Surface modification of TiO2/SiO2 composite hydrosol stabilized with polycarboxylic acid on Kroy-process wool fabric

Self-cleaning of wool fabric has been of increasing interest due to availability and practicability. In this paper, two kinds of wool fabrics, including raw wool and Kroy-process wool fabric, were successfully modified by TiO₂/SiO₂ gel stabilized by 1,2,3,4-butanetetracarboxylic acid (BTCA) and citric acid (CA), respectively. The optimum concentration of carboxylic acids and TiO₂/SiO₂ gel was decided by the crease recovery angles and total color difference (ΔE) values, respectively. The results revealed that wool fabrics treated with BTCA and TiO₂/SiO₂ had better wrinkle resistance in comparison with CA and TiO₂/SiO₂ treated samples. The decomposition of stains was studied using UV irradiation and the presence of TiO₂/SiO₂ gel demonstrated obvious self-cleaning property, in which the color of wool fabric was unchangeable. The hydrophilicity of Kroy-process wool fabric increased relative to raw ones. In addition, Scanning Electron Microscope images demonstrated the layer of TiO₂/SiO₂ nanoparticles coated on treated samples. In general, the adhesion properties coated to the fabric surface showed a slight loss even at harsh processing conditions, however, the anti-UV properties obviously increased due to the decrease in the fabric porosity. And the linkages between carboxylic acid and wool fibers were illustrated using FTIR pattern.     

Transglutaminase‐mediated crosslinking of gelatin onto wool surfaces to improve the fabric properties

In this study, transglutaminase (TGase)‐mediated crosslinking of gelatin on the surface of wool and its effect on the properties of wool fabric were investigated. For the wool fabric used in this study, gelatin (3 g/L) treatment for 1 h combined with 20 U/g of fabric microbial TGase reduced the area shrinkage of KMnO₄‐pretreated wool fabric from 6.53 ± 0.06 to 1.92 ± 0.15%, which was more effective than that treated with gelatin alone (in which the area shrinkage was reduced to 4.02 ± 0.10%). At the same time, the tensile strength recovered from 267 ± 2.0 to 335 ± 2.1 N. The antifelting ability of treated wool fabric exhibited better washing durability. Scanning electron micrographs showed that the gelatin material smoothed the wool fiber surface by coating or filling the raised scales of the wool with TGase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Simultaneous antimicrobial and dyeing of wool: A facial method

This study is carried out to examine the effects of simultaneous dyeing and antimicrobial finishing of wool yarns. Wool yarns were dyed with acid dye along with colloidal silver nanoparticles through the exhaustion method in a one‐bath. Different concentrations of nanosilver were examined to evaluate its influences on the color and the antibacterial properties of the yarns. The antibacterial property of the sample has been tested by a Gram‐negative bacterium Escherichia coli and a Gram‐positive bacterium Staphylococcus aureus. Also, the tenacity of wool yarns, color, and rubbing fastness of the dyed yarns has been measured. The color fastness against washing and antibacterial property of the dyed yarns after 10 laundering cycles was also considered. The fiber morphology was studied by SEM pattern, EDX, and X‐ray diffractometer. The results showed that the wool yarns dyed with acid dye along with 25 ppm of silver nanoparticles exhibited a very good antimicrobial effect even after 10 laundering cycles on S. aureus while the rubbing fastness remained unchanged, and the color fastness and tenacity were even improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyurethane modified with 3‐aminopropyltriethoxysilane as wool antifelting agent

A wool antifelting agent containing polyurethane modified with 3‐aminopropyltriethoxysilane (APTES) was synthesized. Firstly an isocyanate ( NCO) group ended prepolymer was gained by a hydrogen shift reaction between isophorone diisocyanate (IPDI) and poly (propylene oxide triol) (PPT), and then NCO‐group of the prepolymer was blocked by 3‐aminopropyltriethoxysilane to form a precursor PPT‐[Si(OEt)₃]₃. After that a sol of the precursor was prepared for an antifelting agent. During heating the sol gelled and formed inorganic–organic hybrid film that was characterized by using FTIR and TGA. And then the wool fabric samples were treated with sol by pad‐dry‐cure process at different curing temperature (120, 140, and 160°C). The antifelting effects of different curing temperatures were compared. The results indicated that the new agent could endow a better antifelting effect with the low curing temperature at 120°C and 3 min. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Multifunctional properties of polyester fabrics modified by corona discharge/air RF plasma and colloidal TiO2 nanoparticles

In this study the possibility of tailoring the textile nanocomposite materials based on the polyester fabric and TiO₂ nanoparticles that can simultaneously provide desirable level of antibacterial activity, UV protection, and self‐cleaning effects with long‐term durability was investigated. To enhance the binding efficiency of colloidal TiO₂ nanoparticles, the surface of polyester fabrics was activated by low‐pressure RF air plasma, and corona discharge at atmospheric pressure. Obtained functionalized textile materials provided maximum antibacterial efficiency against gram‐negative bacterium E. coli. High values of UV protection factor (UPF) indicate the maximum UV blocking efficiency (50+) of these fabrics. The results of self‐cleaning test with blueberry juice stains and photodegradation of methylene blue in aqueous solution confirmed excellent photocatalytic activity of TiO₂ nanoparticles deposited on the fiber surface. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Photo bleaching of wool using nano TiO2 under daylight irradiation

Wool bleaching is usually carried out on raw wool through treatment with oxidizing or reducing agents. Here, nano TiO₂ as a photocatalyst was applied on raw wool fabric to decompose the naturally occurred pigments under daylight irradiation. To enhance nano particles adsorption on the fabric, it was first treated with protease and then treated with nano TiO₂ along with citric acid. The whiteness and yellowness indexes and hydrophilicity features of the treated wool fabrics indicated a reasonable whiteness with a significant improved hydrophilicity. This new wool bleaching approach was named as “nano photo bleaching” as a most successful bleaching application.     

Multifunctionality of poly(vinyl alcohol) nanofiber webs containing titanium dioxide

We prepared titanium dioxide/PVA nanocomposite fiber webs for application in multifunctional textiles by electrospinning. The morphological properties of the TiO₂/PVA nanocomposite fibers were characterized using scanning electron microscopy and transmission electron microscopy. Layered fabric systems with electrospun TiO₂ nanocomposite fiber webs were developed using various concentrations of TiO₂ and a range of web area densities, and then the UV‐protective properties, antibacterial functions, formaldehyde decomposition ability, and ammonia deodorization efficiency of the fabric systems were assessed. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 2 wt% TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited an ultraviolet protection factor of greater than 50, indicating excellent UV protection. The same system showed a 99.3% reduction in Staphylococcus aureus. Layered fabric systems with TiO₂ nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a 85.3% reduction in Klebsiella pneumoniae. Titanium dioxide nanocomposite fiber webs containing 3 wt % TiO₂ nanoparticles at 3.0 g m^?2 web area density exhibited a formaldehyde decomposition efficiency of 40% after 2 h, 60% after 4 h, and 80% after 15 h under UV irradiation. The same system showed an ammonia deodorization efficiency of 32.2% under UV irradiation for 2 h. These results demonstrate that TiO₂ nanocomposite fibers can be used to produce advanced textile materials with multifunctional properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antibacterial finishing of polyester/cotton blend fabrics using neem (Azadirachta indica): A natural bioactive agent

The study focused on the development of biofunctional polyester/cotton blend fabric using a natural product. An antimicrobial agent extracted from the seeds of Neem tree (Azadirachta indica) was used for imparting antibacterial property to the blend fabric. Resin and catalyst concentrations were optimized to get the maximum crosslinking in the fabric blends using glyoxal/glycol as a crosslinking agent. The optimized concentrations were used to treat the fabric with the antimicrobial agent along with the crosslinking agent. Quantitative analysis was carried out to measure the antimicrobial activity against Gram‐positive and Gram‐negative bacteria. The results showed that the treated fabrics inhibited the growth of Gram‐positive bacteria (Bacillus subtilis) by more than 90% as compared to the control sample. Antimicrobial activity against Gram‐ positive bacteria was retained up to five machine washes and decreased thereafter. The antibacterial activity was higher against Gram‐positive bacteria as compared to Gram‐ negative bacteria (Proteus vulgaris). The treated fabrics also showed improved crease recovery property although the tensile property showed a marginal decrease. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

One pot blending of biopolymer‐TiO2 composite membranes with enhanced mechanical strength

A biopolymer‐TiO₂ composite membrane was prepared by blending of N‐[(2‐hydroxy‐3‐trimethylammonium) propyl] chloride chitosan and cellulose acetate with nano‐TiO₂ particles as the introduced inorganic components. It was verified that the amino groups (? NH₂) of chitosan (CTS) were partly grafted by stronger hydrophilic group ? according to the ¹H‐nuclear magnetic resonance spectra of N‐[(2‐hydroxy‐3‐trimethylammonium) propyl] chloride chitosan and attenuated total reflectance Fourier transform infrared spectroscopy. The structure, microcosmic morphology, water flux, swelling properties, and thermal stability of the composite membranes were characterized. With the mass ratio of cellulose acetate to CTS being 50 wt %, the mole ratio of CTS to glycidyl trimethylammonium chloride being 1 : 1, and drying temperature being 60°C in 70% acetic acid, the formed biopolymer‐TiO₂ composite membranes exhibited enhanced mechanical strength (84.29 MPa), lower swelling degree (101.36%), and improved antibacterial activity against Gram‐negative Escherichia coli (Rosetta and DH5α) and Gram‐positive Bacillus subtilis. The existence of nano‐TiO₂ particles and the introduction of stronger cationic group synergistically improved the antibacterial properties of the biopolymer‐TiO₂ composite membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42732.     

Use of lipoprotein lipase in the improvement of some properties of wool fabrics

Wool fabrics were pretreated with hydrogen peroxide in the presence of different stabilisers; namely, sodium silicate, magnesium sulphate and imino disuccinic acid sodium salt. The effect of stabiliser type and concentration on the properties of the treated wool were studied. Imino disuccinic acid sodium salt was found to be the most effective stabiliser for hydrogen peroxide when added to the bleaching bath of wool fabric. The effect of after‐treatment of the pre‐oxidised wool fabric with commercially produced lipoprotein lipase enzyme on its dyeability with acid and reactive dyes, as well as on some of its physico‐mechanical properties, was assessed. Chemical and microscopic analyses were conducted to assess changes in the chemical composition of wool treated with this system. Wool fabrics treated with hydrogen peroxide/imino disuccinic acid sodium salt/lipoprotein lipase enzyme exhibit improved wettability and, hence, dyeability with both acid and reactive dyes, as well as enhanced resistance to felting shrinkage and pilling, without severe deterioration in the fabric’s inherent properties.     

Cationization of cellulose/polyamide on UV protection,bio‐activity,and electro‐conductivity of graphene oxide‐treated fabric

In this work, cationized cotton/nylon fabric was treated with reduced graphene oxide (rGO) to produce highly conductive fabric. The fabric was cationized with 3‐chloro‐2‐hydroxy propyl trimethyl ammonium chloride to attract more anionic GO. The fabric was then treated with GO followed by reduction with sodium dithionite. The results of energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy indicated entire coverage of the fabric surface with rGO. The color of fabrics changed to gray‐black and the electrical resistance decreased to 0.6 × 103 Ω sq^?1. The washing fastness was measured according to ISO 105‐CO5 for color change and also electrical resistance of the samples demonstrated well stability of rGO on the fabric surface. The antibacterial activities of the treated fabrics improved against Gram‐negative bacteria including Escherichia coli (84.8%) and Pseudomonas aeruginosa (96.4%) and also Gram‐positive bacteria consisting Staphylococcus aureus (100%) and Enterococcus faecalis (98.4%). Further, the treated fabrics indicated an excellent UV reflectance of 100%. Finally heating of the cationized rGO fabric at 220 °C displayed a lower electrical resistance of 0.5 × 103 Ω sq^?1. The thermogravimetric analysis showed that heating has a slight effect on the dimensional thermal stability of the treated fabric as shrunk 2.43%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45493.     

The effect of mordant salts on antibacterial activity of wool fabric dyed with pomegranate and walnut shell extracts

Natural dyes have attracted increasing worldwide attention because of the carcinogenicity and environmental effects of synthetic dyes. In this study, wool fabric was treated with tannin‐rich extracts of Punica granatum peel and walnut shell in combination with some mordants. The effect of various mordants on the colorimetric and antibacterial properties of wool fabrics was investigated. The results showed that pretreatment with metallic mordants substantially improved the dyeing and fastness properties of wool fabrics. The extracts of Punica granatum peel and walnut shell showed a significant antibacterial activity at 5% concentration. In addition, antibacterial activity was dramatically enhanced using metallic salts. The antibacterial activity of samples dyed with natural dyes and without any mordant was not good, while the mordanted samples with copper, aluminum and tin salts obtained considerable antimicrobial properties following lightening and washing fastness. The extracts of Punica granatum peel and walnut shell can be considered as viable alternatives instead of artificial antibacterial agents for hospital textiles as well as an effective anti‐odour agent for sports and household textiles.     

Combination of a hydroxy‐functional organophosphorus oligomer and a multifunctional carboxylic acid as a flame retardant finishing system for cotton: Part II. Formation of calcium salt during laundering

Multifunctional carboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid (BTCA), were used to bond a hydroxy‐functional organophosphorus oligomer (FR) to cotton fabric in the presence of a catalyst, such as sodium hypophosphite (NaH₂PO₂). Previously, it was found that the cotton fabric treated with FR and BTCA showed a high level of phosphorus retention after one home laundering cycle. However, the flame retardant properties quickly deteriorated as the number of home laundering cycles was increased. In this research, it was found that the free carboxylic acid groups bound to the cotton fabric form an insoluble calcium salt during home laundering, thus diminishing the flame retardant properties of the treated cotton fabric. It was also found that the free carboxylic acid groups on the treated cotton fabric were esterified by triethanolamine (TEA), and that the formation of calcium salt on the fabric was suppressed by the esterification of the free carboxylic acid groups by TEA. The cotton fabric treated with BTCA and the hydroxy‐functional organophosphorus oligomer significantly improved its flame retardance when a new catalyst system consisting of hypophosphorous acid (H₃PO₂) and TEA was used in the system. Copyright © 2003 John Wiley & Sons, Ltd.     

Physical properties of crosslinked cellulose catalyzed with nano titanium dioxide

Four different carboxylic acids, 1,2,3,4‐butane tetracarboxylic acid (BTCA), maleic acid (MA), succinic acid (SUA), and citric acid (CA), were used as crosslinking agents to treat cotton fabrics in the presence of nanometer titanium dioxide (TiO₂) as a catalyst under UV irradiation. The dry crease recovery angle (DCRA) and wet crease recovery angle (WCRA) values of the treated fabrics were ranked BTCA > MA > CA > SUA and the tensile strength retention (TSR) values were ranked BTCA < MA < CA < SUA at a given resin concentration, catalyst concentration, and irradiation time period. The physical properties of the treated fabrics for nanometer silver/nanometer titanium dioxide (Ag/TiO₂) catalyst showed the same tendency. At a given DCRA, the WCRA values were ranked in the order BTCA ≒ MA > CA ≒ SUA; and at a given value of the TSR, the WCRA and DCRA values were both ranked in the order BTCA > MA > CA > SUA. The softness values of the carboxylic acid treated fabrics in the presence of nanometer TiO₂ catalyst were all better than that of the untreated fabric. Surface deposition of the treated fabrics for BTCA, which contains one vinyl double bond and four carboxylic acid groups, was higher than that for CA, which contains no vinyl double bond. IR spectra and electron spectroscopy for chemical analysis survey spectra showed the ester bond crosslink between the cellulose molecule and the various acids used in this study. The values of DCRA, WCRA, and add‐on of the CA crosslinked fabrics for the mixed catalysts were in the order ZrO₂/TiO₂ < SiO₂/TiO₂ < Ag/TiO₂. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2450–2456, 2005     

Surface functionalization and antibacterial activity of biomedical textiles with metal oxides-carbon nanocomposites

Carbon nanostructures were synthesized from honey by hydrothermal method. The synthesized nanocarbon structures were treated with synthesized Fe₂O₃ and TiO₂ nanoparticles to form nanocomposites (NC). The synthesized nonaoparticles and their composites with carbon nanostructures were validated by XRD, FTIR, SEM and TEM for their morphology and microstructures. XRD analysis revealed the crystallographic structure of Fe₂O_3, TiO₂ and the amorphous nature of carbon nanostructures . A rod like structure for Fe₂O₃ and TiO_2, and nano sheet like structure for carbon was observed by TEM. The NC was impregnated onto fabrics and the presence of the NC on to the fabrics was confirmed by Laser Raman, FTIR and EDAX. The antibacterial effects of NC impregnated fabrics were evaluated against gram positive and gram negative bacteria by agar diffusion plate test. The NC fabrics showed a clear zone of inhibition, indicating good antibacterial activity against both bacterial strains. The washing test revealed durability of the coated fabrics.     

Electrokinetic and antibacterial properties of needle like‐TiO2/polyrhodanine core/shell hybrid nanostructures

The aim of this study was to fabricate needle like‐TiO₂/polyrhodanine nanostructures by polymerizing rhodanine monomer on the TiO₂ nanoparticles' surfaces and investigate their antibacterial activities. The structural, thermal, morphological, surface and electrical properties of non‐covalently functionalized nanoparticles were characterized by using FTIR, XPS, elemental analysis, TGA, XRD, SEM‐EDX, TEM, contact angle, and conductivity measurements. Characterization results confirmed the formation of needle like‐TiO₂/polyrhodanine (PRh) core/shell hybrid nanostructures. Alterations on the surface and electrokinetic properties of the materials were characterized by zeta (ζ)‐potential measurements with the presence of various salts and surfactants. The ζ‐potential of needle like‐TiO₂ was observed to increase from ?7.6 mV to +28.4 mV after forming a core/shell needle like‐TiO₂/PRh nanocomposite structure and with the presence of cetyltrimethyl ammonium bromide (CTAB) surfactant. Thereby colloidally more stable dispersions were formed. Antibacterial properties of needle like‐TiO₂/PRh were also tested against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli by various methods and they showed good antibacterial activity. The highest killing efficiency was determined for needle like‐TiO₂/PRh against E. coli by colony‐counting method as 0.95. TEM experiments also showed the immobilizations of the nanoparticles on E. coli and revealed the interactions between E. coli and the nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41554.     

Functionalization of cotton fabric with nanosized TiO<Subscript>2</Subscript> coating for self-cleaning and antibacterial property enhancement

In this study, titanium dioxide (TiO₂) was used as coating compound to add self-cleaning and antibacterial functionality properties to the cotton fabric. TiO₂-consisting coating compounds were prepared at four different processing temperatures (20, 40, 60, and 80°C) in order to examine the influence of process temperature on average particle size. Among the prepared solutions, the one prepared at 80°C process temperature was selected for the dip coating application of the 100% cotton fabric, which formed a transparent nanosized TiO₂ film on the fibrous structure of fabric. Dip coating trials were done at five coating temperatures of 20, 40, 60, 80, and 100°C. TiO₂-coated and uncoated fabric samples were then tested to evaluate their self-cleaning and antibacterial activities. A self-cleaning activity test was conducted using uncoated and TiO₂-coated fabric samples which were stained with hot tea solution via dipping method. Stained fabric samples were illuminated under a solar simulator for the color changes to measure photocatalytic degradation of stain colors. Antibacterial performance of TiO₂-coated and uncoated fabric samples was determined against pure cultures of Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 29213.     

UV-induced grafting of organic–inorganic antibacterial membrane on wool fiber

Wool fiber was modified by UV irradiation and then reacted with cross-linked chitosan-coated Ag-loading nano-SiO₂ (CCTS-SLS) composites to prepare antibacterial wool fiber. The results show the topography of wool surface was also modified along with the formation of active radicals during UV irradiation. These active groups were used to graft antibacterial materials CCTS-SLS. Compared with parent wool fiber, the antibacterial wool fiber was improved in dyeing property. The dyeing uptake increased by 98% in a dyeing time of 50 min. Also, the antifelting performance increased as a result of the decrease in directional frictional effect after UV irradiation modification.     

Photosensitive antibacterial and cytotoxicity performances of a TiO2/carboxymethyl chitosan/poly(vinyl alcohol) nanocomposite hydrogel by in situ radiation construction

Nano‐TiO₂/carboxymethyl chitosan (CMCS)/poly(vinyl alcohol) (PVA) ternary nanocomposite hydrogels were prepared by freezing–thawing cycles and electron‐beam radiation with PVA, CMCS, and nano‐TiO₂ as raw materials. The presence of nano‐TiO₂ nanoparticles in the composite hydrogels was confirmed by thermogravimetry, Fourier transform infrared spectroscopy, and X‐ray powder diffraction. Field emission scanning electron microscopy images also illustrated that the TiO₂/CMCS/PVA hydrogel exhibited a porous and relatively regular three‐dimensional network structure; at the same time, there was the presence of embedded nano‐TiO₂ throughout the hydrogel matrix. In addition, the nano‐TiO₂/CMCS/PVA composite hydrogels displayed significant antibacterial activity with Escherichia coli and Staphylococcus aureus as bacterial models. The antibacterial activity was demonstrated by the antibacterial circle method, plate count method, and cell density method. Also, with the Alamar Blue assay, the cytotoxicity of the composite hydrogel materials to L929 cells was studied. The results suggest that these materials had no obvious cytotoxicity. Thus, we may have developed a novel, good biocompatibility hydrogel with inherent photosensitive antibacterial activity with great potential for applications in the fields of cosmetics, medical dressings, and environmental protection. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44150.     

Core‐shell ZrO2/PMMA composites via dispersion polymerization in supercritical fluid: Synthesis,characterization and mechanism

In this study, the polyester (PET) fabric was hydrolyzed with alkali to increase the surface activity and enhance the nano titanium dioxide (nano-TiO₂) adsorption to produce higher functionality. The PET fabric was first treated with sodium hydroxide along with cetyl trimethyl ammonium bromide as a cationic surfactant and then dipped into an ultrasound bath containing nano-TiO₂ followed by curing at high temperature. The weight loss, vertical wicking, and water droplet adsorption time were evaluated and are reported. The photocatalytic activity of TiO₂ nanoparticles deposited on the PET fabric was examined by the degradation of methylene blue as a model stain under daylight irradiation. The residual TiO₂ on the fabric surface after 1 and 10 successive washings was determined to indicate the washing durability of the finished fabric. Also, the UV protection was assessed by UV reflectance spectroscopy. The scanning electron microscopy pictures and energy-dispersive X-ray spectra of some fabrics are also reported. The surface hydrolysis of the PET fabric with sodium hydroxide created some voids and hydrophilic groups on the fabric surface; this led to the higher adsorption of nano-TiO₂ particles and enhanced the wettability, vertical wicking, and higher durability against repeated washings of the nano-TiO₂ treated fabric. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012