Effects of wood flour and chitosan on mechanical,chemical, and thermal properties of polylactide

Composites of polylactide (PLA, 100–60 wt%) and wood flour (0–40 wt%) were prepared to assess the effects of wood filler content on the mechanical, chemical, thermal, and morphological properties of the composites. The polysaccharide chitosan (0–10 wt%) was added as a potential coupling agent for the PLA‐wood flour composites. Addition of wood flour significantly increased the flexural modulus and the storage modulus of PLA‐wood flour composite, but neither the wood flour nor chitosan had an effect on the glass transition temperature (T_g). Fourier transform infrared spectra did not show any evidence of covalent bonding, but chitosan at the interface between wood and PLA is thought to have formed hydrogen bonds to PLA‐carbonyl groups. SEM images of fracture surfaces showed that fiber breakage was far more common than fiber pullout in the composites. No evidence of discrete chitosan domains was seen in SEM micrographs. When added at up to 10 wt% (based on wood flour mass), chitosan showed no significant effect on the mechanical, chemical, or thermal properties of the composites, with property changes depending on wood flour content only. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers.     

Unmodified and esterified Kraft lignin‐filled polyethylene composites: Compatibilization by free‐radical grafting

In this study, the effectiveness of free‐radical grafting as a compatibilization method applied to composites containing Kraft lignin (KL) and esterified lignin was comparatively investigated. Maleated lignin (ML) was first obtained via esterification of KL with maleic anhydride. KL and ML were respectively incorporated into high density polyethylene (HDPE) up to 60% wt and dicumyl peroxide was used as a free‐radical generator. The influence of lignin esterification and free‐radical grafting on the morphological, mechanical, and thermal properties of lignin‐based composites was studied. The incorporation of lignins into HDPE resulted in poor mechanical strength because of low compatibility. Morphological and mechanical evidences indicate improved compatibility between lignins and HDPE following free‐radical grafting. The free‐radical scavenging properties of KL allowed better compatibilization of KL‐based composites compared with ML‐based composites. In addition, thermal analysis results showed that free‐radical grafting increases the thermal stability of ML‐based composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41484.     

Poly(vinyl alcohol)–lignin blended resin for cellulose‐based composites

Wood has limitations in strength because of its biostructural defects, including vessels. To overcome this limitation, composite materials can be innovated by breaking wood down into cellulose and lignin and reassembling them for bio‐originating strong structural materials. In this study, an ecofriendly resin was developed that was suitable for cellulose‐based composites. To overcome the low dimensional stability of lignin and to increase its interactions with cellulose, it was blended with poly(vinyl alcohol) (PVA). The PVA–lignin resin was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, thermal analysis, mechanical tensile testing, and lap‐shear joint testing. The adhesion properties of the PVA–lignin resin increased with increasing PVA content. PVA played the role of synthetic polymer and that of linker between the cellulose and lignin, like hemicellulose does in wood. The PVA–lignin resin exhibited a high miscibility, mechanical toughness, and good adhesion properties for nanocellulose composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46655.     

Comparison of different methods for lignin determination as a basis for calibration of near-infrared reflectance spectroscopy and implications of lignoproteins

Three commonly employed methods for lignin determination, i.e., the thioglycolic acid (TGA), the acetylbromide (AB), and the acid detergent fiber (ADF) method, were compared using leaves and xylem tissue from five species (Nicotiana tabacum, Populus x canescens, Fagus sylvatica. Quercus robur, and Picea abies). In each case, cell walls were isolated before lignin determination. Each of the three methods estimated a different lignin concentration in a given tissue, except for spruce wood. The lignin concentration determined with the AB method was strongly dependent on whether or not the cell walls were subjected to alkaline hydrolysis to remove covalently bound aromatic nonligneous components before lignin determination. Lignin concentrations determined in hydrolyzed cell walls of different tissues and species by the AB method showed a good correlation with those obtained by the TGA method and, thus, were convertible. In contrast, gravimetrically estimated ADF lignins did not or only moderately correlate with lignins measured with methods based on the UV absorbance of the solubilized lignin degradation products. Leaves of a given species generally contained higher ADF-lignin concentrations than the corresponding stem tissue. Both ADF and TGA lignin data of beech were used to calibrate near-infrared reflectance spectra (NIRS) for lignin prediction. Both NIRS calibration procedures gave good statistical fits with correlation coefficients close to 1, indicating that TGA and ADF lignin concentrations of beech can be estimated by NIRS with high accuracy. However, the two calibrations were based on different empirical terms, showing that TGA and ADF lignins did not share the same physical basis for calibration. C/N analysis revealed the presence of 3.1 and 1.4% nitrogen in ADF lignins of beech leaves and wood, respectively. The major fraction of this nitrogen was recovered in amino acids, which corresponded to 14% and 3% protein in ADF lignins of leaves and wood, respectively. These results show that ADF lignins contain significant concentrations of lignin-bound proteins, which renders this method unsuitable to determine genuine lignin.     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

Fracture toughness of poly(lactic acid)/ ethylene acrylate copolymer/wood‐flour composite ternary blends

A fracture mechanics analysis based on the J‐integral method was adopted to determine the resistance of composites with various concentrations of wood‐flour and ethylene acrylate copolymer (EAC) to crack initiation (J_in) and complete fracture (J_f). The J_in and J_f energies of unmodified poly(lactic acid) (PLA)/wood‐flour composites showed the deleterious effect of incorporating wood fibers into the plastic matrix by significantly decreasing the fracture toughness of PLA as the wood‐flour content increased. The reduced fracture toughness of the matrix induced by adding brittle wood‐flour into PLA was well recovered by impact modification of the composites with EAC. Microscopic morphological studies revealed that the major mechanisms of toughening were through the EAC existing as separate domains in the bulk matrix of the composites which tended to act as stress concentrators that initiated local yielding of the matrix around crack tips and enhanced the toughness of the composites. © 2012 Society of Chemical Industry     

Influence of alkali treatment on flax fiber for use as reinforcements in polylactide stereocomplex composites

The flax and equivalent proportion of poly(l ‐lactic acid)/poly(d ‐lactic acid) (PLLA/PDLA) were melt compounded and injection molded to prepare flax‐reinforced polylactide stereocomplex (sc‐PLA) bio‐composite, and the effect of alkali treatment on the structure and properties of flax as well as the flax/sc‐PLA composite was investigated. SEM and FTIR results showed hemicellulose in flax was almost completely removed after alkali treatment and the treated flax (ALK‐flax) bundles were more separated with a cleaner surface than untreated flax (UN‐flax). DSC results showed homo‐crystallites (hc, T_m = 160–170°C) and stereocomplex crystallites (sc, T_m ～210°C) coexisted in sc‐PLA and flax/sc‐PLA composites. Compared with sc‐PLA, the total crystallinity and sc‐crystallinity of flax/sc‐PLA composite increased regardless of whether the flax were treated with alkali, whereas ALK‐flax/sc‐PLA composite showed a little higher crystallinity than UN‐flax/sc‐PLA composite. TGA results confirmed ALK‐flax/sc‐PLA composite had a higher thermal degradation temperature than UN‐flax/sc‐PLA composite. The mechanical tests indicated although the mechanical properties of sc‐PLA increased significantly by reinforcing with flax, the ALK‐flax/sc‐PLA composite showed little lower mechanical properties than UN‐flax/sc‐PLA composite. The alkali treatment of flax had no obvious influence on the Vicat softening temperature (VST) of flax/sc‐PLA composites, a higher heat resistance with VST at ～155°C could be obtained for flax/sc‐PLA composite. POLYM. ENG. SCI., 55:2553–2558, 2015. © 2015 Society of Plastics Engineers     

Poplar wood–methylol urea composites prepared by in situ polymerization. II. Characterization of the mechanism of wood modification by methylol urea

A prepolymer was used to prepare wood/prepolymer composites by a pulse‐dipping machine. The mechanical properties and dimensional stability were evaluated. The characterization of natural and modified woods was performed by Fourier transform infrared spectroscopy, ¹³C‐NMR spectroscopy, X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) with energy‐dispersive X‐ray analysis (EDXA). Cross‐polarization/magic‐angle spinning ¹³C‐NMR analysis revealed that the in situ polymerization between the prepolymer and the hydroxyls in the wood structure took place with the reduction of hydroxyl groups. XPS analysis indicated that the content of carbon decreased, whereas the content of oxygen increased. SEM–EDXA indicated a good dispersion of the modifier in the wood fiber and other vertical cells. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42406.     

Banana/sisal fibers reinforced poly(lactic acid) hybrid biocomposites; influence of chemical modification of BSF towards thermal properties

The present work focused on thermal behavior of biocomposites based on poly(lactic acid) (PLA) reinforced with untreated and benzoyl peroxide (BP) treated banana/sisal fibers (BSF) combination. Fabrication of biocomposites was performed by extrusion followed by injection molding. Fourier transformed infrared (FTIR) spectral technique ascertained the nature of bonding between BSF and PLA. The thermal properties of virgin PLA, UT‐BSF/PLA, and BP‐T‐BSF/PLA composites were studied by DSC and TGA analysis. DSC analysis indicated no significant changes in the glass transition temperature (T _g) and melting temperature (T _m) of virgin PLA, UT‐BSF/PLA, and BP‐T‐BSF/PLA composites and no sign of crystallization for both virgin PLA, UT‐BSF/PLA composites. However, crystallization was observed in BP‐T‐BSF/PLA composites. The BP‐T‐BSF/PLA composite exhibited a delayed thermal degradation pattern from TGA analysis when compared to that of UT‐BSF/PLA composites and virgin PLA as well. Further, the effect of BSF treatment and hybridization of BSF with PLA on the degree of crystallinity (X _c) were explored in detail. The above said composites were also investigated through scanning electron microscope (SEM) micrographs to examine the adhesion between the PLA and BSF. In addition, the results of SEM acquired are in good agreement with the data resulted from FTIR and thermal characterization. POLYM. COMPOS., 38:1053–1062, 2017. © 2015 Society of Plastics Engineers     

Polylactide‐recycled wood fiber composites

Polylactide (PLA)‐recycled wood fiber (RWF) composites with a small amount of silane were compounded using a kinetic‐mixer and molded using an injection molding machine. The molded PLA‐RWF composites were characterized using gel permeation chromatography, scanning electron microscope, X‐ray diffraction, differential scanning calorimeter, tensile testing machine, and a dynamic mechanical analyzer. As observed in the stress–strain plots, the amount of necking before fracture decreased with an increasing RWF content. Similarly, the strain‐at‐break also decreased with the RWF content. The tensile strength remained the same irrespective of the RWF content. Both the tensile modulus and the storage modulus of the PLA‐RWF composites increased with the RWF content. The degree of crystallinity of the PLA increased with the addition of RWF. No reduction in the number–average molecular weight (M_n) was observed for pure PLA and PLA‐10%RWF‐0.5%Silane composites after injection molding; however, substantial reduction in M_n was found in PLA‐20%RWF‐0.5%Silane composites. Finally, a theoretical model based on Halpin–Tsai empirical relations is presented to compare the theoretical results with that of the experimental results. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(lactic acid)–thermoplastic poly(ether)urethane composites synergistically reinforced and toughened with short carbon fibers for three‐dimensional printing

In this study, we prepared short‐carbon‐fiber (CF)‐reinforced poly(lactic acid) (PLA)–thermoplastic polyurethane (TPU) blends by melt blending. The effects of the initial fiber length and content on the morphologies and thermal, rheological, and mechanical properties of the composites were systematically investigated. We found that the mechanical properties of the composites were almost unaffected by the fiber initial length. However, with increasing fiber content, the stiffness and toughness values of the blends were both enhanced because of the formation of a TPU‐mediated CF network. With the incorporation of 20 wt % CFs into the PLA–TPU blends, the tensile strength was increased by 70.7%, the flexural modulus was increased by 184%, and the impact strength was increased by 50.4%. Compared with that of the neat PLA, the impact strength of the CF‐reinforced composites increased up to 1.92 times. For the performance in three‐dimensional printing, excellent mechanical properties and a good‐quality appearance were simultaneously obtained when we printed the composites with a thin layer thickness. Our results provide insight into the relationship among the CFs, phase structure, and performance, as we achieved a good stiffness–toughness balance in the PLA–TPU–CF ternary composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46483.     

Lignin‐based polycondensation resins for wood adhesives

Lignin‐based wood adhesives are obtained that satisfy the requirements of relevant international standards for the manufacture of exterior‐grade wood particleboard. Formulations based on low molecular mass lignin and presenting an increase in the relative proportion of reactive points yield better results than the higher molecular mass lignin used in the past. These lignins allow a higher proportion of hydroxymethylation during preparation of methylolated lignins. These lignin‐based adhesives also yield acceptable results at particleboard pressing times that are sufficiently low to be of industrial significance. Lignin‐based wood adhesives, in which a nonvolatile nontoxic aldehyde (glyoxal) is substituted for formaldehyde in their preparation, are prepared and tested for application to wood panels such as particleboard. The adhesives yield good internal bond strength results for the panels, which are good enough to comfortably pass relevant international standard specifications for exterior‐grade panels. The adhesives also show sufficient reactivity to yield panels in press times comparable to that of formaldehyde‐based commercial adhesives. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1690–1699, 2007     

Modification of wood flour/PLA composites by reactive extrusion with maleic anhydride

MA modified wood flour/PLA composites were prepared by one‐step reactive extrusion, in which wood flour and poly(lactic acid) (PLA) were used as raw material, maleic anhydride (MA) was used as modifier, and dicumyl peroxide (DCP) was used as initiator. The influences of MA concentration on the morphology, thermal stability, rheological, and mechanical properties of the composites were studied. The addition of MA improved the compatibility of the composites significantly. The thermal and rheological results showed that with the increase of the concentration of MA, the thermal stability of the composites decreased, the storage modulus and complex viscosity of the composites also decreased. The MA modified composites had an enhanced mechanical strength compared to the unmodified one. As the concentration of the MA increased, the tensile and flexural strength of the composites first increased and then decreased, and reached a maximum when the concentration of MA was 1 wt %. The MA modified composites showed a better water resistance than the unmodified ones. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43295.     

Evaluation of Kraft lignin as natural compatibilizer in wood flour/polypropylene composites

This study investigated the effect of Kraft lignin as natural compatibilizer on the water absorption, thermal, mechanical, and interfacial properties of poplar wood flour (WF)/polypropylene (PP) composites. Varying contents (0.5, 1, 2, 4, and 8 wt%) of lignin were added to WF and PP by direct mixing, then the composites were prepared by two‐screw extrusion and compression moulding. Results showed that lignin incorporation reduced the water absorption and postponed the thermal decomposition of the composites. Composites with lower lignin contents (0.5% and 1%) could get the optimal properties, and the excess lignin contents (4% and 8%) resulted in slight decrease in the mechanical properties. DMA and calculation of adhesion factor showed that the composites with 0.5% lignin had the best interaction between WF and PP. The morphologies of fractured surface also indicated improved interfacial adhesion between WF and PP from the addition of 0.5% and 1% lignin. POLYM. COMPOS., 38:2387–2394, 2017. © 2015 Society of Plastics Engineers     

Influence of Lignin Type on the Mechanical Properties of Lignin Based Compounds

Several types of sulfur‐free lignins were melt compounded in a Werner & Pfleiderer twin screw extruder (ZSK 25) together with polyamide 11 (PA11), a biodegradable polyester (Ecoflex®) and a biodegradable polyesteramide (BAK®). Sulfur‐free lignins, precipitated from black liquors of alkaline pulping of annual plants, like sisal and abaca, were compared to a sulfur‐free lignin (Alcell™) obtained by organosolv wood pulping. Lignin content and lignin type were varied systematically in order to examine stress/strain characteristics and impact behavior. Compounds with lignins from annual plants showed similar or better mechanical properties in comparison to compounds with Alcell™ lignin. A polyamid 11 compound containing 30 wt.‐% abaca lignin gave a Young's modulus of 1 890 MPa, compared to 1 420 MPa for PA11 and a 28% increase of yield stress. The morphology of the lignin compounds was investigated by means of environmental scanning electron microscopy (ESEM) and transmission electron microscopy (TEM).     

Surface modification of spruce wood flour and effects on the dynamic fragility of PLA/wood composites

Poly (lactic acid) (PLA), a biodegradable aliphatic semicrystalline polyester was filled with 40 wt% spruce wood flour (WF), to produce composite materials. Hydrothermal treatment, as well as maleic anhydride, vinyltrimethoxysilane, and stearic acid surface treatments were applied. The influence of surface modifications for WF was tested in terms of thermal, mechanical, and viscoelastic properties. The recorded results show that in both, the untreated and treated PLA/WF composites, the rigid amorphous phase content has been enhanced. The presence of WF causes a stiffness increase of the PLA/WF composites, while damping factor was decreased. The effect of wood surface modifications on interfacial compatibility with PLA was estimated by dynamic fragility parameter m calculated according the Williams‐Landel‐Ferry equation. The incorporation of untreated WF increased dynamic fragility of PLA/WF composites markedly, whereas used silane, maleic anhydride and hydrothermal treatments lead to lower values of parameter m. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Mechanical properties of poly(l‐lactic acid) composites filled with mesoporous silica

The mechanical properties of mesoporous silica (MCM‐41) filled poly(l ‐lactic acid) (PLA4032D) composites and PLA4032D/poly(ethylene glycol) (PEG) composites were investigated. It was found that the Young's modulus increased while tensile strength decreased with increasing the filler content; the V‐notched impact fracture strengths of both Izod and Charpy for the PLA4032D/PEG/MCM‐41 composites increased while they decreased slightly for the PLA4032D/MCM‐41 composites, the unnotched Charpy impact strength of both the two composites decreased with increasing the filler loading; the flexural modulus increased slightly while the flexural strength decreased slightly with increasing the filler content. The toughening mechanisms of the composites were discussed by means of observing the impact fracture surface with a scanning electronic microscope, and the synergistic effect between the PEG and MCM‐41 should be one of the major toughening mechanisms. POLYM. COMPOS., 38:1118–1126, 2017. © 2015 Society of Plastics Engineers     

Improved Mechanical Properties and Flame Retardancy of Wood/PLA All‐Degradable Biocomposites with Novel Lignin‐Based Flame Retardant and TGIC

In this study, a type of all‐degradable flame retardant wood/poly(lactic acid) (PLA) biocomposite (FPW) with low cost and excellent mechanical properties is prepared and studied. A novel lignin‐based phosphorus‐containing flame retardant (LMD) is synthesized first. PLA, wood powder, poly(butyleneadipate‐co‐terephthalate), triglycidyl isocyanurate (TGIC), and LMD are then melt‐blended to prepare FPW. The limiting oxygen index value of PLAF25L15‐4T (25% of L15MD and 4% of TGIC) reaches 28.6%. Furthermore, the residue at 700 °C is up to 31.3%, which apparently helps to increase the flame retardancy of FPW. Its tensile strength is as high as 48.7 MPa. The interfacial compatibilization is much improved as proved by scanning electron microscopy observation. This should be due to the in situ interfacial reaction between PLA, wood, and TGIC, and the lignin component both in wood and LMD. The obtained PLA biocomposite with improved mechanical and flame retardant properties is promising for its wide applications.     

Environmentally friendly mixed tannin/lignin wood resins

We obtained lignin‐based wood adhesives satisfying the requirements of relevant international standards for the manufacture of wood particleboard. These were based on two different low‐molecular‐mass lignins. These lignin‐based wood adhesives did not use any formaldehyde in their formulation; formaldehyde was substituted with a nonvolatile nontoxic aldehyde, namely, glyoxal. The last formaldehyde present, contributed by a fortifying synthetic phenol–formaldehyde resin, was also eliminated by the substitution of the phenol–formaldehyde resin with a natural, vegetable polyflavonoid tannin extract to which no aldehyde was added. This substitution brought the total content of natural material up to 80 wt % of the total adhesive. The adhesives yielded good internal bond strength results of the panels, enough to pass relevant international standard specifications for interior‐grade panels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Agricultural residue-derived lignin as the filler of polylactic acid composites and the effect of lignin purity on the composite performance

In this study, corn stover lignin with different purities was used as filler in polylactic acid (PLA) matrix. It was found that the impurity metals present in unpurified lignin can significantly affect the performance of the composites in terms of their thermal stability, rheological behavior, mechanical properties, and hydrophobicity. Among the PLA composites, the ones fabricated with the lignin containing 4% of impurities overall had the best thermal stability and tensile strength. From melt rheology analysis, it was also found that the presence of the impurity metals decreases the complex viscosity of the composites. It is suggested that the impurity metals acted as catalysts to promote the interaction between lignin and PLA, resulting in an improved compatibility between PLA and the filler. In the present study, mechanical properties and hydrophobicity of the composites were further improved by acetylating the lignin with the optimum content of impurities. Tensile strength of the composite with the acetylated lignin was comparable to that of pure PLA, whereas the modulus increased to as high as 2.75 GPa. Overall, the study showed that unpurified lignin could be used as filler to achieve similar or better performance than the composites made with highly purified lignin fillers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47915.