Antioxidant and hydrophobic Cotton fabric resisting accelerated ageing

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Abstract

Antioxidant fabrics are excellent shields against oxidative damage by free radicals and can be used in clothing, packaging, cosmetics and preservation. In this study, we developed antioxidant and hydrophobic cotton fabrics using ecofriendly materials and processes. The fabrics were functionalized with a double layer coating. Pristine cotton fabrics were coated with a food grade antioxidant (butylated hydroxytoluene, BHT) incorporated biodegradable polyester (polycaprolactone, PCL). This coating was shielded with an acetoxy functional biocompatible hydrophobic silicone coating. The hydrophobic shielding prevented potential loss of the antioxidant due to interaction with water or ambient humidity over time. Coated fabrics were exposed to extreme peroxidative (concentrated H2O2) and UV light damage conditions using an ad hoc protocol for simulating decades of atmospheric ageing. Chemical changes on the cotton surface and potential oxidation and preventive mechanisms were studied using spectroscopy. Treated fabrics also displayed very low water vapor uptake and remained breathable with no visible color change. Mechanical properties of the original fabric were preserved after the treatment.

Introduction

The preservation of textiles from deterioration is a major issue for conservators and conservation scientists, considering that the category “textiles” includes valuable canvases, carpets, tapestries, curtains, costumes, design objects [1,2]. The preservation of the aforementioned objects is of fundamental importance in cultural heritage. Deterioration of these textiles is primarily governed by the presence of humidity [[3], [4], [5]]. Rapid variations in humidity can cause swelling or shrinkage of cellulose fibers, that are among the principal constituents of the ancient textiles [6], resulting in irreversible tensions, especially when occurring in large artworks or objects [7]. Furthermore, in presence of humidity, the air contaminants SO2, NO2, and CO2 can turn into sulfuric, nitric, and carbonic acids, respectively [8]. Cellulose can react with these acids at room temperature, triggering a hydrolysis process inside the polysaccharide chains, that leads to the scission of original cellulose structures, making the textile less resistant [[9], [10], [11]]. Constant exposure to high humidity can also promote microbial/bacterial growth and proliferation [[12], [13], [14]]. When insects and microorganisms attack a textile, they rapidly degrade it through enzymatic reactions by releasing excrements [15,16]. Hence, humidity has a significant impact on the conservation of artworks [17,18].

Besides humidity, oxidative degradation with ambient light and oxygen (oxidation) [19] is another source of textile deterioration. Experiments demonstrated that fabric samples stored in dark conditions suffered less strength loss compared to others exposed to light [20,21]. However, long periods of storage in the dark is not a viable option for public display and museum profitability. As such, textile preservation against stresses induced by oxidative processes and humidity [22] should involve the use of protective coatings to significantly reduce the diffusion of harmful oxidative peroxide radicals into the fabric. An ideal protective coating should confer hydrophobicity, reduce absorption of ambient moisture and maintain the breathability of the original fabric to prevent humidity accumulation and development of the microorganisms [[23], [24], [25]]. Moreover, it should be transparent, conformal to the textile structure without altering its texture, maintain or improve mechanical properties, and interact with the textile in a non-intrusive way [26,27]. In the past, several polymeric coatings based on acrylic copolymers [[28], [29], [30], [31]], polydimethylsiloxane [[32], [33], [34], [35]] and polymeric composites with nanoparticles [[36], [37], [38], [39]] have been developed for conservation purposes. Due to ecological issues related to fluorinated coatings (C-8 chemistry was expelled by Environmental Protection Agency due to health risks [40]), research on fluorine-free protective coatings has accelerated recently [[41], [42], [43], [44], [45]]. These coatings are usually integrated with active substances such as UV absorbers, antioxidants or oxidizing agent quenchers to minimize the deterioration of the textiles, as summarized by Koussoulou [46]. Antioxidant treatment was applied for conservation purposes by Hackney et al. [20], based on commercial antioxidants: Irganox 1010, Irganox 565, and Topanol CA. Authors observed that 1% wt. concentration produced little visual change, whereas the 2% wt. antioxidant additions resulted in an opaque to white coating. Antioxidant, antibacterial, and UV-resistant properties were successfully tested on not historical fabrics treated with CuO nanoparticles by Altun and Becenen [47]. A colorless and chemically stable solution based on hexamethyltriethylene tetramine and Zn(NO3)∙6H2O has been applied onto cotton fabrics by Shaheen et al. [48] conferring an antibacterial and UV protective function.

Some other studies provided protective treatments against photo-degradation and water uptake-induced deterioration. Hou et al. [49] developed a robust polyhedral oligomeric silsesquioxanes (POSS)- based superhydrophobic treatment, which resulted in fabrics with a water contact angle of 159° with resistance to UV irradiation, high-temperature exposure, ultrasonic washing, and mechanical abrasion. Abd El-Hady et al. [50] coated cotton fabrics by developing multilayers of poly(diallyldimethylammonium chloride), ZnO/SiO2 colloidal solution nanocomposite, and stearic acid. The multilayers conferred UV protection properties to the cotton fabric and improved water repellency. A silica coating on the fabrics was produced by Parhizkar et al. [51] using UV stabilizers, modifying the surface wettability and conferring to the fabrics high abrasion durability and acceptable wash fastness. In another work, cotton fabric with photochromic, hydrophobic, antibacterial, and ultraviolet (UV) blocking properties was developed by Ayazi-Yazdi et al. [52] with a mixture of silica nanoparticles, spirooxazine as a photochromic dye and an alkylsilane compound. Photo-stability in an accelerated ageing environment of a protective acrylic coating and the influence of rutile-TiO2 nanoparticles along with an amine light stabilizer (HALS) have been quantitatively studied by monitoring the chemical modifications occurring upon ageing conditions by Nguyen et al. [53]. Note that in all the aforementioned studies that developed functional protective coatings for fabrics [[54], [55], [56], [57], [58]], no ad hoc protocol for simulating cotton ageing (relevant to long exposure to light and air) under oxidation conditions has been proposed and tested, with little attention paid to chemical changes over the cellulose fiber surfaces [54].

In this study, an antioxidant transparent fluorine-free hydrophobic treatment was designed for the conservation of cotton-based heritage textiles. Cotton fabric was functionalized with food-grade antioxidant butylated hydroxytoluene (BHT) embedded in polycaprolactone (PCL) as a first layer. A second layer of polydimethylsiloxane (PDMS) was applied over the antioxidant coating for water repellency [55]. In addition, an aggressive oxidation protocol was implemented, consisting of exposing the fabrics to H2O2 and UV–vis light to simulate an accelerated exposure to harsh oxidation medium. The antioxidant functionality of the coating was verified by radical scavenging activity tests and using infrared spectroscopy to monitor the chemical changes in the cotton surface. Developed double-layered coatings demonstrated excellent light transmission, water-repellency, antioxidant and mechanical properties achieved by using only ecofriendly and biodegradable polymers, making the treatment a valid candidate for the preservation of cultural heritage textiles.

The main goal of this work is to formulate a hydrophobic cotton treatment free from fluorinated chemicals or polymers but also with polymers or chemicals that are known to be biodegradable, biocompatible and nontoxic. Both PCL and PDMS satisfy these requirements along with food grade BHT. Furthermore, the lipophilic food-grade BHT crystals were easily dispersed within the hydrophobic PCL polymer by using a green co-solvent, benzyl alcohol. Subsequently, a PDMS coating improved the hydrophobicity of the fabric. Note that since the fabrics were dip coated in respective PCL and PDMS solutions with proper polymer concentrations (∼2 wt.%), rather than forming a continuous film or coating over the fabrics, we mainly coated individual fiber surfaces with both polymers enabling pore breathability.

Section snippets

Materials

Plain-woven and bleached 100 % cotton fabric, with 180 ± 5 g/m2 mass density, was selected for the experiments. The textile has 24 threads/cm density both in warp and weft direction. Powdered polycaprolactone (hereafter, PCL) was supplied by Polysciences, Inc. (USA). The antioxidant butylated hydroxytoluene (hereafter BHT) and hydrogen peroxide (H2O2) solution 30 % (w/w) in water were purchased from Sigma-Aldrich. Single component acetoxy moisture cured polydimethylsiloxane resin (hereafter

Morphological characterization

The morphology of the COT, COT-AO, COT-AOP and COT-P samples was analyzed by using SEM microscopy. Figure 2a shows the dense woven structure of the untreated fabric (COT). The typical wrinkle-like and longitudinal fibril structure [63,64] of cotton fibers can be observed at ×2000 magnification (Fig. 2a). The cross-section of the warp at ×1000 magnification highlighted the sharp section of each fiber without any fall-out or partial filament separation among them. On the other hand, in the COT-AO

Conclusions

Woven cotton fabrics were treated with a double layer polymer coating comprising a biodegradable polymer (PCL) and a biocompatible hydrophobic polymer (PDMS) for protection against oxidative ageing and degradation, while rendering them hydrophobic. A food-grade common antioxidant known as BHT was incorporated into the PCL layer that remained effective against aggressive accelerated peroxide and UV ageing conditions, simulating decades of atmospheric ageing. The PDMS-based outer coating was

CRediT authorship contribution statement

Giulia Mazzon: Conceptualization, Methodology, Writing - original draft. Marco Contardi: Methodology, Data curation. Ana Quilez-Molina: Methodology, Data curation. Muhammad Zahid: Methodology, Data curation. Elisabetta Zendri: Supervision, Writing - review & editing. Athanassia Athanassiou: Supervision, Writing - review & editing. Ilker S. Bayer: Supervision, Conceptualization, Methodology, Investigation, Writing - review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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