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     

微波等离子体处理木材表面接枝甲基丙烯酸甲酯的XPS分析

应用X-射线光电子能谱(XPS)技术，对微波等离子体引发木材与甲基丙烯酸甲酯(MMA)发生接枝共聚反应前后的木材表面结构及物理化学特性进行了分析。分析表明：1)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峰的出现，这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；2)微波等离子体接枝材表面的O／C比有所增加，但介于素材与微波等离子体处理材之间，C18谱峰主要变化是强C4峰的出现，这表明木材表面产生了大量的O-C=O官能团；3)微波等离子体接枝材的O1／O2值基本接近1，大于素材(0．11)和微波等离子体处理材(0．21)的值，说明接枝材表面的C=O含量大幅度增大。以上结果表明木材表面接枝上了大量的MMA分子。     

等离子体改性聚丙烯饰面膜的拉曼光谱和XPS分析

采用介质阻挡低温等离子体对木制品聚丙烯(PP)饰面膜表面进行不同放电功率和处理速度的改性处理后,分别对其表面进行X射线光电子能谱(XPS)和激光共聚焦显微拉曼(Raman)光谱分析,研究等离子改性对PP饰面膜的化学成分和元素组成的影响。结果表明:由拉曼光谱可知,未处理的PP饰面膜表面含有大量的C原子和H原子间摇摆振动引起的振动峰、C原子间伸缩振动和C与H原子间弯曲振动引起的振动峰;经等离子体改性处理后,PP饰面膜表面在原有振动峰基础上,同时生成了具有较强拉曼活性的C—C和C—H的弯曲和振动峰等; XPS分析可得,等离子体改性处理前后,PP饰面膜表面主要表现为元素含量和量比的变化,等离子体改性后,C元素含量降低,O元素含量明显增加,O/C量比增大,且C1含量降低,C2含量明显增加。结合拉曼光谱和XPS对PP饰面膜表面进行定性和定量分析,可准确得到等离子体改性对提高PP饰面膜表面含氧官能团数量及表面活性改善的作用和影响。本研究可为等离子体改性处理对提高PP饰面膜表面附着力的理论研究和实践应用提供技术支持。     

微波等离子体处理木材表面接枝甲基丙烯酸甲酯的研究

本研究通过微波等离子体处理木材表面，实现了木材表面与甲基丙烯酸甲酯（MMA）发生接枝共聚反应，研究了不同的反应条件对微波等离子体引发木材表面接枝MMA效果的影响。结果表明：1）接枝率随等离子体处理时间的增加而呈线性增加，但是当处理时间超过30s，后呈下降的趋势；2）随着接技反应时间的增加接枝率也增加；3）单体浓度较低有利于接枝共聚反应，浓度较高则不利于接枝共聚反应；4）经微波等离子体处理过的木材不但在室温下，甚至在更低的温度（-17℃）下也能与MMA发生接枝共聚反应，而且，接枝率随着反应温度的升高而增大；5）与催化加热法的接枝效果相比，微波等离子体法得到的接枝率更高。     

N2和O2冷等离子体处理对木材胶合强度的影响

采用N2、O2两种等离子体气体分别处理木材,处理功率为300 W,处理时间为5 min,将处理后的木材采用MUF胶粘合起来,测试了胶合强度,并对冷等离子体处理前后的木材表面能进行了分析。实验结果表明:经N2、O2冷等离子体处理后的木材表面的接触角明显减小,表面自由能明显增大;经冷等离子体处理后的胶合板的平均干状胶合强度和湿状强度均有明显(50%以上)增大。     

微波等离子体环境下木材表面蚀刻

微波等离子体处理木材表面时引起蚀刻,蚀刻程度的大小与离子能量水平,即与等离子体工作条件和等离子体种类密切相关。本文讨论了微波等离子体工作条件即微波功率、系统压力、样品位置（距谐振腔距离）及处理时间对杉木木材蚀刻的影响,并在相同工作条件下,比较了Ｎ２、Ｏ２及空气等离子体对木材蚀刻程度的影响。结果表明：在影响蚀刻作用的诸因素中,样品位置的影响最显著,处理时间、微波功率其次,而系统压力的影响最弱。在本研究的范围内,杉木样品距谐振腔距离越近、等离子体处理时间越长、微波功率越高则蚀刻越严重;在３种等离子体中,Ｏ２等离子体蚀刻最严重,而Ｎ２等离子体最轻微,空气等离子体蚀刻介于两者之间。     

微波等离子体活化木材表面的ESR分析

采用微波等离子体活化木材和硝酸纤维素的表面 ,并用电子自旋共振波谱技术对样品表面的相对自由基数量变化进行了分析 ,结果表明 :(1)木材和硝酸纤维素的表面经过微波等离子体处理 ,可迅速有效地生成大量的自由基 ;(2 )随着等离子体处理时间的加长 ,木材及硝酸纤维素表面的自由基数量都增大 ;(3)硝酸纤维素表面的相对自由基数量增大速率明显高于木材的增大速率 ,但其相对自由基数量的数值低于木材中的数值     

等离子体处理对6种木材表面润湿性能的影响

【目的】基于现有大量空气等离子体对人工林木材表面改性的研究,采用不同气体辉光放电等离子体对3种人工林和3种天然林木材进行改性处理,对比研究其对木材表面润湿性能的影响,为常压空气等离子体处理木材表面的工业化生产提供理论支持,为等离子体在不同木材表面改性的应用奠定理论基础。【方法】采用空气(Air)、氧气(O2)、氮气(N2)、氩气(Ar)和氦气(He)5种气体辉光放电低温等离子体分别处理山杨、云杉、蓝桉3种人工林木材和实木制品及木质制品表面饰面常用的红栎、白桦和黑胡桃3种天然林木材,测试计算不同等离子体处理条件下木材的接触角和表面自由能,以及经氮气等离子体不同时间处理后木材的表面水接触角,研究不同气体辉光放电低温等离子体对不同材质木材表面润湿性能的影响。【结果】木材表面经空气、氦气、氩气、氮气和氧气5种气体等离子体处理后,表面与水、二碘甲烷的接触角均明显减小,表面自由能增大,润湿性得到显著改善。试验条件下,氦气等离子体处理对云杉、山杨木材表面润湿性能影响最大,而蓝桉、红栎、白桦和黑胡桃木材均为氩气等离子体处理后的表面接触角降幅最大,表面自由能增大明显。等离子体处理时间对木材表面润湿性影响相对较大,一般人工林木材以3 min为宜,天然木材以4 min为宜。【结论】不同气体等离子体处理木材表面后,木材表面润湿性能均得到改善,且以空气作为等离子体处理气体的润湿效果相对较好。在实际生产应用中,可采用空气等离子体处理提高木材及木基复合材料间的胶合、接枝等性能。     

木材表面非极性化原理的研究 Ⅳ.化学分析光电子能谱(ESCA)对木材乙酰化处理表面化学特征的研究

采用化学分析光电子能谱 (ESCA)研究了杉木和杨木在乙酰化处理前后的表面化学结构变化。结果表明 :杉木和杨木的表面化学特征有很大差别 ,杉木表面的碳原子相对含量较杨木表面高 ,而氮原子和氧原子的相对含量较杨木表面低。在杨木表面有钙原子的存在 ;两种木材经乙酰化处理后表面化学特征发生变化 ,非极性的 O- C=O结构相对含量均有不同程度的增加。     

射流等离子体处理对热处理材漆膜附着力的影响

采用氮气射流对热处理材落叶松进行等离子体处理,研究了不同处理高度、不同处理时间对热处理材漆膜性能的影响,通过仪器测定,分析了不同等离子体处理条件下被处理材的漆膜性能变化机理,并得出本实验中改善热处理材落叶松漆膜性能的最佳等离子体处理工艺参数。结果表明:随着等离子体处理高度的降低和处理时间的延长,热处理材漆膜质量损失率降低,漆膜性能逐渐提升;等离子体处理改善热处理材漆膜性能的最佳工艺时间为20 s、高度为15 mm;等离子体处理过程中引入的大量氨基、羟基、羰基、羧基等亲水性基团是被处理材漆膜性能提升的根本原因。X射线光电子能谱分析显示,经过等离子处理后的落叶松,C元素含量降幅为12.63%,O元素和N元素增幅分别为14.32%,83.87%。FT-IR结果表明,处理后的木材表面—OH、C—H、C=O的峰的强度明显加强。因此,对热处理之后的木材进行等离子体处理,可大幅度提升其漆膜性能,从而改善产品缺陷、提高附加值。     

X-ray photoelectron spectroscopy of maleated polypropylene treated wood fibers in a high-intensity thermokinetic mixer

Summary An XPS (X-ray Photoelectron Spectroscopy), also known as ESCA (Electron Spectroscopy for Chemical Analysis) study of wood fiber treated with maleated polypropylene was performed to obtain information on the chemical nature of wood fiber before and after treatment. Wood fiber was treated in a high-intensity thermokinetic mixer with maleated polypropylene at different loading level (relative to wood fiber weight). The XPS results showed that the treatment of maleated polypropylene increased the hydrocarbon concentration of wood fiber, as indicated by the decrease in oxygen-carbon ratio, and the continuous increase of the relative intensity of the component C1 in C1s signal. Based on these values, higher molecular weight maleated polypropylene produced more hydrophobic wood fiber surface than lower molecular weight maleated polypropylene. The decrease in C4 carbon type in C1s signal after treatment suggested that the esterification reaction between wood fiber and maleated polypropylene had not ocurred under the experimental conditions used in this study. Received 5 January 1997     

Infrared spectral characteristics and surface inactivation of wood at high temperatures

Summary Spectra resulting from chemical changes in white spruce [Picea glauca (Moench) Voss] microsections heated in air or nitrogen at high temperatures (100 to 240°C) were continuously recorded on an infrared spectrophotometer.A significant change occurred in the intensity of the 1730 cm^-1 band which indicates a carbonyl absorption of carboxyl and ester groups of wood. This intensity initially decreased and the increased at a greater rate. The time periods to reach the minimum inflection point, termed the times to initiate a significant oxidative carboxylation or oxidation, showed a good curvilinear relationship with heating temperatures.Quantification of this time-temperature relationship required to reach a significant level of oxidation was achieved, using wood microsections that had extractives removed to varying degrees. It was concluded that the extractives served only as catalysts for oxidation. When drying wood at temperatures over 180°C, in addition to oxidation, pyrolytic degradation occurred.Chemical evidence was further confirmed by tests of plywood panels bonded with phenolformaldehyde glue. Three separate types of veneers were investigated—non-extracted, acetone extracted, and veneer with the surface chemically stabilized by treatment with sodium borohydride. The results suggest that the time period to reach a significant level of oxidative carboxylation is also the time period to initiate a wood surface inactivated to polymer adhesion.The author wishes to thank Miss D. Bouchard and Mr. H. N. Mukai for their assistance in the experiments. Appreciation also is due to Mr. H. MacLean for a critical review of this paper.     

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.     

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。     

Influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

The influence of reaction atmosphere on the liquefaction and depolymerization of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), has been systematically studied. The wood samples were treated with [C2mim][Cl] at 120°C under various atmospheres such as oxygen, nitrogen, and carbon dioxide, both dried and humidified. The percentage of residue after the treatment shows that oxygen considerably accelerates the liquefaction of wood in [C2mim][Cl], and humidity hardly affects liquefaction under any atmosphere. Gel permeation chromatography (GPC) and high performance liquid chromatography (HPLC) analyses on the solubilized compounds in [C2mim][Cl] indicate that oxygen and humidity enhance the depolymerization of the wood component. Thus, the reaction atmosphere was revealed to influence, and 1be capable of controlling, the reaction of wood in [C2mim][Cl].     

等离子体改性热塑性树脂薄膜制备环保胶合板试验

为获得无甲醛释放的环保胶合板,将热塑性树脂薄膜(低密度聚乙烯(LLDPE)、聚丙烯(PP)、聚氯乙烯(PVC))用作胶黏剂,并利用空气介质阻挡等离子体对热塑性树脂薄膜进行表面改性处理以提高薄膜与杨木单板的界面相容性,从而获得性能良好的环保胶合板。研究了等离子体处理对胶合板胶合性能的影响,并从等离子体处理对热塑性树脂薄膜表面化学组分及其对胶合板界面形貌的影响分析其胶合机理。结果表明:在等离子体处理功率为4.5 kW、处理时间为8 m/min的条件下处理热塑性树脂薄膜,胶合板的胶合强度得到显著提高,LLDPE/杨木胶合板的胶合强度从0.49 MPa增至0.81 MPa,PP/杨木胶合板的胶合强度从0.65 MPa提高到0.84 MPa,均达到Ⅱ类胶合板标准要求。其中用等离子体处理后PVC与杨木制备的胶合板能满足Ⅰ类胶合板的标准要求,胶合强度达到0.79 MPa。XPS分析表明,等离子体改性热塑性树脂薄膜的表面发生了氧化反应,引入了含氧官能团,提高了薄膜表面极性,有利于提高薄膜与杨木单板之间的相互作用,从而使得胶合板的界面胶合更为紧密,说明等离子体处理后树脂与杨木单板的相容性提高,树脂能在单板表面更好地附着。热塑性树脂薄膜与杨木单板制备的胶合板仅有极微量甲醛释放,其主要源于木材自身,远低于国家标准对人造板甲醛释放限量的要求。研究证明等离子体处理能明显改善热塑性树脂薄膜与杨木单板的界面相容性。     

Changes of chemical properties and the water vapour sorption of <Emphasis Type="Italic">Eucalyptus pellita</Emphasis> wood thermally modified in vacuum

The aim of this study was to evaluate the chemical composition and the dynamic water vapour sorption properties of Eucalyptus pellita wood thermally modified in vacuum. For this purpose, wood samples were thermally modified in a vacuum oven at 160–240 °C for 4 h. Chemical composition were investigated by wet chemical analysis, elemental analysis, as well as Fourier transform infrared (FTIR) analysis, and dynamic water vapour sorption properties were evaluated by dynamic vapour sorption apparatus. The results showed that holocellulose and alpha-cellulose contents decreased and lignin and extractives contents relatively increased during the heat process. Elemental analysis showed a reduction in hydrogen content and an increase in carbon content. FTIR analysis indicated that the degradation of hemicellulose and condensation reactions of lignin occurred. In addition, the thermo-vacuum resulted in a reduction in the equilibrium moisture content of wood during the adsorption or desorption process. And the sorption hysteresis had a decreasing trend with increasing treatment temperature. The development of the hygroscopicity was related to the increase in the relative content of lignin, the degradation of the carbonyl groups in xylan and the loss of carbonyl group linked to the aromatic skeleton in lignin after heat treatment.     

稻草原料表面特性FTIR和XPS分析

运用红外光谱(IR)和X射线光电子能谱分析(XPS)法，考察了热磨处理对稻草表面特性的影响。结果表明：稻草秸秆内表面的活性基团数量和氧碳元素百分比都明显高于外表面；经热磨处理，稻草纤维表面的羟基、甲基、亚甲基等官能团含量显著增加，氧碳元素百分比相对秸秆表面有大幅度提高，证明热磨处理能增强稻草表面活性，为脲醛树脂稻草中纤板制造的技术可行性提供了依据。