Effects of chemical modification of wood flour on the rheological properties of high‐density polyethylene blends

Chemical modification of lignocellulosic fibers can improve interfacial adhesion and dimensionally stabilize the resulting plastic composites. This study examined the rheological properties of wood flour/high density polyethylene (HDPE) melts after poplar wood flour was modified with glutaraldehyde (GA, mainly cell wall cross‐linking) and 1,3‐dimethylol‐4,5‐dihydroxyethyleneurea (DMDHEU, mainly poly‐condensation). Results show improvement in both the dispersibility of treated wood flour in the HDPE and its interfacial compatibility. Treatment with GA decreased melt viscosity, moduli, and shear stress as evidenced by rheometry. However, the modifying effects of DMDHEU were not observed, which was mainly due to reduced HDPE content. This study indicates that chemical modification of wood flour is a promising approach to improve the processability of highly filled wood thermoplastic composites via extrusion/injection molding processing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41200.     

Thermoplastic polymers as modifiers for urea–formaldehyde wood adhesives. III. In situ thermoplastic‐modified wood composites

Acrylic monomers and free‐radical initiators were dispersed in an aqueous urea–formaldehyde (UF) suspension and polymerized in situ to afford a suspension containing 5 wt % thermoplastic (5 g of thermoplastic/100 mL of suspension). The viscosity of the thermoplastic‐modified UF suspension (65 wt % solids at 25°C) ranged from 240 to 437 cP versus 121 cP for the unmodified UF control. Wood‐flour composites (sugar maple and 50 wt % adhesive) were prepared with thermoplastic‐modified UF suspensions and cured with the same cycle used for the composites prepared with the unmodified UF adhesive (control). The effect of the thermoplastic‐modified UF adhesive was evaluated on the notched Izod impact strength and equilibrium moisture uptake of the wood‐flour composites. The notched Izod impact strength of the composites prepared with modified UF adhesives increased by as much as 94% above that of the control. The increase depended on the initiator and the monomer composition. The modification affected the equilibrium moisture uptake and rate of moisture uptake in the wood‐flour composites. Preliminary results for particleboard prepared with 10 wt % modified UF adhesive (5% thermoplastic in the UF resin) and unoptimized cure conditions confirmed a significant effect of the thermoplastic modification on both the internal‐bond strength and thickness swelling of the particleboard. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoplastic polymers as modifiers for urea‐formaldehyde (UF) wood adhesives. II. Procedures for the preparation and characterization of thermoplastic‐modified UF wood composites

Wood composites were prepared by using wood flour (sugar maple, Acer saccharum March) and thermoplastic‐modified urea‐formaldehyde (UF) suspensions. Thermoplastic (5–10% w/v) was introduced into the UF suspension as an aqueous solution, a self‐stabilized dispersion in water, or as a surfactant‐stabilized latex. The modified suspension was blended with wood flour, and the blend was cured by using a cure cycle that was suitable for all the thermoplastic‐modified UF formulations and unmodified UF controls. The wood flour composites were tested by using a notched Izod impact strength test. All formulations containing surfactant decreased the impact strength by ～ 30–40% relative to the unmodified UF control, whereas the water‐soluble thermoplastic had no effect on the impact strength. The formulations with self‐dispersed thermoplastics all increased the notched Izod impact strength, with the greatest increase being 69% more than the UF control, except in a single instance when the molecular weight of the thermoplastic was very high, which decreased resin flow. Increasing the thermoplastic content from 5 to 10% w/v did not further improve the impact test results. Scanning electron microscopy of the fracture surfaces showed morphological differences in the systems that varied with the thermoplastic and method of thermoplastic addition to the UF suspension.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 898–907, 2003     

Effect of maleic anhydride/vinyltrimethoxysilane‐co‐grafting polypropylene on the properties of wood‐flour/polypropylene composites by electron‐beam preirradiation

The electron‐beam preirradiation and reactive extrusion technologies were used to prepare maleic anhydride (MAH)/vinyltrimethoxysilane (VTMS)‐co‐grafting polypropylene (PP) as a high‐performance compatibilizer for wood‐flour/PP composites. The grafting content, chemical structure, and crystallization behavior of the compatibilizers were characterized through Fourier transform infrared spectroscopy, differential scanning calorimetry, and an extraction method. The effects of the compatibilizers on the mechanical properties, water absorption, morphological structure, and torque rheological behavior of the composites were investigated comparatively. The experimental results demonstrate that MAH/VTMS‐g‐PP markedly enhanced the mechanical properties of the composites. Compared with MAH‐g‐PP and VTMS‐g‐PP, MAH/VTMS‐g‐PP clearly showed synergistic effects on the increasing mechanical properties, water absorption, and compatibility of the composites. Scanning electron microscopy further confirmed that the adhesion and dispersion of wood flours in the composites were effectively improved by MAH/VTMS‐g‐PP. These results were also proven by the best water resistance of the wood‐flour/PP composites with MAH/VTMS‐g‐PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of post‐cure on properties of carbon/phenolic resin cured composites and their final carbon/carbon composites

Two‐dimensional (2D) carbon/carbon (C/C) composites were prepared with phenol‐formaldehyde resin and graphite fabric. After curing, polymer composites were post‐cured in air at 160°C and 230°C for several hours and then all polymer composites were carbonized up to 1500°C. The effect of post‐cure on the microstructure and fracture behavior of the resultant carbon/carbon composites was studied. The post‐cure process was characterized by weight loss. This process promoted the crosslinking and condensation reactions and led to the formation of long‐chain, cross‐linked polymeric structures in the matrix. The post‐cured composites had a greater density than the unpost‐cured composite. This study indicates that a longer post‐curing time and higher post‐curing temperature would limit the shrinkage for the post‐cured composites during carbonization. The improvement in linear shrinkage was 22% to 44%. This process also limited the formation of open pores and decreased the weight loss of the resultant C/C composites. The resultant C/C composites developed from post‐cured composites had a greater flexural strength by 7 to 26% over that developed from unpost‐cured composite.     

Incorporation effect of enzymatic hydrolysis lignin on the mechanical and rheological properties of the resulting wood flour/high‐density polyethylene composites

Enzymatic hydrolysis lignin (EHL) from ethanol production was used as an additive to incorporate in the wood flour/high‐density polyethylene (HDPE) composite during the melt extrusion, and the incorporating effects on the mechanical and rheological properties of the resulting composites were investigated. The addition of EHL caused an improvement in both the tensile strength and impact strength, and a reduction in the complex viscosity of the composites as evidenced by the rotational rheometry, which suggests an increased flowability of the composite melt due to incorporation of EHL. The water absorption and swelling of the composites decreased with increasing EHL content during water immersion test. The scanning electron microscopy micrographs of EHL incorporated wood flour/high‐density polyethylene composites showed a homogeneous dispersion of wood flour and EHL in the HDPE matrix. POLYM. COMPOS., 37:379–384, 2016. © 2014 Society of Plastics Engineers     

Incorporation of epoxidized soybean oil as co‐matrix in epoxy resin toward developing plastisol/particulate toughened glass fiber composites

Epoxidized soybean oil was incorporated as a co‐matrix into an epoxy resin, and the hybrid resin system was used for preparing glass fiber‐reinforced composites. Effect of addition of poly(vinyl chloride) plastisol and selected particulate fillers (fly ash and wood flour) to epoxy/epoxidized soybean oil matrix on mechanical and water uptake properties of glass fiber‐reinforced composites were studied. Fourier transform infrared spectroscopy was used to reveal the curing state of these composites. It was observed that tensile strengths and moduli decreased with the inclusion of all additives. However, addition of poly(vinyl chloride) plastisol, fly ash, and wood flour particulate fillers showed significant increase in impact strengths compared with neat epoxy composite in a synergistic manner. Water uptake results of the composites were found to be in good agreement with ? OH peak intensities obtained from Fourier transform infrared spectroscopy. Finally, acousto‐ultrasonic nondestructive technique was successfully used to assess damage states and to relate stress wave factors with tensile strength properties of modified epoxy‐based glass fiber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40586.     

Natural fiber composites of high‐temperature thermoplastic polymers: Effects of coupling agents

Our earlier paper (Jana, S.C.; Prieto, A. J Appl Polym Sci 2002, 86, 2159) on the development of natural fiber composites of high‐performance thermoplastic polymers described a new methodology for the manufacturing of composite materials of a high‐temperature thermoplastic polymer, poly(phenylene ether) (PPE) and wood flour, a cellulosic natural filler. A thermosetting epoxy, used as a reactive solvent, reduced the processing temperature of PPE/epoxy blends to well below the decomposition temperature of natural fillers. In addition, the epoxy component, upon polymerization, formed coating layers around the filler particles to provide resistance against moisture diffusion and attacks by acids and alkali. This article describes the results of an investigation on two outstanding issues: (1) the influence of cellulosic wood particles and coupling agents on the speed of epoxy curing and reaction‐induced phase separation and (2) the effects of coupling agents on the morphology of crosslinked epoxy at the surfaces of natural fillers and mechanical properties of the composites. It was found that wood particles expedited epoxy curing in the composites; the extent of epoxy curing, however, was reduced in the presence of coupling agents. Also, the coupling agents promoted complete coverage of wood flour particles by polymerized epoxy, although the mechanical properties deteriorated over systems without coupling agents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2168–2173, 2002     

Comparative study on the effect of manchurian ash and larch wood flour on mechanical property,morphology, and rheology of HDPE/wood flour composites

Effects of wood flour species and polyethylene grafted with maleic anhydride (MA‐PE) on mechanical properties and morphology and torque rheology of high density polyethylene (HDPE)/wood flour composites have been comparatively investigated. The results demonstrated that without compatbilizer, wood flour species exhibited little influence on mechanical properties. In the presence of MA‐PE, the mechanical properties were obviously increased. On the basis of the mechanical property data obtained from wood flour extracted by different methods, the extractant was an important factor affecting the mechanical properties. Manchurian ash and larch wood flours extracted by hot water presented almost the same mechanical properties, and larch wood flour was the most beneficial to enhance the mechanical properties. The scanning electron microscopy (SEM) and the atomic force microscopy (AFM) further confirmed that interfacial adhesion and dispersion of manchurian ash wood flour in composites were effectively improved by MA‐PE. The torque results demonstrated that the chemical reactions of maleic anhydride groups on MA‐PE with hydroxyl on cellulose in wood flour probably took place due to the increase of the equilibrium torque and the appearance of the torque peak, and larch wood flour was more beneficial to prepare the composites containing the higher wood flour content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Soybean and linseed oil‐based composites reinforced with wood flour and wood fibers

Composites consisting of a conjugated linseed or soybean oil‐based thermoset reinforced with wood flour and wood fibers have been prepared by free radical polymerization. The thermoset resin consists of a copolymer of conjugated linseed oil (CLO) or conjugated soybean oil (CSO), n‐butyl methacrylate (BMA), divinylbenzene (DVB), and maleic anhydride (MA). The composites were cured at 180°C and 600 psi and postcured for 2 h at 200°C under atmospheric pressure. The effect of varying filler load, time of cure, filler particle size, origin of the fillers, and resin composition has been assessed by means of tensile tests, DMA, TGA, Soxhlet extraction followed by ¹H‐NMR spectroscopic analysis of the extracts, and DSC. The best processing conditions have been established for the pine wood flour composites. It has been observed that the addition of MA to the resin composition improves the filler‐resin interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of highly filled wood flour/recycled high density polyethylene composites by in situ reactive extrusion

Highly filled wood flour/recycled high density polyethylene (WF/RHDPE) composites were directly prepared by in situ reactive extrusion using a twin‐screw/single‐screw extruder system. The effects of dicumyl peroxide (DCP) content on extrusion pressure, rheological behavior, mechanical properties, fractured surface morphology of the composites, and melting temperature of RHDPE in the composites were investigated. The extrusion pressure and torque of WF/RHDPE composite melt increased with DCP content. Mechanical property tests and scanning electron microscopy analysis results confirmed that the interfacial interaction of the composites was improved by in situ reaction. The composites show lower melting peak temperature (T_m) than RHDPE. The cooling in profile extrusion shortened the crystallization time, resulting in decrease of crystalline order of RHDPE in the composites. There are no noticeable changes of T_m values with increasing DCP content. Comparative study on composites with maleic anhydride grafted polyethylene as compatibilizer demonstrated that mechanochemical treatment with DCP and maleic anhydride was an effective method to improve interfacial adhesion for WF/RHDPE composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of HDPE/SEBS‐g‐MAH and its effect on mechanical properties of HDPE/wood flour composites

In this article, high density polyethylene/styrene‐ethylene‐butylene‐styrene block copolymer blends (HDPE/SEBS) grafted by maleic anhydride (HDPE/SEBS‐g‐MAH), which is an effective compatibilizer for HDPE/wood flour composites was prepared by means of torque rheometer with different contents of maleic anhydride (MAH). The experimental results indicated that MAH indeed grafted on HDPE/SEBS by FTIR analysis and the torque increased with increasing the content of maleic anhydride and dicumyl peroxide (DCP). Styrene may increase the graft reaction rate of MAH and HDPE/SEBS. When HDPE/SEBS MAH was added to HDPE/wood flour composites, tensile strength and flexural strength of composites can reach 25.9 and 34.8 MPa in comparison of 16.5 and 23.8 MPa (without HDPE/SEBS‐g‐MAH), increasing by 157 and 146%, respectively. Due to incorporation of thermoplastic elastomer in HDPE/SEBS‐g‐MAH, the Notched Izod impact strength reached 5.08 kJ m^?2, increasing by 145% in comparison of system without compatibilizer. That HDPE/SEBS‐g‐MAH improved the compatibility was also conformed by dynamic mechanical measurement. Scanning electron micrographs provided evidence for strong adhesion between wood flour and HDPE matrix with addition of HDPE/SEBS‐g‐MAH. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Chemorheology of thermosetting resins. III. Effect of low-profile additive on the chemorheology and curing kinetics of unsaturated polyester resin

An experimental study was conducted to investigate the effect of low-profile thermoplastic additives on the rheological behavior during cure and the curing kinetics of unsaturated polyester resin. For the study, a general-purpose polyester resin was used and two different types of thermoplastic additive, poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA), were used as low-profile additives. It has been found that, during cure, the resin/PMMA system exhibits shearthinning behavior even before the cure time reaches the critical value tη∞ whereas the resin/PVAc system does not. Also, both PVAc and PMMA help reduce the shrinkage of the resin during cure. However, our study shows that shrinkage control becomes effective only when the shear rate is greater than a certain critical value. The curing behavior determined with the aid of differential scanning calorimetry (DSC) shows that the rate of cure and the final degree of cure are decreased when the amount of low-profile additive is increased.     

Cure kinetics of aqueous phenol‐formaldehyde resins used for oriented strandboard manufacturing: Effect of wood flour

The effect of wood flour on the cure kinetics of commercial phenol‐formaldehyde resins used as oriented strandboard face and core adhesives was studied using differential scanning calorimetry. The wood flour did not change the cure mechanism of the face resin, but lowered its cure temperature and activation energy and increased its cure reaction order. For the core resin (CR), the wood flour lowered the onset cure temperature, and caused separation of the addition and condensation reactions involved in curing of CR. Compared with neat CR, the addition reaction of CR/wood mixture also followed an nth‐order reaction mechanism but with a lower reaction order, while the condensation was changed from an autocatalytic reaction to an nth‐order one. The addition reaction happened at temperatures lower than 90°C, and the condensation reaction was dominant at temperatures higher than 110°C. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (cure degree), cure temperature, and cure time were predicted. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3774–3781, 2006     

Rheological behavior and mechanical properties of wood flour/high density polyethylene blends: Effects of esterification of wood with citric acid

This study explored the modifying effects of wood flour (WF) with citric acid (CA) on the rheological and mechanical properties of WF/high density polypropylene (HDPE) composites. WF was treated with CA, which acts a cross‐linking agent and melt‐blended with HDPE with a twin‐screw extruder. Injection molding was used to make tensile and impact tests samples. The rheological properties of the blends were characterized using a Haake microcompounder, torque‐, capillary‐, and rotational‐rheometer, respectively. Results show that the thermal stability of WF decreased after treatment. Compared with those of untreated composites, the tensile strength, elongation‐at‐break, and impact strength of the composites treated with 5% CA were reduced by 6%, 14%, and 16%, respectively. This reduction was attributed to embrittlement of WF, which may negatively influence the mechanical properties of the resulting composites. Scanning electron microscopy revealed better dispersion of CA‐treated WF in the composites than the untreated WF. For composites treated with 5% CA, the melt torque, viscosity, moduli, and shear stress decreased significantly, indicating an improvement in processibility. This improvement is attributed to uniform dispersion of the modified WF, as well as to better interfacial adhesion between WF and the matrix. Results suggest that treating WF with CA shows promise for improving the processibility of highly filled thermoplastic composites via extrusion/injection molding processing. POLYM. COMPOS., 37:553–560, 2016. © 2014 Society of Plastics Engineers     

Fusion characteristics of rigid PVC/wood‐flour composites by torque rheometry

This study was aimed at examining the effects of wood flour contents, wood species (softwood vs. hardwood), and particle size on the fusion characteristics (fusion time, fusion temperature, fusion torque, and fusion energy) of rigid PVC/wood‐flour composites in a torque rheometer. Neat rigid PVC exhibited one fusion peak, whereas the addition of wood flour into the PVC matrix led to two fusion peaks. Increased wood flour content caused a significant increase in the time, temperature, and energy at which fusion between the primary particles started, thereby leading to increased fusion torque, irrespective of the wood flour species. These results implied that rigid PVC filled with wood flour must be processed at higher temperatures than neat resin. Although fusion characteristics of the composites were influenced by the wood species, a clear trend between softwood and hardwood species could not be established. However, finer particles fused more quickly and needed less energy than coarse ones. J. VINYL ADDIT. TECHNOL., 13:7–13, 2007. © 2007 Society of Plastics Engineers.     

The effect of epoxy‐polyester hybrid resin on mechanical properties,rheological behavior,and water absorption of polypropylene wood flour composites

The effect of epoxy resin on mechanical and Rheological properties, and moisture absorption of wood flour polypropylene composites (WPCs) were investigated. The reactive mixing of epoxy resin with 30, and 40 wt% wood flour and polypropylene (PP) was carried out in twin screw extruder with a special screw elements arrangement. PP grafted maleic anhydrides (MPP) were used as coupling agent to improve the interfacial interactions of wood flour, epoxy resin, and PP. The tensile strength of composites decreased, and elastic modulus and moisture absorption increased with increasing epoxy resin content. The complex viscosity η* increased with increasing epoxy resin content of composites, and a synergistic effect in increasing the η* was observed at 3 wt% resin. The epoxy resin modified wood‐PP composites that chemically coupled by MPP showed minimum water absorption with highest elastic modulus. The experimental oscillation rheologyical data were used to drive a model to predict the flow behavior of WPCs, in a wide range of frequencies. POLYM. ENG. SCI., 47:2041–2048, 2007. © 2007 Society of Plastics Engineers     

Dynamically cured polypropylene/epoxy blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, was used to prepare polypropylene (PP)/epoxy blends. The blends had crosslinked epoxy resin particles finely dispersed in the PP matrix, and they were called dynamically cured PP/epoxy blends. Maleic anhydride grafted polypropylene (MAH‐g‐PP) was used as a compatibilizer. The effects of the reactive compatibilization and dynamic cure were studied with rheometry, capillary rheometry, and scanning electron microscopy (SEM). The crystallization behavior and mechanical properties of PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends were also investigated. The increase in the torque at equilibrium for the PP/MAH‐g‐PP/epoxy blends indicated the reaction between maleic anhydride groups of MAH‐g‐PP and the epoxy resin. The torque at equilibrium of the dynamically cured PP/epoxy blends increased with increasing epoxy resin content. Capillary rheological measurements also showed that the addition of MAH‐g‐PP or an increasing epoxy resin content increased the viscosity of PP/epoxy blends. SEM micrographs indicated that the PP/epoxy blends compatibilized with PP/MAH‐g‐PP had finer domains and more obscure boundaries than the PP/epoxy blends. A shift of the crystallization peak to a higher temperature for all the PP/epoxy blends indicated that uncured and cured epoxy resin particles in the blends could act as effective nucleating agents. The spherulites of pure PP were larger than those of PP in the PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends, as measured by polarized optical microscopy. The dynamically cured PP/epoxy blends had better mechanical properties than the PP/epoxy and PP/MAH‐g‐PP/epoxy blends. With increasing epoxy resin content, the flexural modulus of all the blends increased significantly, and the impact strength and tensile strength increased slightly, whereas the elongation at break decreased dramatically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1437–1448, 2004     

Effects of material parameters on the diffusion and sorption properties of wood‐flour/polypropylene composites

Composites of wood in a thermoplastic matrix (wood–plastic composites) are considered a low maintenance solution to using wood in outdoor applications. Knowledge of moisture uptake and transport properties would be useful in estimating moisture‐related effects such as fungal attack and loss of mechanical strength. Our objectives were to determine how material parameters and their interactions affect the moisture uptake and transport properties of injection‐molded composites of wood‐flour and polypropylene and to compare two different methods of measuring moisture uptake and transport. A two‐level, full‐factorial design was used to investigate the effects and interactions of wood‐flour content, wood‐flour particle size, coupling agent, and surface removal on moisture uptake and transport of the composites. Sorption and diffusion experiments were performed at 20°C and 65 or 85% relative humidity as well as in water, and diffusion coefficients were determined. The wood‐flour content had the largest influence of all parameters on moisture uptake and transport properties. Many significant interactions between the variables were also found. The interaction between wood‐flour content and surface treatment was often the largest. The diffusion coefficients derived from the diffusion experiments were different from those derived from the sorption experiments, suggesting that different mechanisms occur. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 752–763, 2007     

On the development of natural fiber composites of high‐temperature thermoplastic polymers

A new method is presented for the development of natural fiber composites of high‐performance thermoplastic polymers considering poly(phenylene ether) (PPE) and wood flour as an example system. The large gap between the high processing temperature of PPE, typically between 280 and 320°C, and the low decomposition temperature of wood flour, about 200°C, was reduced by using a reactive solvent, a low molecular weight epoxy. The epoxy formed miscible blends with PPE, which offered much lower viscosity compared to PPE and processing temperatures well below the decomposition temperature of wood flour. In addition, the epoxy component accumulated around the polar wood flour particles upon polymerization during the fabrication step. The composite materials consisted of a thermoplastic continuous phase and two dispersed phases, one of polymerized epoxy and the other of wood flour particles coated with polymerized epoxy. These composites offered a significant reduction in density and better mechanical and physical properties when compared to commercially available grades of engineering polymer blends filled with short glass fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2159–2167, 2002