脒基脲磷酸盐和硅酸钠对木材的阻燃作用
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摘要
采用锥形量热仪(CONE)法评价木材经阻燃剂脒基脲磷酸盐(GUP)和硅酸钠(Na_2SiO_3)处理后的阻燃性能,结合热重分析法研究GUP和Na_2SiO_3的阻燃机理.实验结果表明:与未加阻燃剂处理的木材相比,Na_2SiO_3二次处理木材和GUP一次处理木材的热释放速率(HRR_(peak))、总热释放量(THR)、烟释放速率(SPR)、总烟释放量(TSP)和CO_2生成率(Y_(CO_2))显著降低.Na_2SiO_3二次处理木材比GUP一次处理木材显示出更好的阻燃性.从阻燃机理分析,GUP能够加速木材热解过程中的脱水和炭化反应,Na_2SiO_3能够增加纤维素降解反应的活化能,从而增加木材的热稳定性.
Wood was treated by guanyl urea phosphate(GUP) firstly and sodium silicate(Na_2SiO_3) secondly to impart flame retardance. The flame retarding properties of the treated samples were investigated by cone calorimeter and the thermal behaviors of these samples were studied by differential thermogravimetry(DTG) and thermogravimetry(TG) in air. It was found that the combustion parameters including peak of heat release rate(HRR_(peak)), total heat release(THR), smoke production rate(SPR), total smoke product(TSP) and the yield of CO_2(Y_(CO_2)) were decreased considerably by the treatment of GUP and Na_2SiO_3 when compared with those of the untreated samples. Furthermore, wood treated by both GUP and Na_2SiO_3 had better flame retarding properties than that by only GUP possibly because GUP could accelerate dehydration and carbonation, and simultaneously Na_2SiO_3 could relatively increase the activation energy of cellulose, which resulted in the enhancement of wood thermal stabilization.
Wood was treated by guanyl urea phosphate(GUP) firstly and sodium silicate(Na_2SiO_3) secondly to impart flame retardance. The flame retarding properties of the treated samples were investigated by cone calorimeter and the thermal behaviors of these samples were studied by differential thermogravimetry(DTG) and thermogravimetry(TG) in air. It was found that the combustion parameters including peak of heat release rate(HRR_(peak)), total heat release(THR), smoke production rate(SPR), total smoke product(TSP) and the yield of CO_2(Y_(CO_2)) were decreased considerably by the treatment of GUP and Na_2SiO_3 when compared with those of the untreated samples. Furthermore, wood treated by both GUP and Na_2SiO_3 had better flame retarding properties than that by only GUP possibly because GUP could accelerate dehydration and carbonation, and simultaneously Na_2SiO_3 could relatively increase the activation energy of cellulose, which resulted in the enhancement of wood thermal stabilization.
引文
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[23] 全凤玉,纪全,孔庆山,等.无机阻燃粘胶纤维制备及结构性能研究[J].青岛大学学报(工程技术版),2008,23(3):19-22.DOI:10.13306/j.1006-9798.2008.03.002.
[2] 骆介禹,骆希明.纤维素基质材料阻燃技术[M].北京:化学工业出版社,2003:31-35.
[3] 刘山山.关于木结构建筑防火技术的研究[J].消防技术与产品信息,2017(11):17-19.
[4] ENESCU D,FRACHE A,LAVASELLI M,et al.Novel phosphorous-nitrogen intumescent flame retardant system.Its effects on flame retardancy and thermal properties of polypropylene[J].Polymer Degradation & Stability,2013,98(1):297-305.DOI:10.1016/j.polymdegradstab.2012.09.012.
[5] ZHONG Y,WU W,LIN X,et al.Flame-retarding mechanism of organically modified montmorillonite and phosphorous-Nitrogen flame retardants for the preparation of a halogen-free,flame-retarding thermoplastic poly (ester ether) elastomer[J].Journal of Applied Polymer Science,2015,131(22):547-557.DOI:10.1002/APP.41094.
[6] KOROTKOV A S.Melamine/monoammonium phosphate complex as the polyphosphate substitute in flame retardant coatings[J].Journal of Fire Sciences,2016,34(2):89-103.DOI:10.1177/0734904115621583.
[7] 王清文,李坚.木材阻燃剂FRW的阻燃机理[J].林业科学,2005,41(5):123-126.
[8] 杜春贵,张齐生,金春德,等.FRW阻燃杉木积成材的阻燃性能[J].建筑材料学报,2010,13(4):555-559.
[9] 王奉强,王清文,张志军,等.锥形量热仪法研究FRW系列阻燃剂的抑烟性能[J].木材工业,2011,25(3):11-14.DOI:10.19455/j.mcgy.2011.03.004.
[10] GUO C,WANG S,WANG Q.Synergistic effect of treatment with disodium octaborate tetrahydrateand guanyl urea phosphate on flammability of pine wood[J].European Journal of Wood and Wood Products,2018,76(1):213-220.
[11] 张其,肖泽芳,龚宸,等.磷酸脒基脲和季戊四醇磷酸酯复合改性MUF木材涂料的阻燃性能研究[J].林业工程学报,2018,3(6):48-55.DOI:10.13360/j.issn.2096-1359.2018.06.008.
[12] KUMAR S P,TAKAMORI S,ARAKI H,et al.Flame retardancy of clay-sodium silicate composite coatings on wood for construction purposes[J].RSC Advances,2015,5:34109-34116.DOI:10.1039/c5ra04682c.
[13] 李晓东.ZR-M-301阻燃剂浸渍处理木材方法研究[D].天津:天津大学,2005.
[14] WANG Q,LI J,WINANDY J E.Chemical mechanism of fire retardance of boric acid on wood[J].Wood Science & Technology,2004,38(5):375-389.DOI:10.1007/s00226-004-0246-4.
[15] BABRAUSKAS V.Development of the cone calorimeter-A bench-scale heat release rate apparatus based on oxygen consumption[J].Nasa Sti/recon Technical Report N,1984,83(2):81-95.DOI:10.1002/fam.810080206.
[16] 夏燎原,胡云楚,吴义强,等.介孔SiO2-APP复合阻燃剂的制备及其对木材的阻燃抑烟作用[J].中南林业科技大学学报,2012,32(1):9-13.DOI:10.14067/j.cnki.1673-923x.2012.01.042.
[17] HUANG M,LI X.Thermal degradation of cellulose and cellulose esters[J].Journal of Applied Polymer Science,2015,68(2):293-304.
[18] KIM H S,KIM S,KIM H J,et al.Thermal properties of bio-flour-filled polyolefin composites with different compatibilizing agent type and content[J].Thermochimica Acta,2006,451(1):181-188.DOI:10.1016/j.tca.2006.09.013.
[19] VARHEGYI G,JR M J A,SZEKELY T,et al.Kinetics of the thermal decomposition of cellulose,hemicellulose,and sugarcane bagasse[J].Energy & Fuels,1989,3(3):329-335.DOI:10.1021/ef00015a012.
[20] YANG H,YAN R,CHEN H,et al.In-depth investigation of biomass pyrolysis based on three major components:hemicellulose,cellulose and lignin[J].Energy Fuels,2011,20(1):388-393.DOI:10.1021/ef0580117.
[21] BROIDO A.A simple,sensitive graphical method of treating thermogravimetric analysis data[J].Journal of Polymer Science Part A-2 Polymer Physics,1969,7(10):1761-1773.DOI:10.1002/pol.1969.160071012.
[22] GAO M,NIU J,YANG R.Synergism of GUP and boric acid characterized by cone calorimetry and thermogravimetry[J].Journal of Fire Sciences,2006,24(6):499-511.DOI:10.1177/0734904106061522.
[23] 全凤玉,纪全,孔庆山,等.无机阻燃粘胶纤维制备及结构性能研究[J].青岛大学学报(工程技术版),2008,23(3):19-22.DOI:10.13306/j.1006-9798.2008.03.002.
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