【作者】 徐兵；

【导师】 谭伟； 方岩雄；

【作者基本信息】 广东工业大学 ， 化学工程与技术， 2015， 硕士

【摘要】 纸张的老化损坏很大程度上是由于自身的酸化造成的,因此对纸张进行脱酸处理是对纸质文物保护的一种有效措施。然而,目前针对不同时期的纸张进行相应的酸性成份分析工作还比较缺乏。本课题组旨在分析八十年代一种新闻纸张中的酸性成份,归纳其酸性物质分布,筛选制备一种集脱酸加固于一体的脱酸加固保护液,并对旧新闻纸进行脱酸加固研究。对纸张进行酸性成份分析,定性定量确定纸张中的酸性物质种类与含量,对于后期的纸张脱酸加固研究具有一定的指导意义。本论文在综合比较了不同酸性物质分析方法后,采用原子吸收光谱法对新闻纸张中的铁、铜含量进行了定量分析,采用离子色谱法对新闻纸张中的六种无机酸根离子(F-、Cl-、SO42-、PO33-、NO3-、NO2-)进行了定量分析,采用离子交换树脂分离富集酯化-GC/MS联用、PY/MS/GC联用两种分析方法对新闻纸张中的有机酸性物质进行了定性与半定量的分析。结果表明,含字迹油墨的每克新闻纸张中铁元素的含量为3.21×10-2mg,铜元素的含量为2.73×0-2mg。铁铜的氯化物为金属路易斯酸,对纤维素的降解起到一定的催化作用。离子色谱分析法表明纸张中氯离子、硫酸根离子和硝酸根离子含量明显高于其他无机酸根离子。新闻纸张中有机酸性物质的主要来源为纤维酸的老化降解和造纸木材原材料中携带,其中小分子有机酸主要有乙酸、a-羟基丙酸,丁二酸等。大分子酸性物质主要来源于造纸原料中木质素的残留降解,其中以愈创木酚、香兰素含量居多。实验中,我们考察了不同的脱酸剂和加固剂,最终选择了丙酸钙、氢氧化钙作为脱酸试验对照组,研究了四硼酸钠的脱酸性能；选择了乙基纤维素、羟丙基甲基纤维素作为加固剂对照组,研究了季铵型阳离子淀粉的加固性能。在一定条件下对四硼酸钠和阳离子淀粉进行耦合处理,通过浸泡的方法对照脱酸加固处理前后纸张的碱残留,纸张表面的pH值,纸张表面显微结构,纸张白度,机械强度等纸张的宏观性能,分别考察了各脱酸剂、加固剂的单独处理与耦合制备脱酸加固保护剂处理时表现的不同。结果表明,筛选制备的四硼酸钠-季铵型阳离子淀粉脱酸加固保护剂的脱酸加固效果要明显优与其他组合脱酸加固保护剂。在四硼酸钠-季铵型阳离子淀粉溶液中,四硼酸钠存在着特殊的水解平衡,使得处理后的纸张表面pH值保持在最优范围7.0-8.5之间,与其他脱酸剂相比较具有较高的碱残留。阳离子淀粉属于改性淀粉,具有良好的抗氧化能力,满足纸张所需的柔韧性并且与纸张的构成纤维素具有良好的相容性,所以脱酸加固保护剂能够很好的渗入到纸张纤维素内部,通过对纸张纤维包附增粗,增加纤维素之间的吸附力和空隙填充的作用,大大提高了纸张的机械强度。为更好的提高脱酸加保护剂对纸张的处理效果,本文采用了不同的处理方法,对纸张的脱酸加固效果进行了比较。结果表明超声辅助浸泡脱酸加固法,对于纸张的脱酸加固效果最为明显。更多还原

【Abstract】 The aging and damage of paper is largely caused by acidification, to protect culture relic that made by paper, deacidification for paper is an effective measure. However, it is still insufficient to analyze relative acidic component for paper at different times.This paper aims to analyze the acidic components for news paper at 80s and generalize the distribution of acidic substances so that we can prepare a couplant reinforcement deacidification for news paper.The acidic component analysis that to gain a qualitative and quantitative determination about the kinds and contents of acidic materials will have a guidance on later paper deacidification study. After the comparison of the different methods of analysis of acidic substances, this research adopt using atomic absorption spectrometry (AAS) to quantitatively analyze the contents of iron and copper in the newspaper, and six inorganic acid ion (F-、Cl-、 SO42-、PO33-、NO3-、NO2-) were quantitatively analyzed using Ion chromatography as well as an ion exchange resin separation and enrichment esterification-GC/MS spectrometry, pyrolysis-chromatography-mass spectrometry analysis by two methods of news paper the organic acidic substances qualitative and semi-quantitative analysis. The results showed that the choice of the content of iron per gram newsprint containing ink handwriting was 3.21×10-2mg, copper was 2.73×10-2mg. Chloride of iron and copper is metal Lewis acid, and it play a catalytic role to cellulose degradation. Ion chromatography indicated that the paper chloride, sulfate ion and nitrate ion content was significantly higher than other inorganic ions. The main source of news paper organic substance is an acid degradation and aging fiber pulp wood raw material carries, including small molecule organic acids include acetic acid, α-hydroxy acid, succinic acid, etc. Macromolecular acidic substances mainly from residual lignin degradation of paper stock, which guaiacol, vanillin content of the majority.During the experiments, we examined the various deacidification and reinforcing agents, finally chose calcium propionate, calcium hydroxide as an experimental control group of deacidification, and studied sodium tetraborate removal of Acid; choose the ethyl cellulose, hydroxypropyl methylcellulose as a reinforcing agent group control and studied reinforced performance of quaternary ammonium type cationic starch. Under certain conditions, coupling antipyonin and cationic starch,then soaking paper to compare the difference in alkali residual, pH, micro structure, whiteness and mechanical strength of paper between before and after paper deacidification and strengthen. After that we can investigate various deacidification, and different performance of reinforcing agent treated separately and coupled processing performance.The result showed that deacidification reinforcing agent which prepared by antipyonin-cationic midification is significantly superior to other combinations deacidification reinforced coupling agent. Antipyonin has a special hydrolysis equilibrium in antipyonin-cationic midification starch solution, which keep the PH between 7.0-8.5,compared with other deacidification it has a higher residual alkali. Cationic starches belong to modified starch, it has a good antioxidant capacity to meet the required flexibility of paper and has good compatibility with paper cellulose, so reinforcement deacidification coupling agent can penetrate well into the paper cellulose, through the paper fiber coated with thickening, increased adhesive force between cellulose and fill the gap, greatly improving the mechanical strength of the paper.To better improve the effect of deacidification reinforcement coupling agent for paper treatment, this paper took a different approach and compared the result of treating paper by deacidification reinforcement coupling agent, finally found out that using ultrasound-assisted deacidification reinforcement method will have the most obvious effect in paper deacidification reinforcement.更多还原