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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

The removal of heavy metals in aqueous solution by hydroxyapatite/cellulose composite

Hydroxyapatite has an excellent ion-exchangeability and is expected to be used as an agent for the removal of heavy metal ions in wastewater. However, the pure hydroxyapatite is very difficult to use because it exists in the form of white powder. Thus, the pure hydroxyapatite was mixed with cellulose to utilize its ion-exchangeability. In this research, a method for dispersion of hydroxyapatite in cellulose matrix is described and its dispersion is observed with scanning electron microscopy. The removal ratios of some heavy metal ions with hydroxyapatite composite are examined with regard to reaction time and amount of hydroxyapatite composite. The ion-exchangeability of hydroxyapatite composite did not seem to be interfered by cellulose matrix during removing heavy metal ions.     

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.     

Preparation and acid dye adsorption behavior of polyurethane/chitosan composite foams

We prepared a series of polyurethane(PU)/chitosan composite foams with different chitosan content of 5∼20 wt% and investigated their adsorption performance of acid dye (Acid Violet 48) in aqueous solutions with various dye concentrations and pH values. It was observed that PU/chitosan composite foams exhibited well-developed open cell structures. Dye adsorption capacities of the composite foams increased with the increment of chitosan content in composite foams, because amine groups of chitosan serve as the binding sites for sulfonic ions of acid dyes in aqueous solutions. In addition, dye adsorption capacities of composite foams were found to increase with decreasing the pH value, which stems from the fact that the enhanced chemisorption between protonated amine groups of chitosan and sulfonic ions of acid dye is available in acidic solutions. The dye adsoption kinetics and equilibrium isotherm of the composite foams were well described with the pseudo-second order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity (q _max) for the PU/chitosan composite foams with 20 wt% chitosan content is evaluated to be ca. 30 mg/g.     

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.     

Immobilization of Cationic Titanium Dioxide (TiO<Subscript>2</Subscript><Superscript>+</Superscript>) on Electrospun Nanofibrous Mat: Synthesis,Characterization, and Potential Environmental Application

We report a facile approach to fabrication and characterization of cationic titanium dioxide (TiO₂⁺) on poly (vinyl alcohol)/poly (acrylic acid) (PVA/PAA) composite electro-spun nanofibrous mat. The aim of this study is to develop a “functional electrospun nanofibrous mat” as a sustainable approach to superior photocatalytic degradation of organic colorants. For that, the PVA/PAA nanofibrous mat was prepared by electrospinning of PVA and PAA solution according to an aspect ratio of 1:1 and later water stability was induced by the thermal cross linking at an elevated temperature of 145 °C for 30 minute. By means of electrostatic layer-by-layer (LbL) assembly, cationic titanium dioxide (TiO₂⁺, ~19 nm) was immobilized on the surface of the water stable nanofibrous mat. As functionalized composited nanofibrous mat was characterized by using scanning electron microscope (SEM), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) analysis and thermogravimetric analysis (TGA). Superior competency of the functionalized nanofibrous mat towards photocatalytic degradation of organic dye (methyl blue) in aqueous solution was observed by using UV-visible spectrophotometer with quantitative measuring method. The result indicates a complete degradation of methyl blue within 40 mins and superior reusability upto 5 cycles application. The study signifies the prospect of using electrospun nanofibers to manipulate the catalytic activity, which could be a foundation for further rational design of various composite nanofibrous materials.     

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.     

Structure and filtration performance of fibrous composite membranes containing environmentally friendly materials for water purification

A fibrous composite membrane consisting of a chitosan (CS) barrier layer and a poly(hydroxybutyrate-cohydroxyvalerate) (PHBV) fibrous substrate was manufactured as a filter for water purification. The PHBV fibrous supporting layer was fabricated via electrospinning technique, and then the CS solution cast on the PHBV fibers to form the top barrier layer. The structural morphology, mechanical property and adsorption capability of the PHBV/CS membranes were thoroughly investigated. Three heavy metal ions were used to evaluate the equilibrium absorption capacities of the chosen membranes. The equilibrium absorption capacities for Cu(II), Pb(II) and Cd(II) were 64.08 mg/g, 90.32 mg/g and 148.96 mg/ g, respectively. Meanwhile, the rejection ratio of PHBV/CS composite membrane for two disperse dyes could reach to 99 %. The results indicated that PHBV fibrous substrate could not only enhance the mechanical strength of the top barrier layer, but also improve the water permeation of the membrane. This study extended the application of an environmentally friendly material in the water purification without causing much trouble about scrap film.     

Facile fabrication of PVAc-g-PVDF coating on surface modified cotton fabric for applications in oil/water separation and heavy metal ions removal

Selective separation is an effective method for the removal of heavy metal ions and waste oil from wastewater. Polyvinylidene fluoride (PVDF) was functionalized with polyvinyl acetate (PVAc) by in-situ polymerization, and novel PVAc-g-PVDF coating on surface modified cotton fabric were prepared. The contact angle (CA), pure water flux (PWF) and self-cleaning ability of coated cotton fabric were investigated in detail. In addition, the separation performance of coated cotton fabric was reflected by the removal of heavy metal ions in simulated wastewater. The results revealed that the PVAc-g-PVDF-coated cotton fabric was free of waste oil adhesion and was self-cleaning from waste oil in aqueous environment. Meanwhile, this coated cotton fabric can effectively separate oil/water mixtures with a high flux and high oil rejection, and was easily recycled for long-term use. More importantly, the heavy metal ions rejection ratio and adsorption capacity of cotton fabric were also improved with the addition of PVAc-g-PVDF coating. PVAc-g-PVDF-coated cotton fabric exhibited excellent rejection stability and reuse performances after several times fouling and washing tests. It can be expected that the present work will provide insight into a scaled-up fabrication process of PVAc-g-PVDF coating for purifying wastewater.     

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.     

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.     

Coloration and Decoloration of Textiles Using a TiO<Subscript>2</Subscript> Composite Pigment

A colorable pigment was prepared by dye adsorption onto titanium dioxide and subsequent silane coating. The effects of pH value, dye concentration, and adsorption times on dye adsorption were discussed. Large adsorption capacity of an anionic dye was obtained at pH value of 2 and the adsorption process was well described by the Langmuir isotherm model. Good dyeability and color fastness of pigment dyed fabric were achieved in the normal life cycle under sunlight. The decoloration of pigment was realized through photocatalytic degradation of dye molecules by titanium dioxide under ultraviolet irradiation when reusing the pigment dyed textiles after disposal. The new absorption peaks in the FTIR spectrum at 2924.95 cm^-1, 1714.91 cm^-1, 1461.17 cm^-1, and 1289 cm^-1 verified silane modification. Silane modification improved fixation of dyes onto the pigment and immobilization of pigments onto substrates. The close attachment of silane coating layer to titanium dioxide was conducive to photodegradation of dye molecules in the pigment.     

Load of Ag<Subscript>3</Subscript>PO<Subscript>4</Subscript> Particles on Sulfonated Polyphenylene Sulfide Superfine Fibre with High Visible-light Photocatalytic Activity

Ag₃PO₄ was loaded on sulfonated polyphenylene sulfide (SPPS) superfine fibre by a facile precipitation method. Both the structure and properties of the as-synthesized Ag₃PO₄/SPPS composites were characterized via XRD, SEM, EDS, XPS, FTIR, and UV-vis. The photocatalytic performance of Ag₃PO₄/SPPS composites was investigated via degradation of Methylene blue(MB) solution under visible light irradiation. The degradation results revealed that the photocatalytic activity of Ag₃PO₄/SPPS composites was greatly enhanced by the incorporation of Ag₃PO₄ with SPPS superfine fibre. For concentrations of AgNO₃ and Na₂HPO₄ solutions of 0.3 M and 0.06 M in the preparation process, the Ag₃PO₄/SPPS composite showed higher photocatalytic activity under visible light irradiation.