Homogeneous self-cleaning coatings on cellulose materials derived from TIP/TiO2 P25

The aim of this research was to study TiO₂ nanocoatings formation and to investigate their self-cleaning effects when applied on cellulose materials. Two different approaches for achieving nanocoatings were used. First, coatings were generated in situ through an acid and alkaline catalyzed sol-gel process with or without added water. Another type of coatings was prepared starting from commercial TiO₂ P25 powder. In order to acquire homogeneous coatings from TiO₂ P25 nanoparticles with uniform nanoparticles size distribution, pH of aqueous TiO₂ P25 dispersions was varied. The dispersion preparation conditions were studied by dynamic light scattering (DLS) and zeta potential (ζ-potential) analysis. The resulting TiO₂ nanocoatings were analyzed in terms of their surface morphology using scanning electron microscopy (SEM). Nanocoatings obtained from pure aqueous dispersions of TiO₂ P25 nanoparticles were inhomogeneous with huge agglomerates; however by changing the pH of dispersion and consequently changing the surface charge of TiO₂ P25 nanoparticles as well, more homogeneous nanocoatings with uniform TiO₂ nanoparticles distribution were prepared. Significant differences between solgel derived coatings were observed. Sol-gel process without added water yielded more homogeneous coatings than sol-gel process with addition of water. Completely different surface morphologies were obtained using alkaline or acid catalyst. Acid catalyzed sol-gel process yielded nanocoatings with long, extended, thin structures; contrary, under alkaline conditions particles grow in size with decrease in number. Fourier transform infrared (FTIR) spectroscopy was used to study the coatings’ microstructure. Furthermore the formation of mono-disperse nanoparticles on the fiber surface resulted in enhanced photocatalytic activity. Degradation of colored stain applied on TiO₂-treated samples was investigated by colorimetric measurements. Photocatalytic activity of nanocoatings prepared via acid catalyzed sol-gel process without water addition was comparable to that of nanocoatings derived from aqueous dispersions of commercial TiO₂ P25 nanoparticles.     

Surface modification of cellulose fibers by layer-by-layer self-assembly of lignosulfonates and TiO2 nanoparticles: Effect on photocatalytic abilities and paper properties

Depositing of TiO₂ nanoparticles on cellulose fiber surface has potential technological applications in the field of photocatalysis. With this motivation, multilayers composed of lignosulfonates (LS) and TiO₂ nanoparticles were constructed on cellulose fiber surface via layer-by-layer (LBL) self-assembly technique. X-ray photoelectron spectroscopy (XPS), zeta potential measurement and atomic force microscopy (AFM) were used to characterize the LS/TiO₂ multilayers on cellulose fiber surface. Moreover, the photocatalytic activities of modified cellulose fibers (decomposition of methyl orange and antibacterial test) were investigated. The decomposition efficiency of methyl orange for a (LS/TiO₂)₅ multilayer modified cellulose fibers was 74.7 % under 5 h UV irradiation. Photocatalytic decomposition efficiency of methyl orange by LS/TiO₂ multilayer modified cellulose fibers under the same UV irradiation time increased linearly with the number of bilayers. Antibacterial tests results revealed that the cellulose fibers modified with LS/TiO₂ multilayers exhibited excellent antibacterial activity against E.coil. The degree of E.coil growth inhibition for a (LS/TiO₂)₅ multilayer modified cellulose fiber reached as high as 93 %. In addition, the effect of LS/TiO₂ multilayers on properties of handsheets made from modified cellulose fibers was also considered. The air permeability of the handsheet prepared from fibers modified with TiO₂/LS multilayers had 6.1–24.3 % higher compared with that of handsheet prepared from original fibers. The wetting properties measurement results demonstrated that the water contact angle of handsheet oscillated with the increasing number of layers depended on building block which was in the outermost layer.     

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.     

Preparation and characterization of bacterial cellulose/hydroxypropyl chitosan blend as-spun fibers

In the work, N-methylmorpholine-N-oxide monohydrate (NMMO·H₂O) was used as a solvent to solve bacterial cellulose (BC) and hydroxypropyl chitosan (HPCS) together, and regenerated bacterial cellulose (RBC)/HPCS blend as-spun fibers were prepared by blending BC with HPCS via wet-spinning in the Lyocell process. Structure and properties of the blend as-spun fibers were characterized by different techniques, together with the antibacterial activity of the blend as-spun fibers against Staphylococcus aureus. Results revealed that HPCS was mixed with BC very well. The blend as-spun fibers showed a rough and folded surface morphology and an interior pore structure on the cross-section. Compared with pure RBC as-spun fibers, the blend as-spun fibers had lower degree of crystallinity and thermal stability. Although extension at break of the blend as-spun fibers was lower than the pure RBC as-spun fibers, their tensile strength and modulus had been enhanced obviously. The blend as-spun fibers were also found to exhibit excellent antibacterial activities against S. aureus.     

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.     

Enhanced surface property of HMPBO fibers by using γ-aminopropyl triethoxy silane

The silane coupling agent of γ-aminopropyl triethoxy silane combined with ultrasonic vibration was employed to modify the surface of high modulus poly (p-phenylene-2, 6-benzobisoxazole) (HMPBO) fibers. The results showed that polar hydroxyl groups were successfully introduced on the HMPBO surface. The contact angles on HMPBO fibers both for water (θ _water ) and for glycol (θ _glycol ) gradually were decreased, and the surface roughness of HMPBO fibers was also increased. Meanwhile, the single fiber pull-out strength of HMPBO was increased accordingly.     

Self-cleaning and handle properties of TiO2-modified textiles

Self-cleaning surfaces based on photocatalysis are an extremely promising nano-technological field of extensive research and development. Recently comprehensive research work has been performed to evaluate the optical, photocatalytic and antimicrobial properties of TiO₂ nano-particles and composites thereof. The aim of this study was to obtain self-cleaning properties for regenerate cellulose surfaces by nano-modification, using TiO₂ nano-coating and to define the impact of the modification on fabrics end-use properties. Two different modified fabrics with self-cleaning effect were prepared and analysed, i.e. the modification efficiency was determined. In addition, the influence of fibre modification on several textile properties was determined. However, a soft handle, good appearance and some other surface properties accompanied by appropriate mechanical properties represent the basis for a high quality fabric therefore the influence of the modification procedure on textiles handle was studied.     

The synergy effect of Graphene/SiO<Subscript>2</Subscript> hybrid materials on reinforcing and toughening epoxy resin

Based on the situ preparation of silica nanoparticles (SiO₂) on the surface of Graphene nanoplatelets (GNPs) in the previous work, these unique three dimensional (3D) materials were introduced into epoxy resin to study the reinforcing and toughening synergy effect on the composites. Firstly, the tensile tests showed that Graphene/SiO₂ hybrid materials attached with different size of SiO₂ particles exhibited different reinforcing and toughening effect on the composites. With the increasing of the diameter of SiO₂ particles, the toughness and strength properties of the composites firstly improved and then decreased, and when the average diameter was 0.14 μm, the elongation reached the max.. Meanwhile, the fractured surfaces presented on SEM images were consistent with the results of the tensile tests, which further explained the hybrid materials increased the interfacial adhesion between the fillers and matrix, leading to significant improvement in mechanical properties. Moreover, the DSC curves demonstrated that Graphene/SiO₂ hybrid materials accelerated the curing process of epoxy resin due to the cross-link structure between fillers and matrix. Lastly, the crack propagation modes were built to clarify the synergy effect mechanism of reinforcing and toughening on nanoparticles/epoxy resin composites.     

Novel fibers prepared from cellulose in NaOH/thiourea/urea aqueous solution

The regenerated cellulose fibers were prepared by wet-spinning from NaOH/thiourea/urea aqueous solvent system for the first time. The effects of coagulation and stretch conditions on the structure, morphology, and mechanical properties of the prepared fibers were investigated by wide-angle X-ray diffraction (WAXD), scanning electron microscope (SEM), and tensile tester, respectively. When the cellulose spinning dope was coagulated in 10% H₂SO₄/12.5% Na₂SO₄ aqueous solution at 15 °C, the prepared fibers had a typical crystalline structure of cellulose II and circular cross-sectional shapes with smooth surface and slightly high tensile properties to viscose fibers.     

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.     

Surface modification of HMPBO fibers by silane coupling agent of KH-560 treatment assisted by ultrasonic vibration

The surface modification of poly (p-phenylene-2,6-benzobisoxazole) (HMPBO) fibers by silane coupling agent of ??-aminopropyl triethoxy silane (KH-560) treatment assisted by ultrasonic vibration was investigated. The chemical composition and surface morphologies of the HMPBO fibers were analyzed and characterized by XPS, FTIR, TGA and SEM. The tensile properties of the HMPBO fibers were also studied. The results indicated that polar hydroxyl groups were successfully introduced on the HMPBO surface after the proposed treatment processes, and the surface roughness of HMPBO fibers was increased. Moreover, the treated HMPBO maintained relatively excellent tensile strength, and the single fiber pull-out strength of HMPBO was improved from 0.94 MPa to 1.07 MPa.     

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 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.     

Modification and Characterization of Nano-TiO<Subscript>2</Subscript> for Efficient Fixation on Cotton Fibers

In this paper, a silane coupling agent, 3-aminopropyltriethoxysilane, was reacted with nano-TiO₂ to introduce amino group onto it which was then reacted with trichlorotriazine to obtain a dichlorotriazine functionalized nano-TiO₂ for the firm fixation of it on cotton fibers. The reaction process was monitored by the titration of primary and secondary amino groups, and the reaction conditions were optimized with orthogonal method accordingly. The dichlorotriazine functionalized nano-TiO₂ was reacted with cotton fabric by the nucleophile substitution reaction to afford nano-TiO₂ functionalized cotton fabric, the structure and surface morphology of the nano-TiO₂ finished cotton fibers were studied by FT-TR and SEM. In addition, the fixation duration of the nano-TiO₂ modified cotton was studied according to AATCC test method 61–2010. The results show that the washing fastness of the nano-TiO₂ is excellent.     

Preparation and properties of fibers produced from a cellulose/complex PA solvent system precipitating in diverse coagulants

Ethanol, as the first coagulation bath, and several common organic solvents, as well as aqueous solutions of NH₄Cl, NaHCO₃ and NaOH were explored and demonstrated to be adopted as the second coagulation bath for cellulose/phosphoric acid/tetraphosphoric acid (cellulose/complex PA solvent) solution to produce novel cellulose fibers by two-stage dry-wet spinning in a laboratory scale, and effect of coagulants, cellulose concentration, solvent concentration (P₂O₅ concentration) and coagulation temperature on crystal structure and properties of corresponding fibers were investigated. Surface morphology of regenerated fibers as-spun from different coagulants was observed by scanning electronic microscope (SEM), indicating that methanol and 8 wt% NaOH aqueous solution all rendered cellulose fibers relatively dense and smooth surface. X-ray diffraction (XRD) analysis showed that cellulose fiber precipitated from 8 wt% NaOH aqueous solution had pronounced characteristic peak of cellulose II than those of fibers precipitated from other coagulants, and highest crystallinity and orientation. Meanwhile, those two coagulants referred above also gave cellulose fibers relatively higher tensile strength under the same prerequisite. TGA curves exhibited that fibers were thermally stable produced from two salt aqueous solutions (8 wt% NH₄Cl and NaHCO₃) since they had the relatively higher onset decomposition temperatures. By evaluating the effect of cellulose concentration, P₂O₅ concentration and coagulation temperature on the structure and properties of asprepared fibers, it was preferable to produce cellulose fiber from a solution at 20 wt% cellulose concentration, 73 % P₂O₅ concentration, and coagulating in methanol at coagulation temperature of 60 °C at the second-stage.     

Electrospun titanium dioxide nanofibers: Fabrication,properties and its application in photo-oxidative degradation of methyl orange (MO)

In this study, we synthesed two kind of TiO₂ nanomaterial (nanoparticles and nanofiber) for photocatalitic degradation of methyl orange (MO) as pollutant. TiO₂ nanoparticles were synthesized by sol-gel technique using titanium (IV) isopropoxide as precursor. Polyvinyl acetate (PVAc)/TiO₂ hybrid nanofibers were fabricated by combining sol-gel process with electrospinning technology, which consisted of PVAc as organic segment and TiO₂ as inorganic part. Crystalline phase of TiO₂ nanomaterials was investigated by X-ray diffraction (XRD). The XRD results show that the TiO₂ nanomaterials crystallize in anatase with some rutile phase and these consist of titanium dioxide nano-crystals. The surface structures of TiO₂ nanomaterials were examined using scanning electron microscopy (SEM). SEM scanning revealed that the nanoparticle and nanofibrous structure was formed. Fourier transform infrared spectroscopy (FTIR) was employed to analyze the chemical structures of the PVAc/TiO₂ hybrid nanofibers. The FTIR analysis indicated the newly formed associated hydrogen bond because of the hybrid effect between PVAc and TiO₂ sol. Finally, The photooxidative decomposition of methylene blue by using the titania nanomaterials was examined and compared.     

Mechanical properties and crystallization behavior of polypropylene non-woven fabrics reinforced with POSS and SiO2 nanoparticles

PP/POSS and PP/SiO₂ composite non-woven fabrics filled with polyhedral oligomeric silsesquioxanes (POSS) and SiO₂ respectively using a convenient blending method were prepared through melt-blown process with corona charging. The morphology of the composite fibers and the distribution of POSS and SiO₂ nanoparticles in PP matrix were investigated by field-emission scanning electron microscope (FSEM) and transmission electron microscope (TEM), respectively. POSS and SiO₂ can act as nucleating agent and accelerate the crystallization process during nonisothermal cooling. The shear storage modulus G??, loss modulus G??, and complex viscosity ??* of non-woven fabric reduce when 1 wt % POSS was added and increase for PP5/POSS composite non-woven fabric compared with pure PP non-woven fabrics. However, all G??, G?? and ??* of PP/SiO₂ non-woven fabric decrease with increasing SiO₂ content owing to plasticization by SiO₂. Both stress and elongation at break of the PP/POSS melt-blown non-woven fabrics are improved compared with PP non-woven fabrics, however decrease when SiO₂ was added, as compared to the neat PP non-woven fabric. The onset temperature of decomposition for both the PP/POSS and PP/SiO₂ composite non-woven fabrics is higher (5?C10 °C) than pure PP and char content is increased with increasing POSS and SiO₂.     

Study on damping and mechanical properties of nano-titanium dioxide/acrylonitrile butadiene-rubber hollow fiber

TiO₂/NBR-PVC hollow fibers were spinned by NBR casting solution blended PVC with nano-titanium dioxide (TiO₂). The effect of NBR-PVC hollow fiber damping and mechanical properties aroused by loading TiO₂ were studied. Results showed that the hollow fibers loaded TiO₂ increased in tensile strength, storage modulus, stiffness and glass transition temperature, while decreased in tanδpeak and breaking tensile elongation. The damping of the TiO₂/NRR-PVC hollow fiber were not only linked to the dosage of TiO₂, but also related to the degree of dispersion in matrix.     

Nano-SiO2 filled rice husk/polypropylene composites: Physico-mechanical properties

In this research, reinforcing effect of hybrid filler including rice husk (RH), beech bark (BB) and nano-SiO₂, in polypropylene has been investigated. In the sample preparation, four levels of filler loading were used for waste lignocellulosic materials (55-58 wt.%) and nano-SiO₂ (0-4 wt.%). In order to increase the interphase adhesion, polypropylene grafted with maleic anhydride was added as a coupling agent to all the composites studied. The physical properties, viz. the thickness swelling and water absorption, and mechanical properties, namely, the tensile, flexural and notched Izod impact strengths, of the composites were determined. Generally, high amount of filler content in composites can lead to the reduction of interfacial adhesion between matrix polymer and filler, and it limits their applications. The results showed that while flexural properties and elongation at break were moderately improved by the increase in the amount of filler in the matrix, tensile and Izod impact strengths decreased dramatically. However, the composites had acceptable mechanical strength levels. The mechanical properties of composites filled with RH are generally greater than BB composites. The thickness swelling and water absorption of the composites increased with the increase in the filler loading, but to a negligible extent as compared with the wood-based composites and the solid woods. Nano-SiO₂ addition showed little positive effect on the mechanical properties. It can be concluded from this study that the used waste lignocellulosic materials are attractive reinforcements from the standpoint of their physico-mechanical properties.     

Development of nanofibrous membranes with far-infrared radiation and their antimicrobial properties

This study investigated the incorporation of nanoscale germanium (Ge) and silicon dioxide (SiO₂) particles into poly(vinyl alcohol) (PVA) nanofibers with the aim of developing nanostructures with far-infrared radiation effects and antimicrobial properties for biomedical applications. Composite fibers containing Ge and SiO₂ were fabricated at various concentrations of Ge and/or SiO₂ using electrospinning and layered on polypropylene nonwoven. The morphological properties of the nanocomposite fibers were characterized using a field-emission scanning electron microscope and a transmission electron microscope. The far-infrared emissivity and emissive power of the nanocomposite fibers were examined in the wavelength range of 5-20 μm at 37 °C. The antibacterial properties were quantitatively assessed by measuring the bacterial reductions of Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli. Multi-component composite fibers electrospun from 11 wt% PVA solutions containing 0.5 wt% Ge and 1 wt% SiO₂ nanoparticles exhibited a far-infrared emissivity of 0.891 and an emissive power of 3.44·102 W m^?2 with a web area density of 5.55 g m^?2. The same system exhibited a 99.9 % bacterial reduction against both Staphylococcus aureus and Escherichia coli, and showed a 34.8 % reduction of Klebsiella pneumoniae. These results demonstrate that PVA nanofibrous membranes containing Ge and SiO₂ have potential in medical and healthcare applications such as wound healing dressings, skin care masks, and medical textile products.