阻燃处理瓦楞纸板的性能及表征
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摘要
目的研究阻燃处理对瓦楞纸板阻燃性能和物理性能的影响。方法以磷酸胍、纳米二氧化硅、NH_4Cl改性4A分子筛、甲基纤维素、Cu(NO_3)_2改性4A分子筛共混制备无机无卤复合阻燃剂,利用超声波浸渍的方法制备阻燃型瓦楞纸板,根据国标对瓦楞纸板的主要物理性能进行测量,采用垂直燃烧实验和极限氧指数(LOI)测试瓦楞纸板的阻燃效果,采用热重分析(TG)、场发射扫描电镜(FE-SEM)、X射线能谱仪(EDS)和傅里叶红外光谱(FTIR)表征阻燃前后瓦楞纸热稳定性、残炭率、微观形貌、元素组成剂含量以及化学官能团的变化。结果经阻燃处理后,瓦楞纸板的吸水性、边压强度和耐破度分别提高了33.3%,53.7%,14.5%,剥离强度下降了4.5%;阻燃瓦楞纸板的炭化长度为20.3 mm,达到了GB/T 14656—2009中的阻燃纸板技术性能指标,氧指数达到28%(比对照样提高了47.4%);TG分析显示阻燃瓦楞纸板的成炭率提高了111.09%;FE-SEM、EDS和FTIR分析结果显示,阻燃瓦楞纸板的纤维表面存在微米级粒子,这些粒子中的元素除C和O外,还有N,P,Cu等阻燃剂成分。结论复合阻燃剂的施加可提高瓦楞纸板的阻燃性能和物理强度,阻燃剂的覆盖和燃烧时热分解产生的气体均对抑制燃烧起到了重要的凝固相阻燃和气相阻燃作用。
The work aims to study the influence of fire-retardant treatment on the flame retardancy and physical properties of corrugated paperboard. Inorganic halogen-free composite flame retardant was prepared by blending guanidine phosphate, nano-silica, 4 A molecular sieves which was modified by NH_4Cl and Cu(NO_3)_2 and methyl cellulose. Flame-retardant corrugated paperboard was prepared by ultrasonic impregnation. According to the national standard, the main physical properties of corrugated paperboard were measured, and the flame-retardant effect of corrugated paperboard was tested by vertical combustion test and limiting oxygen index(LOI). Thermo gravimetric analysis(TG), field emission scanning(FE-SEM), X ray energy spectrometer(EDS) and Fourier transform infrared spectroscopy(FTIR) were used to characterize thermal stability, carbon residue rate, micro morphology, element composition content and change of chemical functional groups before and after flame-retardant treatment. The water absorption, edge compressive strength and burst strength of corrugated paperboard were increased by 33.3%, 53.7% and 14.5%, respectively. The peeling strength was decreased by 4.5%. The char length of flame-retardant corrugated paperboard was 20.3 mm, which reached technical performance index of flame-retardant board in GB/T 14656—2009, and the oxygen index reached 28%(47.4% higher than the control). TG analysis indicated that the carbon deposition rate of flame-retardant corrugated paperboard was in-creased by 111.09%. The results of FE-SEM, EDS and FTIR showed that there were micron-sized particles on the fiber surface of the flame-retardant corrugated paperboard. Other than C and O, the elements of these particles also included such components of flame retardants as N, P and Cu. The application of composite flame retardant can improve the flame retardancy and physical strength of corrugated paperboard. In addition, both the covering effect of flame retardant and the gas produced by the thermal decomposition during combustion play an important role in inhibiting the combustion with respect to the solidified phase flame resistance and the gas phase flame resistance.
The work aims to study the influence of fire-retardant treatment on the flame retardancy and physical properties of corrugated paperboard. Inorganic halogen-free composite flame retardant was prepared by blending guanidine phosphate, nano-silica, 4 A molecular sieves which was modified by NH_4Cl and Cu(NO_3)_2 and methyl cellulose. Flame-retardant corrugated paperboard was prepared by ultrasonic impregnation. According to the national standard, the main physical properties of corrugated paperboard were measured, and the flame-retardant effect of corrugated paperboard was tested by vertical combustion test and limiting oxygen index(LOI). Thermo gravimetric analysis(TG), field emission scanning(FE-SEM), X ray energy spectrometer(EDS) and Fourier transform infrared spectroscopy(FTIR) were used to characterize thermal stability, carbon residue rate, micro morphology, element composition content and change of chemical functional groups before and after flame-retardant treatment. The water absorption, edge compressive strength and burst strength of corrugated paperboard were increased by 33.3%, 53.7% and 14.5%, respectively. The peeling strength was decreased by 4.5%. The char length of flame-retardant corrugated paperboard was 20.3 mm, which reached technical performance index of flame-retardant board in GB/T 14656—2009, and the oxygen index reached 28%(47.4% higher than the control). TG analysis indicated that the carbon deposition rate of flame-retardant corrugated paperboard was in-creased by 111.09%. The results of FE-SEM, EDS and FTIR showed that there were micron-sized particles on the fiber surface of the flame-retardant corrugated paperboard. Other than C and O, the elements of these particles also included such components of flame retardants as N, P and Cu. The application of composite flame retardant can improve the flame retardancy and physical strength of corrugated paperboard. In addition, both the covering effect of flame retardant and the gas produced by the thermal decomposition during combustion play an important role in inhibiting the combustion with respect to the solidified phase flame resistance and the gas phase flame resistance.
引文
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[12]WANG N,LIU Y,LIU Y,et al.Properties and Mechanisms of Different Guanidine Flame Retardant Wood Pulp Paper[J].Journal of Analytical&Applied Pyrolysis,2017,128:224—231.
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[14]夏寅,金芳芳,毛纵文,等.填料对不同膨胀型阻燃体系的影响[J].高分子材料科学与工程,2015,31(5):44—50.XIA Yin,JIN Fang-fang,MAO Zong-wen,et al.Effects of Fillers on Different Intumescent Flame-Retardant Systems[J].Polymer Materials Science&Engineering,2015,31(5):44—50.
[15]刘应杰,郭玉忠,陈冬华.磷氮系水基型纤维阻燃剂[J].材料导报,2010,24(S2):477—479.LIU Ying-jie,GUO Yu-zhong,CHEN Dong-hua.The Water-based Fire Retardant of Nitrogen Phosphorus for Fibers[J].Materials Review,2010,24(S2):477—479.
[16]李为义,赵丽娟,张求慧.纳米有机蒙脱土在膨胀型阻燃剂中的协效和抑烟性[J].材料导报,2016,30(S1):90—94.LI Wei-yi,ZHAO Li-juan,ZHANG Qiu-hui.Synergistic Effect and Smoke Suppression Performance of Nanometer Organic Montmorillonite in Intumescent Flame Retardant[J].Materials Review,2016,30(S1):90—94.
[17]王冬.含磷氮阻燃单体和功能化二氧化硅的设计与阻燃不饱和聚酯的研究[D].合肥:中国科学技术大学,2017.WANG Dong.Design of Phosphorus and Nitrogen-containing Monomers and Functionalized Silica and Investigation on Flame Retardance of Unsaturated Polyester Resin[D].Hefei:University of Science and Technology of China,2017.
[18]马海云,宋平安,方征平.纳米阻燃高分子材料:现状、问题及展望[J].中国科学:化学,2011,41(2):314—327.MA Hai-yun,SONG Ping-an,FANG Zheng-ping.Flame Retarded Polymer Nanocomposites:Development,Trend and Future Perspective[J].Scientia Sinica(Chemica),2011,41(2):314—327.
[19]张蕾,常晓雅,吴静,等.4A分子筛对膨胀型木材阻燃涂料阻燃性能的影响[J].浙江农林大学学报,2015,32(1):156—161.ZHANG Lei,CHANG Xiao-ya,WU Jing,et al.Fire-retardant Properties of an Intumescent Fire Retardant Coating for Wood Using 4A Zeolite[J].Journal of Zhejiang A&F University,2015,32(1):156—161.
[20]田梁材,胡云楚,夏燎原,等.金属改性13x分子筛在木材阻燃中的抑烟减毒作用[J].中南林业科技大学学报,2015,35(2):103—108.TIAN Liang-cai,HU Yun-chu,XIA Liao-yuan,et al.Study on Smoke Suppression and Toxicity Reducing by Metal-modified 13x Molecular Sieves in Wood Flame Retardant[J].Journal of Central South University of Forestry&Technology,2015,35(2):103—108.
[21]宋晓卉.分子筛的改性对无卤阻燃聚丙烯复合材料燃烧性能的影响[D].北京:北京化工大学,2016.SONG Xiao-hui.Effects of Modified Zeolite on Fire Performance of Halogen Free Polypropylene Composites[D].Beijing:Beijing University of Chemical Technology,2016.
[22]常建栋.硅灰石的改性及其在造纸工业中的应用[D].青岛:青岛科技大学,2014.CHANG Jian-dong.Modification of Wollastoniteandits Application in Papermaking Industry[D].Qingdao:Qingdao University of Science and Technology,2014.
[23]张培.表面施胶对高强瓦楞芯纸强度和防潮性的影响[J].造纸科学与技术,2010,29(4):28—30.ZHANG Pei.Effect of Surface Sizing on Strength and Moisture-proof of High-strength Corrugating Medium[J].Paper Science&Technology,2010,29(4):28—30.
[24]ESTEVES B M,PEREIRA H M.Wood Modification by Heat Treatment:a Review[J].Bioresources,2009,4(1):370—404.
[25]宁永成.有机波谱学谱图解析[M].北京:科学出版社,2010.NING Yong-cheng.Interpretation of Organic Spectra[M].Beijing:Science Press,2010.
[2]李忠文,熊涛涛,孟海.瓦楞纸产品在生活中的应用研究[J].家具与室内装饰,2010(9):56—57.LI Zhong-wen,XIONG Tao-tao,MENG Hai.The Application Research of Corrugated Paper's Production in Life[J].Furniture&Interior Design,2010(9):56—57.
[3]GAO De,WANG Yu,LU Fu-de.Cushioning Packaging Design of Article Based on Polyethylene Foam Constitutive Model[C]//Thirteenth National Conference on Packaging Engineering,2010:51—55.
[4]TJEERDSMA B F,MILITZ H.Chemical Changes in Hydrothermal Treated Wood:FTIR Analysis of Combined Hydrothermal and Dry Heat-treated Wood[J].Holzals Roh-und Werkstoff,2005,63(2):102—111.
[5]BAI X L,JOHNSTON P,SADULA S,et al.Role of Levoglucosan Physiochemistry in Cellulose Pyrolysis[J].Journal of Analytical&Applied Pyrolysis,2013,99:58—65.
[6]YAN K,XIE X,LI J,et al.Preparation,Characterization,and Catalytical Application of Mg Co AlHydrotalcite Like Compounds[J].Journal of Natural Gas Chemistry,2007,16(4):371—376.
[7]SHAH A U R,PRABKAKAR M N,SONG J I.Current Advances in the Fire Retardancy of Natural Fiber and Bio-based Composites—a Review[J].International Journal of Precision Engineering and Manufacturing-Green Technology,2017,4(2):247—262.
[8]路风辉,冯岸红,陈满英,等.珠三角表层沉积物的有机碳及其与卤系阻燃剂的关系[J].地球与环境,2015,43(1):49—54.LU Feng-hui,FENG An-hong,CHEN Man-ying,et al.Total Organic Carbons and Their Correlations with Halogenated Flame Retardants in Surface Sediments from the Pearl River Delta,China[J].Earth and Environment,2015,43(1):49—54.
[9]MO Li,WU Jiang-Ping,LUO Xiao-Jun,et al.Dechlorane Plus Flame Retardant in Kingfishers(Alcedoatthis)from an Electronic Waste Recycling Site and A Reference Site,South China:Influence of Residue Levels on the Isomeric Composition[J].Environmental Pollution,2013,174(5):57—62.
[10]刘跃军,郝宗贤,刘亦武.多元层状双羟基金属复合氧化物用作阻燃填料制备阻燃纸[J].中国造纸,2012,31(7):17—21.LIU Yue-jun,HAO Zong-xian,LIU Yi-wu.Manufacture of Flame Retardant Paper with Multiple-element Layered Double Hydroxides(LDHs)as Filler[J].China Pulp&Paper,2012,31(7):17—21.
[11]魏微.高效无卤阻燃纸制备工艺及阻燃性能研究[D].福州:福建农林大学,2017.WEI Wei.Study on the Preparation Process of Paper with Non-halogen Flame Retardant and it’s Efficient Property on Fire[D].Fuzhou:Fujian Agriculture and Forestry University,2017.
[12]WANG N,LIU Y,LIU Y,et al.Properties and Mechanisms of Different Guanidine Flame Retardant Wood Pulp Paper[J].Journal of Analytical&Applied Pyrolysis,2017,128:224—231.
[13]孙昊,倪敏娜,张新昌,等.阻燃型包装纸板材料的阻燃剂制备及性能研究[J].包装工程,2014,35(23):63—67.SUN Hao,NI Min-na,ZHANG Xin-chang,et al.Preparation of a Flame Retardant Agent for Flame Retardant Type Packaging Paperboard and Its Properties[J].Packaging Engineering,2014,35(23):63—67.
[14]夏寅,金芳芳,毛纵文,等.填料对不同膨胀型阻燃体系的影响[J].高分子材料科学与工程,2015,31(5):44—50.XIA Yin,JIN Fang-fang,MAO Zong-wen,et al.Effects of Fillers on Different Intumescent Flame-Retardant Systems[J].Polymer Materials Science&Engineering,2015,31(5):44—50.
[15]刘应杰,郭玉忠,陈冬华.磷氮系水基型纤维阻燃剂[J].材料导报,2010,24(S2):477—479.LIU Ying-jie,GUO Yu-zhong,CHEN Dong-hua.The Water-based Fire Retardant of Nitrogen Phosphorus for Fibers[J].Materials Review,2010,24(S2):477—479.
[16]李为义,赵丽娟,张求慧.纳米有机蒙脱土在膨胀型阻燃剂中的协效和抑烟性[J].材料导报,2016,30(S1):90—94.LI Wei-yi,ZHAO Li-juan,ZHANG Qiu-hui.Synergistic Effect and Smoke Suppression Performance of Nanometer Organic Montmorillonite in Intumescent Flame Retardant[J].Materials Review,2016,30(S1):90—94.
[17]王冬.含磷氮阻燃单体和功能化二氧化硅的设计与阻燃不饱和聚酯的研究[D].合肥:中国科学技术大学,2017.WANG Dong.Design of Phosphorus and Nitrogen-containing Monomers and Functionalized Silica and Investigation on Flame Retardance of Unsaturated Polyester Resin[D].Hefei:University of Science and Technology of China,2017.
[18]马海云,宋平安,方征平.纳米阻燃高分子材料:现状、问题及展望[J].中国科学:化学,2011,41(2):314—327.MA Hai-yun,SONG Ping-an,FANG Zheng-ping.Flame Retarded Polymer Nanocomposites:Development,Trend and Future Perspective[J].Scientia Sinica(Chemica),2011,41(2):314—327.
[19]张蕾,常晓雅,吴静,等.4A分子筛对膨胀型木材阻燃涂料阻燃性能的影响[J].浙江农林大学学报,2015,32(1):156—161.ZHANG Lei,CHANG Xiao-ya,WU Jing,et al.Fire-retardant Properties of an Intumescent Fire Retardant Coating for Wood Using 4A Zeolite[J].Journal of Zhejiang A&F University,2015,32(1):156—161.
[20]田梁材,胡云楚,夏燎原,等.金属改性13x分子筛在木材阻燃中的抑烟减毒作用[J].中南林业科技大学学报,2015,35(2):103—108.TIAN Liang-cai,HU Yun-chu,XIA Liao-yuan,et al.Study on Smoke Suppression and Toxicity Reducing by Metal-modified 13x Molecular Sieves in Wood Flame Retardant[J].Journal of Central South University of Forestry&Technology,2015,35(2):103—108.
[21]宋晓卉.分子筛的改性对无卤阻燃聚丙烯复合材料燃烧性能的影响[D].北京:北京化工大学,2016.SONG Xiao-hui.Effects of Modified Zeolite on Fire Performance of Halogen Free Polypropylene Composites[D].Beijing:Beijing University of Chemical Technology,2016.
[22]常建栋.硅灰石的改性及其在造纸工业中的应用[D].青岛:青岛科技大学,2014.CHANG Jian-dong.Modification of Wollastoniteandits Application in Papermaking Industry[D].Qingdao:Qingdao University of Science and Technology,2014.
[23]张培.表面施胶对高强瓦楞芯纸强度和防潮性的影响[J].造纸科学与技术,2010,29(4):28—30.ZHANG Pei.Effect of Surface Sizing on Strength and Moisture-proof of High-strength Corrugating Medium[J].Paper Science&Technology,2010,29(4):28—30.
[24]ESTEVES B M,PEREIRA H M.Wood Modification by Heat Treatment:a Review[J].Bioresources,2009,4(1):370—404.
[25]宁永成.有机波谱学谱图解析[M].北京:科学出版社,2010.NING Yong-cheng.Interpretation of Organic Spectra[M].Beijing:Science Press,2010.