仿生合成石质文物二氧化硅保护膜的研究
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摘要
我国拥有许多珍贵的石质文物，它们大都暴露野外，在经历漫长的历史变迁后，已遭受到不同程度的风化腐蚀，近现代工业发展所造成的环境污染更加剧了文物的损坏。目前应用于石质文物的保护材料有很多，对文物的保护起到了一定的效果，但也存在许多问题。为了能更有效的保护石质文物，新型保护材料的开发研究就显得尤为重要。
国内外的野外考察都曾发现一些石刻古迹表面天然形成了一层防护膜，膜的主要成分是一水草酸钙。这些保护膜的存在使文物历经千年而完好无损，表现出极其优良的性能。现对石材表面一水草酸钙膜的仿生合成和评价已有初步研究。通过对天然一水草酸钙膜的研究和仿制，文物保护工作者注意到仿生无机材料具有优越的耐候性、与基底石材相容性好、合成条件(常温常压)温和以及对环境无污染等优点，认为是一种很有潜力的新型石质文物保护材料。
受天然草酸钙保护膜的启发，首次采用仿生合成方法，分别以正硅酸乙酯(TEOS)和氟硅酸钠(Na_2SiF_6)为硅源，在室温条件下于青石基片表面上制备出一层SiO_2保护膜。方法一以乙醇为溶剂，用氨水催化TEOS水解，在模板剂十六烷基三甲基溴化铵(CTAB)的调控下于青石表面生长SiO_2膜。方法二以Na_2SiF_6为硅源，加入硼酸(H_3BO_3)促进其水解，在CTAB的调控下于青石表面生长SiO_2膜。讨论了青石预处理、合成组分配比、催化剂及用量、添加剂、处理时间、干燥条件等制备工艺对膜制备和膜性能的影响，探讨了反应机理，获得了优化的制备工艺，实验了膜的耐酸、耐污、接触角、吸水透气等性能，并利用XRD、SEM、FTIR等表征了膜的结构。
实验结果表明：两种方法保护处理的青石，与原青石相比，均具有优良的耐酸、耐污性能；透气性略有下降，水的接触角有所提高，但仍保持良好的透气性和亲水性；外观没有明显变化，且具有一定的耐候性。特别是以Na_2SiF_6为硅源时膜的耐酸性和耐污性更优。添加丙三醇及在湿度较大的环境中干燥都可以防止膜的开裂。用CTAB预处理青石基片，获得的膜具有更好的性能。采用仿生合成方法制备二氧化硅保护膜用于石质文物保护具有可行性，表明是一种很有潜力的新型保护材料。
China is home to many precious historic stones, mostly exposed the wild, which have been subjected to varying degrees of weathering erosion in a lengthy historical changes, and especially been aggravated damage by the pollution caused with the development of modern industrial. At present, the application of many materials in historic stone conservation has a certain effect. But there are also some problems, so the research of new materials appears to be particularly important in order to provide more effective protection historic stone.
Recently, the researchers have found a layer of natural protective coating formed on the surface of carved stone in the field investigation at home and abroad, whose main component is the calcium oxalate. The historic stones with this protective film are intact after Millennium, showing the film's good performance. After the preliminary biomimetic synthesis and evaluation of oxalate calcium film, the heritage conservation workers note the biomimetic inorganic material is a new potential protecting material in stone conservation for its advantages of excellent weatherability. suitable compatibility with the basement of stone, moderate reaction condition and environment pollution-free.
Enlightened by the natural oxalate calcium protective films, for the first time the SiO_2 film was prepared on the surface of stone substrates, respectively Ethyl silicate (TEOS) and Sodium fluosilicate (Na_2SiF_6) as silicon source, at room temperature conditions in the way of biomimetic synthesis. One method is that the SiO_2 film was prepared on the surface of stone, by ammonia catalytic hydrolysis of TEOS in alcohol solvent, under the control of Cetyltrimethyl ammonium bromide(CTAB) templates. The other is that the CTAB templated silica film was prepared by hyfrolysis of Sodium fluosilicate under the condition of adding boric acid. The pretreatment of stone, the resource ratio, the amount of catalyst, the additive, the time of reaction, and the condition of drying etc. on the preparation and capability of film were investigated in the experiments of resisting acid, soil and water, the contact angle, water permeability, XRD. SEM, and FTIR. The optimized preparation process was determined. Furthermore, the reaction mechanism was simply discussed.
Experimental results show: the protected stone in previous ways, compared with the original stone, has an excellent performance of resisting acid and soil; a slight decline breathe, the improved contact angle, but still maintains the good breath and hydrophilicity, and no significant changes in appearance. Especially, the resisting acid and soil performance of prepared film is better when Na_2SiF_6 as the silica source. Adding Glycerin and increasing humidity can prevent film cracking in the drying process. After pretreatment by using CTAB. the film on the stone surface has a better performance. The prepared biomimetic SiO_2 film is a new potential protecting material in stone conservation for its feasibility and superiority.
国内外的野外考察都曾发现一些石刻古迹表面天然形成了一层防护膜，膜的主要成分是一水草酸钙。这些保护膜的存在使文物历经千年而完好无损，表现出极其优良的性能。现对石材表面一水草酸钙膜的仿生合成和评价已有初步研究。通过对天然一水草酸钙膜的研究和仿制，文物保护工作者注意到仿生无机材料具有优越的耐候性、与基底石材相容性好、合成条件(常温常压)温和以及对环境无污染等优点，认为是一种很有潜力的新型石质文物保护材料。
受天然草酸钙保护膜的启发，首次采用仿生合成方法，分别以正硅酸乙酯(TEOS)和氟硅酸钠(Na_2SiF_6)为硅源，在室温条件下于青石基片表面上制备出一层SiO_2保护膜。方法一以乙醇为溶剂，用氨水催化TEOS水解，在模板剂十六烷基三甲基溴化铵(CTAB)的调控下于青石表面生长SiO_2膜。方法二以Na_2SiF_6为硅源，加入硼酸(H_3BO_3)促进其水解，在CTAB的调控下于青石表面生长SiO_2膜。讨论了青石预处理、合成组分配比、催化剂及用量、添加剂、处理时间、干燥条件等制备工艺对膜制备和膜性能的影响，探讨了反应机理，获得了优化的制备工艺，实验了膜的耐酸、耐污、接触角、吸水透气等性能，并利用XRD、SEM、FTIR等表征了膜的结构。
实验结果表明：两种方法保护处理的青石，与原青石相比，均具有优良的耐酸、耐污性能；透气性略有下降，水的接触角有所提高，但仍保持良好的透气性和亲水性；外观没有明显变化，且具有一定的耐候性。特别是以Na_2SiF_6为硅源时膜的耐酸性和耐污性更优。添加丙三醇及在湿度较大的环境中干燥都可以防止膜的开裂。用CTAB预处理青石基片，获得的膜具有更好的性能。采用仿生合成方法制备二氧化硅保护膜用于石质文物保护具有可行性，表明是一种很有潜力的新型保护材料。
China is home to many precious historic stones, mostly exposed the wild, which have been subjected to varying degrees of weathering erosion in a lengthy historical changes, and especially been aggravated damage by the pollution caused with the development of modern industrial. At present, the application of many materials in historic stone conservation has a certain effect. But there are also some problems, so the research of new materials appears to be particularly important in order to provide more effective protection historic stone.
Recently, the researchers have found a layer of natural protective coating formed on the surface of carved stone in the field investigation at home and abroad, whose main component is the calcium oxalate. The historic stones with this protective film are intact after Millennium, showing the film's good performance. After the preliminary biomimetic synthesis and evaluation of oxalate calcium film, the heritage conservation workers note the biomimetic inorganic material is a new potential protecting material in stone conservation for its advantages of excellent weatherability. suitable compatibility with the basement of stone, moderate reaction condition and environment pollution-free.
Enlightened by the natural oxalate calcium protective films, for the first time the SiO_2 film was prepared on the surface of stone substrates, respectively Ethyl silicate (TEOS) and Sodium fluosilicate (Na_2SiF_6) as silicon source, at room temperature conditions in the way of biomimetic synthesis. One method is that the SiO_2 film was prepared on the surface of stone, by ammonia catalytic hydrolysis of TEOS in alcohol solvent, under the control of Cetyltrimethyl ammonium bromide(CTAB) templates. The other is that the CTAB templated silica film was prepared by hyfrolysis of Sodium fluosilicate under the condition of adding boric acid. The pretreatment of stone, the resource ratio, the amount of catalyst, the additive, the time of reaction, and the condition of drying etc. on the preparation and capability of film were investigated in the experiments of resisting acid, soil and water, the contact angle, water permeability, XRD. SEM, and FTIR. The optimized preparation process was determined. Furthermore, the reaction mechanism was simply discussed.
Experimental results show: the protected stone in previous ways, compared with the original stone, has an excellent performance of resisting acid and soil; a slight decline breathe, the improved contact angle, but still maintains the good breath and hydrophilicity, and no significant changes in appearance. Especially, the resisting acid and soil performance of prepared film is better when Na_2SiF_6 as the silica source. Adding Glycerin and increasing humidity can prevent film cracking in the drying process. After pretreatment by using CTAB. the film on the stone surface has a better performance. The prepared biomimetic SiO_2 film is a new potential protecting material in stone conservation for its feasibility and superiority.
引文
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