Cellulose Nanowhiskers and Chitosan/poly(vinyl alcohol) Blends

Cross-linked hydrogels of chitosan/poly(vinyl alcohol) (PVA)/oxidized cellulose nanowhiskers (CNWs) were prepared by using oxidized CNWs as a cross-linker. The effects of the oxidation level of CNWs on the swelling behavior, thermal stability, viscoelastic properties and compressive strength of the hydrogels were studied. Chemical cross-links, hydrogen bonds, as well as nanofiller reinforcement between the three materials played a major role in determining the properties of the hydrogels. Swelling test results showed that the incorporation of oxidized CNWs decreased the water absorbability of the hydrogels due to the increase in cross-linking degree. Viscoelastic properties of the hydrogels with oxidized CNWs was increased by 537 % in storage modulus, from 4.65 kPa to 29.6 kPa. Compressive strength of 181.5 kPa at 50 % strain was observed from the cross-linked hydrogels, compared with 21.2 kPa of the non-cross-linked hydrogels. The thermal experiments showed that the chemical cross-linking slightly increase the resistance toward thermal degradation of the hydrogels.     

Mechanical properties of denim fabric reinforced poly(lactic acid)

Denim, a twilled cotton fabric, was used to enhance the mechanical and thermal properties of poly(lactic acid) (PLA). The denim fabric reinforced composites with different numbers of denim layers were fabricated by using a hand layup method. The impact, tensile, and dynamic mechanical properties of the composites were observed with increasing denim layers to examine the reinforcing effect of denim fabrics. Numerical analysis was carried out to model the elastic modulus of the composite by using a commercial software. Three-dimensional geometry of the denim fabric reinforced PLA composite was generated through a CAD program, and the elastic modulus was calculated by applying uniform deformation on one surface. The impact strength, tensile strength, and thermal properties of the composites were improved by piling denim fabrics. The denim fabric reinforced composites exhibited outstanding impact strength due to the retarded crack propagation as well as large energy dissipation. The 3 layer denim reinforced composite showed best results among all specimens, and its impact strength, tensile strength, and tensile modulus were measured to be 82 J/m, 75.76 MPa, and 4.65 GPa, respectively. The PLA/denim composites have good mechanical properties and can substitute traditional composites such as glass fiber or carbon fiber reinforced composites.     

Evaluation of cotton byproducts as fillers for poly(lactic acid) and low density polyethylene

Polymeric composites based on cotton burr and cottonseed bull have been prepared by melt blending and extrusion. For poly(lactic acid) (PLA) and low-density polyethylene (LDPE), addition of the fillers slightly changed the composite's thermal properties but significantly decreased the composite's mechanical properties. Heat treatment prior to extrusion resulted in composites with better tensile strength and Young's modulus. The use of maleic anhydride and peroxide only slightly improved the physical properties of the LDPE materials, but the effect was less clear for the PLA materials. The PLA-filler composites may be useful for lowering the cost of the materials in applications that can tolerate the decreased properties. In addition, the addition of fillers to LDPE might be beneficial in applications to improve stiffness or to improve biodegradability.     

Influence of noncellulosic contents on nano scale refinement of waste jute fibers for reinforcement in polylactic acid films

In the present study, nanofibrils of cellulose are extracted from waste jute fibers using high energy planetary ball milling process in wet condition. The rate of refinement of untreated fibers having non-cellulosic contents was found slower than treated fibers due to strong holding of fiber bundles by non-cellulosic contents. At the end of three hours of wet milling, untreated fibers were refined to the size of 850 nm and treated fibers were refined to the size of 443 nm. In the subsequent stage, composite films of poly lactic acid (PLA) were prepared by solvent casting with 3 wt% loading of untreated jute nanofibrils, treated jute nanofibrils and microcrystalline cellulose. The influence of non-cellulosic contents on mechanical properties of PLA films are investigated based on results of tensile test, dynamic mechanical analysis and differential scanning calorimetry. The maximum improvement was observed in case of treated jute nanofibril/PLA composite film where initial modulus and tensile strength increased by 207.69 % and 168.67 %, respectively as compared to neat PLA film. These improvements are attributed to the increased interaction of treated jute nanofibrils with PLA matrix due to their higher precentage of cellulosic contents and mechanically activated surface.     

Preparation and properties of pineapple leaf fiber reinforced poly(lactic acid) green composites

Green composites from Pattawia pineapple leaf fiber (PALF) and poly(lactic acid) (PLA) were prepared. The mechanical method was chosen to extract PALF from fresh leaves due to this method gave high yield of fiber, short extraction time, and environmental friendly. Tensile and thermal properties, together with morphology of the fibers were disclosed. The fibers were conducted into a specified length of 1–3 mm and blended with PLA, using a twin screw extruder, with the PALF content of 10–50 wt%. Tensile testing, morphology investigation and thermogravimetric analysis were applied. Preliminary results showed that tensile modulus of the composites depended on PALF content. The tensile modulus and elongation at break of the composite containing 40 % PALF was about 48 %, and 111 % increase, respectively, compared with that of PLA. With addition of maleic anhydride coupling agent, such the composite showed the tensile modulus of 5.1 GPa, which was 34 % higher than that of the non-coupling agent composite, and about 104 % higher than that of PLA. Although the elongation at break of the composite containing 40 % PALF was found to dramatically increase by 111 %, the introduction of maleic anhydride in such the composite caused only 57 % increase in the elongation at break compared with that of PLA. Finally, a pilot product of square boxes was produced successfully from the proposed composite, by conventional injection molding process.     

Nanocellulose reinforced PVA composite films: Effects of acid treatment and filler loading

Nanocellulose was prepared by acid hydrolysis of microcrystalline cellulose (MCC) at different hydrobromic acid (HBr) concentrations. Polyvinyl alcohol (PVA) composite films were prepared by the reinforcement of nanocellulose into a PVA matrix at different filler loading levels and subsequent film casting. Chemical characterization of nanocelluloses was performed for the analysis of crystallinity (X_c), degree of polymerization (DP), and molecular weight (M_w). The mechanical and thermal properties of the nanocellulose reinforced PVA films were also measured for tensile strength and thermogravimetric analysis (TGA). The acid hydrolysis decreased steadily the DP and M_w of MCC. The crystallinity of MCC with 1.5 M and 2.5 M HBr showed a significant increase due to the degradation of amorphous domains in cellulose. Higher crystalline cellulose showed the higher thermal stability than MCC. From X-ray diffraction (XRD) analysis, nanocellulose samples showed the higher peak intensity than MCC cases. Reduction of MCC particle by acid hydrolysis was clearly observed from scanning electron microscope (SEM) images. The tensile and thermal properties of PVA composite films were significantly improved with the increase of the nanocellulose loading.     

Preparation and characterization of intumescent flame retardant biodegradable poly(lactic acid) nanocomposites based on sulfamic acid intercalated layered double hydroxides

A novel sulfamic acid intercalated MgAl-LDH (SA-LDH) was prepared by intercalating NH₃SO₃^? into MgAl-layered double hydroxides (LDH), and it was then introduced into poly(lactic acid) (PLA) resin in association with intumescent flame retardant (IFR) by melt blending to prepare a flame-retardant biodegradable PLA composite. The effects of SA-LDH on the flame retardancy of PLA composites were characterized by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test (CONE). The results showed that the composite sample containing 19.0 wt% IFR and 1.0 wt% SA-LDH achieved the maximal LOI value of 48.7 %, passed the UL-94 V-0 rating, and significantly decreased the peak heat release rate from 306.3 kW/m² of neat PLA to 58.1 kW/m². Thermogravimetric analysis showed that both the thermal stability and the char formation were enhanced. The char morphology observation revealed that SA-LDH was beneficial to form dense and compact char layers. It was demonstrated that there existed a synergistic effect between IFR and SA-LDH in promoting the char formation and enhancing the fire resistance. The mechanical and crystallization properties were also tested and discussed.     

Effect of kenaf and EFB fiber hybridization on physical and thermo-mechanical properties of PLA biocomposites

Kenaf/empty fruit bunch/polylactic acid (kenaf/EFB/PLA) hybrid biocomposites were prepared using hot press technique. The ratio of fiber to polylactic acid was set at 60:40 with 1:1 ratio between kenaf and empty fruit bunch fibers. Physical, mechanical and thermal properties of hybrid biocomposites were subsequently characterized using Fourier transform infrared spectroscopy, scanning electron microscope, X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, tensile and water absorption tests. Test results indicated that mechanically stronger fiber was able to support the weaker fiber. Hybrid fiber biocomposite had higher crystallinity as compared to single fiber biocomposite. Water absorption of hybrid composite was higher as compared to single fiber composite. Thermal result revealed that hybridization of fiber was not significantly influence the thermal properties of composites. However, the presence of two different fibers proposed good wettability properties, which could reduce the formation of voids at the fibers-polymer interface and produce composites with high stiffness and strength.     

Compatibilizing effects of polypropylene-g-itaconic acid on the polypropylene composites

We prepared long carbon fiber (LCF)-reinforced thermoplastic composites using a compatibilizer of itaconic acid grafted polypropylene (PP-g-IA). We confirmed the structure of PP-g-IA and investigated the compatibilizing effects of PPg- IA on LCF/polypropylene composites. The tensile strength, tensile moduli, flexural strength, and flexural moduli of the composites increased with increasing PP-g-IA content in the thermoplastic composites. Using single pull-out analyzing system, we found PP-g-IA improved interfacial strength between the carbon fiber and PP matrix. The thermal properties of the composites were measured by thermogravimetric analysis (TGA). We could observe that LCF enhanced the mechanical properties and thermal decomposition temperature of the polypropylene (PP) composites, compared with neat PP. The fractured surfaces of PP/PP-g-IA/LCF composites showed that PP-g-IA was effective for improving the interfacial adhesion between LCF and PP matrix.     

Thermo-mechanical and morphological properties of short natural fiber reinforced poly (lactic acid) biocomposite: Effect of fiber treatment

Untreated oil palm empty fruit bunch (REFB), alkali treated EFB (AEFB), ultrasound treated EFB (UEFB) and simultaneous ultrasound-alkali treated EFB (UAEFB) short fibers were incorporated in poly(lactic acid) (PLA) for fabricating bio-composites. The REFB fiber-PLA (REPC) and treated EFB (TEFB) fiber-PLA (TEPC) composites were prepared and characterized. Glass transition temperature, crystal melting temperature, decomposition temperature, melt flow index, density and mechanical properties (tensile strength, tensile modulus and impact strength) of TEPC are found to be higher than those of REPC. The observed crystallization temperature of TEPC is lower than that of REPC. Among all samples, TEPC prepared from UAEFB fiber shows better performances than other samples fabricated by REFB and AEFB fibers. Scanning electron microscopy, Fourier transform infrared spectroscopy and XRD analyses well support all the observed results.     

Mechanical properties,morphology and dynamic mechanical properties of LGF/TPU/SAN composites

A series of the long glass fiber reinforced thermoplastic polyurethane elastomers and poly (styrene-acrylonitrile) (LGF/TPU/SAN) composites with different contents of long glass fiber were prepared by using self-designed impregnation device. Dynamic mechanical properties of TPU/SAN matrix reinforced with 10, 20 and 30 % by weight long glass fibers have been investigated by using dynamic mechanical thermal analysis (DMA). The results indicated that the content of long glass fiber and scanning frequency had some influence on dynamic mechanical properties and glass transition of LGF/TPU/SAN composites. In addition, the Arrhenius relationship has been used to calculate the activation energy of a-transition of the LGF/TPU/SAN composites. SEM demonstrates the relatively good dispersion of the long glass fiber in the TPU/SAN matrix. In addition, Effects of the content of long glass fiber on mechanical properties of the LGF/TPU/SAN composites are investigated.     

Preparation and UV-protective property of PVAc/ZnO and PVAc/TiO<Subscript>2</Subscript> microcapsules/poly(lactic acid) nanocomposites

The poly(vinyl acetate) (PVAc)/zinc oxide (ZnO) microcapsule and PVAc/titanium dioxide (TiO₂) microcapsule were synthesized via in-situ emulsion polymerization method. The PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis(TG), transmission electron microscopy (TEM), and UV-visible spectroscopy (UV-vis). Effect of PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule on properties of poly(lactic acid) (PLA) was evaluated by UV-vis, SEM and mechanical properties test. The results showed that the addition of PVAc/ZnO and PVAc/TiO₂ microcapsules as a UV-blocking additive could significantly enhance UV-blocking property of PLA/PVAc/ZnO microcapsule composites and PLA/PVAc/TiO₂ microcapsule composites compared with pure PLA, PLA/ZnO composites and PLA/TiO₂ composites. The mechanical properties of PLA/PVAc/ZnO microcapsule composites were better than those of PLA/ZnO composites due to good dispersability and compatibility of PVAc/ZnO microcapsule in PLA matrix. Also, the mechanical properties of PLA/PVAc/TiO₂ microcapsule composites were better than those of pure PLA and PLA/TiO₂ composites. This study demonstrates the great potentials of the intrinsically UV shield additive PVAc/ZnO and PVAc/TiO₂ microcapsules in the application of high performance matrix resin and composite material.     

Preparation of new polymer nanocomposites based on poly(lactic acid)/fatty nitrogen compounds modified clay by a solution casting process

In this study, different organoclays (OMMTs) were prepared using various fatty nitrogen compounds (FNCs) and natural clay, sodium montmorillonite (MMT). The clay modification was carried out by stirring the clay particles in an aqueous solution of fatty amides (FA), fatty hydroxamic acids (FHA), and carbonyl difatty amides (CDFA). These OMMTs were then used for nanocomposites production to improve the property balance of poly(lactic acid) (PLA) by solution casting process. All sets of OMMTs and nanocomposites were characterized using various apparatuses. In the nanocomposites, where the clay surface is pretreated with FA, FHA and CDFA, the basal spacing of the clay increased to 2.94, 3.26 and 3.80 nm, respectively The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirmed the production of nanocomposites. PLA modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with pure PLA.     

The effects of blend composition and blending time on the ester interchange reaction and tensile properties of PLA/LPCL/HPCL blends

PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly(ε-caprolactone) (LPCL), and high molecular weight poly(ε-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable filament sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by¹H-NMR, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreased by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at 220 °C for 30–60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three polymers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.     

Influence of citric acid and water on thermoplastic wheat flour/poly(lactic acid) blends. I: Thermal, mechanical and morphological properties

Wheat flour was plasticized with glycerol and compounded with poly(lactic acid) in a one-step twin-screw extrusion process in the presence of citric acid with or without extra water. The influence of these additives on process parameters and thermal, mechanical and morphological properties of injected samples from the prepared blends, was then studied.Citric acid acted as a compatibilizer by promoting depolymerization of both starch and PLA. For an extrusion without extra water, the amount of citric acid (2 parts for 75 parts of flour, 25 parts of PLA and 15 parts of glycerol) has to be limited to avoid mechanical properties degradation. Water, added during the extrusion, improved the whole process, minimizing PLA depolymerization, favoring starch plasticization by citric acid and thus improving phases repartition.     

Surface-Modified Cellulose Nanocrystal-incorporated Poly(butylene succinate) Nanocomposites

In this work, surface acetylation of cellulose nanocrystals was performed to improve their interfacial adhesion with hydrophobic polymer matrix and to restore their thermal stability by removing the sulfate groups. The morphological, chemical, and thermal characteristics of the surface-modified cellulose nanocrystals (ACNs) were confirmed by field emission-transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Furthermore, poly(butylene succinate) (PBS)/ACNs nanocomposites were also prepared via melt-mixing process, and the reinforcing effects of ACNs on the thermal, mechanical, and biodegradable properties of the nanocomposites were investigated. The Young’s modulus and tensile strength of the PBS/ACN nanocomposites increased from 115.36 and 33.67 MPa for the neat PBS to 130.55 MPa and 39.97 MPa, respectively. The thermal stability and biodegradability of the nanocomposites also increased with increasing ACN content.     

Antibacterial blend films of cellulose and chitosan prepared from binary ionic liquid system

A new hybrid ionic liquids solvent, 1-allyl-3-methylimidazolium chloride (AMIMCl) and glycine hydrochloride (Gly·HCl) was utilized to dissolve chitosan and fabricate chitosan/cellulose (Cs/Ce) blend films with chitosan proportion varying from 2 to 35 wt.% through solution casting method. FTIR, XRD, TG, SEM and EA were used to evaluate the prepared composites. Besides, the mechanical property and antibacterial activity were also analyzed. The shifting of the characteristic peaks of -NH and C=O for chitosan, similar crystal pattern with low intensity diffraction peaks at 2θ of around 20°, superior thermal stability (increased T_onset) with chitosan ratio below 10 wt.% in the composites suggested that the interactions via hydrogen bonds formed between chitosan and cellulose. Besides, the elemental analysis showed that the actual N% contents from the chitosan in the blend films were roughly equivalent to the theoretical value though the inevitable residue of ionic liquids. Furthermore, the blends not only presented compact structure but also processed high bacterial reduction to E. coli and S. aureus at pH 6.3, which indicated that the Cs/Ce blend films prepared via the Gly·HCl/AMIMCl dissolution method were suitable for production of degradable antibacterial materials.