铜基木材防腐剂及其处理材的金属腐蚀性研究现状

木材防腐剂及其处理材所引起的金属腐蚀,日益引起人们的广泛关注。金属腐蚀产物会使金属附近的木材降等,从而导致连接强度减弱和结构完整性受损。笔者介绍了国内外关于铜基木材防腐剂及其处理材对金属的腐蚀性方面的研究进展,并在此基础上分析和展望了今后铜基木材防腐剂及其处理材对金属的腐蚀性方面的研究重点。     

Moisture sorption and swelling of Norway spruce [Picea abies (L.) Karst.] impregnated with linseed oil

Abstract

The moisture sorption and swelling of spruce specimens impregnated with linseed oil and unimpregnated controls were studied in two sorption experiments: from 0 to 55% relative humidity (RH) and from 55% RH to water saturation. Sorption isotherms were also determined using a sorption balance. The impregnated specimens had lower rates of both moisture sorption and swelling than the unimpregnated controls; however, there was no significant difference in final moisture contents. In addition, the linseed oil impregnation did not improve the dimensional stability of the wood; in most cases the specimens impregnated with linseed oil swelled more than the unimpregnated controls. For the impregnated specimens, reductions in swelling rates were in most cases seen without corresponding reductions in final swelling. The moisture sorption rate was reduced for the impregnated specimens but there were generally no reductions in equilibrium moisture content.     

硼防腐剂与涂料复配处理木材的抗流失性能研究

文章研究了SGB硼防腐剂处理的马尾松试材经环保型水溶性涂料（WAQ）、天然植物油涂料（TRQ）及木材用户外涂料（KJQ）分别处理后的硼流失性能。结果表明硼防腐处理材经涂料再次处理后试件的抗流失性能均有改善,其中效果最好的是TRQ涂料,它与SGB共同处理的试件比单用SGB防腐剂处理的试件硼的抗流失率平均提高了36.5个百分点。     

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.     

Influence of the pore structure of wood on moisture desorption at high relative humidities

Abstract

The influence of the porous structure on moisture desorption of two temperate and five tropical hardwoods was studied. Two experimental techniques were used to perform moisture desorption tests from full saturation at 25°C. The first one was the saturated salt solutions [between 33% and 90% relative humidity (RH)] and the second one was the pressure membrane method (above 96% RH). More emphasis was given to results obtained at high RH, given that sorption in that case is mainly governed by the capillary forces. The porous structure of these hardwoods was characterized by mercury intrusion porosimetry (MIP) and by quantitative anatomical analysis. The results showed that desorption of liquid water was very different among the hardwood species. The MIP technique appeared as an important tool to evaluate the fluid paths within wood, which permitted the prediction of water behavior in wood during drainage from full saturation at high RH. Quantitative anatomical results were very useful for explaining the first steps of drainage and mercury penetration in wood.     

反相高效液相色谱法测定木材防腐剂中戊唑醇含量

鉴于戊唑醇优异的杀菌功效,目前已逐渐被引入木材防腐行业.然而,时于木材防腐剂中戊唑醇的检测,尚处于研究阶段.本试验采用反相高效液相色谱法,样品回收率可达97.7%.该方法简单、有效,可用于对木材防腐剂中戊唑醇的定量分析.     

Impregnated wooden claddings and the influence of nanoparticles on the weathering performance

Abstract

This work was an investigation of the effect of nanoparticles on the durability of wood specimens exposed to artificial weathering. TiO₂ and clay nanoparticles were mixed with preservative (Wolmanit CX-8) for improving the durability of Norway spruce (Picea abies). Impregnated and untreated specimens were subjected to Atlas Solar Simulator accelerated ageing test chamber for solar radiation and water spray exposure. The effectiveness of the treatment against colour and chemical changes was investigated using CIEL*a*b* colour measurements system and Fourier transform infrared analysis. The present study showed that the wood specimens that had been treated with preservatives containing nanoparticles were slightly more stable against artificial ageing than both untreated specimens and specimens treated with preservative alone.     

心材提取物和专用木材防腐剂作为木材保护剂的相对功效

本文调查了三种耐用木材(Afzelia africana J.E. Smith; Erythrophleum suaveolens (Guill & Perr.) Brenam. Syn. E guinensis G.Don. or Milicia excelsa (Welw) C.C. Berg. Syn. Chlorophora excelsa (Welw) Benth.)的心材提取物（在60%的甲醇中风干提取）和两种专用木材防腐剂（CCA和Penta）在暴露的土壤区组设计条件下，抑制三种木材腐朽菌(Coridopsis Polyzona Klotzch; Lenzites trabea; or Trametes cingulata Fr.)对见血封喉边材的侵袭的相对潜能，并测定其阈值。提取物和防腐剂的剂量分别是8.009、24.778、48.056、96.111、144.167 kg·m-3 ，样品的暴露处理时间与ASTM D1413-72规定的一致分别是14周和18周。结果显示：在阈值范围内，任何一种心材提取物或木材防腐剂在研究中对木材腐朽菌的抑制能力在0.01的显著水平下，差异显著。这些生物杀灭剂的相对功效是取决于真菌的种类。没有任何一种心材提取物或木材防腐剂（除在用最高的存留水平处理被侵袭的非洲毒箭木的条件下）对于被处理的木材能够授予"非常持久"等级。本土树种的心材提取物相对持久力的减少的可能原因是复杂的。在最高的存留量（144.167 kg·m-3）水平下，在0.05显著水平下每种心材提取物和任一种专用木材防腐剂（CCA和Penta）之间的功效差异不显著.     

Combined effect of wood moisture content,drill bit rotational speed and feed rate on drilling resistance measurements in Norway spruce (Picea abies (L.) Karst.)

ABSTRACT

An IML-RESI PD 400 drilling tool and a standard spade drill bit (IML System GmbH, Wiesloch, Germany) were used to study the combined effect of wood moisture content (MC), drill bit rotational speed and feed rate on drilling resistance (DR) and feeding force (FF). Tests were made with Norway spruce (Picea abies (L.) Karst.) conditioned in a normal climate (20°C/65% RH), at 20°C/95% RH, vacuum-pressure impregnated in water, and oven-dried. Rotational speeds and feed rates had an impact on feed rate per cutting edge for the major cutting edge of the drill bit which was used for correlation with DR and FF for various MC. Impact of MC on DR and FF depended on rotational speeds and feed rates of the drill bit. For feed rates per cutting edge less than 0.09?mm, DR was higher for water saturated (WS) specimens. Negligible differences between DR for various MC were found for feed rates per cutting edge between 0.09 and 0.15?mm. DR was higher at low MC for feed rates per cutting edge which were higher than 0.15?mm. FF extremely increased in conditioned (20°C/95% RH) and WS specimens at feed rates per cutting edge less than 0.1?mm.     

Dynamic water vapour sorption properties of wood treated with glutaraldehyde

The dynamic water vapour sorption properties of Scots pine (Pinus sylvestris L.) wood samples were studied to investigate the modifying effects of glutaraldehyde. Pine sapwood was treated with solutions of glutaraldehyde and a catalyst (magnesium chloride) to obtain weight per cent gains of 0.5, 8.6, 15.5, and 21.0%, respectively. The sorption behaviour of untreated and treated wood was measured using a Dynamic Vapour Sorption apparatus. The results showed considerable reduction in equilibrium moisture content of wood and the corresponding equilibrium time at each target relative humidity (RH) due to glutaraldehyde treatment. The moisture adsorption and desorption rates of modified and unmodified wood were generally faster in the low RH range (up to approximate 20%) than in the high range. Modification primarily reduced the adsorption and desorption rates over the high RH range of 20–95%. Glutaraldehyde modification resulted in a reduction in sorption hysteresis due to the loss of elasticity of cell walls.     

国外木材防腐技术和研究现状

从木材防腐剂、防腐处理工艺、改性处理及环境特性等几个方面对国外的木材防腐技术及研究现状进行较为系统、全面的介绍,并在此基础上指出木材防腐研究的几个主要方向.木材防腐剂的发展趋势是近期以水载防腐剂为主导,以开发综合性能优良的不含金属的有机防腐剂作为未来的发展方向;木材防腐处理工艺的重点在于增强防腐剂在木材中的渗透性,加速防腐剂与木材之间的固着反应以及开发新型的防腐处理工艺以适应新的防腐剂的需要.改性处理方面主要介绍木材的热处理和化学改性处理在防腐方面的应用现状.木材防腐处理的环境特性则着重介绍LCA技术(生命循环分析技术)以及防腐处理材的废弃处理问题.另外,还简要介绍木材防腐研究机构和协会、木材防腐标准等方面的情况.本文旨在使国内的木材研究者对当前木材防腐技术和研究有一个总体的认识,并在此基础上结合国内的实际情况,发展适于处理中国国内树种及适合市场需求的木材防腐技术,为更科学、更高效地利用国内木材资源提供新途径.     

Monoethanolamine extraction of copper-preservative-treated wood and reuse of the extract for wood preservation

Remediation of copper-based alkaline copper quat (ACQ) and micronized copper quat (MCQ) wood-preservative-treated weathered southern pine mulch samples by monoethanolamine (Mea) extraction was studied. The potential reuse of Mea extract in ACQ wood preservative application was also evaluated. Continuous column extraction of copper-preservative-treated samples for 32 h, using 12 % Mea removed 66–86 % (between top and bottom of the column) and 65–80 % of Cu, respectively, from ACQ- and MCQ-treated wood. Mea extracts of treated wood could be reused in ACQ-treating solutions that met the American Wood Protection Association standard specifications for ACQ wood preservatives. This was achieved either by mixing the extract with industrial Cu–Mea solution at 1:4 ratio or by adding cupric acetate salt directly into the Mea extract. ACQ-treating solutions reformulated using Mea extracts of ACQ- and MCQ-treated wood performed similarly to wood treated with industrial ACQ solution and freshly prepared solution using cupric acetate. All treated wood had similar penetrations of Cu in wood during preservative treatment, Cu leaching from the treated wood in contact with water, corrosion of nails in contact with treated wood, and ability to protect wood from mold growth.     

Efficacy of wood preservatives formulated from okara with copper and/or boron salts

As a substitute for high-cost copper azole (CuAz) and alkaline copper quaternary (ACQ) wood preservatives, alternative wood preservatives were formulated with okara, which is an organic waste from the production of tofu, and copper chloride and/or borax. Each preservative was used in treatment of wood blocks in a reduced-pressure method to measure its treatability. The treated wood blocks were placed in hot water for 3 days to examine the stability of the preservatives against hot-water leaching. The preservatives successfully penetrated into wood blocks, probably due to the use of ammonium hydroxide as a dissociating agent. However, the stability of okara-based preservatives dropped as the concentration of acid in the solutions used for hydrolysis of okara increased. The treatability and leachability of the preservatives were not affected by hydrolysis temperature but were negatively affected by the addition of borax. Leached wood blocks treated with okara-based preservatives and exposed to decay fungi Gloeophyllum trabeum and Postia placenta over 12 weeks showed good decay resistance. Okara-based wood preservatives can protect wood against fungal attack as effectively as CuAz, and have potential for use as environmentally friendly wood preservatives.     

木材保护体系的发展

住宅用途的木材防腐剂正逐步走向包括微粒铜在内的新复合防腐剂体系,及无重金属的全有机体系.为了提高这些新防腐剂的性能,一类称为性能增强添加剂已经开发出来,如水分控制稳定剂,表面活性剂和乳化剂,防霉剂和着色剂等;针对人们对于化学防腐剂处理的木材越来越负面的看法,以及监督管理的审查和限制的加强,一些非传统的木材保护体系形成,如阻隔保护体系,化学改性和非化学改性,天然耐久树种木材也出现.笔者在文中对这些问题进行了回顾和讨论.     

木材防腐标准框架探讨

对我国重要的木材防腐标准进行了简要概述,并提出了国内标准框架草案,包括木材防腐剂及其分析方法、防腐处理材及木制品、木材防腐剂的抗虫抗菌评价方法、防腐木材的使用分类及防腐处理质量要求、产品标识等。     

木材防腐剂登记药效试验方法和评价标准探讨

根据《农药管理条例》,对木材防腐剂实施登记管理,有利于提高木材防腐剂产品质量,规范市场秩序,保护人畜健康和环境安全。但由于防腐剂与大田农药存在一定的差异,要求其渗透到木材内部而且需在木材中保持尽可能长久的药效。笔者根据木材使用分类等相关标准的规定,探讨了木材防腐剂在登记时需要进行的试验方法和评价标准。     

Dielectric properties of copper-ethanolamine treated Chinese fir (Cunninghamia lanceolata Hook.)

In order to clarify the interaction between copper and wood substances in wood treated with copper containing water-borne wood preservatives, the dielectric constant ε′ and dielectric loss factor ε″ of untreated wood and wood treated with four concentration levels of copper-ethanolamine (Cu-EA) solutions were determined within a temperature range from –100 to 40°C and a frequency range from 100 to 1 MHz. Three dielectric relaxation processes were observed in the ε″ spectrum; among them R-I is based on the reorientation of methylol groups in the amorphous region of wood cell walls and R-II is related to wood extractives. R-III appeared in Cu-EA treated wood, and its magnitude decreases with the concentration of Cu-EA solutions used in this experiment. This relaxation process was considered to be based on the reorientation of copper-ethanolamine-wood complexes in wood cell walls. At low copper retention, the hydrogen in the complex can form hydrogen bonding with adjacent hydroxyl groups, which results in a strong bonding state between copper and wood; at high copper retention, the numerous copper-ethanolamine complexes not only hinder them from forming hydrogen bonding with adjacent wood molecules due to steric hindrance, but also weaken the interaction between wood molecules themselves, which corresponds to reducing ε″ values of both R-I and R-III processes. The results explain the fact of in-creasing copper leaching in wood treated with high concentration copper-based water-borne preservatives.     

Rapid detection of propiconazole and tebuconazole in wood by solid phase desorption: ion mobility spectrometry

The durability of wood is improved by wood preservatives. Due to new environmental legislation, commonly used active ingredients such as chromium and arsenate are being replaced by alternative and more environmentally friendly preservatives. However, the alternative wood preservatives are more difficult to detect in the wood. Detection of the preservatives is necessary in order to monitor millwork production for qualitative assessment of the wood preservative uptake. The aim of this study is to examine the use of solid phase desorption-ion mobility spectrometry (SPD-IMS) can be used for rapid detection of the wood preservatives propiconazole and tebuconazole in Scots pine (Pinus sylvestris). The findings proved that SPD-IMS is capable of detecting and distinguishing wood preservatives directly from treated wood shavings. SPD-IMS requires no additional sample preparation or extraction of the wood sample. The findings show that SPD-IMS is a fast and easily applied method for direct detection of propiconazole and tebuconazole in small wood samples.     

Corrosiveness of Copper-based Preservatives to 4 Types of Metals

The corrosive rates of 4 types of metals as well as epoxy-coated metal in a variety of preservatives derived from different copper sources and ingredients were .measured in this paper. The main results show that： CCA is less corrosive to red brass and Q235A steel than other copper formulations; Copper-based preservatives such as ACQ and CuAz derived from basic cupric carbonate or cupric hydroxide are much less corrosive to Q235A steel than those from cupric sulfate; Ethanolamine is less corrosive to Q235A steel than ammonia in ACQ derived from cupric hydroxide, while other ingredients are the same; Epoxy resin coating could be used for protecting red brass, Q235A steel and zinc hotdipped galvanized mild steel from corrosion.     

双钩异翅长蠹生物学特性及用防腐剂TWP防治试验

双钩异翅长蠹是橡胶树锯材及其制品的严重害虫。在海南岛1年完成二至三代,约有16种阔叶材被害。用新的水溶性木材防腐剂TWP进行防治试验的结果:①TWP在木材中保持量1.0kg/m~3,初龄幼虫死亡率100％;②新鲜橡胶树锯材用2％TWP真空加压或振荡加压法处理,药剂保持量不少于3.7kg/m~3,可获得长久的保护效力;③TWP不含氯化酚化合物,对人畜和环境十分安全。