Functionalization of cotton fabrics with rutile TiO<Subscript>2</Subscript> nanoparticles: Applications for superhydrophobic,UV-shielding and self-cleaning properties

The superhydrophobic cotton fabrics were prepared by combining the coating of titanium dioxide (TiO₂) with the subsequent dodecafluoroheptyl-propyl-trimethoxysilane (DFTMS) modification. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements revealed that the nanosized TiO₂ sphere consisted of granular rutile. The TiO₂ layer coated on the cotton altered both the surface roughness for enhancing the hydrophobicity and UV-shielding property. The cotton fabric samples showed excellent water repellency with a water contact angle as high as 162°. The UV-shielding was characterized by UV-vis spectrophotometry, and the results indicated that the fabrics could dramatically reduce the UV radiation. The photocatalytic progress showed that organic stains were successfully degraded by exposure of the stained fabric to UV radiation. Such multifunctional cotton fabrics may have potentials for commercial applications.     

Organic–inorganic hybrid silica film coated for improving resistance to capsicum oil on natural substances through sol–gel route

This study concerns the organic–inorganic hybrid coating of silica sol based on dyed cotton, silk and wool fabrics in order to increase the repellence to capsicum oil via adding methyltriethoxysilane, octyltriethoxysilane, hexadec-ltrimethoxysilane or tridecafluorooctyltriethoxysilane (FAS) in the inorganic silica sol. The dyed cotton fabric treated with hybrid silica sol doped with FAS (F-silica sol, FAS 4 %) presents oil-repellent capability, and the contact angles of capsicum oil on the treated cotton, silk and wool fabrics are 98.5°, 111.59° and 122.15°, respectively. A high FAS concentration (20 %) can improve the oil-repellent ability to 5 grades comparing to the untreated fabrics. The color strengths (K/S) of the coated fabrics change slightly, while the maximum absorption wavelengths of the coated fabrics are the same as the untreated fabrics. Although the drape coefficient of cotton fabric is increased to 54 % from 39 % after coated with F-silica sol, the effect is not significant. Compared to the weight gain rate of untreated cotton, silk and wool samples (1.89, 1.23 and 2.38 %), the weight gain rate of the cotton, silk and wool samples coated with F-silica sol are 6.99, 4.76 and 7.69 %, respectively. The calculated sol–gel weight gains (5.10, 3.53 and 5.31 %) of coated fabrics indicate that the silica coating is subsistent on the fiber surfaces.     

Effects of plasma treatments for improving extreme wettability behavior of cotton fabrics

A simple, environmentally benign and energy efficient process for fabricating single faced superhydrophilic/hydrophobic cotton fabrics by controlling surface texture and chemistry at the nano/microscale is reported here. Stable ultra-hydrophobic surfaces with advancing and receding water droplet contact angles in excess of 146° as well as extreme superhydrophilic surfaces are obtained. Hydrophobic water-repellent cotton fabrics were obtained following plasma treatment through diamond-like carbon (DLC) coating by plasma enhanced chemical vapour deposition. The influence of changing different precursor’s plasma pre-treatments such as H₂, Ar or O₂ on the properties of DLC coatings is also evaluated using atomic force microscopy, X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, and analysed in terms of contact angle measurements. Because of the DLC coating, the coated fabric showed to endure its superhydrophobic character even after 12 months.     

Durable,water-cleanable,superhydrophilic coatings for oil/water separation under harsh conditions

A simple, economical, and efficient method for fabricating stable hydrophilic/underwater superoleophobic coating under harsh conditions remains a significant challenge. Here, by the hydrolysis of 3-(Methacryloyloxy) propyltrimethoxysilane (TMSPMA) on cotton fabric and the free radical polymerization of [2-(Methacryloyloxy) ethyl] dimethyl-(3-sulfonic acid propyl) ammonium hydroxide (SBMA) and TMSPMA, a superhydrophilic coating was fabricated. The coating can withstand harsh environments, such as strong acid and alkali. In addition, the coated cotton fabrics show an effective separation of surfactant-stabilized oil-in-water emulsions with extreme flux as high as 1500 Lm^?2 h^?1 only under gravity. Importantly, the oil-contaminated coated cotton fabrics can be cleaned only by water washing. The outstanding properties of the coating including durability, recyclability and resistance to harsh environment, highlight its practical application in emulsion separation and oily wastewater purification.     

One-pot sonochemical synthesis of superhydrophobic organic–inorganic hybrid coatings on cotton cellulose

Inspired by the surface structure of lotus leaves, different types of superhydrophobic cellulosic materials with contact angle (CA) of higher than 150° are currently provided. However, fabrication of these surfaces in a facile one-step coating process is one of the challenging issues. This paper describes a facile method to sonochemically synthesize superhydrophobic organic–inorganic hybrid coatings on cotton fabric by an alkaline-catalyzed co-hydrolysis and co-condensation of tetraethylorthosilicate and alkyltrialkoxysilanes. The influence of alkyl chain length (methyl, octyl, hexadecyl) of silane and reaction time was investigated. Surface structure of the fabrics was investigated by SEM, EDS, FTIR spectroscopies, and reflectance spectrophotometry. Wettability properties were studied by measuring water CA, shedding angle (SHA) and resistance to wetting by a series of ethanol–water mixtures of different surface tensions. The results showed that the treated fabrics were coated with a homogeneous thin nano-scaled coating of hybrid silica nano-particles. The fabrics demonstrated CA of higher than 150°, SHA in the range of 6–24° and different stickiness to water droplets. The fabrics treated by silanes with longer alkyl chain length and at higher reaction time revealed better water repellency. The coatings were nearly transparent, could not affect the color of the fabrics and had high stability against repeated washing. In addition, mechanical properties of the fabrics were not substantially affected.     

Novel UV-protective formulations for cotton, PET fabrics and their blend utilizing irradiation technique

A novel coating formulation to impart ultraviolet (UV) protection property to cotton, Polyethylene trephethalate (PET) and cotton/PET fabrics was prepared and gamma rays as an ionizing radiation was utilized for surface curing. Natural occurring aluminum potassium sulfate (Alum) was used individually and in binary coat with Zinc Oxide (ZnO), to induce the UV-blocking properties. It was found that using Alum (0.3 g/ml) caused a prompt increase in ultraviolet protection factor (UPF) over the uncoated fabrics. Moreover, the incorporated ZnO in the binary coat increased the UPF for two to threefold than the stand-alone Alum coating, specially in case of PET coated fabric. Water absorbance and moisture regain of ZnO and Alum/ZnO coated fabrics showed a decrease over the blank samples, due to the usage of oligomer/monomer combination. On contrary, Alum showed a hydrophilic effect with the increase in its content in the formulation. Surface Electron Microscope showed the homogenous coating of fibers. X-ray diffraction (XRD), energy dispersive X-ray (EDX) and water vapor permeability were also tested for coated samples.     

Growth and fire resistance of colloidal silica-polyelectrolyte thin film assemblies

Thin films of colloidal silica were deposited on cotton fibers via layer-by-layer (LbL) assembly in an effort to reduce the flammability of cotton fabric. Negatively charged silica nanoparticles of two different sizes (8 and 27 nm) were paired with either positively charged silica (12 nm) or cationic polyethylenimine (PEI). PEI/silica films were thicker due to better (more uniform) deposition of silica particles that contributed to more than 90% of the film weight. Each coating was evaluated at 10 and 20 bilayers (BL). All coated fabrics retained their weave structure after being exposed to a vertical flame test, while uncoated cotton was completely destroyed. Micro combustion calorimetry confirmed that coated fabrics exhibited a reduced peak heat release rate, by as much as 20% relative to the uncoated control. The 10 BL PEI-8 nm silica recipe was the most effective because the coating is relatively thick and uniform relative to the other systems. Soaking cotton in basic water (pH 10) prior to deposition resulted in better assembly adhesion and flame-retardant behavior. These results demonstrate that LbL assembly is a useful technique for imparting flame retardant properties through conformal coating of complex substrates like cotton fabric.     

阻燃超疏水棉纤维的制备及性能

将氢氧化镁(Mg(OH)₂)凝胶沉积到棉纤维上,以提高棉纤维表面粗糙度和阻燃性能,随后将含有Mg(OH)₂的棉纤维浸渍到聚二甲基硅氧烷(PDMS)溶液,获得阻燃超疏水棉织物。 并对棉纤维进行了傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)、疏水性、热稳定性、阻燃性能和耐久性测试。 结果表明,Mg(OH)₂负载到织物上,使得织物表面具有一定的微/纳米结构,形成了粗糙涂层。 当Mg(OH)₂浓度为1.0 mol/L时,Mg(OH)₂/PDMS改性的织物接触角(CA)可达158°,极限氧指数(LOI)提升至24.5%,导热系数为0.0525 W/(m·K), 具有超疏水和阻燃性能。 整理后织物经过20次洗涤,100次磨擦,极端条件处理后,CA仍大于150°,LOI值高于23%,显示了较好的耐久性。     

Surface hydrophobization of cotton via laccase-mediated polydopamine deposition and dodecyl gallate grafting

Natural fibers containing components with phenolic hydroxyl groups, such as jute, wool, and silk, can be directly modified by laccase-catalyzed grafting. However, cellulosic fibers like cotton cannot be functionalized in this manner. In this work, we developed a facile two-step method to graft polymers on cotton fabric via laccase catalysis. First, polydopamine (PDA) coating was deposited on the surface of the cotton fabrics via catalysis of laccase/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) system. Then, the newly formed PDA coating acted as the secondary reaction platform for subsequent laccase-mediated grafting of hydrophobic monomer dodecyl gallate (DG). The oxidation of dopamine (DA) catalyzed with the laccase/TEMPO system was investigated using UV–visible (UV–vis) spectroscopy. The scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results verified that the PDA was coated on the surface of cotton fibers. Fourier transform infrared (FTIR) spectra indicated that the PDA-coated cotton was successfully grafted with DG (DG-PDA-cotton). According to the weighting method, the grafting percentage was about 1.06%. The hydrophobicity of the DG-PDA-cotton fabrics was greatly improved with a contact angle of 133°. Also, the grafted cotton fabrics show repellency of water-soluble stains like coffee, milk, and tea. This study provides a new strategy for surface modification of cotton by laccase-mediated grafting, which offers the references for the green fabrication of cotton fabrics with improved functionalization.     

Bactericidal activity and UV-filtering property of TiO<Subscript>2</Subscript>-based photocatalysts coated on curtain fabrics

Synthesized and commercial titanium dioxide (TiO₂) were coated onto household curtain fabrics for anti-microbial and ultraviolet (UV) shielding functions. The coating was performed by inducing a deposition of the TiO₂ layer from the Ti precursor onto the fabric surface. A silane adhesive agent was employed to improve the adhesion between the coating and the fabric. Ag nanoparticles were also incorporated into some samples to further improve the anti-bacterial activity, which was evaluated by a standard qualitative test (AATCC 147). Efficiency for UV shielding was evaluated by measuring a UV–visible reflection of the coated fabrics both before and after subjecting it to several washing cycles. The results showed that the TiO₂-coated fabrics had potential as both anti-bacterial and UV shielding for the curtain industry.     

Polyhedral oligomeric silsesquioxane‐based fluoroether‐containing terpolymers: Synthesis,characterization and their water and oil repellency evaluation for cotton fabric

A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS‐co‐methyl methacrylate ?co‐ 4‐vinylbenzyl fluoroether carboxylate) ( P(POSS‐MMA‐VBFC) ) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X‐ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (T_d > 250 °C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133° to 159° and from 127° to 141° respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

WPU/Cu2-XSe coated cotton fabrics for photothermal conversion and photochromic applications

Cellulose - Multifunctional cotton fabrics were fabricated by coating of anionic waterborne polyurethane (WPU)/Cu2-XSe. The surface morphology of WPU/Cu2-XSe coated cotton fabric was characterized...     

Improved UV stability of antibacterial coatings with N-halamine/TiO2

The outstanding advantages of N-halamine materials over other antimicrobial materials are their durable and rechargeable antimicrobial properties, as well as their efficacies in inactivating a broad spectrum of pathogens. Theoretically, the oxidative chlorine of antimicrobial cotton coated with N-halamine hydantoin diol can be restored upon loss of its biocidal efficacy after exposure to ultraviolet light. In this work nano-titania particles were added into the coating solutions containing N-halamine diol and 1,2,3,4-butanetetracarboxylic acid (BTCA), and the coatings were applied to produce antimicrobial cellulose with improved UV stability. The treated cotton fabrics were characterized by FT-IR, SEM, XRD, and XPS. The effects of the coatings on tensile strength and wrinkle recovery angle were investigated. Biocidal efficacies of fabrics coated with hydantoin diol and diol/TiO₂ against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895) were determined using a modified AATCC 100-1999 method and showed excellent antimicrobial properties against these two bacterial species within a brief contact times. It was found that the addition of Nano-TiO₂ in the antimicrobial coatings, especially rutile titanium dioxide, could improve the UV light stability of the chlorinated fabrics coated with hydantoin diol significantly. The UV light stability of N-halamine coatings were enhanced with increasing amounts of rutile TiO₂.     

Hexamethyldisiloxane‐modified ZnO‐SiO2‐coated superhydrophobic textiles for antibacterial application

A superhydrophobic cotton textile with high antibacterial properties has been fabricated. The cotton textile was coated through the in situ growth of ZnO‐SiO₂ nanoparticles in presence of chitosan as the template agent via a hydrothermal process at 95 °C. This process was followed by the coating of additional layers of hexadecyltrimethoxysilane (HDTMS). The obtained cotton textile showed antibacterial property against Staphylococcus epidermis and Escherichia coli with inhibition zones up to 18.26 and 8.48 mm, respectively. Scanning electron microscopy (SEM) revealed that the coating had a rough surface, which was attributed to the distribution of ZnO‐SiO₂ nanorods of hexagonal shape. This rough surface creates a superhydrophobic layer that repels the bacteria, as proven by the large water contact angle of approximately 150°. Nevertheless, the HDTMS layers prolong the durability of hydrophobicity for up to 3 h.     

Comparison of copolymer emulsions of fluorine and siloxane‐containing acrylates with core–shell structure for water‐repellent cotton fabrics coatings

This paper described the synthesis of copolymer emulsions of fluorine and siloxane‐containing acrylates for water‐repellent cotton fabrics coatings. Chemical composition, morphology structure, and properties of the latex copolymers were investigated by Fourier transform infrared (FTIR), dynamic light scattering (DLS), gel permeation chromatography (GPC), and transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Effects of water‐repellent functional monomers (R_f) on surface morphology, water contact angle, and water‐repellent properties of the coated fabric surface were also studied. The results indicated that R_f greatly influenced molecular mass distribution of the latex copolymers, the molecular aggregation states and orientation of R_f on the coated fabric surface, and water‐repellency of coated cotton fabrics. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrophobicity modification of woven cotton fabric by hydrophobic fumed silica coating

Water repellency of woven cotton fabric was achieved by coating with the aqueous dispersion containing organosilane agent (HDTMS) and fumed silica. The coating agents were applied using padding method and then followed by batching the coated fabric at the ambient temperature for 24 h to allow the condensation reaction between HDTMS silanol group and fumed silica silanol group, rendering silica particles hydrophobic. An ultrasonicator was employed to prepare the homogenous coating dispersion. The water repellency evaluated by water contact angle determination which showed the contact angle over 110° was obtained with low amount of applied HDTMS of 1 wt%. The effect of fumed silica addition on an increase in fiber surface roughness geometry showed the influential result in improving the water contact angle. From durability to washing test, the hydrophobic coatings evidenced from SEM and ATR/FTIR remained adhering to fiber surface, indicating the durability. After washing, the coating on the fabric with fumed silica addition appeared to be scatter particles which made a contribution to the higher contact angle value when compared to sheet-like layer coating in case of HDTMS coating alone.     

Modified Silica Sol Coatings for Water-Repellent Textiles

The preparation of water repellent textiles by coating with different modified silica sols has been investigated. For this, pure and with 3-glycidoxypropyl triethoxysilane co-condensed silica sols were modified by three types of additives: alkyltrialkoxysilanes, polysiloxane derivatives and a fluorine containing silane. Hydrophobic properties of the coated fabrics of polyamide and of polyester mixed with cotton were determined using contact angle measurements. The hydrophobicity increases with increasing concentration of the alkylsilane additive in the silica sol and the length of the alkyl chain but with high additive concentrations plateau values in hydrophobicity were reached. Analogously textile coatings with high hydrophobicity were gained using hydrophobic polysiloxane or fluorine containing silicon compounds. The comparison of the different variants reveals that high wash-out stabilities were reached only by silica sols containing fluorine compoundsand hexadecylsilane additives. Therefore long-chain alkyltrialkoxysilane compounds could be used as substitutes for fluorine compounds for the surface modification of textiles in some practical applications.     

Using graphene/TiO2 nanocomposite as a new route for preparation of electroconductive,self-cleaning,antibacterial and antifungal cotton fabric without toxicity

A novel and efficient process is reported for fabrication of electroconductive, self-cleaning, antibacterial and antifungal cellulose textiles using a graphene/titanium dioxide nanocomposite. Cotton fabric was loaded with graphene oxide using a simple dipping coating method. The graphene oxide-coated cotton fabrics were then immersed in TiCl₃ aqueous solution as both a reducing agent and a precursor to yield a fabric coated with graphene/titanium dioxide nanocomposite. The crystal phase, morphology, microstructure and other physicochemical properties of the as-prepared samples were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and UV-Vis reflectance spectroscopy. Electrical resistance, self-cleaning performance, antimicrobial activity and cytotoxicity of treated fabrics were also assessed. The electrical conductivity of the graphene/titanium dioxide nanocomposite-coated fabrics was improved significantly by the presence of graphene on the surface of cotton fabrics. The self-cleaning efficiency of the treated fabrics was tested by degradation of methylene blue in aqueous solution under UV and sunlight irradiations. The results indicated that the decomposition rates of methylene blue were improved by the addition of graphene to the TiO₂ treatment on fabrics. Moreover, the graphene/titanium dioxide nanocomposite-coated cotton samples had negligible toxicity and possessed excellent antimicrobial activity.     

Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics

In this study, we report the functionalization of silica nanoparticles with highly photoreactive phenyl azido groups and their utility as a negatively charged building block for layer-by-layer (LbL) electrostatic assembly to produce a stable silica nanoparticle coating. Azido-terminated silica nanoparticles were prepared by the functionalization of bare silica nanoparticles with 3-aminopropyltrimethoxysilane followed by the reaction with 4-azidobenzoic acid. The azido functionalization was confirmed by FTIR and XPS. Poly(allylamine hydrochloride) was also grafted with phenyl azido groups and used as photoreactive polycations for LbL assembly. For the photoreactive silica nanoparticle/polycation multilayers, UV irradiation can induce the covalent cross-linking within the multilayers as well as the anchoring of the multilayer film onto the organic substrate, through azido photochemical reactions including C-H insertion/abstraction reactions with surrounding molecules and dimerization of azido groups. Our results show that the stability of the silica nanoparticle/polycation multilayer film was greatly improved after UV irradiation. Combined with a fluoroalkylsilane post-treatment, the photoreactive LbL multilayers were used as a coating for superhydrophobic modification of cotton fabrics. Herein the LbL assembly method enables us to tailor the number of the coated silica nanoparticles through the assembly cycles. The superhydrophobicity of cotton fabrics was durable against acids, bases, and organic solvents, as well as repeated machine wash. Because of the unique azido photochemistry, the approach used here to anchor silica nanoparticles is applicable to almost any organic substrate.     

Preparation of durable superhydrophobic surface by sol–gel method with water glass and citric acid

Durable superhydrophobic surface on cotton fabrics has been successfully prepared by sol–gel method. Cellulose fabric was first coated with silica sol prepared with water glass and citric acid as the acidic catalyst. The silica coated fabric was then padded with hydrolyzed hexadecyltrimethoxysilane afterwards obtaining low surface energy. Water contact angle and hydrostatic pressure were used to characterize superhydrophobicity and washing durability. Scanning electron microscopy was used to characterize the surface morphology changes after certain washing times. All results showed good durable hydrophobicity on cellulose fabrics. In addition, the influence of citric acid and sodium hypophosphite (NaH₂PO₂) on the durability of hydrophobicity was also investigated. The durability of treated cotton improved with the increase of concentration of citric acid in the presence of NaH₂PO₂. It could be concluded that citric acid acted as multi-functional heterogeneous grafting chemicals to improve washing durability of hydrophobicity by forming the ester bonds between cotton fabric and silica sol and improved the durability of hydrophobicity.