Baglioni Michele, Sekine Felipe Hidetomo, Ogura Taku, Chen Sow-Hsin, Baglioni Piero
Department of Chemistry and CSGI, University of Florence, via della Lastruccia, 3, Sesto Fiorentino (FI) 50019, Italy.
NIKKOL GROUP Nikko Chemicals Co., Ltd, 1-4-8, Nihonbashi-Bakurocho, Chuo-ku, Tokyo 103-0002, Japan.
J Colloid Interface Sci. 2022 Jan 15;606(Pt 1):124-134. doi: 10.1016/j.jcis.2021.07.078. Epub 2021 Jul 29.
Nanostructured fluids (NSFs) based on water, organic solvents and surfactants are a valid alternative to the use of neat unconfined organic solvents for polymer coatings removal in art conservation. The physico-chemical processes underpinning their cleaning effectiveness in terms of swelling/dewetting of polymer films were identified as key in this context. The role of surfactants on polymers' dewetting was considered to be mainly restricted to the lowering of interfacial tensions. However, recent experiments evidenced that surfactants have an important role in swelling polymer films.
Five different amphiphiles were selected, namely: sodium dodecylsulfate, dimethyldodecyl amine oxide, hexaoxyethylene decyl ether (CE), pentadecaoxyethylene dodecyl ether (CE), and methyoxypentadecaoxyethylene dodecanoate (CCOECH). They were combined with a carefully selected organic solvents' mixture (1-butanol/butanone/dimethyl carbonate) to formulate new NSFs, differing for the surfactant only, and used to perform cleaning tests on surfaces coated with Paraloid B72® and Primal AC33®. Here for the first time, polymer swelling induced by surfactants was quantified and correlated with the glass transition temperature of the two polymers by differential scanning calorimetry, before and after the exposure to the fluids. Confocal laser scanning microscopy and small-angle X-ray scattering provided additional insights on the interaction mechanism.
Nonionics were proven more efficient than zwitterionic/ionic amphiphiles in the polymer swelling, and, overall, methyoxy pentadecaoxyethylene dodecanoate resulted the most effective among the selected surfactants. A direct relation between the effect of surfactants on the polymers' glass transition temperature and cleaning capacity was established. This finding, fundamental to understand the interaction mechanism between NSFs and polymer coatings or paint layers, is key to achieve a selective, effective and complete removal of polymer coatings, as recently shown in the removal of vandalism and over-paintings from street art.
基于水、有机溶剂和表面活性剂的纳米结构流体(NSFs)是在文物保护中去除聚合物涂层时,替代使用纯无限制有机溶剂的有效选择。在这种情况下,支撑其在聚合物薄膜溶胀/去湿方面清洁效果的物理化学过程被确定为关键因素。表面活性剂对聚合物去湿的作用被认为主要限于降低界面张力。然而,最近的实验证明表面活性剂在溶胀聚合物薄膜中具有重要作用。
选择了五种不同的两亲物,即:十二烷基硫酸钠、二甲基十二烷基氧化胺、六氧乙烯癸醚(CE)、十五氧乙烯十二烷基醚(CE)和甲氧基十五氧乙烯十二烷酸酯(CCOECH)。它们与精心挑选的有机溶剂混合物(1-丁醇/丁酮/碳酸二甲酯)混合,以配制仅因表面活性剂不同的新型NSFs,并用于对涂有Paraloid B72®和Primal AC33®的表面进行清洁测试。在此首次通过差示扫描量热法在暴露于流体前后对表面活性剂引起的聚合物溶胀进行了量化,并将其与两种聚合物的玻璃化转变温度相关联。共聚焦激光扫描显微镜和小角X射线散射提供了关于相互作用机制的更多见解。
在聚合物溶胀方面,非离子型表面活性剂被证明比两性离子/离子型两亲物更有效,总体而言,甲氧基十五氧乙烯十二烷酸酯在所选表面活性剂中效果最为显著。建立了表面活性剂对聚合物玻璃化转变温度的影响与清洁能力之间的直接关系。这一发现对于理解NSFs与聚合物涂层或漆层之间的相互作用机制至关重要,是实现选择性、有效和完全去除聚合物涂层的关键,正如最近在去除街头艺术中的破坏行为和覆盖涂层时所显示的那样。