A Novel Green Stabilization of TiO<Subscript>2</Subscript> Nanoparticles onto Cotton

Facile embedding of TiO₂ nanoparticles onto cotton fabric has been successfully attained by ultraviolet light irradiations. The adhesion of nanoparticles with fibre surface, tensile behaviour and physicochemical changes before and after ultraviolet treatment were investigated by scanning electron microscopy, energy dispersive X-ray and inductive couple plasma-atomic emission spectroscopy. Experimental variables i.e. dosage of TiO₂ nanoparticles, temperature of the system and time of ultraviolet irradiations were optimised by central composite design and response surface methodology. Moreover, two different mathematical models were developed for incorporated TiO₂ onto cotton and tensile strength of cotton after ultraviolet treatment and used further to testify the obtained results. Self-clean fabric through a synergistic combination of cotton with highly photo active TiO₂ nanoparticles was produced. Stability against ultraviolet irradiations and self-cleaning properties of the produced fabric were evaluated.     

Multifunctional modification of wool fabric using graphene/TiO<Subscript>2</Subscript> nanocomposite

In this study, a new finishing technique is introduced through treatment of wool fabric with graphene/TiO₂ nanocomposite. Graphene oxide/titanium dioxide nanocomposite first applied on the wool fabric by hydrolysis of titanium isopropoxide in graphene oxide suspension and then this coating chemically converted by sodium hydrosulfite to graphene/TiO₂ nanocomposite. The homogenous distribution of the graphene/TiO₂ nanocomposite on the fiber surface was confirmed by field emission scanning electron microscopy (FE-SEM), Energy-dispersive X-ray spectroscopy (EDS) and X-ray mapping. X-ray diffraction patterns proved the presence of titanium dioxide nanoparticles with a crystal size of 127 Å on the treated wool fabric. Also, the defect analysis based on X-ray photoelectron spectroscopy (XPS) established the composition of the nanocomposite. Other characteristics of treated fabrics such as antibacterial activity, photo-catalytic self-cleaning, electrical resistivity, ultraviolet (UV) blocking activity and cytotoxicity were also assessed. The treated wool fabrics possess significant antibacterial activity and photo-catalytic self-cleaning property by degradation of methylene blue under sunlight irradiation. Moreover, this process has no negative effect on cytotoxicity of the treated fabric even reduces electrical resistivity and improves UV blocking activity.     

Development of UV Protective,Superhydrophobic and Antibacterial Textiles Using ZnO and TiO<Subscript>2</Subscript> Nanoparticles

In this research work, multifunctional cotton fabric comprising of UV protection, superhydrophobicity and antibacterial activity has been developed using facile pad-dry-cure method. In the first step, the concentration of repellent chemical has been optimized. Then, formulations containing nanoparticles of ZnO or TiO₂ along with optimized concentration of repellent chemical and organic-inorganic binder have been applied to cotton fabric followed by the evaluation of functional properties. The surface morphology and elemental composition of treated fabric has been characterized through SEM and EDX, respectively. The treated samples have shown promising UV protection, superhydrophobicity and antibacterial properties durable upto 20 washing cycles.     

Self-cleaning Properties of Nylon 6 Fabrics Treated with Corona and TiO<Subscript>2</Subscript> Nanoparticles under Both Ultraviolet and Daylight Irradiations

Nylon 6 fabric with self-cleaning properties was prepared by corona discharge pre-treatment and coating with TiO₂ nanoparticles (NPs) using pad-dry-cure technique. The self-cleaning property was studied by discoloration of methylene blue (MB), ketchup, tea and coffee stains from the corona+TiO₂ treated nylon-6 fabric. Color difference (ΔΕ*), reflectance (R) and K/S of MB stain were investigated by diffuse reflectance spectrophotometry. The MB stain was almost completely removed from the corona+TiO₂ treated nylon surface after 24 h under UV light/daylight irradiation. Both of these phenomena (corona and TiO₂) led to an increase in the discoloration of stains under UV and daylight irradiations. The EDS analysis showed an increase in the concentration of deposited TiO₂ NPs coating after corona treatment. The FE-SEM images revealed that the surface of nylon 6 was coarser after the corona treatment. Also, the FE-SEM micrographs exhibited that a uniform layer of TiO₂ NPs was formed on the corona treated nylon fabric. The corona+TiO₂ treated nylon illustrated antibacterial activity against E. coli and B. subtillis microorganisms. The EDS and FE-SEM analysis confirmed that after 5 washing cycles, the amount of TiO₂ NPs was higher on the surface of corona+TiO₂ treated nylon than that of the fabric only treated with TiO₂ without corona pretreatment. This result justifies that the corona+TiO₂ treated nylon fabric with appropriate self-cleaning property can be applied cost-effectively in the textile industry.     

Nano-TiO<Subscript>2</Subscript> based multilayer film deposition on cotton fabrics for UV-protection

Nano-TiO₂ based multilayer nanocomposite films were fabricated on cationically modified woven cotton fabrics by layer-by-layer molecular self-assembly technique. Cationization process was used to obtain cationic surface charge on cotton fabrics. Attenuated total reflectance Fourier transform infrared spectroscopy analyses were used to verify the presence of cationic surface charge and multilayer films deposited on the fabrics. Scanning electron microscope micrographs of poly(sodium 4-styrene sulfonate)/TiO₂, nano polyurethane/TiO₂, and TiO₂/poly(diallyldimethylammonium chloride) multilayer films deposited on cotton fabrics were taken. With nano-TiO₂ based multilayer film deposition, the protection of cotton fabrics against UV radiation is enhanced. The UV protection durability of the self-assembled multilayer films deposited on the cotton fabrics was analyzed after 10 and 20 washing cycles at 40 °C for 30 min. Air permeability and whiteness value analysis were performed on the untreated and multilayer film deposited cotton fabrics. The effect of layer-by-layer deposition process on tensile strength properties of the warp and weft yarns was determined.     

Polyaniline-doped TiO<Subscript>2</Subscript>/PLLA fibers with enhanced visible-light photocatalytic degradation performance

A simple and practical strategy has been developed for preparing polyaniline(PANi)-doped TiO₂/poly(l-lactide) (P@TiP-C) fibers by a combination of coaxial-electrospinning and in-situ polymerization. The TiO₂/PLLA composite fibers with TiO₂ located on the surface were fabricated by coaxial-electrospinning, with PLLA as the core phase and a dispersion of TiO₂ particles, a well-known photocatalyst, in the sheath phase. The aniline monomers were also located in the core phase and in-situ polymerized by ammonium persulfate (APS) after electrospinning. SEM images show that TiO₂ particles were located on the surface of PLLA fibers. Photocatalytic degradation tests show that the P@TiP-C fibers exhibit enhanced photocatalytic activity for degradation of methyl orange under visible light, likely due to the synergistic effect of PANi and TiO₂.     

Experimental study on dyeing technical PET yarns having different TiO<Subscript>2</Subscript> contents

TiO₂ contents in yarns can influence color yield so that dyeing quality of industrial poly ethylene terephthalate (PET) yarns can be improved through the adjustment of TiO₂ contents. To evaluate the dyeing performance of color yield, the chips which included the different TiO₂ contents of 330, 550, and 1,100 ppm respectively were used to produce the yarns of different TiO₂ content by a spin-draft machine. The physical and structural properties of the yarns were measured to investigate effect of the TiO₂ contents on them. Dye uptake and dyeing rate were also evaluated using a colorimeter to compare the yarns having different TiO₂ contents. The experimental results showed that there were no appreciable variation in physical and structural properties among the yarn samples and no difference were observed among the dyed fabric samples with regard to dyeing uptake and dyeing rate. However, the color yield of dyed fabrics increased as TiO₂ contents decreased in the yarns especially when the fabric samples were dyed to pale shade. The physical reasoning could be proposed on why the yarns having low TiO₂ contents appeared to have higher color yield after dyeing.     

Effect of UV irradiation on cellulase degradation of cellulose acetate containing TiO<Subscript>2</Subscript>

Cellulose acetate (CA) films containing anatase type titanium dioxide (TiO₂) nanoparticles were prepared by solution casting. The film surface was modified by UV irradiation using a grid type UV irradiator. The UV irradiation caused slight increase in photodegradation of the CA films with TiO₂ compared to the CA film alone. However, CA films irrespective of TiO₂ content did not show a significant enzymatic degradation by a cellulase fromAspergillus niger without UV irradiation. Upon UV irradiation, the biodegradability remarkably improved even in the CA film without TiO₂. The irradiation of CA films decreased both the water contact angle and the degree of substitution (DS) implying the decrease in acetyl groups of the CA film surface due to the photo-scission of the acetyl group and photooxidation, resulting in more facile biodegradation of the surface film layer. The substantial enhancement in biodegradation of the UV irradiated CA film containing TiO₂ was attributed to the increased hydrophilicity, lowered DS and zeta potential due to the photoscission and the photooxidation effect of UV light. Also the increased surface area of the CA film due to the photocatalysis of TiO₂ particles may encourage the facile biodegradation.     

Preparation and UV-protective property of PVAc/ZnO and PVAc/TiO<Subscript>2</Subscript> microcapsules/poly(lactic acid) nanocomposites

The poly(vinyl acetate) (PVAc)/zinc oxide (ZnO) microcapsule and PVAc/titanium dioxide (TiO₂) microcapsule were synthesized via in-situ emulsion polymerization method. The PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis(TG), transmission electron microscopy (TEM), and UV-visible spectroscopy (UV-vis). Effect of PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule on properties of poly(lactic acid) (PLA) was evaluated by UV-vis, SEM and mechanical properties test. The results showed that the addition of PVAc/ZnO and PVAc/TiO₂ microcapsules as a UV-blocking additive could significantly enhance UV-blocking property of PLA/PVAc/ZnO microcapsule composites and PLA/PVAc/TiO₂ microcapsule composites compared with pure PLA, PLA/ZnO composites and PLA/TiO₂ composites. The mechanical properties of PLA/PVAc/ZnO microcapsule composites were better than those of PLA/ZnO composites due to good dispersability and compatibility of PVAc/ZnO microcapsule in PLA matrix. Also, the mechanical properties of PLA/PVAc/TiO₂ microcapsule composites were better than those of pure PLA and PLA/TiO₂ composites. This study demonstrates the great potentials of the intrinsically UV shield additive PVAc/ZnO and PVAc/TiO₂ microcapsules in the application of high performance matrix resin and composite material.     

In situ loading TiO<Subscript>2</Subscript> and its photocatalysis and UV resistance on cotton fabric

Anatase TiO₂ nanoparticles was in-situ formed on the cotton fabric by using tetrabutyl titanate (TBT) as a precursor through the normal pressure hydrothermal method. X-ray diffraction (XRD), Scanning electron microscopy (SEM), UV visible spectra (UV-VIS), ATR-IR were used as the characterization techniques. Photocatalytic performance of TiO₂ on the fabric surface was evaluated by methylene blue (MB), 4 kinds of the common living stains and three dyes under ultraviolet and visible light radiation. XRD analysis found that the TiO₂ loaded on the fabric was mainly anatase crystalline phase with particle size of 6.4 nm. SEM observed that a large number of nano TiO₂ particles are distributed on the fabric surface. UV-VIS test indicated that theTiO₂-coated fabric possessed an obvious absorption for ultraviolet. ATR-IR analysis indicated that the nano-TiO₂ possesses a strong affinity with the hydroxyl group of the cotton fabric, and the soaping tests showed that the TiO₂ was firmly bonded with the fabrics. The treated fabrics have good degradation ability for MB aqueous solution, and could degrade azo, anthraquinone and phthalocyanine dyes. The order of degradation of the common life stains was: pepper oil> tea > coffee > soy sauce.     

Spherical Bacterial Cellulose/TiO<Subscript>2</Subscript> Nanocomposite with Potential Application in Contaminants Removal from Wastewater by Photocatalysis

Contaminants are often found in aquatic environments, for instance, heavy metals, dyes, parasites, pesticides, hormones and pharmaceuticals. Therefore, large amounts of these contaminants reaches wastewater via industrial and domestic effluents, causing major concern to human health. Heterogeneous photocatalysis is a technique for removing these contaminants in order to achieve better efficiency in water treatment. Then, bacterial cellulose (BC) produced in an agitated culture can form spherical bodies composed of nanofibers with high specific surface area. Moreover, Titanium dioxide (TiO₂) is a semiconductor containing high photocatalytic activity capacity. Thus, the main objective in this work was to produce spherical BC/TiO₂ nanocomposites for contaminants removal from wastewater by photocatalysis process. The incorporation of TiO₂ nanoparticles in the spherical BC matrix was performed by ex situ and in situ methods. In addition, Scanning Electron Microscope (SEM), Energy Dispersive Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA) were used as tools of morphological, chemical and thermal characterizations of the nanocomposites. Besides, photocatalysis tests were performed in order to evaluate the removal efficiency of methylene blue from aqueous solutions. The results of these tests exhibited a percentage of methylene blue removal of 70.83 and 89.58 % after 35 minutes for spherical BC/TiO₂ nanocomposites both, in situ and ex situ, respectively. Therefore, these results demonstrated that BC/TiO₂ to be a low cost material with high capacity of contaminants removing and a great potential for industrial applications.     

Preparation and characterization of (POSS/TiO2)n multi-coatings based on PBO fiber surface for improvement of UV resistance

The application of poly (p-phenylene-2, 6-benzobisoxazole) (PBO) fiber as reinforcement in composite material was restricted by its photo-degradation, therefore, some measures should be considered to protect PBO fiber against UV aging. In this study, A series of multilayer coating for (POSS/TiO₂)_n was prepared on PBO fiber surface via LbL assembly technique for enhancement of UV resistance. TiO₂ as UV absorbing material was used to relieve UV-degradation of PBO. Surface elemental composition, surface morphology, mechanical and interfacial properties, and UV resistance of uncoated and coated PBO fibers were investigated. These experimental results show multilayer coating of (POSS/TiO₂)_n was uniform deposition on fiber surface after treatment, tensile strength decreased to certain extent, interfacial shear strength increased in a small range and UV resistance is obvious enhanced. After the same accelerated aging time under UV irradiation, the retention of tensile strength and intrinsic viscosity of coated PBO fibers were much better than that of untreated PBO fibers.     

Preparation of TiO<Subscript>2</Subscript>-coated ZnO Nanoparticles and Their Effect on the UV Absorption of a Poly(vinyl alcohol) Composite Film

Titanium oxide (TiO₂) and zinc oxide (ZnO) composite structured nanoparticles were prepared by combining a sol-gel process and a solvothermal method. Titanium (IV) isoproxide (TTIP), used as a TiO₂ precursor, was dissolved in a colloidal ZnO nanoparticle solution synthesized by the sol-gel method, and TiO₂ was synthesized via solvothermal synthesis onto the ZnO nanoparticles. The effects of reaction conditions such as pH, reaction temperature, and reaction time on the morphology of the composite nanoparticles and the ultraviolet (UV) absorbance of their polymer composite films were investigated. The UV absorption of the poly(vinyl alcohol) (PVA) composite film with TiO₂-coated ZnO nanoparticles was higher than that of the TiO₂, ZnO, and ZnO-coated TiO₂ composite films. The reaction pH was found to have the strongest influence on the UV absorbance of the PVA/(TiO₂/ZnO) composite film. A pH of 7.0, reaction temperature of 250 °C, and reaction time of 24 h were the optimum conditions for UV absorption.     

Novel Spray Dried Glycerol 2-Phosphate Cross-Linked Chitosan Microparticulate Vaginal Delivery System—Development,Characterization and Cytotoxicity Studies

Chitosan microparticulate delivery systems containing clotrimazole were prepared by a spray drying technique using glycerol 2-phosphate as an ion cross-linker. The impact of a cross-linking ratio on microparticle characteristics was evaluated. Drug-free and drug-loaded unmodified or ion cross-linked chitosan microparticles were examined for the in vitro cytotoxicity in VK2/E6E7 human vaginal epithelial cells. The presence of glycerol 2-phosphate influenced drug loading and encapsulation efficacy in chitosan microparticles. By increasing the cross-linking ratio, the microparticles with lower diameter, moisture content and smoother surface were observed. Mucoadhesive studies displayed that all formulations possessed mucoadhesive properties. The in vitro release profile of clotrimazole was found to alter considerably by changing the glycerol 2-phosphate/chitosan ratio. Results from cytotoxicity studies showed occurrence of apoptotic cells in the presence of chitosan and ion cross-linked chitosan microparticles, followed by a loss of membrane potential suggesting that cell death might go through the mitochondrial apoptotic pathway.     

Functionalization of lyocell fibers with TiO2, SiO2, and GLYMO

In the research self-cleaning coatings based on photocatalytically active nano titanium dioxide (TiO₂) were prepared. When applied directly to cellulose fiber surfaces, TiO₂ coatings form weak bonds with fibers. Therefore 3-glycidooxypropyl-trimethoxysilane was used as a coupling agent. It had been applied on the surface of cellulose fibers before the TiO₂ coating was performed. In this case, the silane is in the interface region, where it can be most effective as an adhesion promoter. Silane coupling agents have unique chemical and physical properties not only to enhance bond strength, but more importantly to prevent de-bonding at the interface during composite aging and use as well. The coupling agent provides a stable bond between two otherwise poorly bonding surfaces. Surface properties of these coatings have been examined, such as surface morphology and surface microstructure. TiO₂ nanoparticles were irreversibly attached to the surface of monodisperse silica (SiO₂) spheres and to the surface of Lyocell fibers coated with an epoxy-containing silane coupling agent. Analysis using scanning electron microscopy showed uniform distribution of nanoparticles in the resulting coatings. Fourier transform infrared spectroscopy revealed changes in the surface microstructure occurring after different modifications. In addition, the influence of photocatalytic activity on the mechanical properties of Lyocell fibers was determined. In addition to that, the results indicated that SiO₂ and the coupling agent provide a protection against high oxidizing power of TiO₂ under exposure to daylight irradiation.     

Synthesis of Ag-Loaded TiO<Subscript>2</Subscript> Electrospun Nanofibers for Photocatalytic Decolorization of Methylene Blue

Titanium dioxide (TiO₂) is one of the excellent photocatalysts used for degradation of environmetal pollutants. In this work, 2.5, 5.0 and 7.5 wt.% of silver (Ag)-loaded TiO₂ nanofibers of mean size 52–134 nm were synthesized by electrospinning method. These electrospun nanofibers were calcined at 500 °C to enable the transformation of Rutile (R) phase to Anatase (A), elimination of reaction moieties from the TiO₂ matrix and subsequently formation of Ag clusters. The effect of Ag loading on the morphology, crystal structure, phase transformation, and band gap of these electrospun nanofibers have been characterized by scannining electron microscopy (SEM), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), raman spectroscopy and UV-visible spectroscopy. These nanofibers exhibited a red-shift in the absorbance edge and a significant enhancement of light absorption in the wavelength range of 250–550 nm. These electrospun nanofibers were investigated for photodecomposition of methylene blue (MB), and photocatalytic decolorization rates were determined by pseudo-first-order equation. The rate constants for the pure and those of 2.5, 5.0, and 7.5 wt% Agloaded TiO₂ nanofibers were computed to be 0.1439 min^-1, 0.1608 min^-1, 0.1876 min^-1, and 0.2251 min^-1 respectively.     

Preparation and characterization of inner-pressure hollow fiber composite membrane via two-way coating technique for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

High-selectivity inner-pressure hollow fiber composite (HFC) membrane for CO₂/CH₄ separation was prepared through the Two-way coating (TWC) technique. The blends of poly(vinylamine) (PVAm)/polyvinyl alcohol (PVA) were coated onto porous hollow fiber polysulfone (PSF) ultrafiltration (UF) membrane with an effective membrane area of 0.4 m². The effects of fabrication parameters on the permselectivity of the resultant HFC membrane were investigated and the optimum preparation conditions were obtained as follows: coating time for 30 min and air blowing time for 30 min after the coating. The prepared HFC membrane showed the typical characteristic of fixed carrier membrane with a high selectivity of CO₂ and CH₄: the separation factor of CO₂/CH₄ (40 vol% CO₂ at 25 °C and 0.2 MPa) was 36.6 and the CO₂ permeability was 56.3 GPU. Field emission scanning electron microscopy (FESEM) images indicated that the HFC membrane prepared by TWC technique had a uniform coating layer along the whole hollow fiber. Membrane permselectivity showed almost no difference between different membrane sections. The HFC membrane showed a good stability during the continuous testing process of 540 h. And the HFC membrane preserved at 30 °C and 40 % humidity exhibited a good durability with a basically unchanged separation factor after 30 days.     

Maltodextrin and Gum Arabic-Based Microencapsulation Methods for Anthocyanin Preservation in Juçara Palm (<Emphasis Type="Italic">Euterpe edulis</Emphasis> Martius) Fruit Pulp

The juçara fruits (Euterpe edulis Martius), native to the Atlantic Forest, are rich in anthocyanins. To preserve the anthocyanins in juçara fruit pulp, this study aimed to evaluate the effectiveness of microencapsulation by spray drying and freeze drying with maltodextrin (dextrose equivalent 16.5 to 19.5) and gum arabic in different proportions. The obtained microparticles were characterized by quantifying the total polyphenol and anthocyanin contents, by performing differential scanning calorimetry, thermogravimetry, and infrared spectroscopy and by using scanning electron microscopy to analyze the morphology of the particles. The total amount of polyphenols in the fruit pulp was 750?±?16.7 mg GAE/100 g of the freeze-dried sample. The total anthocyanins in the fruit pulp was 181.25?±?5.36 (mg/100 g). The microparticles were formed by employing maltodextrin and gum arabic in a 1:1 proportion as the polymeric matrix; the mixtures of pulp and polymeric matrix were prepared in proportions of 2:3 and 2:1, preserving up to 83.69% of the anthocyanin content. Lyophilization of the 2:1 mixture resulted in an anthocyanin content of 116.89?±?4.43 (mg/100 g), whereas lyophilization of the 2:3 mixture resulted in 151.68?±?1.39 (mg/100 g) anthocyanin content, which did not differ from the value obtained by spray drying the 2:3 mixture (150.76?±?5.79 (mg/100 g)). Thermal analyses showed that the microparticles obtained by freeze drying at a ratio of 2:3 presented greater resistance to degradation with increasing temperature. The incorporation of the pulp in the polymeric matrix was demonstrated by IR analyses. Microparticles obtained by freeze drying showed the formation of various-sized flakes, whereas those obtained by spray drying were spherical in shape. Microencapsulation is a possible alternative for improving the stability of the anthocyanins in this fruit.     

Immobilization of TiO2 nanoparticles on PET fabric modified with silane coupling agent by low temperature hydrothermal method

PET fabric was first modified with silane coupling agent KH-560, and then was loaded with a layer of nano-scaled TiO₂ particles using tetrabutyl titanate as precursor by low temperature hydrothermal method, followed by dyeing with Disperse Blue 56. The morphology, crystalline phase, chemical modification, thermal stability and optical property of PET fiber before and after treatments were studied by scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, thermal gravimetric and diffuse reflectance spectrum techniques. The properties of tensile, air permeability, luster, ultraviolet (UV) protection, photocatalytic activity, K/S value and color fastness were also measured. It was found that compared with the TiO₂-coated fabric without modification with KH-560, the loading of TiO₂ nanoparticles on the surface of the TiO₂-coated fabric modified with KH-560 was obviously improved. The pure anatase TiO₂ nanoparticle was grafted onto the fiber surface. The onset decomposition temperature increased. The absorbing capability to ultraviolet radiation was enhanced. The properties of tensile, air permeability, luster, K/S value and color fastness changed slightly. The UV protection ability and photodegradation of methyl orange under UV illumination were enhanced to some extent.     

Polyacrylonitrile/electroconductive TiO<Subscript>2</Subscript> nanoparticles composite fibers <Emphasis Type="Italic">via</Emphasis> wet-spinning

For the first time, novel polyacrylonitrile (PAN)/electroconductive TiO₂ (EC-TiO₂) nanoparticles composite fibers have been successfully spun via wet-spinning. The composite fibers had uniform diameter and homogeneous surface. Moreover, at low content of EC-TiO₂ nanoparticles, the composite fibers realized a transition from an insulator to a conductor. This work has provided a simple and effective avenue for the production of PAN/EC-TiO₂ nanoparticles composite fibers that have great potential applications in the antistatic textiles.