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Long-Term Protection Efficiency of Biodegradable Polymer Treatments on Limestone
(Izmir Institute of Technology, 2019) Kaplan, Zişan; Böke, Hasan; Sofuoğlu, Aysun; İpekoğlu, Başak
Synthetic polymers can be replaced by biodegradable ones as adhesive, water repellents and consolidants in stone conservation to preserve historic buildings from further deterioration. In this study, the long-term stabilities of two biodegradable polymers, polyhydroxybutyrate (PHB) and poly-l-lactide (PLA) and an acrylic polymer (Paraloid B72), which are commonly used in conservation works of artefacts, were evaluated on limestone through an UV lamp-weathering chamber. Chemical and morphological changes induced by accelerated weathering test were followed by Fourier Transform Infrared spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM) analysis. The protection efficiencies of the polymers were determined by following the changes in the color, capillary water absorption and static contact angle on the limestone surfaces in accordance with CEN standards developed by the European Committee of Standardization (CEN) for conservation of cultural property. PHB, PLA and Paraloid B72 coatings significantly increased hydrophobicity, decreased capillary water absorption and caused negligible change in the color of the limestone. All polymers showed chemical, physical and optical changes under accelerated weathering conditions. Paraloid B72 decomposed by the reduction of molecular weight, decomposition of ester group and formation of gamma lactones and hydro peroxides. PHB and PLA decomposed with formation of CO2 and hydro peroxide, hydrolysis of ester groups and reduction of the molecular weight. Chemical changes cause to etching, holes, voids, cracks and slight color differentiations on the coatings by chain scission, breaking of polymer bonds and formation of volatile gaseous products. Protection efficiencies of the PLA and PHB polymers almost same as that of the widely used acrylic polymer Paraloid B72. However, PLA and PHB seem to be promising polymers as protective agents due to their reversibility and biodegradability, low chromatic changes, good hydrophobic behavior and good stability to weathering in reducing the effects of outdoor exposure on limestone surfaces.
Use of Bio-Nano Composites as Protective Coating on Natural Stone Surfaces
(Izmir Institute of Technology, 2013) Ocak, Yılmaz; Sofuoğlu, Aysun
Historical monuments are important heritages to pass cultural values to next generations. Most of the historical monuments were composed of natural stones like marble. SO2 and NOx reacts with marble composed primarily of calcite (CaCO3) is a dry deposition process, gypsum (CaSO4.2H2O) and nitrocalcite (Ca(NO3)2.4H2O) are formed after reaction. The polylactic acid (PLA), 2, 5 and 7 wt.% montmorillonite (MMT) clay added PLA (PLA/MMT2, PLA/MMT5 and PLA/MMT7) bio-nano composites coated and uncoated surfaces were tested for capillary water absorption, water vapor permeability, color alteration, and surface hydrophobicity regarding the nanofiller concentrations before reaction. Results indicated that the bio-nano composite coatings didn’t alter the color of the marble, improved the hydrophobicity and barrier properties of the marbles. The level of layered silicate delamination in the PLA matrix and structural characterizations of PLA nanocomposite coatings were affected the barrier properties of the composites coatings. The X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning transmission electron microscopy (STEM) analysis pointed out that 5% layered silicates were homogenously dispersed in the polymer matrix, exfoliated structures also were observed in some parts of the polymer matrix and nano particles enhanced the nano-composite coating barrier performance. The protection capabilities of the bio-nano composite coatings were studied in laboratory setup (include nearly 8 ppm SO2) and ambient city atmosphere (include nearly 8 ppb SO2 and 64 ppb NO2). The PLAMMT5 bio-nano composite showed significant reduction (~5 times) in the crust formation after 180 days SO2-calcite reaction in laboratory and 9-10 times after 20 months ambient city exposures for outdoor conditions. Bio-nano composites also decreased the kinetic parameters such as rate constant (ks) and effective diffusivity (De) values of the marbles. These results indicated that PLA/MMT bio-nano composite coating seems to be significant promising materials as protective coating agents in reducing the effects of atmospheric pollutants on the marble surfaces.

Phd Degree / Doktora

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