摘要
目前有关高分子材料稳定性的研究报道很多,有人采用X衍射分析、扫描电镜、红外光谱等手段检测了涂层在光、热老化过程中分子结构、降解深度及理化性能等方面的变化,但对用于彩绘文物保护的高分子材料的性能研究很少。传统彩绘文物保护材料的研究主要是着眼于文物保护材料的基本要求:无色、透明、不改变原状等,对于材料的耐光老化性能并没有予以足够的重视。因而有时就产生了施加到彩绘文物上的保护材料很容易受光照的影响而发生变色、脱粘等老化现象,这样一来使得保护材料非但没有起到保护彩绘文物的作用,应用后不久还在彩绘文物表面形成鳞片状剥落、泛黄、产生斑纹、堵塞微孔等状况。因此就要求彩绘文物保护材料要具有优异的光稳定性能。
本研究采用傅立叶红外光谱技术跟踪了目前常用的11种高分子保护材料在降解期间发生的化学变化、鉴定了降解产物。实验结果表明各种材料老化前后的红外谱图均有不同程度的改变,说明它们的分子结构都或多或少发生了变化。特别是聚醋酸乙烯酯、PU乳液、芳香族聚氨酯、丙烯酸清漆等的分子结构变化较大,而Primal AC 33、B72、有机硅和UV326改性B72相对较小,材料的耐老化性能较好。
采用分光光度仪测量保护材料加固后颜料在老化前后的颜色改变,可以看出环氧树脂、聚醋酸乙烯酯引起颜色的改变较大,随老化时间的延长,改变幅度增大。同一保护材料对于不同颜料的影响也不相同,老化后的铅丹、朱砂颜色变化大于其它颜料的变化。这是因为不同的颜料吸收不同波长的光子,实现基态向激发态的跃迁,光照射改变了颜料的分子结构和内在成分,造成颜料的晶相转变、化学键的断裂等。
关于用作彩绘文物类保护材料加固后颜料粘接强度的定量测试至今未见报道。本论文采用自行改制的粘接强度仪定量测量保护材料老化后粘接强度的改变。实验结果表明所有加固材料均提高了颜料的粘接强度,不同加固材料对颜料的粘接强度改善作用有差别。PrimalAC33、改性B72、B72的粘接性能相对较好,环氧树脂、有机硅、聚乙烯醇的粘接性能次之,而聚醋酸乙烯酯、芳香族聚氨脂、PU乳液、丙烯酸清漆和聚乙二醇600的粘接性能较差;同种加固材料对不同颜料粘接强度提高的程度也不相同。老化后加固的朱砂、铅丹的粘接强度大于石绿、石青,这与颜料特性、颗粒度、颜料颗粒与加固材料之间的结合力等因素有关。
实验进一步将B72和UV326紫外线吸收剂改性的B72保护材料施加于彩绘文物表面,采用分光光度仪和粘接强度仪测量加固文物样品在老化前后颜色、粘接强度的变化。老化后改性B72保护的文物颜色改变比B72保护的文物颜色改变小,老化后粘接强度高,说明加入紫外线吸收剂UV326降低了B72材料的光降解速率,有效的抑制了材料的光老化,并且提高了材料与文物颜料之间的粘结力。
监测B72和改性B72保护文物的吸水率、耐酸碱等物理性能。实验数据表明文物经保护后的吸水性、耐酸性均有所提高。改性B72的提高程度比B72大。
采用热失重老化实验有效的预测出B72和改性B72保护材料在常温下的使用寿命分别约为10.65年和12.80年,为文物保护提供了更为有效的科学依据。
综上所述,实验通过分析应用于不同颜料的11种高分子材料老化前后的颜色、粘接强度以及高分子材料的红外光谱等指标的变化,筛选出性能较好的B72和改性B72保护材料应用于彩绘文物的保护之中,进而通过耐光老化、粘接强度、吸水率、耐酸性等性能测试证明了加入紫外线吸收剂UV326可以降低B72材料的光降解速率,有效的抑制了材料的光老化,起到一定的屏蔽作用,建议在彩绘文物的保护中应推广使用。
There were a lot of reports on the stability of polymeric organic-coating materials. The changes of molecular structures, degradation depth, physical and chemical properties on the photo-degradation or thermal-degradation of these materials were detected by XRD, SEM and FTIR etc. Traditional requests for colored relic protection materials with a view to some basic requirements such as color, transparence and original state etc. However, there was little systemic, scientific and complete research on polymeric materials' photo-stability, especially researched for colored relic protection. Therefore, the ageing phenomenon happened, the surface of relics would yellow, dapple and shed off, the protective materials for colored relics were required with the excellent photo-stability.
Eleven polymeric materials' degradation process and degradation mechanism were systematically studied by attenuated total reflection-Fourier transform infrared spectroscopy (FTIR- ATR). The results indicated that the changes of infrared spectra of these materials were different and the quantitative analysis results were not the same. Especially molecular structure changes for poly(vinyl-acetic acid) , MDI-polyurethane, polyurethanes and poly (acrylic acid) varnish were larger, while those of Primal AC33, B72, organic-silicon and UV326 modified B72 were smaller, which had the favorable ageing property.
The color determinations for different pigments protected by these protective materials before and after ageing were investigated by a spectrophotometer, from which we can see that the changes for epoxy-resin and poly(vinyl-acetic acid) were larger than for other protective materials with the time of ageing. And what is more important for same protective material, different changes happened in different pigments. The changes of red lead and cinnabar were larger than those of other pigments. The reason was that different pigment absorbed different wavelength photons, which would complete the transition of the ground state to the excited state. Photo-irradiation changed the molecular structure and component of pigment, made the rupture of the chemical bond, and then lead the color change.
Nowadays there is scarcely report on quantitative analysis adhesive strength of protective materials. We refitted a domestic instrument to the adhesive strength testing apparatus. The results indicated all materials after ageing enhanced the adhesive strength of pigments. For different protective materials, the degree of improvement was different. The adhesive strength of PrimalAC33, modified B72 and B72 was comparably better, followed the epoxy-resin, organic-silicon and poly(vinyl alcohol), the worst was that of poly(vinyl acetic acid), MDI-polyurethane, polyurethane and poly(acrylic acid) varnish. For different pigments, the adhesive strength in cinnabar and red lead were better than that in malachite and azurite, which related to the pigments' specialty, granularity, bonding force between pigment and protective materials, etc.
B72 and B72 modified with UV326 were applied for protecting colored relics slice. Color determinations and adhesive strength were investigated by the spectrophotometer and the adhesive-strength testing apparatus, respectively. The results indicated that the color change of the modified B72 was less than that of B72, and the adhesive strength was higher in the modified B72, from which we could concluded that adding UV-absorber 326 to B72 reduced the ratio of the photo degradation and had the excellent resistance function to the photo irradiation.
Thermal degradation experiment was adopted for effectively estimating the service life at room temperature of B72 and the modified B72. It could be estimated that the life length of B72 and the modified B72 were 10.65 years and 12.80 years respectively, which provided the scientific evidence for relic conservation.
In conclusion, with the aim of determining the photo-oxidative stability of protective materials, the molecular structure changes, color determinations and adhesive strength were investigated, from which we picked out B72 and modified B72 with the excellent photo-oxidative stability into protecting the colored relics, the changes of color and adhesive strength were tested. From these experimental results, we concluded that adding UV-absorber 326 to B72 reduced the ratio of the photo-degradation. The UV-326 converted the ultraviolet into the harmless energy and had the excellent resistance function to the photo-irradiation. In all, the modified B72 was suitable to replace B72 and would be widely employed as the protective material in the relic conservation.
引文
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