Preparation of acetylated wood meal and polypropylene composites I: acetylation of wood meal by mechanochemical processing and its characteristics

Wood meals of Sugi (Cryptomeria japonica D.Don) passing 2.0 mm and retained on 1.0 mm mesh screens were milled along with acetic anhydride (AA) and pyridine as a catalyst in a high-speed vibration rod mill at ambient temperature. The weight percent gain (WPG) of the chemically modified wood was calculated based on the yield after washing with deionized water. The effects of amounts of AA and catalyst added, pulverization time, and saponification of the acetylated wood on WPG were examined. In addition, FT-IR analysis, and water vapor adsorption and desorption tests were performed as functions of the WPG. Increases in WPG, the acetyl contents of the acetylated wood after saponification, changes in the FT-IR spectra after pulverization, and the water vapor sorption isotherms showed that the one-step acetylation systematically modified the hydroxyl groups of the wood into acetyl groups. Up to 38 % WPG was obtained at 100 phr AA and 15 phr catalyst, and 120 min pulverization. Pulverization time and the amounts of AA and catalyst added to the wood meals could be adjusted to obtain acetylated wood meal with the desired WPG. These demonstrated that the mechanochemical acetylation is a method to prepare acetylated wood meals with high WPG at less reaction time and required AA addition.     

Effects of low bondability of acetylated fibers on mechanical properties and dimensional stability of fiberboard

Fiberboards were prepared from acetylated fibers with various weight gains: 0, 4.7, 9.4, 18.5, and 24.8 weight percent gain (WPG). The effects of low bondability of acetylated fibers on mechanical properties and dimensional changes were determined. The decreased mechanical properties of acetylated fiberboard are mainly due to low bondability. To improve bending strength, high face density is also needed. The thickness swelling according to JIS and the linear expansion under relative humidity changes decreased with increasing WPG. As for accelerated weathering and the outdoor exposure test, the thickness changes in 4.7–18.5 WPG boards were much higher than those in OWPG board and 24.8 WPG board. The high thickness change in 4.7–18.5 WPG boards is due to low bondability. Although 24.8 WPG board also has low bondability, the thickness change of 24.8 WPG board decreased. The high dimensional stability of acetylated fibers, caused by high WPG, probably outweighs the dimensional change caused by low bondability. On the other hand, during the boiling test the thickness changes in 24.8 WPG board and the 4.7–18.5 WPG boards were higher than those in 0 WPG board. The effect of the boiling test on the boards is more severe than that seen with the accelerated weathering and outdoor exposure test; therefore, the effects of the low bondability probably cancel the effects of the high WPG. It is necessary to increase the bondability of acetylated fibers to improve the dimensional stability and the mechanical properties.     

Micromorphology,moisture sorption and mechanical properties of a biocomposite based on acetylated wood particles and cellulose ester

Abstract

One of the major issues in a long-term perspective for the use of wood–plastic composites (WPCs) in outdoor applications is the moisture sensitivity of the wood component and the consequent dimensional instability and susceptibility to biological degradation of the composite. In this work, the effects of using an acetylated wood component and a cellulose ester as matrix on the micromorphology, mechanical performance and moisture uptake of injection-moulded WPCs have been studied. Composites based on unmodified and acetylated wood particles, specially designed with a length-to-width ratio of about 5–7, combined with both cellulose acetate propionate (CAP) and polypropylene (PP) matrices were studied. The size and shape of the wood particles were studied before and after the processing using light microscopy, and the micromorphology of the composites was studied using a newly developed surface preparation technique based on ultraviolet laser irradiation combined with low-vacuum scanning electron microscopy (LV-SEM). The water vapour sorption in the composites and the effect of accelerated weathering were measured using thin samples which were allowed to reach equilibrium moisture content (EMC). The length-to-diameter ratio was only slightly decreased for the acetylated particles after compounding and injection moulding, although both the unmodified and the acetylated particles were smaller in size after the processing steps. The tensile strength was about 40% higher for the composite based on acetylated wood than for the composite with unmodified wood using either CAP or PP as matrix, whereas the notched impact strength of the composite based on acetylated wood was about 20% lower than those of the corresponding unmodified composites. The sorption experiments showed that the EMC was 50% lower in the composites with an acetylated wood component than in the composites with an unmodified wood component. The choice of matrix material strongly affected the moisture absorptivity of the WPC. The composites with CAP as matrix gained moisture more rapidly than the composites with PP as matrix. It was also found that accelerated ageing in a Weather-Ometer® significantly increased the moisture sensitivity of the PP-based composites.     

Field test of resistance of modified wood to marine borers

Abstract

Five mineral fillers were tested for wood–plastic composites (WPCs): calcium carbonate, two different types of wollastonite, soapstone and talc. The impact of the fillers on the mechanical properties of the composites was studied. The experiments included bending tests, tensile tests, Brinell hardness and scanning electron microscopy experiments. The amount of wood, mineral and plastic (polypropylene) was kept steady. Only the mineral type was changed during the tests. A control sample without any mineral added was also manufactured. The mineral addition improved the tensile strength of the WPCs. The hardness of the composite was also improved when the minerals were added, and along with the increasing mineral hardness, the hardness of the composite increased. The wollastonite acicular shape was crushed during the manufacturing process, so the phase of the process in which the minerals are added requires careful consideration.     

Preliminary study of viscoelastic properties of MAPP-modified wood flour/polypropylene composites

Viscoelastic properties of maleated polypropylene (MAPP)-modified wood flour/polypropylene composites (WPC) were investigated by both a compression stress relaxation method and dynamic mechanical analyses (DMA). Three wood to polymer ratios (40:60, 60:40, and 80:20) and five MAPP loading levels (0, 1, 2, 4 and 8%) were used to study their effects on the viscoelastic properties of MAPP-WPC. The results show that: 1) higher wood to polymer ratio corresponds to higher stress relaxation levels for unmodified WPC. The modification with MAPP has an obvious effect on the stress relaxation of MAPP-WPC at higher wood to polymer ratios (60:40 and 80:20), but almost no effect at the 40:60 wood to polymer ratio. The optimal MAPP loading level for the wood to polymer ratio of 60:40 appears at 1%; 2) the storage modulus reaches its maximum at a MAPP loading level of 1% for wood to polymer ratios of 40:60 and 60:40, while for the 80:20 wood to polymer ratio, a higher storage modulus is observed at higher MAPP loading levels, which is quite consistent with the stress relaxation results. The results suggested that a suitable loading level of MAPP has a positive effect on the viscoelastic properties of WPC at higher wood to polymer ratios. Excessive MAPP loading would have resulted in adverse effects.     

Acetylation of wood in combination with polysiloxanes to improve water-related and mechanical properties of wood

Scots pine sapwood was acetylated with ethyltriacetoxysilane using acetic acid as a solvent and sulfuric acid as a catalyst. A weight percent gain (WPG) of 14 % and cell wall bulking of 7 % were obtained after 5 h of reaction time. Pine specimens were acetylated with acetic anhydride in the presence of 1 % ethyltriacetoxysilane, dihydroxy-functional siloxane, acetoxy-functional siloxane, amino-functional siloxane and non-functional siloxane, respectively. Acetoxy-functional siloxane induced the greatest reduction in water uptake with a water repellent effectiveness after 24 h of up to 62 % as compared to acetylated wood. WPG and cell wall bulking increased compared to solely acetylated wood with increasing concentrations of acetoxy-functional siloxane in acetic anhydride; anti-shrink efficiency, however, did not increase. Fungal resistance of pine sapwood and beech as well as mechanical strength properties did not change when 20 % acetoxy-functional siloxane was added to acetic anhydride compared to solely acetylated specimens.     

Potassium acetate-catalyzed acetylation of wood: extraordinarily rapid acetylation at 120°C

The catalytic effect of potassium acetate (KAc) on wood acetylation was investigated. Spruce wood specimens were impregnated with KAc and then heated in acetic anhydride at 120°C. The degree of acetylation was evaluated by the weight percent gain (WPG). In the presence of KAc, the reaction time to achieve a 20% WPG decreased by a factor of 200: 2 min was required in the KAc-catalyzed acetylation, while the uncatalyzed acetylation required at least 5 h. The hygroscopicity and dimensional stability of acetylated wood depended on the WPG irrespective of the treatment methods. This fact proved that KAc had no adverse influence on the dimensional stability of acetylated wood. As KAc is a cheap, water-soluble and non-toxic salt it can be a useful catalyst for the extraordinarily rapid acetylation of wood.     

Effects of previous solvent exchange on acetylation of wood

Wood specimens were prepared in a swollen state using solvent exchange (PS) treatment. The swollen wood specimens were acetylated using acetic anhydride by heating at 80–120°C. At the beginning of heating, the weight percent gain (WPG) of PS-treated wood was greater than that of conventionally acetylated wood. This acceleration effect of the PS treatment was explained by the introduction of treating reagent into the wood polymers where the intermolecular hydrogen bonds were previously broken. On the other hand, the PS treatment had no influence on the final WPG and moisture sorption characteristics of acetylated wood. This indicated that the intrinsic reactivity of wood constituents was unaffected by the PS treatment. The acetylation of PS-treated wood produced greater bulking and slightly higher dimensional stability than that in the case of conventional acetylation at the same WPG. It was speculated that the expansion of cell lumina due to the PS treatment resulted in greater bulking on acetylation and lesser swelling of acetylated wood with moisture sorption.     

Potassium acetate-catalyzed acetylation of wood: reaction rates at low temperatures

Spruce wood blocks were acetylated in the presence of potassium acetate (KAc) at 20, 40, 60, 80 and 120°C. At 20°C, the weight percent gain (WPG) due to the KAc-catalyzed acetylation reached 20% in 18 days, whereas that due to pyridine-catalyzed acetylation did not exceed 8%. The hygroscopicity and dimensional stability of the KAc-acetylated wood were the same as those of conventionally acetylated wood at the same WPG, irrespective of reaction temperature. These facts suggest that the KAc enables simplified acetylation of wood at room temperature. The activation energy (E _a) of the KAc-acetylation in the lower temperature range (20–40°C, 121–131 kJ/mol) was comparable to that of the acetylation of wood meal (140–146 kJ/mol). It was speculated that diffusion became a minor factor at reduced reaction rates in the lower temperature range, thus requiring a greater E _a.     

木纤维PP/PE共混物复合材料的流变和力学性能(英文)

For evaluation of the rheological and mechanical properties of highly filled wood plastic composites （WPCs）, polypropylene/polyethylene （PP/PE） blends were grafted with maleic anhydride （MAH） to enhance the interfacial adhesion between wood fiber and matrix. WPCs were prepared from wood fiber up to 60 wt.% and modified PP/PE was blended by extrusion. The rheological properties were studied by using dynamic measurement. According to the strain sweep test, the linear viscoelastic region of composites in the melt was determined. The result showed that the storage modulus was independent of the strain at low strain region （〈0.1%）. The frequency sweep resuits indicated that all composites exhibited shear thinning behavior, and both the storage modulus and complex viscosity of MAH modified composites were decreased comparing to those unmodified. Flexural properties and impact strength of the prepared WPCs were measured according to the relevant standard specifications. The flexural and impact strength of the manufactured composites significantly increased and reached a maximum when MAH dosage was 1.0 wt%, whereas the flexural modulus after an initial decreased, also increased with MAH dosage. The increase in mechanical properties indicated that the presence of anhydride groups enhanced the interracial adhesion between wood fiber and PP/PE blends.     

The effect of acetylation on the mechanical properties, hydrophobicity, and dimensional stability ofPinus sylvestris

Summary Strips and blocks ofPinus sylvestris were acetylated for different periods of time. These, along with control samples, were tested for their tensile modulus, hydrophobicity and dimensional stability. The modulus of elasticity (tensile modulus) for each sample was derived using a statistical approach. The observations in this work suggest that the acetylation process significantly reduces the tensile modulus of the wood compared to its untreated state in an irreversible manner, and that the extent of the deterioration in tensile modulus is a function of the acetylation conditions. Acetylation improved significantly the hydro-phobicity and the dimensional stability of the wood as measured by the roll angle and swelling tests respectively. It appears therefore that acetylation using acetic anhydride in xylene has an optimum set of reaction conditions that compromise between the gains in water repellence and dimensional stability with the deterioration in mechanical properties.We would like to acknowledge the support of Unilever Research in providing the materials testing machine used in this work, and for the supportive discussions with Hickson & Welsh concerning the results     

Chemical modification of wood by anhydrides without solvents or catalysts

Acetylated, propionylated, butyrylated, isobutyrylated, and hexanoylated woods were prepared at several temperatures. The reaction rate, dimensional stability, and changes in the ratios of specific gravity and dimensions in the tangential and radial directions were estimated. The reaction rate of propionylation was slow at temperatures under 90°C but increased with the temperature. The butyrylated, isobutyrylated, and hexanoylated woods showed little or no weight percent gain (WPG) and little or no antiswelling efficiency (ASE) below 110°C even for 24h, but they achieved significant WPG and ASE values at 140°C with a longer reaction time. The acetylated, propionylated, and butyrylated woods showed almost the same values for dimensional stabilization efficiency based on WPG (DSE). The specific gravity and dimensions ratios for acetylated, propionylated, and butyrylated woods compared to those of untreated wood increased with an increase in WPG.     

Fundamental studies on wood/cellulose-plastic composites: effects of composition and cellulose dimension on the properties of cellulose/PP composite

Although wood/cellulose-plastic composites (WPC) of low wood/cellulose content have been more accepted worldwide and are promoted as low-maintenance, high-durability building products, composites containing high wood/cellulose content are not yet developed on an industrial scale. In this study, flow properties, mechanical properties, and water absorption properties of the compounds of cellulose microfiber/polypropylene (PP) and maleic anhydride-grafted polypropylene (MAPP) were investigated to understand effects of the high cellulose content and the dimensions of the cellulose microfiber. The molding processes studied included compression, injection, and extrusion. It was found that fluidity is not only dependent on resin content but also on the dimension of the filler; fluidity of the compound declined with increased fiber length with the same resin content. Dispersion of the composite was monitored by charge-coupled device (CCD) microscope. Increasing the plastic content in the cellulose-plastic formulation improved the strength of mold in addition to the bond development between resin and filler, and the tangle of fibers. The processing mode affected the physicomechanical properties of the cellulosic plastic. Compression-molded samples exhibited the lowest modulus of rupture (MOR) and modulus of elasticity (MOE) and the highest water absorption, while samples that were injection-molded exhibited the highest MOR (70 MPa) and MOE (7 GPa) and low water absorption (2%).     

Effect of organoclay platelets on the mechanical properties of wood–plastic composites formulated with virgin and recycled polypropylene

Abstract

This study investigated the effects of organoclay platelet contents (0, 3 and 5 wt%) and polypropylene type (virgin and recycled) on the mechanical properties of polypropylene/wood flour composites. Composite samples were made by melt compounding and consequent injection moulding. The tensile, flexural and impact properties of resultant composites were determined. X-ray diffraction (XRD) analysis of composites with 3 and 5% nanoclay content was also conducted. The results indicated that tensile and flexural properties of the composites increased with the addition of nanoclay particles up to 3 wt% and decreased thereafter. The impact strength of the composites, however, decreased with the incorporation of nanoclay. The mechanical properties of the recycled polypropylene-based nanocomposites were statistically comparable with those based on virgin polypropylene. XRD analysis revealed that the degree of intercalation in the nanocomposites containing 3% nanoclay was higher than in those containing 5%. Based on these results, it can be concluded that recycled polypropylene could be used instead of virgin polypropylene in the production of value-added products with no significant adverse effects on the mechanical properties.     

Mode of action of brown rot decay resistance of acetylated wood: resistance to Fenton’s reagent

Acetylation is known to enhance the resistance of wood to brown rot fungi. As initial decay by some brown rot fungi is assumed to be caused by the Fenton reaction, pine micro-veneers acetylated to various weight percent gains (WPG) were exposed in a solution containing iron ions and hydrogen peroxide, i.e., Fenton’s reagent. Mass loss and tensile strength loss as well as the decomposition of hydrogen peroxide within the incubation time decreased with increasing WPG of the veneers. Incubation of untreated and acetylated veneers in acetate buffer containing ferric ions without H₂O₂ revealed that the modification strongly reduced the uptake of Fe ions by the wood cell wall. FT-IR analysis indicated oxidation of the unmodified control veneers but did not show predominant decay of specific cell wall components. Spectra of acetylated veneers did not reveal any significant changes induced by Fenton’s reagent. It was concluded that one possible reason for the enhanced resistance of acetylated wood to the Fenton reaction could be the reduced or almost completely prevented uptake of Fe ions by the wood cell wall.     

Potassium acetate-catalyzed acetylation of wood at low temperatures II: vapor phase acetylation at room temperature

Ezomatsu wood blocks were impregnated with potassium acetate (KAc) and then exposed to acetic anhydride vapor at 25°C and 120°C. The KAc-impregnated wood was rapidly acetylated at 120°C, and only 6 min was needed to achieve 20% weight percent gain (WPG). The WPG increased with increasing catalyst loading (CL), but it turned to decrease above 20% CL probably because the diffusion of acetic anhydride vapor was hindered by excess KAc depositing in the cell lumina. Thus, careful control of CL is necessary in the vapor-phase acetylation. KAc was also effective in catalyzing the vapor-phase acetylation at 25°C: the KAc-impregnated wood attained 20% WPG within 7 days, whereas the WPG did not exceed 10% even after 1 month in the uncatalyzed system. Irrespective of treatment methods, the hygroscopicity of wood was reduced and its dimensional stability was improved with an increase of WPG. These results confirm that the use of KAc simplifies the acetylation process at room temperature with minimal loss of acetic anhydride.     

Properties of flat-pressed wood plastic composites as a function of particle size and mixing ratio

This paper presents the effects of particle size and mixing ratio on the properties including physical, mechanical, and decay resistance of wood plastic composites (WPCs). In addition, it also presents the effects of immersion temperatures on water absorption (WA) and thickness swelling (TS) of the WPCs. WPCs with a thickness of 6 mm were fabricated from Albizia richardiana King & Prain wood particles and recycled polyethylene terephthalate (PET) by the flat-press method. To prepare the WPCs, two different wood particle sizes (0.5–1.0 and 1.01–2.0 mm) were used along with four different mixing ratios (w/w). Subsequently, the physical properties include density, moisture content, WA, and TS, and mechanical properties include modulus of elasticity (MOE) and modulus of rupture (MOR) of the produced WPCs was evaluated. Furthermore, decay resistance was evaluated by the weight loss percentage method. Moreover, the effects of immersion temperatures on WA and TS of WPCs after 24 h of immersion in water at three different temperatures, i.e., 25, 50, and 75 °C were investigated. Results showed that the wood particle size had impact on WPC’s density (only 6% decreased with the increase of particle size); however, the density decreased by 29% when the wood particle content increased from 40 to 70%. The WA and TS gradually increased with the increase of particle content and decrease of particle size. In addition, WA and TS increased proportionately with increasing immersion temperature from 25 to 75 °C. Furthermore, the highest MOE (2570 N/mm²) was found for the WPCs fabricated from large wood particles having the ration of 50:50 (wood particle:PET). For decay resistance, WPCs consisted of larger particles and higher PET content showed greater resistance against decay. Therefore, it is comprehensible that fabrication of the WPCs from 50% large particles and 50% PET is technically feasible and further improvement of WPC performance like enhancement of MOE and reduction of density using coupling agent and agricultural waste fibers, respectively, in the WPC formulation is recommended.     

Effect of chemical modification on the properties of wood/polypropylene composites

对以铝酸酯为偶联剂对木粉进行表面改性处理后制备的木粉/聚丙烯复合材料的力学性能和形态学特征进行了研究。结果表明:铝酸酯偶联剂可以增加木塑复合材料的抗冲击强度,但会对复合材料的抗拉强度和抗弯强度造成负面的影响。对木塑复合材料的动态力学性能和微分扫描热量分析研究表明,以铝酸酯作为偶联剂,对木塑复合材料的储存模量和损失模量有少许增加,同时可降低材料的熔点和熔解热。利用扫描电镜观察木塑复合材料的木材与塑料界面发现,经铝酸酯处理过的木材与聚丙烯复合界面之间具有更好的相容性。这些研究结果表明,在木塑复合材料制造过程中利用廉价的铝酸酯作为木材化学改性剂,对改善复合材料的性质同样起作良好的作用。图6 表2 参16。     

Optimum preparation technology for Chinese fir wood/Ca-montmorillonite （Ca-MMT） composite board

For this study, an intercalation compounding method was used to prepare Chinese fir wood/Ca-montmorillonite （Ca-MMT） composite board to improve its properties such as surface mechanical properties, flame retardance and dimensional stability. By virtue of water-soluble phenolic resin （PF）, Chinese fir wood and Ca-MMT were mixed by pressure and vacuum impregnation. The optimum impregnation technology of Chinese fir wood/Ca-MMT composite board was obtained by using an orthogonal design and a single factor design of pressure and vacuum impregnation, using weight percent gain （WPG） as the basic index. The results are as follows： 1） On the basis of the orthogonal design and an actual experiment, the optimum preparation technology of Chinese fir wood/Ca-MMT composite board is 20% PF resin dispersion concentration （wt%）, 1.0 CEC amount of organic intercalation agent, 0.098 MPa vacuum degree, 5% concentration of Ca-MMT and 1.0 MPa pressure. 2） The WPG of the composite board samples of 450 mm length was much larger than that of the samples of 600, 750 and 900 mm length. Warm water extraction contributed little to WPG     

Effect of thermo-hydro-mechanical densification on microstructure and properties of poplar wood (<Emphasis Type="Italic">Populus tomentosa</Emphasis>)

This study aimed at developing a thermo-hydro-mechanical (THM) processing to compress poplar wood and investigating the effects of high temperature, moisture, and pressure during the THM processing on the changes in microstructure, porosity, mechanical properties, and dimensional stability of compressed poplar wood. The variations in these properties were correlated and their mathematical relations were determined. Poplar woods with high moisture content were compressed using different pressures at a temperature of 160 °C for different periods. The compression level was characterized by the volume compression ratio (CR), which is defined as the ratio of the compression volume and the original volume of sample before and after THM processing. The obtained results indicated that the high pressure of THM process caused the collapsing of wood cell lumens and the developing of a certain amount of fractures in the cell wall. The damage level of wood cells increased with increasing pressure and time. Moreover, the pressure narrowed the cell lumens, which decreased significantly the pore volume in wood substrate. The pore size distribution shifted from the level of macropores to those of mesopores and micropores after THM process. The THM process created superior mechanical property, especially for those with higher CR. Besides, it was revealed that the process decreased dramatically the set recovery of treated woods and improved their dimensional stability. A significant improvement was achieved in terms of the mechanical and physical properties of compressed poplar wood via the structural reformation during the THM process.