Preparation of monodisperse poly(vinyl alcohol) (PVA) nanoparticles by dispersion polymerization and heterogeneous surface saponification

Monodisperse poly(vinyl alcohol) (PVA)/poly(vinyl acetate) (PVAc) nanoparticles with a skin-core structure were prepared through heterogeneous surface saponification of PVAc nanoparticles. For the preparation of PVAc nanoparticles with a uniform particle size distribution, vinyl acetate (VAc) was dispersion polymerized in a mixed solvent of ethanol and water using PVA with a low degree of saponification as a stabilizer. Increase of the amount of ethanol in media, the resulting PVAc nanoparticle size increases due to increasing solubility of VAc and oligomer PVAc. To preserve the sphericity and size uniformity of PVAc nanoparticles, we restricted saponification to the surface of the nanoparticles by using a small amount of aqueous sodium hydroxide solution. To determine the proper concentration of alkali solution for heterogeneous saponification, monodisperse PVAc nanoparticles were saponified with different concentrations of alkali solution at 25 °C for 0.5–3.0 h. The PVA/PVAc nanoparticles obtained by the heterogeneous saponification with 4 % (relative to the amount of the VAc) alkali solution for 2.0 h were uniformly shaped and monodispersed with diameter ranging from 428 to 615 nm. Transmission electron microscopy (TEM) confirmed the spherical nature and regular skin-core structure of the PVA/PVAc nanoparticles.     

Preparation of poly(vinyl acetate)/clay and poly(vinyl acetate)/poly(vinyl alcohol)/clay microspheres

Poly(vinyl acetate) (PVAc)/poly(vinyl alcohol)(PVA)/montmorillonite (MMT) clay nanocomposite microspheres with a core/shell structure have been developed via a suspension polymerization approach. In order to prepare the PVAc/MMT and PVAc/PVA/MMT nanocomposite microspheres, which are promising precursor of PVA/MMT nanocomposite microspheres, suspension polymerization of vinyl acetate with organophilic MMT and heterogeneous saponification were conducted. A quaternary ammonium salt, cetyltrimethylammonium bromide, was mixed with the MMT in the monomer phase prior to the suspension polymerization. The rate of conversion decreased with an increase in MMT concentration. The incorporation of MMT into the PVAc was verified by FT-IR spectroscopy. Organic vinyl acetate monomers were intercalated into the interlayer regions of organophilic clay hosts and followed by suspension polymerization. Partially saponified PVA/MMT nanocomposite microspheres with a core/shell structure were successfully prepared by heterogeneous saponification.     

Low temperature suspension polymerization of methyl methacrylate for the preparation of high molecular weight poly(methyl methacrylate)/silver nanocomposite microspheres

In order to prepare high molecular weight poly(methyl methacrylate) (PMMA)/silver nanocomposite microspheres, methyl methacrylate was suspension-polymerized in the presence of silver nanoparticles at low temperature with 2,2′-azobis(2,4-dimethylvaleronitrile) as an initiator. The rate of conversion was increased by increasing the initiator concentration. When silver nanoparticles were added, the rate of polymerization decreased slightly. High monomer conversion (about 85 %) was obtained in spite of low polymerization temperature of 30°C. Under controlled conditions, PMMA/silver microspheres with various number-average degrees of polymerization (6,000–37,000) were prepared. Morphology studies revealed that except for normal suspension microspheres with a smooth surface, a golf ball-like appearance of the microspheres was observed, due to the migration and aggregation of the hydrophilic silver nanoparticles at the sublayer beneath the microsphere’s surface.     

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.     

Studies on a novel polyacrylonitrile copolymer/cellulose acetate blending water absorbency fiber

Polyacrylonitrile copolymer (CPAN) was obtained by water-deposit polymerization, using acrylonitrile (AN), vinyl acetate (VAc), potential crosslinking moiety (hydropropyl acrylate, HQ) as monomer, NaClO₃ as initiator. CPAN was blended with cellulose acetate (CA) to prepare CPAN/CA blending fiber via wet spinning. The fiber was post-crosslinked and hydrolyzed to get water absorbency fiber. The structures and properties of the fibers were studied and the results showed that potential crosslinking moiety was necessary in making CPAN/CA blending water absorbency fiber. The saponification reaction was accelerated after blended with CA and the interfacial microvoids enhanced the water absorbency ability.     

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.     

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.     

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.     

Multifunctional melt-mixed Ag/TiO2 nanocomposite PP fabrics: Water vapour permeability, UV resistance, UV protection and wear properties

This research deals with the investigating the effect of nanoparticles on the various properties of nanocomposite fabrics produced from melt spinning of various blend ratios of prepared masterbatch containing Ag/TiO₂ nanoparticles. The results revealed that the wear properties of modified fabrics improved as compared to pure fabrics with a trend justified considering modulus or crystallinity of fabrics with opposite effects. About 40 % UV protection enhancement has been obtained applying this kind of nanoparticles in the close relationship with the crimp contraction of textured yarns. A considerable improvement in the garment comfort has been recorded for nanocomposite sample containing 1 wt% nanoparticles. The lower permeability at low environment temperature and a higher at higher one, as compared to the pure sample, were obtained using this sample. It is highly interesting that these desirable changes in permeability can be achieved in the range of common environment temperatures (15–35 °C) being adapted to the human body requirements. The changing point is about 25 °C exactly meeting the body requirements by changing environment temperatures. A UV-induced solid state nanocomposite interaction increasing wear properties of UV-irradiated nanocomposite fabrics has been discovered.     

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.     

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.     

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.     

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.     

Processing and Characterisation of Hybrid Aramid Fabrics Reinforced with Cross-linked Electrospun PVB Composite Nanofibres

The aim of this study was to fabricate a new kind of hybrid fabric composites with the cross-linked electrospun poly(vinyl butyral) (PVB) composite nanofibres. The experiments were performed with the 10 wt.% PVB/ethanol solution for electrospinning where the modified silica nanoparticles (mSiO₂), the oxidised single-walled carbon nanotubes (o-SWCNT) and the o-SWCNT/mSiO₂ hybrid nanoparticles were added to the solution. The electrospun fibres were crosslinked with glutaraldehyde (GA) afterwards in order to reinforce the composite structure by bonding to the p-aramid fabrics. The chemical and thermo-mechanical properties of the hybrid fabric composites were evaluated. The greatest improvement in thermo-mechanical properties was achieved by the sample which contained the cross-linked PVB fibres with the o-SWCNT/mSiO₂ hybrid nanoparticles.     

Preparation of poly(vinyl alcohol)/silver-zeolite composite hydrogels by UV-irradiation

Poly(vinyl alcohol) (PVA)/Ag-zeolite nanocomposite hydrogels were prepared by UV irradiation using PVA solution mixed with Ag-zeolite nanoparticles. Physical properties and changes in morphology of the PVA/Ag-zeolite hydrogels were investigated. The PVA/Ag-zeolite hydrogels were prepared at a PVA concentration of 9 wt% with a UV irradiation distance of 15 cm, where gel fraction and swelling ratio were optimized. Hardness of the PVA/Ag-zeolite hydrogels decreased with increasing amounts of Ag-zeolite, reaching that of soft elastomer when the amount of Ag-zeolite was 5 % by weight. The PVA/Ag-zeolite hydrogels showed strong antimicrobial activities against Staphylococcus aureus and Klebsiella pneumoniae, inducing a reduction of bacteria of over 99.9 % at a Ag-zeolite content of 3 wt%.     

Preparation and Characterization of Chitosan Poly(acrylic acid) Magnetic Microspheres

Spherical microparticles, capable of responding to magnetic fields, were prepared by encapsulating dextran-coated Fe₃O₄ nanoparticles into chitosan poly(acrylic acid) (PAA) microspheres template. The obtained magnetic microspheres were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and thermogravimetry (TG). The results showed that the microspheres were formed and demonstrated magnetic behavior in an applied magnetic field. In addition, magnetite particles were well encapsulated and the composite particles have high magnetite content, which was more than 40%.     

Dispersion polymerization of styrene using poly(4-vinylpyridine) macro-RAFT agent under UV radiation

The dispersion polymerization of styrene using a poly(4-vinylpyridine) (P4VP) macromolecular RAFT (macro-RAFT) agent as both a macro-initiator and a colloidal stabilizer under UV radiation was investigated for the first time. The P4VP macro-RAFT agent (M _n,GPC=49,000 g/mol, PDI=1.14) was prepared by the RAFT polymerization of 4-vinylpyridine using 2-cyanoprop-2-yl dithiobenzoate as a chain transfer agent. The resulting polystyrene (PSt) particles had hairy P4VP chains, which could successfully immobilize very small Au nanoparticles on the surface of the PSt particles. It was found that hairy polymeric particles could be produced by photo-initiated dispersion polymerizations of vinyl monomers using macro-RAFT agents that are susceptible to UV radiation as both macro-initiators and colloidal stabilizers.     

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.     

Multifunctional polyester fabric using a multicomponent treatment

In this study, multifunctional polyester fabrics with the features of self-cleaning, water and stain repellency, and thermal stability were prepared utilizing a multicomponent system. To this end, both unmodified and alkaline-hydrolyzed modified fabrics were treated with nano TiO₂/citric or maleic acid/sodium hypophosphite/polysiloxane and triethanolamine via a pad-dry-cure method. Surface morphology and color variation of the samples were studied utilizing field emission scanning electron microscopy (FESEM) and CIE-Lab system, respectively. Also, energy-dispersive X-ray (EDX) analysis indicated the content of Ti, P and Si on the surface of fabrics. Thermal stability of the specimen was scrutinized through thermal gravimetric analysis (TGA) and char yield. Both hydrolysis treatment and silicone softener increased the uptake of the nanoparticles. Also, in a comparison between the utilized carboxylic acids, citric acid demonstrated superior features. Generally, the treated fabrics showed desirable self-cleaning and stain repellency with some enhanced thermal stability.     

Hard Surface-adhesive Properties of TiO<Subscript>2</Subscript> Nanoparticles-encapsulated Microparticles Prepared by Spray Drying and Surface Coating Method

The aim of this study is to compare hard surface-adhesive properties of TiO₂ nanoparticles (TNPs)-encapsulated microparticles prepared by spray drying and surface coating method. Thus, TNPs were encapsulated with chitosan by spray drying and poly(L-lysine) by surface coating method, which were selected as positively charged materials. And then, the TNPs-encapsulated microparticles were investigated by particle surface properties and adhesion properties on hydroxyapatite (HAP) surface as model for hard surface-adhesion. The characteristics of TNPs-encapsulated Chitosan microcapsules (CM) and TiO₂ nanoparticles coated with cationic poly(L-lysine) polymer (TNPs-PLL) were determined with scanning electron microscope (SEM) image and zeta-potentials. The hard surface-adhesive properties on HAP surface were confirmed with SEM and whitening test. The zeta-potentials of TNPs and HAP were negative, -13 mV and -18 mV respectively, while TNPsencapsulated CM, and TNPs-PLL of positively charged polymers were positive, 13 mV and 57 mV respectively. Whitening test was carried out on model surface when shaking the samples. TNPs-PLL were adhered to HAP surface very much more than those of TNPs-encapsulated CM. Also, the change value of whiteness of the HAP surface treated with TNPs-PLL is large evidently, compared with TNPs-encapsulated CM.