【作者】 尤飞；

【导师】 胡源；

【作者基本信息】 中国科学技术大学 ， 安全技术及工程， 2008， 博士

【摘要】 西藏古建筑由于藏传佛教文化而呈现出神秘而独特的历史价值,其中应用的大量各式具有鲜明图案和色彩的悬挂类装饰织物成为这一宗教价值的直接载体。然而,其易燃性则为这种独特价值带来安全隐患。本文基于西藏古建筑中典型悬挂类装饰织物的阻燃性和宗教性需求,探索可实现高效、环保、透明、简捷和新型的阻燃方法:首先对代表性织物的热解和燃烧特性进行了测定,并对其纤维成分进行鉴别,以此确定阻燃基材布料;其次,通过溶胶-凝胶技术制备了一系列无机氧化物溶胶,将其单独整理纯棉和纯涤织物,探讨了其阻燃性能和机理;第三,运用各种成碱金属盐溶液整理纯棉和纯涤织物,探讨了其阻燃性能和机理;最后,将具有高效阻燃性的溶胶、金属盐和传统阻燃剂进行配伍,先后用于复合整理纯棉和纯涤织物,探讨了其间的阻燃协效性。全文的主要工作如下:（1）通过极限氧指数、垂直燃烧、锥形量热、小火源燃烧和热失重等方法测定了从布达拉宫采集的代表性装饰织物的热解和燃烧特性,结果发现:大多数织物整体热解温度偏低,残炭量较少;LOI值低于20.0,属于易燃织物;燃烧速率很快,持续时间很短（＜60s）,热释放量大（最大热释放速率高于50kW/m²）。（2）通过热解法、燃烧法、光学显微投影法和傅立叶变换红外光谱法等方法对典型悬挂类装饰织物纤维成分进行鉴别,结果发现应用最多的纤维种类依次为纤维素纤维（粘胶和棉等）、人造聚合物纤维（涤纶、锦纶和丙纶）和蛋白质纤维（蚕丝和羊毛）。据此,本文选择棉和涤纶纤维作为阻燃基材布料。（3）利用溶胶-凝胶法,制备了SiO₂、TiO₂、SnO₂和Fe₂O₃等一系列溶胶,将其浸渍整理纯棉和涤纶织物,通过极限氧指数、热失重、微型量热等方法判定了其阻燃效应以及测定了其热解和燃烧特性,通过动态红外和扫描电镜等方法探讨了溶胶的阻燃机理,结果发现:无机氧化物溶胶对纯棉和涤纶织物阻燃性能有限,整理后棉和涤纶织物ΔLOI分别为0.0-3.0和0.0-2.2,达不到GA 504-2004阻燃装饰织物标准推荐的B2级阻燃要求（LOI≥26.0）;SnO₂溶胶对纯棉织物阻燃效应最好,其作用机理在于对棉纤维有催化脱水和成炭效应,且可维持成炭反应。（4）制备了一系列金属氯化物、硫酸盐、硝酸盐和醋酸盐等工作液,将其浸渍整理纯棉和涤纶织物,通过极限氧指数、热失重、微型量热等方法判定了其阻燃效应以及测定了其热解和燃烧特性,通过动态红外和扫描电镜等方法探讨了金属盐的阻燃机理,结果发现:金属盐对棉织物有高效阻燃性,其阻燃效应依金属氯化物、金属硫酸盐、金属醋酸盐和金属硝酸盐顺序逐渐下降,整理后织物的ΔLOI分别为1.3-15.3、0.4-14.4、0.0-6.5和0.0-3.0;FeCl₃·6H₂O、MgCl₂·6H₂O、ZnCl₂和Al₂（SO₄）₃·18H₂O等4种金属盐可使整理织物达到GA 504-2004阻燃装饰织物标准推荐的B1级阻燃要求（LOI≥32.0）,整理织物最大热释放速率降幅约为67-90%,热解残炭量增幅约为4.01-8.12%;这些高效金属盐的阻燃机理在于能够持续催化棉纤维脱水和成炭;这些金属盐对涤纶织物的阻燃效应有限,达不到B2级,阻燃效应依金属氯化物、金属硫酸盐、金属硝酸盐和金属醋酸盐顺序逐渐下降,整理后织物的≡LOI分别为0.5-5.7、0.0-3.9、0.0-3.5和0.0-2.2。（5）将具有良好阻燃性的溶胶、金属盐和传统阻燃剂相互配伍,将其浸渍整理纯棉和涤纶织物,通过极限氧指数、热失重、微型量热等方法判定了其阻燃效应以及测定了其热解和燃烧特性,利用ΔLOI_复合整理＞{ΔLOI_{传统阻燃剂},ΔLOI_溶胶,ΔLOI_金属盐}的原则确定阻燃协效性,结果发现:（硼酸/硼砂）与MgCl₂·6H₂O、ZnCl₂与SnO₂溶胶、MgCl₂·6H₂O与SnO₂溶胶以及CuSO₄·5H₂O与SnO₂溶胶等复合体系整理织物可达到B1级,其ΔLOI最高为20.6-21.5（SnO₂溶胶/MgCl₂·6H₂O）,最大热释放速率最大降幅为95%（CuSO₄·5H₂O/SnO₂溶胶）,热解残炭量最大增幅为9.67%（SnO₂溶胶/CuSO₄·5H₂O）;其阻燃机理在于催化脱水和成炭效应的加和性增强。对于涤纶织物,这些金属盐无法使其达到B2级。更多还原

【Abstract】 Due to the culture of Tibetan Buddhism,Tibetan historical buildings display mysterious and particular historical values.The large amounts of hanging decorative textiles with various clear patterns and lustrous colors are the direct carriers of such religious values.However,the flammability of these fabrics poses great potential safety hazards on such particular values.In this paper,based on the requirement for both flame retardancy and religiousness of typical hanging decorative textiles in Tibet historical buildings,high efficient,environment-friendly,transparent,convenient and novel flame retardant methods are explored.Firstly,the pyrolysis and burning properties of typical textiles were measured;secondly,the compositions of typical textiles were identified to confirm the base fabrics;thirdly,a series of transparent inorganic oxide sols were prepared via sol-gel technique and used to finish cotton and PET fabrics by dipping-drying,the flame retardant effects and mechanisms of such finished fabrics were studied;fourthly,various base forming metal salt solutions were prepared to finish cotton and PET fabrics by dipping-drying,the flame retardant effects and mechanisms of such finished fabrics were studied;finally,sols,metal salts and traditional flame retardants of high efficiency were selected to compound finish cotton and PET fabrics successively,the synergistic effects between them was investigated.The main work in this paper is summed up as follows:（1） Limiting oxygen index,vertical burning,cone calorimeter,simple burning using small ignition source and thermal gravimetric analysis methods were used to measure the pyrolysis and combustion properties of typical hanging textiles sampled from the Potala Palace.The results show that most of them are flammable fabric with LOI values lower than 20.0;they degrade at lower temperature and lead to less char residues;in the cone calorimeter test,they show high burning rates（ignition time values are usually lower than 60s） and high heat release rates（higher than 50kW/m²）. Therefore,the demand for flame retardancy is very high.（2） The fiber compositions of typical hanging textiles were identified via thermal gravimetric analysis,simple burning,optical microscope projecting and Fourier Transition Infrared Spectrum（FTIR） methods.It is found that cellulose fibers （viscose and cotton）,manmade polymer fibers（PET＜terylene＞,PA＜nylon＞and PP） and protein fibers（silk and wool） are applied most widely.Hence,cotton and PET fibers are selected as flame retardant bases.（3） A series of inorganic oxide sols like SiO₂,TiO₂,SnO₂ and Fe₂O₃ were prepared via sol-gel technique.They were used to finish cotton and PET fabrics via dipping-spraying.Flame retardant effect was determined via limiting oxygen index method and the pyrolysis and combustion properties of finished fabrics were measured by thermal gravimetric analysis and micro-calorimeter methods.Flame retardant mechanism was explored via dynamic FTIR and scanning electronic microscope（SEM）.The results show that inorganic oxide sols play limited role in flame retarding cotton and PET fabrics.The△LOI values of finished cotton and PET fabrics lie only in 0.0-3.0 and 0.0-2.2 respectively.Finished fabrics cannot reach the B2 rating（LOI≥26.0） recommended by the department standard GA 504-2004 （Flame-retardant decorative textile）.SnO₂ sol shows the best flame retardant capacity on cotton fabrics.Its primary mechanism is to catalyze and maintain the dehydration and char-forming reactions.（4） A series of solutions of base forming metal chlorides,sulfates,nitrates and acetates were prepared and used to finish cotton and PET fabrics via dipping-drying. Flame retardant effect was determined via limiting oxygen index method and the pyrolysis and combustion properties of finished fabrics were measured by thermal gravimetric analysis and micro-calorimeter methods.Flame retardant mechanism was explored via dynamic FTIR and scanning electronic microscope（SEM）.The results show that metal salts show high flame retardant effect on cotton fabrics in the descending order of metal chlorides,sulfates,acetates and nitrates.Their finished fabrics show/kLOI values of 1.3-15.3,0.4-14.4,0.0-6.5 and 0.0-3.0.Cotton fabrics finished by FeCl₃·6H₂O,MgCl₂·6H₂O,ZnCl₂ and Al₂（SO₄）₃·18H₂O can reach the B1 rating（LOI≥32.0） recommended by GA 504-2004 standard.The peak heat release rate values can be reduced by 67-90%and the amounts of char residues can be increased by 4.01-8.12%.The high flame retardant efficiency of such metal salts lie in their durative catalyzing dehydration and char-forming reactions.However,there are only limited role in flame retarding PET fabrics since B2 rating cannot be reached.Their flame retardant effect is descended in the order of metal chlorides,sulfates,nitrates and acetates.The△LOI values finished by such salts are 0.5-5.7,0.0-3.9,0.0-3.5 and 0.0-2.2.（5） Sols,metal salts and traditional flame retardants showing high flame retardant effects were selected to compound finish cotton and PET fabrics via dipping-drying method.Flame retardant effect was determined via limiting oxygen index method and the pyrolysis and combustion properties,of finished fabrics were measured by thermal gravimetric analysis and micro-calorimeter methods.The synergistic effect can be determined if the△LOI_复合整理 is higher than all of△LOI traditional flame retardants,△LOI sols and△LOI metal salts.It was found that cotton fabrics finished by the complex systems of（Boric Acid/Borax） and MgCl₂·6H₂O,ZnCl₂ and SnO₂ sol,MgCl₂·6H₂O and SnO₂ sol,and CuSO₄·5H₂O and SnO₂ sol can reach B1 rating.The highest values for△LOI,peak heat release rate reduction and char residue amplitude are 20.6-21.5（SnO₂ sol/MgCl₂·6H₂O）,95%（CuSO₄·5H₂O/SnO₂ sol） and 9.67%（SnO₂ sol/CuSO₄·5H₂O）,respectively.The flame retardant mechanism lies in the additive effects of dehydration and char-forming capacities.However,for PET fabrics,these complex systems show limited flame retardant effects（finished fabrics fail to reach B2 rating）,更多还原