微波等离子体处理西南桤木表面的ESR和XPS分析

采用电子顺磁共振波谱 (ESR)和X射线光电子能谱 (XPS)技术 ,分析了微波等离子体处理前后西南桤木木材表面的性质。ESR图谱分析表明 :经过微波等离子体处理后 ,木材表面可迅速有效地产生大量的自由基 ;XPS图谱分析表明 :微波等离子体处理使木材表面O C原子比增加 ,C1 含量降低 ,而C2 、C3含量增加 ,并有C4 的出现。这些结果表明经微波等离子体处理后木材表面产生了大量的含氧官能团或过氧化物     

Chemical modification and wetting of medium density fibreboard panels produced from fibres treated with maleated polypropylene wax

Medium density fibreboard (MDF) was produced from fibres treated with maleated polypropylene wax. The objectives of this study were to investigate the effect of fibre treatment with maleated polypropylene wax on the advancing and receding contact angle and wicking of MDF panels by the Wilhelmy plate method; to verify the chemical reactions occurring between fibres and maleated polypropylene wax by infrared spectroscopy, and to verify if there are relationships with the water absorption of panels. Three maleated polypropylene wax contents (0, 3, 5%) and two resin types (urea–formaldehyde, UF and melamine–urea–formaldehyde, MUF) were considered in this study. Our results showed that the treatment increased the advancing contact angle of panels bonded with UF resin. The receding contact angles of MDF panels produced from treated fibres with 5% maleated polypropylene wax content were also increased by the treatment. Also, the wicking was reduced by the treatment independent of the maleated polypropylene wax content. Reductions of the wicking were 59% for panels bonded with UF resin and 73% for panels bonded with MUF. Relationships between the wicking and water absorption were observed. Chemical analysis realized by infrared spectroscopy did not detect the presence of an esterification reaction between wood fibres and anhydride groups of the maleated polypropylene wax. This suggests, therefore, that an esterification reaction did not take place or that chemical modifications were so small that they are not visible by infrared spectroscopy.     

Dimensional stability of MDF panels produced from fibres treated with maleated polypropylene wax

Medium-density fibreboard (MDF) was produced from fibres treated with maleated polypropylene wax. The objectives of this study were to improve the dimensional stability of MDF panels by this treatment; to observe the maleated polypropylene wax distribution within the MDF panels using conventional fluorescence microscopy; and to determine the effects of the treatment on the mechanical properties and vertical density profile of the panels. MDF panels were produced from two resin types (urea-formaldehyde and melamine-urea-formaldehyde) and three maleated polypropylene wax contents (0, 3 and 5%). Photomicrographs show that maleated polypropylene wax forms agglomerates within the MDF panels which is an evidence of its poor distribution in our experimental conditions. Our results show an important reduction on thickness swelling and water absorption after water soaking for panels produced from treated fibres. Linear expansion and contraction in adsorption and desorption conditions between 80 and 50% relative humidity increased following fibre treatment. However, thickness swelling and shrinkage in similar conditions showed an important reduction following fibre treatment. The fibre treatment did not have negative effects on the mechanical properties or the vertical density profile of MDF panels. The modulus of rupture and modulus of elasticity in bending were increased by the treatment independently of maleated polypropylene wax content. The internal bond strength increased following the addition of 5% maleated polypropylene wax content.     

Surface characterization of esterified cellulosic fibers by XPS and FTIR Spectroscopy

 X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy techniques were used to study the surface chemical compositions of cellulosic fibers before and after treatments. The fibers were treated with phthalic anhydride and maleated polypropylene for surface modifications. Both XPS and FTIR spectroscopy analysis indicated that chemical bonds between hydroxyl groups of cellulosic fibers and anhydride moieties of phthalic anhydride and maleated polypropylene have occurred through esterification reaction. These chemical reagents have been added to the surface of cellulosic fibers in the form of monoester, i.e., the formation of esterified cellulosic fibers bearing a pendent carboxylic group. Received 20 July 1997     

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.     

微波等离子体处理木材表面光电子能谱分析

XPS是固体木材表面组成分析最有效和最灵敏的工具之一。本研究使用XPS研究木材微波等离子体处理前后表面化学组成的变化。经微波等离子体处理后 ,C1的含量降低而C2 、C3含量增加 ,并伴随C4生成 ,表明纤维素和 /或木素上羟基含量的增加。微波等离子体处理还在木材表面引入了N元素 ,推测有亲水的 -NH2 生成。比较了相同工作条件下 ,N2 、O2 及空气等离子体对木材表面化学组成影响 ,结果表明 :O2的影响最显著而N2 最弱 ,氧的影响还存在其特殊性。     

Limitation of XPS for analysis of wood species containing high amounts of lipophilic extractives

Chemical composition of Norway spruce and pine, two softwood species, has been investigated by X-ray Photoelectron Spectroscopy (XPS). Contrary to results previously obtained with beech wood, which allow to obtain information on bulk chemical composition from surface composition analysis, XPS analysis appears to be unsuitable for the characterisation of Norway spruce and pine wood chemical composition. Indeed, chemical compositions calculated from XPS data differ strongly from those obtained from microanalyses which are in good agreement with theoretical composition described in the literature. XPS analysis of both the softwood surfaces indicated high carbon contents explained by migration of lipophilic extractives to the surface under the influence of the vacuum necessary for XPS analysis. Nonvolatile extractives contained in wood were extracted and deposited on glass plates and analysed. Survey and detailed C1s spectra indicated similar signals to those recorded on wood surfaces. This phenomenon was not observed when samples had been previously extracted before analysis. These results strongly evidenced that extractives present in both species are able to migrate through resin canals from the bulk of the sample to the surface when put into ultra high vacuum. XPS presents, therefore, some limits in the case of the analysis of softwood species containing extractives able to migrate to the surface during analysis. This behaviour, difficult to control, could lead to erroneous interpretations due to extractives enrichment of the surface under the effect of vacuum.     

Superheated steam treatment of rubberwood to enhance its mechanical,physiochemical, and biological properties

ABSTRACT

This research was aimed to investigate mechanical properties, color and cell-wall components changes, and durability of pre-dried rubberwood (Hevea brasiliensis) after superheated steam (SS) treatment. Wood samples were treated at different SS temperatures (140–180°C) for 1–3?h. The highest compression strength parallel-to-grain, hardness and impact strength were found for samples treated at 160°C for 3?h (30.7% higher than untreated), at 150°C for 1?h (26.6% higher than untreated) and at 150°C for 2?h (52.6% higher than untreated), respectively. The surface color became darker after each treatment in comparison with the untreated wood. The number of accessible hydroxyl groups decreased and the relative cellulose crystallinity increased with SS temperature, indicating decreased hygroscopicity of the treated wood. Also, SEM micrographs of wood surface showed consistent decrease in starch particles with treatment temperature. Both decay and termite resistances of treated rubberwood improved with treatment temperature. All the analyzes showed that dried rubberwood treated with SS had some improvements in the mechanical properties, decreased hygroscopicity, and increase resistance to decay.     

聚丙烯比例对木塑复合材料性能的影响

以木材纤维和废旧聚丙烯塑料为原料,异氰酸酯(MDI)或马来酸酐(MA)为偶联剂,压制木材纤维/聚丙烯复合材料;通过正交试验,研究聚丙烯(PP)用量对木塑复合材料性能的影响.结果表明:PP比例对复合材料的内结合强度、吸水厚度膨胀率、静曲强度和弹性模量有不同程度的影响.在热压时间、热压温度、复合材料密度相同的条件下,在用MDI做偶联剂,PP用量为40%时,复合材料的性能最佳;在用MA做偶联剂,PP用量为50%时,复合材料的性能最佳.     

聚丙烯比例对木塑复合材料性能的影响

通过正交试验,以木材纤维和废旧聚丙烯塑料为原料,异氰酸酯或马来酸酐作偶联剂,压制木材纤维/聚丙烯复合材料,研究聚丙烯(简称PP)用量对木塑复合材料性能的影响。结果表明,聚丙烯比例对复合材料的内结合强度、吸水厚度膨胀率、静曲强度和弹性模量有不同的影响。在热压时间、热压温度、复合材料密度相同的条件下,用异氰酸酯(简称MDI)作偶联剂,聚丙烯用量40%时复合材料的性能最佳;而用马来酸酐(简称MA)作偶联剂,聚丙烯用量50%时复合材料的性能最佳。     

Strength properties of thermally modified softwoods and its relation to polymeric structural wood constituents

Thermal modification at relatively high temperatures (ranging from 150 to 260 °C) is an effective method to improve the dimensional stability and resistance against fungal attack. This study was performed to investigate the impact of heat treatment on the mechanical properties of wood. An industrially-used two-stage heat treatment method under relative mild conditions (< 200 °C) was used to treat the boards. Heat treatment revealed a clear effect on the mechanical properties of softwood species. The tensile strength parallel to the grain showed a rather large decrease, whereas the compressive strength parallel to the fibre increased after heat treatment. The bending strength, which is a combination of the tensile stress, compressive stress and shear stress, was lower after heat treatment. This decrease was less than the decrease of only the tensile strength. The impact strength showed a rather large decrease after heat treatment. An increase of the modulus of elasticity during the bending test has been noticed after heat treatment. Changes and/or modifications of the main wood components appear to be involved in the effects of heat treatment on the mechanical properties. The possible effect of degradation and modification of hemicelluloses, degradation and/or crystallization of amorphous cellulose, and polycondensation reactions of lignin on the mechanical properties of heat treated wood have been discussed. The effect of natural defects, such as knots, resin pockets, abnormal slope of grain and reaction wood, on the strength properties of wood appeared to be affected by heat treatment. Nevertheless, heat treated timber shows potential for use in constructions, but it is important to carefully consider the stresses that occur in a construction and some practical consequences when heat treated timber is used.     

提高钢琴键盘尺寸稳定性的研究

文章采用PEG的分子量、质量体积浓度、压力的变化作为影响因子,探讨了不同条件下的PEG对鱼鳞云杉尺寸稳定性能的影响,结果表明,PEG处理过的鱼鳞云杉具有较高的尺寸稳定性,PEG的分子量、处理液浓度、抽真空度和浸渍加压压力对木材尺寸稳定性都有一定的影响。     

Compressive deformation of phenol formaldehyde (PF) resin-impregnated wood related to the molecular weight of resin

The effects of molecular weight of PF resin on the deformation behaviour of NaClO₂ treated resin-impregnated wood during compression were investigated. Blocks of Japanese cedar were subjected to 2% NaClO₂ aqueous solution. This was repeated up to four times resulting in a weight loss of 28%. Treated and untreated samples were impregnated with PF resin having different molecular weight. With increasing molecular weight, weight gain and volume gain decreased for untreated PF resin-impregnated wood, while NaClO₂ treated wood impregnated with high molecular weight PF resin showed almost double the weight gain compared to untreated condition. NaClO₂ treatment has shown considerable potential for high compression of PF resin-impregnated wood at lower pressing pressure regardless of the molecular weight of the resin. Low to high molecular weight resin was shown to penetrate into NaClO₂ treated wood as estimated by weight gain contributing to the plasticization of cell wall considerably and thus resulting in cell wall collapse at low pressing pressure. The density of NaClO₂ treated wood impregnated with high molecular weight resin attained a value of over 0.8 g/cm³ which is close to the density of untreated wood impregnated with low molecular weight resin. Such compressed wood exhibited high dimensional stability after boiling for 3 h. Thus, the penetration of resin into wood contributes to highly compressed dimensional stable resin-impregnated wood at low pressing pressure.     

添加丙纶纤维及其改性处理对木塑复合材料性能的影响

就木塑纤维复合材料组分中添加丙纶纤维和对丙纶纤维进行改性预处理,改性剂的种类及改性剂的添加方式等引起材料物理力学性能和成网性能、模压性能的变化进行了研究。试验表明：添加丙纶纤维有助于改善材料的成网性能,使之成为具有良好模压性能的材料;对丙纶纤维进行改性的预处理可提高复合材料的物理力学性能;改性剂添加到木纤维中的工艺过程比对丙纶纤维进行预处理的工艺过程简单,并可以达到对丙纶纤维进行预处理的相同效果。     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin V: effects of steam pretreatment

This study evaluated the potential of steam pre-treatment for making highly compressed phenol-formaldehyde (PF) resin-impregnated wood at a low pressing pressure. Sawn veneers of Japanese cedar (Cryptomeria japonica) were first subjected to saturated steam at different steaming temperatures (140°-200°C), followed by impregnation with a 20% low molecular weight PF resin aqueous solution resulting in a weight gain of around 50%-55%. Four oven-dried treated veneers were laminated and compressed up to a pressing pressure of 1 MPa at a pressing temperature of 150°C and pressing speed of 5 mm/min, and the pressure was held for 30 min. Steam treatment, causing partial hydrolysis of hemicellulose, accelerated the compressibility of Japanese cedar in the PF resin-swollen condition. As a consequence, a discernible increment in density was achieved at a pressing pressure of 1 MPa due to steam pretreatment between 140° and 200°C for 10 min. It was also found that even a short steaming time such as 2 min at 160°C is sufficient for obtaining appreciable compression of PF resin-impregnated wood. The density, Young’s modulus, and bending strength of steam-treated (200°C for 10 min) PF resin-impregnated wood composite reached 1.09 g/cm³, 20 GPa, and 207MPa, respectively. In contrast, the values of untreated PF resin-impregnated wood composite were 0.87 g/cm³, 13 GPa, and 170MPa, respectively.     

Comparison of chitosans with different molecular weights as possible wood preservatives

Fungi cause serious problems in wood utilization, and environmentally benign wood protection is required as an alternative to traditional chemicals. Chitosan has shown promising antimicrobial properties against several microorganisms. In this study, we present the characterization of and antifungal properties of a commercial chitosan formulation developed for impregnation of wood. A broad range of chemical and mycological methods were used to evaluate the uptake, fixation, and antifungal properties of chitosan for wood preservation. The results show that the higher the uptake of chitosan the lower the relative recovery of chitosan in wood after leaching, and the higher the molecular weight of chitosan the higher the recovery. Chitosan with high molecular weight proved to be more efficient against decay fungi than chitosan with low molecular weight. The fungi tested on chitosan-amended nutrient agar medium were totally inhibited at 1% (w/v) concentration. In decay studies using small wood blocks, 4.8% (w/v) chitosan concentration gave the best protection against brown rot fungi.     

Properties of PEG/thermally modified wood flour/polypropylene (PP) composites

In order to improve the dimensional stability of wood-polymer composites, wood flour pre-treated by polyethylene glyco1 (PEG) at two different concentrations and then thermally treated at 140°C, was used as raw material to produce wood flour/polypropylene (PP) composites at a wood content of 40%. The structure of modified wood flour was analyzed with a scanning electron microscope (SEM) and its effect on the physical and mechanical properties of wood flour/PP composites was evaluated. The SEM results indicated the "bulking" effect of PEG on wood flour, which resulted in reduced water uptake. The combination of PEG and heat treatment further improved the moisture resistance of the composites. However, PEG modification had a negative effect on the flexural modulus of rupture (MOR) and the modulus of elasticity (MOE); whereas heat treatment partly compensated for this reduction. For dynamic mechanical properties, PEG treatment decreased the storage modulus (E′). However, the heat treatment resulted in an increase of E′ of the wood flour/PP composites, with the temperature of loss factor peaks shifting to a higher temperature.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin III: effects of sodium chlorite treatment

To obtain high-strength phenol–formaldehyde (PF) resin-impregnated compressed wood at low pressing pressure, we investigated the effects of sodium chlorite (NaClO₂) treatment on wood prior to low molecular weight PF resin impregnation. Sawn veneers of Japanese cedar (Cryptomeria japonica) were treated with 2% aqueous NaClO₂ solution at 45°C for 12 h to remove lignin, and the process was repeated up to four times, resulting in weight loss of 21%. NaClO₂ treatment has shown considerable potential for high compression of PF resin-impregnated wood at low pressing pressure, especially after adding moisture to a content of 10%–11%. This deformation is further enhanced during pressure holding by creep deformation. The density, Young’s modulus, and bending strength of PF resin-impregnated veneer laminated composites that were treated with NaClO₂ four times and compressed at 1 MPa, reached 1.15 g/cm³, 27 GPa, and 280 MPa, respectively. The values in untreated PF resin-impregnated wood reached 0.8 g/cm³, 16 GPa, and 165 MPa, respectively.     

表面光电子能谱（XPS）及其在木材科学与技术领域的应用

表面光电子能谱分析是固体木材及纤维表面化学组成分析最有效及最灵敏的工具之一。本文简要介绍表面光电子能谱的基本原理、分析方法、木材表面化学组成基本特征以及表面光电子能谱在木材科学与技术领域的应用。     

竹模板湿变形特性的初步研究

本文研究了在使用竹模板浇成的混凝土结构产生严重变形的原因，是由于竹模板吸收了现浇混凝土的水分所造成。进一步测定了竹模板的相对吸水率对其静曲强度和弹性模量的显著影响，并给出了计算公式，供在竹模板的间距支撑设计和使用时参考。