以光譜分析評估黴菌劣化後紙張性質之變化

Spectroscopic Analyses of the Properties of Mildew-Damaged Paper

楊菀仁(Wan-Jen Yang)

指導教授 ： 張惠婷

國立臺灣大學/生物資源暨農學院/森林環境暨資源學研究所/碩士(2011年)

https://doi.org/10.6342/NTU.2011.02175

摘要

本研究探討3種常見紙質文物黴菌Aspergillus niger、Aspergillus terreus與Chaetomium globosum對濾紙與道林紙文化用紙之黴害，並透過數種光譜分析瞭解紙張在遭受不同種黴菌危害時之化學元素、官能基與結構之變化，未來可應用於紙張黴害瞭解與紙質文物黴害機制評估。
表面顏色分析結果顯示，A. terreus及C. globisum各自對紙張之黃色值（b*）、明度與白度影響最劇，整體而言以A. terreus對紙張顏色的影響最顯著，A. niger則較為輕微。由掃描式電子顯微鏡（SEM）可看出紙張在受不同菌種危害時，其表面特徵與菌絲型態也產生不同之差異。由紅外線光譜（FTIR）與近紅外線光譜（NIR）分析得知，道林紙與濾紙受3菌劣化的趨勢相同，3種黴害濾紙之纖維素吸收峰強度皆隨生長時間降低，意即隨黴菌生長時間增長，對纖維素降解越趨嚴重，而不同黴菌對纖維素結構改變方式又各有不同，其中同屬之A. terreus與A. niger對纖維素降解的形式較為相近。配合X光粉末繞射（XRD）結果，更可確知3種黴菌對纖維素結晶度降低皆有一定的影響，其中同屬之A. terrus與A. niger對紙張的劣化主要在生長初期發生，並以A. niger與C. globosum對纖維素結晶區的降解最劇烈，結晶度最低可降至59%。從X光螢光分析（XRF）結果可發現隨著黴菌生長時間增長，黴菌菌絲與孢子所含磷與硫的含量有升高的趨勢。

關鍵字

紙張 ； 生物劣化 ； 黴菌 ； 傅立葉轉換紅外線光譜 ； 近紅外線光譜 ； X 光螢光光譜 ； X 光粉末繞射分析

並列摘要

In this research, three fungi, Aspergillus niger, Aspergillus terreus and Chaetomium globosum, commonly found in mildew-caused paper deterioration are selected to investigate their damaging effects on filter paper and wood-free printed paper. Various methods of spectroscopic analysis are employed to examine the changes of structure and chemical properties of paper in the degradation test. In the future, the research can be applied to the investigation of biodegraded historical paper products.
Results of the study indicate that, among these three types of fungi, A. terreus causes the greatest change of the paper color, while A. niger has the slightest effect on it. The scanning electron microscope (SEM) analysis also shows that different types of fungi create different types of hyphae growth patterns and of different surface damage characteristics on paper. The data of Fourier transform infrared spectroscopy (FTIR) and near infrared spectroscopic (NIR) analysis reveal similar degradation patterns on both filter paper and wood-free printed paper, with signals of mold continuing to rise over the deterioration span. In addition, the changes of the cellulose structure of the specimens caused by Aspergillus species are very similar. The signal of cellulose decreases both in filter paper and wood-free printed paper. The results from X-ray diffraction spectroscopy (XRD) also confirm the role of the three kinds of fungi in the degradation of cellulose crystalline region of paper. Both A. terrus and A. niger destroy the crystallinity of cellulose mainly in their initial growth stage. A. niger and C. globosum cause greatest damage on crystallinity of paper with crystallinity reduced to as low as 59% in some specimens. The X-ray fluorescence (XRF) analysis shows that that with the growth of the fungi, the content of phosphorus and sulfur in the fungi hyphae and spores increases over time.

並列關鍵字

Biodegradation ； paper ； mildew ； Fourier transform infrared spectroscopy ； Near infrared spectroscopy ； X-ray fluorescence spectroscopy ； X-ray diffraction spectroscopy

參考文獻

May, E. and M. Jones (2006) Methods in Conservation. pp.33-55. In Charola, A. E. and R. J. Koestler, eds. Conservation science: heritage materials. Royal Society of Chemistry, Cambridge. 390 pp.

Bhat, M. K. and S. Bhat （1997） Cellulose degrading enzymes and their potential industrial applications. Biotechnology Advances 15:583-620.

Castro, K., E. Princi, N. Proietti, M. Manso, D. Capitani, S. Vicini, J. M. Madariaga and M. L. De Carvalho (2011) Assessment of the weathering effects on cellulose based materials through a multianalytical approach. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 269:1401-1410.

Chang, H.-T., T.-F. Yeh and S.-T. Chang (2002) Comparisons of chemical characteristic variations for photodegraded softwood and hardwood with/without polyurethane clear coatings. Polymer Degradation and Stability 77:129-135.

Colom, X., F. Carrillo, F. Nogues and P. Garriga (2003) Structural analysis of photodegraded wood by means of FTIR spectroscopy. Polymer Degradation and Stability 80:543-549.