【作者】 杨富巍；

【导师】 张秉坚；

【作者基本信息】 浙江大学 ， 物理化学， 2011， 博士

【摘要】 我国有为数众多的不可移动文物。这些不可移动文物往往体量巨大,而且大多暴露在野外坏境中。由于自然风化、环境污染和人为因素,加之缺乏有效的保护,这些珍贵的历史遗迹都受到了不同程度的损坏。如不采取有效的保护措施,许多文物古迹将逐渐消亡。不过,现有的材料大多都不能完全满足此类文物的保护需求。所以,研制高性能的文物保护材料已成为文物保护领域的重要任务之一本论文概述了土遗址和石质文物等不可移动文物的病害类型、破坏机理、保护方法、保护材料及传统砌筑灰浆的研究现状和存在问题,并结合当今文物保护材料的发展趋势,以潮湿环境土遗址、古建筑和石质文物的原址加固保护为目标,在课题组前期工作的基础上开展了传统胶凝材料作用机制、新型无机胶凝材料设计制备以及有关应用研究,主要包括以下内容：液态水硬性材料加固保护潮湿环境土遗址的研究。参照石灰和水泥稳定土的机理,设计了一种液态、可渗透型水硬性材料,并将之用于潮湿环境遗址土的稳定和加固。该材料为硅、钙双液体系。其中钙源为氧化钙或氢氧化钙的醇分散体系,硅源为硅酸钾水溶液。考虑到南方潮湿环境遗址土的弱酸性,加固处理时先渗透呈碱性的钙源,再渗透硅源。利用SEM, XRD, EDX,抗压强度测试、耐水浸泡性测试等研究了该水硬性材料的加固保护效果。结果表明,硅源和钙源之间的水硬性反应改变了土的片状结构,生成了丝网状凝胶体,该凝胶体能把松散的土颗粒固结起来。本研究提出了液态水硬性材料的概念,为潮湿环境土遗址的保护提供了一条新的研究思路。传统砌筑灰浆科学原理及其现代应用的探索性研究。考证并评述了中国古代石灰基砌筑灰浆的发展及传统糯米灰浆在中国建筑史上的作用。作为一项重要的技术发明,糯米灰浆技术出现在大致南北朝时期,曾在许多重要建筑物中广为使用。采集了多处古建筑的灰浆样品,并利用FT-IR, XRD, TG-DSC,碘-淀粉试验等方法对样品进行了分析测试。分析测试结果表明,糯米灰浆曾用于明代西安城墙和明代南京城墙的建造。探讨了糯米灰浆技术的内在科学原理。研究表明,糯米支链淀粉对石灰灰浆的硬化过程有调控作用,它通过抑制碳酸化过程中碳酸钙晶粒的生长而使糯米灰浆形成致密的有机-无机复合结构,该结构应该是糯米灰浆良好性能的内在原因。古灰浆中糯米成分长期存在的原因在于石灰的防腐作用。在自然条件下,灰浆的完全碳化是个漫长的过程。石灰的强碱性可以使糯米成分在相当长的时间内免受微生物的侵袭而得以保存。以古建筑修复保护为目的,对糯米灰浆技术进行了科学化研究。优化了糯米灰浆的配方,并对仿制灰浆的物理化学性质进行了测试。结果表明,糯米灰浆比纯石灰灰浆物理化学性质更稳定、强度更大、与古建筑材料如砖的兼容性也更好,适合于古建筑的保护和修复。以糯米灰浆为修复灰浆,参与了国家级文物保护重点单位德清寿昌桥和杭州梵天寺石经幢的修复保护工程。糯米灰浆的研究对于传统技术的科学利用,特别是对于使用原来的材料和工艺修复保护古建筑具有重要意义。风化石质文物的仿生加固研究。仿照骨头的生长原理,将钙源(纳米氢氧化钙的异丙醇分散体系)和磷源(磷酸铵溶液)引入风化的石质文物,经常温矿化后在风化石材内部生成多孔、相互连接的磷灰石加固相。该加固相可以把风化、破碎的石块和作为填料引入的氢氧化钙粘结起来而给出良好的加固效果。磷灰石加固相利用XRD, SEM, EDX进行了表征；加固效果利用抗压强度、STT实验、毛细水吸收、透气性和抗风化实验等进行了测试。结果表明,经仿生加固处理后,风化石灰石的表面强度、整体抗压强度和抗风化能力都有了显著提高。此外,由于磷灰石本身的多孔性,该仿生加固方法基本不改变风化石灰岩文物本身的透气性和毛细水吸收,保持了石质文物固有的“呼吸功能”。本研究将仿生技术引入石质文物的加固保护中,解决了现有无机材料自身及其与风化岩石的结合问题,为石质文物保护材料的开发探索了一条新的途径。总之,本论文结合不可移动文物保护材料的研究现状,以土遗址、古建筑和石质文物的加固保护为目标,分别研究了液态渗透型水硬性材料,传统砌筑灰浆和磷灰石仿生加固材料,在微观机理探讨、实验室材料设计制备和文物保护实践等方面做了一些探索性的工作,取得了一定的进展。更多还原

【Abstract】 There are numerous immovable cultural relics in China. Most of these relics are huge and are situated in open air. Because of natural weathering, air pollution, human factors as well as inadequate protection, these precious historical relics have suffered damage in varying degrees. If this situation goes as it is, many of these cultural relics will disappear gradually in the near future. However, existing materials can not give enough conservation for these kinds of relics. Therefore, it is vital and urgent to develop high-performance materials for the protection of the open-air sites.This paper summarizes the common diseases, failure mechanism, conservation materials and methods of the immovable relics including earthen sites, ancient buildings and historic stones. The progress of the conservation materials has been discussed. Based on the development of protection materials for cultural heritages and the precious work of our laboratory, the application of inorganic gelling material for the conservation of immovable relics has been studied in this thesis. The followings are the main points:The liquid hydraulic material for the in situ consolidation of earthen sites was studied. Based on the mechanism of the lime or cement stabilized soil, a kind of liquid and hydraulic material was developed. The calcium source adopted was the alcohol dispersion of calcium hydroxide and the silicon source adopted was the solution of potassium silicate. The strategy was like below:first, the alcohol dispersion of calcium hydroxide was applied on the surface of the earth samples by spraying. Then the solution of potassium silicate was applied on the surface of the earth samples by the same method. SEM, XRD, EDX, compressive strength test and water resistance test were employed to evaluate the efficiency of the conservation. The results indicate that the introduced calcium and silicon source reacts and produce a kind of net-shape structure. This net-shape structure composed of Si, Ca and K can joint the loose soil particles together. The concept of liquid hydraulic materials is proposed for the first time, which provides a new perspective for the conservation of earthen sites.The mechanism of sticky rice lime mortar and its application in the conservation of ancient buildings were studied. The development and the role sticky rice lime mortar played were reviewed. The sticky rice lime mortar technology appeared about in the North-south Dynasty. It was widely used in many of the important buildings in the past. As a kind of inorganic-organic material, sticky rice lime mortar was an important technology innovation in that time. Mortar samples from ancient constructions were analyzed by FT-IR, XRD, TG-DSC, iodine-starch test. The results indicate that the siticky rice lime mortar was used in the construction of Xi’an city wall of Ming Dynasty and the Nanjing city wall of Ming Dynasty. Modeling sticky rice-lime mortar was fabricated and analyzed, and the role sticky rice amylopectin played in the sticky rice-lime mortar was explored. It was found that amylopectin in the mortar acted as an inhibitor-the growth of the calcium carbonate crystal was controlled and a compact micro-structure was produced, which should be the cause of the good performance of this kind of organic-inorganic mortar. For the conservation of ancient constructions, sticky rice lime mortar was fabricated and tested. The test results of the modeling mortars show that the sticky rice-lime mortar has more stable physicochemical properties, greater mechanical strength and better compatibility than pure lime mortar, which make it a suitable restoration mortar for ancient masonry building. Sticky rice-lime mortar has been used in the restoration of some ancient masonry constructions like Shouchang Bridge built in Song Dynasty and Fantianshi stone censers buit in the Five Dynasties. The study of sticky rice lime mortar is important for the reuse of tradition technology, especially for the conservation and restoring of ancient buildings.Conservation of the weathered historic calcareous stones by apatite was studied. By mimicking the growth of bone, calcium and phosphorus were introduced into the weathered stone and then mineralized at room temperature. The conservation efficiency was investigated by SEM, EDX, XRD, "Scotch Tape Test" (STT), compressive strength test, capillary water uptake test, water vapor permeability test and weather resistance test. The results of SEM, EDX and XRD show that the produced bone-like hydroxyapatite can bind the introduced calcium carbonate and the weathered stone blocks together. The test results also indicate that this conservation method can improve the surface strength, compressive strength and weather resistance of the treated samples significantly. Besides, due to the porous nature of the bone-like apatite, the water vapor permeability of treated stone is not affected and its "breathe function" is retained. Therefore, the proposed method will be a good candidate for the in situ conservation of historic calcareous stones. This study gives a good solution for the problem of adhesion between the existing inorganic consolidants and the weathered historic stones.In conclusion, for the conservation of earthen sites, ancient constructions and historic stones, liquid hydraulic material, traditional sticky rice lime mortar and biomimic apatite were studied, respectively. These exploring works presented here provide new insights for the conservation of immovable cultural relics.更多还原