本文選題：木材 + 竹材　； 參考：《中國(guó)林業(yè)科學(xué)研究院》2016年博士論文

【摘要】：速生木材和竹材的優(yōu)勢(shì)是生長(zhǎng)速度快,輪伐期短,但性能缺陷也十分明顯。如何克服人工林木材、竹材的天然性能缺陷,延長(zhǎng)使用壽命,提升其使用和商業(yè)價(jià)值,是我國(guó)林業(yè)產(chǎn)業(yè)可持續(xù)發(fā)展面臨的一個(gè)重大難題。加強(qiáng)速生人工林木材和竹材的科學(xué)利用也是緩解我國(guó)木材供需矛盾,保障國(guó)家木材安全的的重要途徑之一。木材糠醇樹(shù)脂改性技術(shù)是近年來(lái)再次興起的一種環(huán)境友好、商業(yè)化前景極為廣闊的木質(zhì)材料改性技術(shù)。本文作者在課題組自主研發(fā)糠醇處理液配方的基礎(chǔ)上,以我國(guó)人工林木材代表?xiàng)钅竞蜕寄?特色速生資源毛竹為研究對(duì)象,開(kāi)展木、竹材糠醇樹(shù)脂改性技術(shù)及改性機(jī)理研究。研究?jī)?nèi)容包括兩部分:(1)木竹材糠醇樹(shù)脂改性技術(shù)研究。根據(jù)速生針、闊葉材代表?xiàng)钅竞蜕寄炯爸癫淖陨淼牟男浴⒔Y(jié)構(gòu)特點(diǎn)以及產(chǎn)品目標(biāo)用途,以增重率、吸濕性、尺寸穩(wěn)定性、部分力學(xué)性能、防霉、耐腐、抗白蟻等性能為主要評(píng)價(jià)指標(biāo),對(duì)糠醇樹(shù)脂改性技術(shù)關(guān)鍵參數(shù),如浸漬方式、改性溶液濃度、固化時(shí)間及固化溫度進(jìn)行優(yōu)化。(2)木竹材糠醇樹(shù)脂改性機(jī)理研究。采用環(huán)境掃描電鏡觀察糠醇樹(shù)脂在木、竹材細(xì)胞腔中的分布;應(yīng)用激光共聚焦顯微鏡觀察糠醇樹(shù)脂在細(xì)胞壁和細(xì)胞腔中的分布差異;采用納米壓痕儀測(cè)試改性前后木、竹材細(xì)胞壁微觀力學(xué)性能,進(jìn)一步明確糠醇樹(shù)脂是否進(jìn)入細(xì)胞壁,并測(cè)試改性對(duì)木竹材細(xì)胞壁力學(xué)性能的影響。應(yīng)用紅外光譜和核磁共振等理化性能表征技術(shù),明確糠醇樹(shù)脂與細(xì)胞壁組分之間是否存在化學(xué)鍵結(jié)合。論文主要研究結(jié)論如下:低分子量、極性糠醇改性溶液極易浸入木竹材內(nèi)部。經(jīng)一次真空加壓浸漬處理,楊木、杉木和竹材的改性材增重率最高可達(dá)60%、85%和32%�？反紭�(shù)脂改性顯著降低了木、竹材的吸濕性,使其平衡含水率降低40~50%(65%RH,25℃)。糠醇樹(shù)脂改性顯著提高了木、竹材的尺寸穩(wěn)定性。楊木的弦向、徑向和體積的抗?jié)衩浵禂?shù)分別提高79.98%、91.88%和90.32%;杉木分別提高71.3%、78.74%和74.86%;室溫浸泡處理的竹材的弦向、徑向、順紋方向和體積的抗?jié)衩浵禂?shù)分別提高49.28%、51.28%、52.44%和50.99%�？反紭�(shù)脂改性技術(shù)賦予木、竹材優(yōu)異的抗生物劣化性能。糠醇樹(shù)脂改性木、竹材擁有高效防霉性能。改性材增重率僅為20%的改性楊木和杉木試樣和增重率僅為10%的竹材試樣,經(jīng)三種霉菌和變色菌侵染后,表面沒(méi)有任何菌絲殘留,防霉效率達(dá)100%。實(shí)驗(yàn)室耐腐測(cè)試結(jié)果顯示,糠醇樹(shù)脂改性木、竹材屬?gòu)?qiáng)耐腐等級(jí)。增重率20%的改性楊木和杉木試樣,經(jīng)三種腐朽菌侵蝕后,失重率低于3%;增重率僅為10%的改性竹試樣,失重率低于7%,且測(cè)試后改性木、竹材均保持完好無(wú)損�？拱紫佇阅軠y(cè)試證明糠醇樹(shù)脂改性木、竹材對(duì)白蟻有很好趨避能力。增重率達(dá)20%以上的改性木材經(jīng)白蟻蛀蝕后,失重率低于0.7%,且表面沒(méi)有出現(xiàn)任何蛀蝕痕跡,顯示出優(yōu)異的抗白蟻性能。對(duì)于改性竹材,增重率較低時(shí)(wpg=5.4%),白蟻蛀蝕等級(jí)為“1”級(jí)。中等增重率(wpg=15%)的改性竹材,白蟻蛀蝕等級(jí)為“0”級(jí)�？反紭�(shù)脂改性對(duì)木竹材力學(xué)性能的影響因樹(shù)種不同而存在差異。本研究發(fā)現(xiàn)相同工藝條件下,改性楊木的抗彎強(qiáng)度和順紋抗壓強(qiáng)度可顯著提高、彈性模量略有改善或影響不明顯。但僅少許工藝條件下改性杉木的力學(xué)性能獲得改善,部分工藝條件下,改性杉木的力學(xué)性能反而呈降低趨勢(shì)。綜合考慮改善木竹材尺寸穩(wěn)定性和抗生物耐久性,且對(duì)力學(xué)性能影響較小等因素。推薦糠醇樹(shù)脂改性楊木較優(yōu)工藝為:50%糠醇濃度,固化溫度105℃,固化時(shí)間8h;杉木改性工藝:50%糠醇濃度,固化溫度115℃,固化時(shí)間5h;真空加壓浸漬竹材改性工藝:15%糠醇濃度,固化溫度105℃,固化時(shí)間3-5h;室溫浸泡竹材改性工藝:50%糠醇濃度,固化溫度105℃,固化時(shí)間5h。環(huán)境掃描電鏡和激光共聚焦顯微鏡觀察發(fā)現(xiàn)糠醇樹(shù)脂填充在木材管胞、導(dǎo)管和木射線細(xì)胞中,且將細(xì)胞內(nèi)壁完全覆蓋,阻塞了胞壁上大部分紋孔。竹材薄壁細(xì)胞中豐富的淀粉粒被溶解脫除,并有部分胞腔被樹(shù)脂填充。樹(shù)脂的填充阻塞了水分進(jìn)入孔道,并潤(rùn)脹細(xì)胞壁,從而使改性后木竹材吸濕性降低、尺寸穩(wěn)定性顯著改善。納米壓痕技術(shù)測(cè)試發(fā)現(xiàn),糠醇樹(shù)脂改性后楊木、杉木和竹材細(xì)胞壁的硬度和模量比對(duì)照樣分別提高32%、24%、65%和4%、51%、53%,從細(xì)胞壁微力學(xué)角度證明糠醇樹(shù)脂浸入細(xì)胞壁�？反紭�(shù)脂在木竹材細(xì)胞腔和細(xì)胞壁中的填充潤(rùn)漲改變了微生物和昆蟲(chóng)的寄生環(huán)境,從而提高木竹材的抗生物劣化性。紅外光譜測(cè)試發(fā)現(xiàn)木材纖維素、半纖維素和木質(zhì)素的特征峰減弱變寬,證明木竹材細(xì)胞壁組分在糠醇樹(shù)脂改性過(guò)程中可能被降解。此外,代表羰基的特征峰顯著加強(qiáng)和偏移,說(shuō)明糠醇樹(shù)脂改性木竹材可能發(fā)生了酯化反應(yīng)。當(dāng)然,糠醇聚合物的引入也是重要原因。核磁共振波譜分析發(fā)現(xiàn),改性木竹材譜圖上除未改性材和糠醇樹(shù)脂對(duì)應(yīng)化學(xué)位移處特征峰疊加外,并無(wú)新的特征峰出現(xiàn)。因此,本研究尚可證明糠醇樹(shù)脂填充與木竹材細(xì)胞腔和細(xì)胞壁中,可推測(cè)糠醇樹(shù)脂在細(xì)胞壁中可能發(fā)生酯化反應(yīng),但因?qū)嶒?yàn)儀器的分辨率及知識(shí)積累有限,尚不能確切證明糠醇樹(shù)脂與木竹材胞壁組分發(fā)生化學(xué)反應(yīng)。
[Abstract]:The advantages of fast-growing wood and bamboo are fast growth rate and short cutting period, but the performance defects are also obvious. How to overcome the natural performance defects of wood, bamboo and prolong the use and commercial value of bamboo is a major problem for the sustainable development of forestry industry in China. The use of science is also one of the important ways to alleviate the contradiction between the supply and demand of wood in China and ensure the safety of the country. The technology of the wood furfuryl alcohol resin modification is a kind of environmentally friendly and highly commercialized wood material modification technology in recent years. The author of this paper is based on the basis of the author's research group to develop the formula of furfuryl alcohol treatment solution. The study on the modified technology and modification mechanism of wood and bamboo furfuryl alcohol resin was carried out in China. The research contents included two parts: (1) study on the modification technology of the furfuryl alcohol resin of wood bamboo. Structure characteristics and product target use, with weight gain, hygroscopicity, dimensional stability, mechanical properties, mildew proof, corrosion resistance, termites and other properties as the main evaluation indexes, the key parameters of furfuryl resin modification technology, such as impregnation mode, modified solution concentration, curing time and curing temperature are optimized. (2) the modification mechanism of the furfuryl alcohol resin of wood bamboo The distribution of furfuryl alcohol resin in the cell cavity of wood and bamboo was observed by environmental scanning electron microscope, and the distribution difference of furfuryl alcohol resin in cell wall and cell cavity was observed by laser confocal microscope, and the micromechanical properties of the modified wood and bamboo cell wall were tested by the nano indentation instrument and whether the furfuryl alcohol resin entered the cell or not. The effects of modification on the mechanical properties of the cell wall of wood bamboo were tested. The chemical bonds between the furfuryl alcohol resin and the cell wall components were determined by using the physical and chemical characterization techniques such as infrared spectrum and nuclear magnetic resonance. The main conclusions are as follows: low molecular weight, polar furfuryl alcohol modified solution is easily immersed inside wood bamboo. The maximum weight gain of the modified wood, Chinese fir and bamboo was up to 60% in vacuum pressure impregnation treatment. The modification of 85% and 32%. furfuryl alcohol resin significantly reduced the moisture absorption of wood and bamboo, and reduced the balance water content by 40~50% (65%RH, 25). The modification of furfuryl alcohol resin significantly improved the dimensional stability of wood and bamboo wood, the chord direction, radial and volume resistance of poplar wood. The expansion coefficient increased by 79.98%, 91.88% and 90.32%, and the Cunninghamia lanceolata increased by 71.3%, 78.74% and 74.86%, respectively. The wet expansion coefficient of the bamboo material treated at room temperature was increased by 49.28%, 51.28%, 52.44% and 50.99%. furfuryl resin modified technology. The excellent biodegradation properties of bamboo were given to wood and bamboo. The modification of furfuryl alcohol resin was improved. Wood and bamboo have high anti mildew resistance. The modified wood and Cunninghamia lanceolata with the weight increase rate of only 20%, and the bamboo samples with only 10% weight gain. After three kinds of mould and chromotropic bacteria, there is no mycelium residue on the surface. The anti mould efficiency is shown by the 100%. laboratory corrosion test results, the furfuryl resin modified wood, and the bamboo is strong corrosion resistance grade. The weight loss rate of the modified poplar and Cunninghamia lanceolata samples with the weight increasing rate of 20% was less than 3%, the weight gain rate was only 10%, the weight loss rate was less than 7%, and the bamboo material remained intact after the test. The test proved that the termite modified wood, the bamboo material had a good avoidance ability to the termites. The weight gain rate was 20%. After termite decaying, the weight loss rate of the modified wood was less than 0.7%, and there was no erosion mark on the surface, showing excellent resistance to termite. For the modified bamboo, the grade of termite decay was "1" when the weight gain was lower (wpg=5.4%). The modified bamboo with medium weight gain (wpg=15%), the grade of termite decay was "0" grade. Furfuryl alcohol resin was modified. The effect of sex on the mechanical properties of wood bamboo varies with the tree species. Under the same technological conditions, it is found that the flexural strength and the compressive strength of the modified poplar can be significantly improved, the modulus of elasticity is slightly improved or the influence is not obvious. However, the mechanical properties of the modified Chinese fir are improved under only a few technological conditions, and under some technological conditions. The mechanical properties of the modified Cunninghamia lanceolata have been reduced. The factors such as the improvement of the size stability and the Biological durability and the mechanical properties of the wood bamboo are considered. The better technology of the modified Poplar with furfuryl alcohol resin is 50% furfuryl alcohol concentration, the curing temperature 105 degrees C, the curing time 8h, and the Cunninghamia lanceolata modification process: 50% furfuryl alcohol concentration and 11 curing temperature. 5 C, curing time 5h, vacuum pressure impregnating bamboo material modification process: 15% furfuryl alcohol concentration, curing temperature 105 degrees C, curing time 3-5h; room temperature soaking bamboo material modification process: 50% furfuryl alcohol concentration, curing temperature 105 degrees, curing time 5h. environment scanning electron microscope and laser confocal microscope observation found that furfuryl alcohol resin filling in wood tracheids, ducts and wood rays In the cell, the inner wall of the cell is completely covered and most of the grain holes on the wall of the cell are blocked. The rich starch grains in the bamboo parenchyma cells are dissolving and removed, and some of the cavities are filled with resin. The filling of the resin blocks the water into the channel and expands the cell wall, thus reducing the moisture absorption of the modified wood bamboo and improving the dimensional stability significantly. The hardness and modulus of the cell wall of poplar, Cunninghamia lanceolata and bamboo were increased by 32%, 24%, 65% and 4%, 51%, 53% respectively after the modification of the furfuryl alcohol resin. The filling and swelling of furfuryl alcohol resin in cell wall and cell wall of bamboo wood changed the microorganism and Kunming. The parasitic environment of the insects increased the biodegradability of wood bamboo. The infrared spectrum test found that the characteristic peaks of wood cellulose, hemicellulose and lignin weakened and broadened. It proved that the cell wall components of wood bamboo could be degraded in the process of furfuryl alcohol resin modification. In addition, the characteristic peaks representing carbonyl groups were significantly strengthened and offset, indicating the furfuryl alcohol resin. There may be an esterification reaction in the modified wood bamboo. Of course, the introduction of the furfuryl alcohol polymer is also an important reason. The NMR spectroscopy analysis shows that there is no new characteristic peak in the modified wood bamboo spectrum except the unmodified material and furfuryl alcohol resin, and there is no new characteristic peak. In the cell wall and cell wall of bamboo, it is presumed that the esterification of furfuryl alcohol resin may occur in the cell wall, but because of the limited resolution and knowledge accumulation of the experimental instrument, the chemical reaction of the furfuryl alcohol resin and the cell wall component of the bamboo wood can not be confirmed.
【學(xué)位授予單位】：中國(guó)林業(yè)科學(xué)研究院
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：S781.7

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