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.     

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.     

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     

In-depth material characterization of polyhydroxybutyrate from a forest biorefinery

Large-scale replacement of petroplastics with compostable plastics, like polyhydroxybutyrates (PHB) will contribute to elimination plastic pollution, decrease greenhouse gas emissions, and valorize local biomass resources. Lignocellulose hydrolysates have emerged as potentially sustainable carbon sources for PHB production. For industrial processing, it is necessary to know the polymer properties. Yet, most studies on PHB samples from lignocellulose report few material properties. PHB samples produced from a pilot scale hardwood holocellulose hydrolysate conversion process were characterized and compared with PHB from a sugar hydrolysate and a commercial PHB powder. PHB from hardwood holocellulose hydrolysate was found to be comparable with commercial PHB in all properties. Differential scanning calorimetry and thermal gravimetric analysis showed that all samples had similar thermal behavior, where the melting temperature was 176°C and the decomposition temperature was 293°C. From the melting enthalpy, all samples showed 63% crystallinity. Dynamic mechanical analysis showed a glass transition temperature at 5°C and a crystallization temperature of 57°C. Fourier transform infrared spectroscopy and nuclear magnetic resonance confirmed that the samples were homopolymers comprised of hydroxybutyrate units. The difference among the samples was the number average molecular mass, being lower for wood hydrolysate (246.4 kDa) than sugar hydrolysate (670.3 kDa).     

Processing and thermal properties of composites based on recycled PET,sisal fibers,and renewable plasticizers

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (T_m ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40386.     

Poly(lactic acid)–thermoplastic starch–cotton composites: Starch-compatibilizing effects and composite biodegradability

Poly(lactic acid) (PLA) is a biodegradable, brittle, and high-cost polymer, which can be applied over structural components and green packaging. In this study, we reinforced PLA with natural cotton (10 wt %) and thermoplastic starch (TPS; 3 wt %) to obtain a biodegradable and lower cost composite. TPS was incorporated in three distinct ways: it was blended, coated, and blended and coated. In this study, we investigated the compatibilization of TPS in the improvement of matrix-reinforcement adhesion and increase in the tensile behavior without a compromise in biodegradation. The samples were investigated with thermal analysis, dynamic mechanical thermal analysis, tensile testing, scanning electron microscopy, confocal laser scanning microscopy, and hydrolytic degradation. The results show that the coupling effect was more pronounced in the PLA_TPS–cotton_TPS (hybrid system with PLA and cotton) hybrid system. This formulation presented a higher glass-transition temperature, thermal stability, storage modulus, wettability, and ductility. The TPS addition improved the adhesion between the matrix and starched cotton fiber and retarded abiotic biodegradation. These properties will allow for green applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47490.     

Sustainable bionanocomposite from d,l‐lactide/δ‐valerolactone triblock and bionanowhiskers: Preparation,characterization, and properties

Bionanocomposites were prepared using d ,l ‐lactide–δ‐valerolactone–d ,l ‐lactide triblock and unmodified and modified cellulose nanowhiskers (CNs) at different loadings (0, 2, 4, 8 wt %). Poly(δ‐valerolactone) chains were grafted on CNs for modification. These were characterized by various techniques. The broadening of OH (hydroxyl) stretching region and the presence of low‐intensity peaks at 1064 cm^?1 for C? O/C? C stretching vibration and 1426 cm^?1 for bending vibration of CH₂ group_, were evident in Fourier transform infrared spectra of the nanocomposites. The increase in crystallinity was noticed as the amount of nanowhiskers was increased. The nanowhiskers having the width in the range of 80–300 nm were uniformly dispersed in the triblock matrix. The tensile strength and modulus increased by 130% and 50% respectively at 8 wt % of filler loading. The storage modulus, loss modulus, complex viscosity, and tan δ values increased with increased filler loading. Further improvement in mechanical properties was observed with the modified CNs. The modulus mapping from atomic force microscopy confirmed the effective reinforcement behavior of the nanowhiskers. Scaffold fabrication using the bionanocomposite exhibited porous nature, having a homogeneous dispersion of CNs on the surface of the scaffold. The 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay confirmed the suitability of the composite material for scaffold application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 135, 46035.     

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.     

Poly(lactic acid)/pulp fiber composites: The effect of fiber surface modification and hydrothermal aging on viscoelastic and strength properties

Poly(lactic acid) (PLA)/kraft pulp fiber (30 wt%) composites were prepared with and without a coupling agent (epoxidized linseed oil, ELO, 1.5 wt%) by injection molding. The non-annealed composite samples, along with lean PLA, were exposed to two hydro-thermal conditions: cyclic 50% RH/90% RH at 23 and 50°C, both up to 42 days. The aging effects were observed by size exclusion chromatography, differential scanning calorimetry, dynamic and tensile mechanical analysis, and fracture surface imaging. ELO temporarily accelerated the material's internal transition from viscous to an increasingly elastic response during the aging at 50°C. ELO also slowed down the tensile strength reduction of the composites at 50°C. These observations were explained with the hydrophobic ELO molecules' coupling and plasticizing effects at fiber/matrix interfaces. No effects were observed at 23°C.     

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.     

Super‐absorbent resin preparation utilizing spent mushroom substrates

To find high value‐added utilization for spent mushroom substrates (SMS), a series super‐absorbent sample were prepared with SMS mass ratio between 0% and 100% based on acrylic acid plus SMS, heated with microwave. The maximum absorbency of the composite with 25% SMS ratio in water and saline corresponding to 0.3 wt % initiator is 458 and 61 g/g, respectively; the gel strength of the composite with 25% SMS is two times as high as that of the noncomposited polyacrylate. On SEM pictures, as SMS mass ratio increases the composites resin continuity was interrupted by SMS particles meanwhile some SMS particles are bare; micro‐particles of SMS uniformly dispersed in the acrylic resin forming submicroscopically homogeneous composites. IR spectra show that the composite has different chemical groups and structures from the mechanical mixture. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1098‐1103, 2013     

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.     

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.     

Preparation and analysis of poly(l-lactic acid) composites with oligo(d-lactic acid)-grafted cellulose

α-Cellulose extracted from jute fiber was grafted with oligo( d -lactic acid) (ODLA) via a graft polycondensation reaction in the presence of para-toluene sulfonic acid and potassium persulfate in toluene at 130 °C for 9 h under 380 mmHg. ODLA was synthesized by the ring-opening polymerization of d -lactides in the presence of stannous octoate (0.03 wt % lactide) and d -lactic acid at 140 °C for 10 h. Composites of poly( l -lactic acid) (PLLA) with the ODLA-grafted α-cellulose were prepared by the solution-mixing and film-casting methods. The grafting of ODLA onto α-cellulose was confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The analysis of the composites was performed with FTIR spectroscopy, SEM, wide-angle X-ray diffraction, and thermogravimetric analysis. The distribution of the grafted α-cellulose in the composites was uniform and showed better compatibility with PLLA through intermolecular hydrogen bonding. Only homocrystalline structures of PLLA were present in the composites, and the thermal stability increased with increasing percentage of grafted α-cellulose. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47424.     

Alkaline extraction of xylan from wood using microwave and conventional heating

This study aims to investigate the effect of microwave heating versus conventional heating for the alkaline hydrolysis of xylan from birch wood to understand the effect of the heating process on the dissolution of wood, the yield of xylan, and the degree of polymerization of the isolated xylan. The results indicate that the rate of wood dissolution is significantly higher (0.020/s) during microwave extraction than the conventional extraction (0.001/s). Wood solubilization, after an initial rapid removal of damaged fibers, is linear with time for both conventional and microwave extraction, with microwave showing a rate 20 times faster. The yield of xylan reaches a limit of about 60% for both processes but then declines slowly as thermal degradation become significant. Microwave heating provides 60% yield in 1/10th the time of the conventional process. This is found to be associated with the rapid temperature rise, and also with local “hot spots” generated during microwave treatment. The results indicated that xylan degradation was significant above 95°C. The nature of the isolated xylan was different for the two heating methods: the xylan isolated using microwave extraction for 20 min exhibits higher molecular weight (i.e., a greater degree of polymerization, about 150) than the xylan isolated using conventional extraction for the same duration (degree of polymerization, about 124) demonstrating the effectiveness of microwave heating for extraction of xylan from wood. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41330.     

Bio‐sorbents from cassava waste biomass and its performance in removal of Pb2+ from aqueous solution

Cassava xanthogenate and their derivatives, as adsorbents to remove Pb²⁺ from aqueous solution, are studied based upon orthogonal factorial design. The structural and thermal properties, adsorption performance as well as equilibrium‐kinetics are comprehensively investigated with multiple tools, such as Fourier transform infrared spectroscopy, thermal gravimetric analysis (TGA), and UV–visible spectrum technique. The influence of multiple parameters, including initial Pb²⁺ concentrations, compositions, pH values, and temperatures, on the adsorption performance is emphasized. The crosslinked cassava xanthogenate serves as an effective bio‐sorbent to remove Pb ions from aqueous solution, allowing regeneration in dilute acid solution. The findings in this study are beneficial for the development of adsorbents from cassava waste biomass and may contribute to environment recovery in “nature‐to‐nature” manner. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39780.     

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.     

Controlling lignin particle size for polymer blend applications

Softwood lignin produced by the LignoForce System^TM was physically processed using different milling approaches to ascertain effective and scalable means to yield micro to submicron particles of controllable and uniform size. Our work suggests that wet ball‐milling using a small milling medium is the most reliable method in terms of processing efficiency and particle‐size controllability. Controllable particle size reduction would permit lignin to be used as an effective filler in polymer blends. We show that wet‐milled lignin could, subsequently, be oven‐ or spray‐dried, and, subsequently, blended with, for instance, polypropylene (PP) through co‐extrusion. The spray‐drying method produced spherical lignin aggregates smaller and more uniform than oven‐dried ones. As a consequence, spray‐dried lignin demonstrated a more uniform distribution within the polymer melt, leading to noticeable improvement in the strain—or flexibility—of the lignin‐PP polymer blends. Furthermore, it is confirmed that the investigated drying methods had no effect on the thermal stability of the resulting lignin‐PP blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44669.     

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 (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