林業(yè)工程學(xué)報(bào),2016,1(2):17-20Doi:10.13360/isn,2096-139.2016.02.03炭化楊木單板制備膠合板的氧指數(shù)和熱重分析關(guān)明杰',常馨曼',薛明慧',王炳忠2’,翟通軍2(1南京林業(yè)大學(xué)材料科學(xué)與工程學(xué)院南京210037;2連云港南方木業(yè)有限公司,江蘇灌南222500)摘要:通過研究不同炭化處理溫度下的楊木單板制備膠合板的氧指教和熱重分析,以評(píng)價(jià)其阻燃性能。分別將160,180和200℃炭化處理后的單板熱壓制成5層對(duì)稱結(jié)構(gòu)膠合板,氧指數(shù)和熱重分析結(jié)果表明:炭化處理后的膠合板氧指數(shù)均高于未處理的膠合板,當(dāng)炭化條件為200℃和2h時(shí),膠合板氧指數(shù)最大值為30.3%,達(dá)到B3級(jí)難然材料標(biāo)準(zhǔn)。由TG-DIG曲線可知,炭化處理前后膠合板的TG、DTC曲線變化趨勢(shì)完全一致,主要差異體現(xiàn)在最終的成炭率、肩峰及特征峰對(duì)應(yīng)的具體溫度上。炭化條件為200℃和2h時(shí)的最終成炭奉為21·04%達(dá)到最大值;肩峰對(duì)應(yīng)溫度隨炭化溫度的升高而降低,炭化處理后膠合板特征峰對(duì)應(yīng)溫度均小于未處理的膠合板。關(guān)鍵詞:楊木;炭化處理;氧指數(shù);熱重分析;膠合板中圖分類號(hào):TU531.2;T653.3文獻(xiàn)標(biāo)志碼:A文章編號(hào):2096-1359(2016)02-0017-04Oxygen index and thermalgravimetric analysis ofpoplar plywood by carbonized veneerGUAN Mingjie, CHANG Xinman, XUE Minghui, WANG Bingzhong, ZHAI Tongjun(1. College of Materials Science and Engineering, Nanying Forestry Univeristy, Nanying 210037, China;2. Nanfang Wood Products Ltd. Co. Liangyungang, Guannan 222500, Jiangsu, China)Abstract: This paper aimed at investigating the effect of veneer carbonization treatment on the fire resistance propertieof poplar plywood by means of Oxygen Index(OI)and thermalgravimetric analysis. The poplar veneers carbonized in160, 180 and 200 C respectively for 2 h were used to produce five-layer plywood with melamine-urea-formaldehyderesin. a series of parameters of the carbonized plywood were tested in aspects of bonding shear strength, Modulus of Elasticity( MOE), Modulus of Rupture( MOR)and Ol Thermalgravimetric analysis was also used to analyze the thermalproperties of plywood correspondingly. The results showed that the bonding shear strength and mor decreased as the in-crease of carbonized temperature of poplar veneer, while MOE of plywood increased with the increase of carbonized temperature slightly. As a whole, bonding shear strength, MOE, MOR of the plywood from carbonized veneer declined obviously compared with those of control group. Bonding shear strength and mOR of the carbonized plywood from 200C and2 h decreased by 12. 7% and 38. 3% respectively, and MOE of the three carbonized plywood declined 26% to 30%. TheOI results showed that the oI in carbonization treatment groups were higher than that of control group. At the carbonize-tion condition of 200 and 2 h, the ol of the carbonized plywood was 30. 3%, reaching grade B, standard of refractorynaterials according to the classification for burning behavior of building materials and products( GB 8624-2012) Fromthe TG-DTG analysis curves, the variation tendency of the four groups were consistent, the differences were mainly inthe specific temperatures of final char yield, the acromion and characteristic peaks. Under the condition of 200C andh, the final char yield was 21. 04%, reaching the maximum value among four plywood groups. The temperature of acromion decreased with the rising of carbonization temperature, and the temperature of characteristic peaks in the carbon-ized groups were lower than that of control plywood. Generally, carbonization treatment on veneer improves the final charyield and Ol of plywood. It is supposed to be a new way to improve the fire resistance of plywood without any chemicalKey words: poplar; carbonization treatment; oxygen index; thermalgravimetric analysis; plywood修回日期:2015-11-03中國(guó)煤化工收稿日期:2015-07-3基金項(xiàng)目:蘇北科技發(fā)展計(jì)劃-科技型企業(yè)技術(shù)創(chuàng)新項(xiàng)目(BC2013425);江蘇高校優(yōu)勢(shì)學(xué)利CNMHG作者簡(jiǎn)介:關(guān)明杰,女,副教授研究方向?yàn)橹衲静牡募庸だ谩?E-mail; mingjieguand@ hotmailcom林業(yè)工程學(xué)報(bào)第1卷?xiàng)顦涫侵匾乃偕鷺浞N,基本密度為0.35g/汽對(duì)單板進(jìn)行炭化處理。炭化時(shí)間均為2h時(shí),設(shè)cm3,顏色淺,含水率高極易加工,我國(guó)南北方均定炭化溫度分別為160,180和200℃,分別標(biāo)記為有廣泛種植。但楊木單板材質(zhì)軟尺寸穩(wěn)定性差,a、b、c組,另設(shè)對(duì)照組d(表1)。制成的膠合板易吸濕產(chǎn)生變形,因此其應(yīng)用受到廣表1楊木單板炭化分組泛限制。為充分利用楊木資源,增加產(chǎn)品的附Tab,1 Carbonization treatment group of poplar veneer加值,需要對(duì)楊木單板進(jìn)行改性處理。目前常用的炭化時(shí)間/h炭化溫度/℃改性方法包括物理和化學(xué)改性方法,物理改性方法中常用的是炭化改性,化學(xué)改性方法則包括乙?；瘑伟褰n等方法23)。由于化學(xué)改性方法引入未處理了其他化學(xué)成分,會(huì)對(duì)楊木單板的膠合產(chǎn)生消極影響污染大且后期處理工藝復(fù)雜。而炭化處理是通122楊木膠合板制備過對(duì)木材進(jìn)行熱處理降低其組分中吸水羥基的密單板涂膠量為220g/m2(雙面),涂膠后的板度,從而減弱木材的吸濕性及內(nèi)應(yīng)力加強(qiáng)木材的坯采用5層對(duì)稱結(jié)構(gòu)組坯陳放熱壓。熱壓工藝尺寸穩(wěn)定性4。炭化處理很少添加化學(xué)藥劑,污為100℃、1.0MPa、1min/mm,自然冷卻在20染問題少、處理工藝簡(jiǎn)單且炭化后木材具有良好的℃、(65±2)%的調(diào)制箱中調(diào)質(zhì)平衡,制得與表1耐老化性能、尺寸穩(wěn)定性及安全、環(huán)保等突出優(yōu)對(duì)應(yīng)試驗(yàn)編號(hào)下的膠合板每組膠合板試驗(yàn)張數(shù)為點(diǎn)。而國(guó)內(nèi)外對(duì)炭化木質(zhì)材料的物理、力學(xué)、化5張。學(xué)性能研究主要集中在炭化木材上70,對(duì)炭化單1.23楊木膠合板物理力學(xué)性能測(cè)試板制備的膠合板的可燃性能評(píng)估關(guān)注極少。參照GB/T17657-2013《人造板及飾面人造筆者通過炭化楊木單板制備膠合板,測(cè)試膠合板理化性能試驗(yàn)方法》測(cè)定楊木膠合板的膠合強(qiáng)板的極限氧指數(shù),并對(duì)其進(jìn)行熱重分析,以期找到度、彈性模量和靜曲強(qiáng)度等物理力學(xué)性能。炭化處理工藝對(duì)膠合板性能的影響規(guī)律,從而為今1.2.4楊木膠合板氧指數(shù)(OD)測(cè)定后國(guó)內(nèi)外對(duì)炭化木質(zhì)復(fù)合材料燃燒性能研究提供將制得的楊木膠合板鋸制成尺寸為100mm技術(shù)參數(shù),為速生材的綜合利用開發(fā)、產(chǎn)出高附加10mm(厚度<10.5mm)的試樣,每組試件數(shù)量15值產(chǎn)品提供技術(shù)指導(dǎo)參考。個(gè),在每個(gè)試件距離一端50mm處劃線做標(biāo)記。材料與方法參照GB/T2406-2009,將試件未劃線一端固定在燃燒筒中,使氧氮混合氣流由下向上流過,用1.1試驗(yàn)材料點(diǎn)火器點(diǎn)燃試樣頂端,同時(shí)觀察并記錄試件燃燒時(shí)楊木單板500mm×500mm×2mm,取自江蘇間及燃燒長(zhǎng)度。試件燃燒時(shí)間達(dá)到3min或者燃省灌南縣,單板氣干含水率為7%-10%;三聚氰胺燒長(zhǎng)度超過50mm時(shí),所需最低氧氣濃度即為試改性脲醛樹脂,固含量52.6%,黏度190mPa·s,由件氧指數(shù)。經(jīng)反復(fù)測(cè)試,找出達(dá)到臨界值的氧氣濃江蘇舜天利華木業(yè)有限公司提供。度,得到試件的氧指數(shù)。炭化箱,南京恒裕儀器設(shè)備制造有限公司,型1.2.5楊木膠合板熱重分析號(hào)THX-3;電加熱蒸汽鍋爐,上海捷士服裝機(jī)械有將制得的楊木膠合板研磨成粉末并過60目限公司,型號(hào)DZC-4.5E。JF-3氧指數(shù)測(cè)定儀,南(0.25mm)篩網(wǎng),將所得粉末置于高純動(dòng)態(tài)氮?dú)饩┦薪瓕巺^(qū)分析儀器廠;TG209F3 Tarsus型熱重內(nèi),從室溫升至700℃(升溫速率為10℃/min),分析儀,德國(guó) NETZSCH公司。進(jìn)行熱重分析。1.2試驗(yàn)方法1.2.1楊木單板炭化2結(jié)果與分析由電加熱蒸汽鍋爐提供炭化處理過程中所需2.1膠合板物理力學(xué)性能的過熱蒸汽作為保護(hù)氣體,隔絕氧氣的同時(shí)參與部楊木膠合板的膠合強(qiáng)度、彈性模量和靜曲強(qiáng)度分加熱,使溫度過高時(shí)木材不致燃燒損毀。測(cè)試結(jié)果見表2。隨著炭化溫度的升高,膠合板的將楊木單板放入炭化箱中調(diào)節(jié)炭化箱溫度至膠合強(qiáng)度和靜rV凵中國(guó)煤化工彈性模量卻預(yù)設(shè)溫度。溫度達(dá)到后,打開電加熱蒸汽鍋爐維略有提高這可CNMH板的表面潤(rùn)持蒸汽壓力0.2MPa,持續(xù)向炭化箱中通入過熱蒸濕性降低膠液滲透少,形成的膠層更厚膠層為脆第2期關(guān)明杰,等:炭化楊木單板制備膠合板的氧指數(shù)和熱重分析性多孔高密度層,可提高膠合板的彈性模量,但對(duì)規(guī)定:B1級(jí)為難燃材料,B2級(jí)為可燃材料,B1級(jí)氧強(qiáng)度的貢獻(xiàn)不大。因此,隨著炭化溫度的升高,處指數(shù)O≥30%,B2級(jí)氧指數(shù)OI≥26%。由圖1可理后的單板壓制的板材抗彎彈性模量有增高的現(xiàn)知,C組的氧指數(shù)達(dá)到B級(jí)難燃材料的標(biāo)準(zhǔn),而A、象,但與對(duì)照組相比,炭化單板所制膠合板的3項(xiàng)B、D組均為B2級(jí)可燃材料。單板炭化處理可以在性能指標(biāo)都有明顯下降,抗彎彈性模量的下降最明定程度上提高膠合板燃燒的氧指數(shù),從而降低膠顯,降幅達(dá)到26%~30%,而C組的靜曲強(qiáng)度下降合板的燃燒性能達(dá)到38.3%,膠合強(qiáng)度的下降達(dá)到12.7%。表2炭化單板膠合板的基本物理力學(xué)性能Tab 2 Basic physical and mechanical properties ofplywood by carbonized veneer/M編號(hào)膠合強(qiáng)度彈性模量靜曲強(qiáng)度A2.2244.33B2.14C2.06D2.36673753.17圖1膠合板氧指數(shù)Fig 1 Oxygen index of plywood2.2膠合板氧指數(shù)膠合板的氧指數(shù)如圖1所示,D組的氧指數(shù)為2.3膠合板熱重分析9.2%,A組為29.8%,B組為29.5%,C組為采用熱重法得到程序控制溫度,各組試件的質(zhì)30.3%,即炭化組膠合板的氧指數(shù)均大于對(duì)照組,量隨溫度變化的曲線(TG曲線)及對(duì)熱重曲線進(jìn)但測(cè)試出的炭化組之間氧指數(shù)差異不明顯。根據(jù)行一次微分所得的微商熱重曲線(DTG曲線)如圖GB8624202《建筑材料及制品燃燒性能分級(jí)》2所示。80A組2.580B組TO7.5§240-10.02010020030040050060070012500200300400500600700溫度/℃80+C組TO80D組DTG50004005006000100200300400500600700溫度/℃C溫度/℃圖2各組試件的TG-DIG曲線Fig 2 TG-DTG curves of carbonized groups and control group由TG和DTG曲線可看出:在室溫至100℃范是由于殘余木質(zhì)素的熱解。4組試件在280~295圍內(nèi)出現(xiàn)一個(gè)失重峰,此階段主要是楊木膠合板的℃之間均出現(xiàn)一個(gè)肩峰,該峰值說明以半纖維素和水分析出,當(dāng)溫度達(dá)到80℃時(shí)已基本完全失重;在木質(zhì)素為主要的聚合物在此溫度階段達(dá)到熱解最100-400℃范圍內(nèi)出現(xiàn)一個(gè)較大失重峰,這是由大程度,楊木膠合板進(jìn)入以纖維素和木質(zhì)素為主要于大量的揮發(fā)分析出,溫度達(dá)到400℃時(shí),膠合板熱解聚合物的20-35,之間,DTG曲的失重率約為70%;溫度高于400℃后,隨著溫度線出現(xiàn)一個(gè)牛中國(guó)煤化質(zhì)素出現(xiàn)熱的增加,失重速率逐漸放緩,這時(shí)木材的失重主要解高峰1,互,曲線變化趨勢(shì)20林業(yè)工程學(xué)報(bào)第1卷完全一致,主要差異體現(xiàn)在最終的成炭率、肩峰及nal of Central South University of Forestry Technology, 2014特征峰對(duì)應(yīng)的具體溫度上。34(3):99-1034組膠合板熱解的最終成炭率、肩峰及特征喹[2]雷得定,周軍浩,劉波,等.木材改性技術(shù)的現(xiàn)狀與發(fā)展趨勢(shì)[J].木材工業(yè),2009,23(1):37對(duì)應(yīng)溫度見表3,未處理組最終成炭率為20.55%,Lei DD, Zhou J H, Liu B, et al. 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