Study on flax fiber toughened poly (lactic acid) composites

Poly (lactic acid) (PLA) is a renewable and biodegradable polymer with high modulus, high strength but low toughness. Blending PLA with plant fiber has been believed an available strategy to improve the toughness of PLA. PLA/Flax composites were fabricated by extrusion and injection molding processes. The flax fiber surfaces were modified before blending to improve the compatibility, and the chemical structures of both untreated and treated fiber were characterized by Fourier transform infrared spectroscopy. Results of mechanical test showed that the impact strength and elongation at break of PLA/Flax composites were remarkably higher than PLA. The impact fractures of PLA/Flax composites were also observed by scanning electron microscope. The results showed uniform dispersion of fibers in PLA matrix and good compatibility between treated fibers and PLA matrix. Moreover, it can be observed that crazing propagation was hindered by fibers and transcrystalline developed along fibers by polarized optical microscope. Differential scanning calorimetry analysis was carried out to study the crystallinity of PLA and it was found that incorporation of fiber improved the crystallinity of PLA. The toughening mechanism of PLA/Flax composites was discussed according to the results. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42573.     

Enhanced biodegradation and processability of biodegradable package from poly(lactic acid)/poly(butylene succinate)/rice-husk green composites

This work aims to study the possibility to process PLA/PBS/RH green composites into hexagonal plant-pots employing a large-scale industrial operation using injection molding. Green composites based on poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and rice husk (RH) with various RH contents (10–30%wt.) were produced successfully using a twin-screw extruder. The compatibility of RH-matrix was improved by chemical surface modifications using a coupling agent. RH was analyzed as an effective filler for PLA to develop green composites with low cost, high biodegradability, improved processability, and comparable mechanical properties as unfilled PLA. With increasing RH content, tensile modulus of the composites increased gradually. The addition of PBS, at PLA/PBS ratio of 60/40, improved the elongation at break and impact strength of PLARH30 by 55% and 7.1%, respectively. The suitable processing temperatures for PLA decreased from 220–230°C to 170–180°C when 30%wt. RH was composited into PLA matrix and were further reduced when PBS was applied. After biodegradation via either enzymatic degradation or hydrolysis, surface erosion with a large number of voids, mass loss, and the substantial decrease in tensile strength of all the composites were observed. In addition, the biodegradation of the composites has been improved by the addition of either RH or PBS.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (I): Morphology and thermal properties

In this study, ethylene‐vinyl alcohol copolymer (EVOH) nanocomposites were prepared by melt compounding both plant cellulose nanowhiskers (CNW) and bacterial cellulose nanowhiskers (BCNW) as nanofillers. Electrospinning and a “dissolution precipitation” method were used as strategies for the incorporation of CNW in EVOH before melt compounding with the aim of enhancing the degree of dispersion of the nanocrystals when compared with direct melt‐mixing of the freeze‐dried product with the polymer. As revealed by morphological characterization, the proposed preincorporation methods led to a significant improvement in the dispersion of the nanofiller in the final nanocomposite films. Furthermore, it was possible to incorporate concentrations as high as 4 wt % BCNW without causing significant agglomeration of the nanofiller, whereas increasing the CNW concentration up to 3 wt % induced agglomeration. Finally, DSC studies indicated that the crystalline content was significantly reduced when the incorporation method led to a poor dispersion of the nanocrystals, whereas high‐nanofiller dispersion resulted in thermal properties similar to those of the neat EVOH. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and thermomechanical properties of nanocrystalline cellulose reinforced poly(lactic acid) nanocomposites

A two‐step process was developed to prepare nanocrystalline cellulose (NCC) reinforced poly(lactic acid) (PLA) nanocomposites using polyethylene glycol (PEG) as a compatibilizer. It was composed of solvent mixing and melt blending. The NCC was well dispersed in the PLA matrix. A network was formed at high NCC‐to‐PEG ratio at which the amount of the PEG was not enough to cover all the surfaces of the NCC. The formation of the network was confirmed by the occurrence of a plateau for the storage modulus at low frequency. The incorporation of the PEG and NCC could improve the crystallinity of the PLA. The elongation at break increased from 11.0% for the neat PLA to 106.0% for the composites including 6 wt % NCC, impact strength was improved from 0.864 to 2.64 kJ m^?2 and tensile strength did not change significantly for the same 6 wt % NCC composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44683.     

New biocomposite obtained using poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) and microfibrillated cellulose

This research evaluates the effects of filler content and silanization on thermal, morphological and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)-based composites. Microfibrillated cellulose (MFC) was obtained by a mechanical treatment of high-pressure homogenization, starting from oat hull fiber, a byproduct of the agri-food sector. MFC reinforced PHBH composites were prepared by melt compounding. SEM and FT-IR analysis showed a good dispersion of the filler in the polymeric matrix, denoting the effectiveness of the surface silanization process. The thermal stability of PHBH composites remains substantially unchanged, and the glass transition temperature marginally increases with the increase of the filler content. Furthermore, silanized MFC shows slightly reinforcing mechanical effects on PHBH composites, such as the increase of 10% of the Young modulus with an increase of the maximum tensile stress as well. This finding has an economical interest since the results showed that MFC, deriving from a byproduct, can be successfully used as filler, decreasing the cost of the bio-based compound leaving substantially unaltered its mechanical and thermal properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48953.     

Preparation of artificial wood films with controlled biodegradability

Artificial wood films containing cellulose, xylan, and lignin were easily prepared by the dissolution of wood components in 1‐ethyl‐3‐methylimidazolium acetate followed by reconstitution with distilled water. The composition and characteristics of wood films were highly controllable and predictable through the variation of the concentration of each component in the wood solution. The water vapor solubility of the wood films was increased when the xylan content was increased and the content of lignin was decreased. The biodegradability of the artificial wood films was investigated with cellulase from Trichoderma viride. The relative degradability of the wood film prepared with 5% cellulose and 5% lignin was 42%, whereas that of the wood film made with 5% cellulose and 5% xylan was 189%. The biodegradability of cellulose in the wood films correlated well with the content of xylan and lignin, and it was enhanced when the xylan content was increased and the content of lignin was decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42109.     

Halloysite nanotubes immobilized by chitosan/tannic acid complex as a green flame retardant for bamboo fiber/poly(lactic acid) composites

In order to develop an environmentally benign flame retardant for bamboo/PLA composites (BPC), chitosan (CS) and tannic acid (TA) were used as cationic and anionic polyelectrolyte respectively to stabilize halloysite nanotubes (HNT) on the surface of bamboo fiber (BF) and poly(lactic acid) (PLA). Mechanical performance tests showed that the flexural properties of BPC were moderately enhanced with the addition of HNT, while the incorporation of CS/TA complex (FR) exhibited a slight increase. The results of thermogravimetric analysis demonstrated that CS/TA complex and HNT improved the thermal stability of the BPC synergistically, which increased the char residue. Limiting oxygen index and cone calorimetry tests were used to study the flammability of BPC and the results showed that the addition of CS/TA complex and HNT had a synergistic effect on the flame retardant performance of BPC materials. The macroscopic and microscopic morphological studies confirmed the formation of HNT layer in the matrix of BPC/5FR@5HNT samples, which facilitated more stabile char residue with the best flame retardant performance.     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

PBAT/PLA/cellulose nanocrystals biocomposites compatibilized with polyethylene grafted maleic anhydride (PE-g-MA)

The use of biodegradable polymers has grown exponentially due to their lower environmental impact when compared to conventional polymers. In this sense, biocomposites are an alternative due to their promising properties, maintaining biodegradability. For this purpose, in the present study, a biodegradable biocomposite of PBAT (poly [butylene adipate co-terephthalate]) and PLA (polylactide) blend containing cellulose nanocrystals (CNC) were obtained, using polyethylene grafted with maleic anhydride (PE-g-MA) as a coupling agent. Seven formulations were produced by extrusion and had their structure, morphology, thermal, and rheological properties analyzed. The results showed a significant improvement of adhesion among the components using PE-g-MA as a coupling agent. Moreover, CNC and PE-g-MA increased the PLA crystallinity degree and reduced the complex viscosity. These results are unprecedented in the literature using these compositions and extrusion processing conditions. Therefore, these new insights provide a vast horizon for the use of biodegradable mixtures using PBAT/PLA and CNC.     

Biodegradable poly(lactic acid)/cellulose-based superabsorbent hydrogel composite material as water and fertilizer reservoir in agricultural applications

The work presents a fully degradable superabsorbent composite material to be used in agricultural and horticultural applications. It is designed to retain and release fertilizer solutions to the soil in a controlled manner, permitting resource optimization. Because of its ability to absorb and release large amounts of saline water, a natural superabsorbent hydrogel derived from cellulose was chosen. Potassium nitrate was chosen to model the fertilizer. Poly(lactic acid) was added to the final composition in order to delay solution release. The composite material was obtained using easily available and low-cost starting materials and using a simple manufacturing process, using a standard mixer. After being analyzed for morphological (scanning electron microscopy), physical (X-ray diffraction), chemical (energy-dispersive X-ray spectroscopy), and thermal properties (thermogravimetric analysis and differential scanning calorimetry), the material was tested using two different Mediterranean cultivations (Pomodoro di Morciano di Leuca and Cicoria Otrantina) and two different kinds of soil (red and white soils). The analysis revealed different water release characteristics for different soils. These findings have been confirmed by measuring plant growth for both species, as well as fruit yield of the tomatoes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47546.     

Nanomechanical properties and thermal stability of recycled cellulose reinforced starch–gelatin polymer composite

Samples of starch?gelatin polymer reinforced with 5% of recycled cellulose were prepared using an extrusion‐compression molding process. Nanoindentation and atomic force acoustic microscopy (AFAM) techniques were used to study the effect of reinforcement at nanoscale level. Nanoindentation tests show a 163% increase in hardness and 123% of elastic modulus enhancement after recycled cellulose inclusion. AFAM shows that distribution of recycled cellulose into the polymer matrix is rather homogeneous at nanoscale which improves load transfer. Thermogravimetric analysis indicates an increase in thermal stability of the cellulose reinforced polymer matrix samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41787.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (II): Water barrier and mechanical properties

In the present work, the crystallinity and crystalline morphology, thermal stability, water barrier, and mechanical properties of ethylene vinyl alcohol copolymer (EVOH) nanocomposites prepared by melt compounding and incorporating both plant (CNW) and bacterial cellulose nanowhiskers (BCNW) are reported. An improvement in the water barrier performance was observed, that is, 67% permeability drop, only for the microcomposite sample incorporating 2 wt % of bacterial cellulose fibrils. No significant differences in the water‐barrier properties of the nanocomposites generated through the two studied preincorporation methods were observed despite the fact that an excellent dispersion was observed in the previous study. On the other hand, direct melt‐mixing of the freeze‐dried nanofiller with EVOH resulted in increased water permeation. The aggregation of the filler in the latter nanocomposite was also ascribed to the detrimental effect on the mechanical properties. Interestingly, by using the precipitation method, an increase in the elastic modulus and tensile strength of ～36 and 22%, respectively, was observed for a 3 wt % BCNW loading, which was thought to coincide with the percolation threshold. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Esterified PVA-lignin resin by maleic acid applicable for natural fiber reinforced composites

This article reports an esterified polyvinyl alcohol (PVA)-lignin resin that is applicable for natural fiber reinforced polymer composites. To meet the requirement for the composites, a biopolymer-based resin is necessary, which should well interact with the natural fiber with good waterproof behavior. By mimicking the relationship between cellulose, lignin and hemicellulose in wood, the esterified PVA-lignin resin with maleic acid is provided. The preparation and characterization of the environment-friendly resin are illustrated in this article. 180 °C of esterification reaction temperature and 40% of maleic acid contents are shown to be an optimum condition for the preparation of the resin. The esterified PVA-lignin resin exhibits 13, 31, and 55% increase of its tensile strength, toughness, and failure strength, respectively. The water contact angle of the esterified PVA-lignin resin is improved from 0 to 57°. The prepared resin is originally thermoplastic composite and it turned to be a thermoset resin by the esterification reaction at 180 °C, which is beneficial for composite processing. The developed resin is applicable for environment-friendly and high strength-natural fiber reinforced polymer composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48836.     

Effects of biocide treatments on durability of wood and bamboo/high density polyethylene composites against algal and fungal decay

The main objective of this study was to investigate the algal and fungal resistance of biocide‐treated wood flour (WF)/high density polyethylene (HDPE) and bamboo flour (BF)/HDPE composites. The biocides included 4,5‐dichloro‐2‐octyl‐isothiazolone (DCOIT), zinc pyrithione (ZPT), and carbendazim (MBC). Resistance to algae and fungi was evaluated by artificially accelerated tests. Treated and untreated samples were exposed to algae (Chlorella vulgaris, Ulothrix sp., Scenedesmus quadricauda, and Oscillatoria sp.) and fungi (Coriolus versicolor and Poria placenta) for 21 days and 12 weeks, respectively. The volatile components of WF and BF extractives were analyzed by gas chromatography‐mass spectrometry (GC‐MS). The results indicated that incorporation of DCOIT, ZPT, and MBC effectively enhanced the durability of WF/HDPE and BF/HDPE composites against algal and fungal decay. Accordingly, DCOIT, ZPT, and MBC can be used as potential biocides for both WF/HDPE and BF/HDPE composites. GC‐MS analysis suggested that palmitic acid, oleic acid, stigmasta‐3,5‐dien‐7‐one, and vanillin in WF possibly provided some resistance to fungal attack, whereas di (2‐ethylhexyl) phthalate and linoleic acid in BF were responsible for algal resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45148.     

Liquid crystal behavior of cellulose nanoparticles-ethyl cellulose composites: Preparation,characterization, and rheology

This work deals with assessing the approach for preparation of cellulose nanoparticles (CNPs) to be acted as synergistic component in liquid crystal (LC) ethyl cellulose composite (EC-CNPs). In this respect different structures of CNPs were prepared by acid and salt agents. These prepared CNPs were characterized by carboxyl content, IR, transmission electron microscope (TEM), and zeta potential, while their composites with EC were characterized by rheological measurements as a key factor for measuring the critical concentration of LC behavior. The results showed that, the crystallinity of CNPs obtained by ammonium persulfate exceeded that prepared by sulfuric acid hydrolysis. TEM images of stained CNPs showed both methods led to produce nanoparticles have rod like shape with aspect ratio (L/W) between 7.69 ± 3 and 31.3 ± 5. For the rheological measurements, it demonstrated the efficient of incorporating the CNPs to EC (EC-CNPs composites) to decrease the critical concentration of EC from 40 wt% to approximately 34 wt%.     

Fire retardant cellulose aerogel with improved strength and hydrophobic surface by one-pot method

Bio-based materials with multifunctional performance are getting immense attention nowadays for their environment friendly and renewable character. Inspired by toughening effect of graphene nanosheets and borate chemistry, a simple in-situ borate crosslinking in water and freeze-drying method was employed to fabricate a fire retarded bio-based aerogel. The structure of the material was evaluated and analysis by SEM, XRD, FTIR, Raman and XPS. Importantly, the bio-based aerogel has improved strength and adsorption properties due to unique structure. The compressive strength of rGO(reduced graphene oxide) + CMC (carboxymethyl cellulose) aerogel could reach 128 ± 2.1 kPa which is five times that of neat CMC aerogel. The bio-based aerogel can load more than 2500 times of self-weight. The adsorption capacity for organic solvents and oil of rGO+CMC aerogel is also greatly improved by a little rGO (1%) introducing due to its unique porous structure and hydrophobic nature of rGO. Additionally, rGO+CMC aerogel is also found fire resistant with relatively low thermal conductivity due to the borate and GO introduction.     

Regenerated cellulose aerogel: Morphology control and the application as the template for functional cellulose nanoparticles

This article focuses on controlling the morphology of regenerated cellulose aerogel (RCA) and its application as a template for the preparation of functional cellulose nanoparticles (FCNPs). RCA is prepared by lyophilizing cellulose hydrogel which is fabricated through a sol–gel method in sodium hydroxide (NaOH)/urea aqueous solution. The morphology of RCA is adjusted by varying the gelation temperature and time. With the gelation temperature and time increasing, lamellar RCA transforms into strings of cellulose nanoparticles. Subsequently, RCA with the morphology of "strings of nanoparticles" is modified through the bulk condensation of l -lactic acid and RCA. Eventually, the prepared functionalized RCA (FRCA) is dispersed in an organic solvent to obtain purified FCNPs. The results demonstrate that single FCNP can be obtained by dispersing FRCA in dimethyl sulfoxide. Moreover, the prepared FCNPs have uniform size, good thermal-stability, and increasing hydrophobicity, which are ideal candidates for polymer composites in terms of fillers.     

Modification of the wood-plastic composite for enhancement of formaldehyde clearance and the 3D printing application

As the formaldehyde is one of the main indoor pollutants, the purpose of this study is to effectively remove indoor formaldehyde pollution by using environmentally friendly 3D printing ornaments. The wood 3D printing filaments cellulose/polylactic acid composite (Cellu/P) was selected as the starting material, and 3-aminopropyltriethoxysilane (APTES) was used for chemical modification to obtain a series of cellulose composite materials with amino groups. The modified composite materials (APTES@Cellu/P) were characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, thermogravimetric analysis, and mechanical tests, and a formaldehyde removal experiment was performed. The feasibility of 3D printing was evaluated, and the process of 3D printing-functionalized customized ornaments was proposed, and then a school emblem was used for modeling, printing, and surface modification. Compared with the commercially traditional activated carbon, 3D printing-customized ornaments of APTES@Cellu/P material has a better formaldehyde removal effect, and can even avoid the secondary pollution that is common to the activated carbon.     

High oxygen barrier materials from paper to regenerated cellulose films

A transparent, bendable, high oxygen barrier cellulose-based film was prepared, which has far better oxygen barrier properties than conventional polyethylene, polypropylene and cellophane materials. A series of regenerated cellulose films (RCs) were prepared from filter paper lacking oxygen barrier properties under different cellulose concentrations and gelation times. It was shown that the cellulose concentration and gel time had a greater effect on the oxygen barrier properties of RCs. When the cellulose concentration was 4 wt% and the gel time was 3 h, the RCs obtained the lowest oxygen permeability coefficient (OPC) down to 2.21 × 10⁻¹⁷ cm³ cm cm⁻² s⁻¹ Pa⁻¹. The films have a tensile strength of 109.5 MPa, an elongation at break of 27.3% and a light transmission rate of 89%. In further, molecular dynamics simulations showed that when the filter paper was converted to RCs, the increase in hydrogen bonding and the decrease in free volume between cellulose chains caused a decrease in the diffusion coefficient of oxygen. As a novel biobased high oxygen barrier material, the film has broad application prospect in packaging and chemical industry.     

Construction of porous cellulose tubes and the evaluations of mechanical properties and cytocompatibility

In this work, regenerated cellulose (RC) tubes with the porous structure were successfully fabricated for constructing the non-invasive detection platform of vascular microenvironment. Polyethylene oxide (PEO) as a porogen was applied to induce porous structure of cellulose tubes. Tensile and burst pressure tests were carried out to evaluate the effects of PEO molecular weight and amount on the mechanical properties of cellulose tubes. The results showed that tensile strength of RC tubes was increased with increasing PEO molecular weight. The compliance of cellulose tubes decreased with increasing the PEO content. When 120 kDa PEO was applied, the average tensile strength of RC tubes could reach 1.27 MPa. The maximum burst pressure and compliance of RC tubes could reach 488.25 ± 35 mmHg and 7.50 ± 3.7%/100 mmHg, respectively. Human umbilical vein endothelia cells (HUVECs) exhibited obvious proliferation on cellulose tubes, and the collagen coating further improve the biocompatibility. The incorporated collagen further improved adhesion of the cells and growth on cellulose tubes. This work provided a kind of cellulose-based tube material with potential application for the construction of the vitro vascular microenvironment.