Antioxidant and hydrophobic Cotton fabric resisting accelerated ageing
Graphical abstract
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.
References (78)
Application of infrared spectroscopy and thermal analysis to the examination of the degradation of cotton fibers
Polym. Degrad. Stab.
(2012)- et al.
Study of the chemical composition and the mechanical behaviour of 20th century commercial artists’ oil paints containing manganese-based pigments
Microchem. J.
(2016) - et al.
Obtainment and characterization of nanocellulose from an unwoven industrial textile cotton waste: effect of acid hydrolysis conditions
Int. J. Biol. Macromol.
(2019) - et al.
Production of new cellulose nanomaterial from red algae marine biomass Gelidium elegans
Carbohydr. Polym.
(2016) - et al.
Fabrication of cotton fabrics with both bright structural colors and strong hydrophobicity
Colloids Surf. A Physicochem. Eng. Asp.
(2020) - et al.
The influence of water-repellent admixtures on the behaviour and the effectiveness of Portland limestone cement mortars
Cem. Concr. Compos.
(2015) Factors influencing the stability of man-made fibers: a retrospective view for historical textiles
Polym. Degrad. Stab.
(2014)The long-term effect of selected conservation materials used in the treatment of museum artefacts on some properties of textiles
Polym. Degrad. Stab.
(2005)- et al.
Superhydrophobic coatings based on raspberry-like nanoparticles and their applications on cotton
Colloids Surf. A Physicochem. Eng. Asp.
(2020) - et al.
Facile construction of robust superhydrophobic cotton textiles for effective UV protection, self-cleaning and oil-water separation
Colloids Surf. A Physicochem. Eng. Asp.
(2019)
Superhydrophobic cotton fabric with excellent healability fabricated by the “grafting to” method using a diblock copolymer mist
Chem. Eng. J.
Methyltrimethoxysilane as a multipurpose chemical for durable superhydrophobic cotton fabric
Prog. Org. Coat.
Effect of different nanoparticles based coating on the performance of textile properties
Prog. Org. Coat.
Rational design of multi-layered superhydrophobic coating on cotton fabrics for UV shielding, self-cleaning and oil-water separation
Mater. Des.
Fabrication of Cu species functionalized cotton fabric with oil/water separating reusability by in-situ reduction process
Surf. Coat. Technol.
Superhydrophobic, superoleophobic coatings for the protection of silk textiles
Prog. Org. Coat.
Fabrication of fluorine-free superhydrophobic cotton fabric using fumed silica and diblock copolymer via mist modification
Prog. Org. Coat.
Bioresin-based superhydrophobic coatings with reduced bacterial adhesion
J. Colloid Interface Sci.
Superhydrophobic coatings made from biocompatible polydimethylsiloxane and natural wax
Prog. Org. Coat.
Durable antibacterial and UV protections of in situ synthesized zinc oxide nanoparticles onto cotton fabrics
Int. J. Biol. Macromol.
Facile generation of robust POSS-based superhydrophobic fabrics via thiol-ene click chemistry
Chem. Eng. J.
Accelerated degradation of water borne acrylic nanocomposites used in outdoor protective coatings
Polym. Degrad. Stab.
Accelerated ageing of cotton canvas as a model for further consolidation practices
Journal of Cultural Heritage
UV protection from cotton fabrics dyed with different tea extracts
Dye. Pigment.
Economically viable UV-protective and antioxidant finishing of wool fabric dyed with Tagetes erecta flower extract: Valorization of marigold
Ind. Crops Prod.
Comparison of physicochemical, mechanical and antioxidant properties of polyvinyl alcohol films containing green tealeaves waste extracts and discarded balsamic vinegar
Food Packag. Shelf Life
Superhydrophobic surfaces on cotton textiles by complex coating of silica nanoparticles and hydrophobization
Thin Solid Films
Changes in the cell wall and cellulose content of developing cotton fibers investigated by FTIR spectroscopy
Carbohydr. Polym.
FTIR study of polycaprolactone chain organization at interfaces
J. Colloid Interface Sci.
Cellulose oxidative and hydrolytic degradation: in situ FTIR approach
Polym. Degrad. Stab.
Permeability, diffusivity, and solubility of benzene vapor and water vapor in high free volume silicon- or fluorine-containing polymer membranes
J. Memb. Sci.
TiO2–SiO2–PDMS nano-composite hydrophobic coating with self-cleaning properties for marble protection
Prog. Org. Coat.
Antimicrobial, antioxidant, and waterproof RTV silicone-ethyl cellulose composites containing clove essential oil
Carbohydr. Polym.
A History of Textile Art, Pasold Research Fund in Association With Sotheby Parke Bernet
ICCROM, Conserving Textiles: Studies in Honour of Ágnes Timár-balázsy
Nanostructured coatings for the protection of textiles and paper
Ge-Conservación/Conservação.
Investigation and conservation of a historical woman’s coat decorated with Fur parts
JTATM.
The application of FTIR microspectroscopy in a non-invasive and non-destructive way to the study and conservation of mineralised excavated textiles
Herit. Sci.
Monitoring for Gaseous Pollutants in Museum Environments
Cited by (17)
PFAS-free superhydrophobic chitosan coating for fabrics
2024, Carbohydrate PolymersFacile fabrication of self-roughened surfaces for superhydrophobic coatings via polarity-induced phase separation strategy
2022, Journal of Colloid and Interface ScienceCitation Excerpt :As the droplet becomes larger, it is able to roll down at a small angle. The competition between surface tension and gravity is responsible for this phenomenon, which is common in previous studies on superhydrophobic treatments of fabrics[52–54]. The surface morphology of the fabrics before and after treatment was characterized by SEM.
Preparation of superhydrophobic conductive CNT/PDMS film on paper by foam spraying method
2022, Colloids and Surfaces A: Physicochemical and Engineering AspectsCitation Excerpt :Paper is mainly composed of reticulate plant fibers, which has the advantages of biodegradability, sustainability, biocompatibility and low cost, and is very attractive in technical application [2,3]. However, owing to the hydrophilicity of plant fiber in paper, the mechanical properties of paper will be reduced after absorbing water, which limits its application field [4,5]. Superhydrophobic paper has obvious advantages of moisture-proof, pollution-proof and self-cleaning, which can solve this problem.
Gallic acid functionalized polylysine for endowing cotton fiber with antibacterial, antioxidant, and drug delivery properties
2022, International Journal of Biological MacromoleculesCitation Excerpt :Textile materials with good antioxidant activity are conducive to the scavenging of free radicals in order to provide protections for biological systems from the damage of peroxidation caused by oxidative stress [5]. Natural bioactive extracts from plants have been proved quite useful to impart textiles with a valid antioxidant activity [6]. Moreover, textile materials are also believed to be a promising drug delivery system through direct contact with human skin and wound [7].
Polylactic acid-graphene emulsion ink based conductive cotton fabrics
2022, Journal of Materials Research and TechnologyCitation Excerpt :The slight increase in the Young's Modulus of the uncoated cotton fabric after the hot pressing can be attributed to the better alignment of the fibers of the woven structure, giving higher rigidity to the material; however, such increase is not significantly relevant. The textile's flexural rigidity is also an important mechanical feature that specifies the coated fabric's bending stiffness [72]. Measurements from the cantilever tests are reported in Fig. 4d.