Effect of polymer concentration,needle diameter and annealing temperature on TiO2-PVP composite nanofibers synthesized by electrospinning technique

In this study, TiO₂-PVP nanofibers were successfully synthesized on an aluminium collector by using cost-effective electrospinning technique. The nanofibers were prepared at different polymer concentrations, needle diameters and annealing temperatures and properties were studied by various characterizations. The structural properties were studied by X-ray diffraction (XRD) and Raman spectroscopy techniques. Surface morphology and elemental analysis of the samples were investigated by scanning electron microscopy (SEM) attached with energy dispersive spectroscopy (EDS). The optical properties were carried out by UV–Visible absorption spectroscopy (UV–Vis). By varying the polymer concentration and needle diameter, the effect of viscosity and surface tension on the formation of TiO₂-PVP nanofibers was clearly observed by SEM micro images. EDS spectrum shows effective composition of pure TiO₂ nanofibers. XRD peaks observed at temperatures 500 °C, 700 °C and 900 °C confirmed the anatase, mixed and rutile phases of TiO₂ nanofibers respectively. Raman studies also confirmed these phases of TiO₂ nanofibers. The optical band-gap values calculated using Kubelka-Munk function lies in the range of 3.02–3.22 eV.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

Flexible supercapacitor electrodes based on TiO2/rGO/TiO2 sandwich type hybrids

The flexible nanostructured supercapacitors have gained vast majority of interests during recent years. In this article, flexible supercapacitor electrode based on TiO₂/rGO/TiO₂ sandwich is fabricated through a facile low cost solution process method based on pre-synthesized vapor assisted GO paper and titania sol. The XRD and FTIR spectroscopy analyses confirm the in-situ reduction of GO paper when faced with the titania sol. The Raman spectroscopy shows the coexistence of titania anatase phase beside rGO layers. Moreover, FESEM analysis demonstrates that the sandwich electrodes are composed of titania and rGO layers with thickness of about 660 nm and 15 µm, respectively. The optimum parameter for film deposition is 0.17 M concentration, water to Ti precursor ratio of 4, acid catalyst to Ti precursor ratio of 0.5, and solvent of 1-propanol. The supercapacitor electrode based on this optimum deposited sandwich illustrates capacitance of 83.7 F/g at scan rate of 5 mV/s and appreciable charge-discharge behavior. These hybrid pseudo- and electric double layer capacitance behavior in this supercapacitor not only can dramatically improve the performance of the future energy storage devices but also can be applicable in cost-effective wearable electronics.     

Preparation,characterization and the antimicrobial properties of metal ion-doped TiO2 nano-powders

TiO₂ samples doped with lithium, sodium, magnesium, iron or cobalt were prepared by high-energy ball milling for different periods of time. The crystalline phase, chemical composition, crystalline size and photo-absorption were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS) and Ultraviolet visible diffuse reflectance spectroscopy (UV - Vis - DRS), Fourier transform infrared spectroscopy (FT - IR) and scanning electron microscopy (SEM). The antimicrobial properties of the modified TiO₂ samples were evaluated with E. coli and S.aureus assays. The results of the XRD show that the TiOSO₄, Ti₃O₅, Li₂TiO₃ and NaTi₂O₄ phases appear along with Li, Na and Mg doped TiO₂. However, XPS spectra indicated that Ti exists as both Ti³⁺ and Ti⁴⁺ in Na-doped TiO₂ samples. Ti³⁺, due to its narrow band gap, is highly active in promoting visible light-induced photocatalytic activity. SEM images showed that the crystalline size of TiO₂ is reduced and has a common-round and hexagonal plate morphology after milling. The modified TiO₂ samples had the best antimicrobial activities after 3 h of milling. In particular, the antimicrobial rate of TiO₂ 5% doped with transition metals (Co, Fe) reached 100% against E. coli, but the antibacterial rate against S. aureus for Co and Fe dopants was 98.4% and 98.2%, respectively.     

Microstructure and elastic modulus of electrospun Al2O3-SiO2-B2O3 composite nanofibers with mullite-type structure prepared at elevated temperatures

In the present work, Al₂O₃-SiO₂-B₂O₃ composite nanofibers with mullite-type structure were prepared using electrospinning technique. The microstructure and elastic modulus of the composite nanofibers obtained at elevated temperatures were studied. The results showed that Al₄B₂O₉ phase formed at 900 °C and then transformed to Al₁₈B₄O₃₃ at 1100 °C. Mullite was also detected in the nanofibers prepared at 1100 °C. Amorphous SiO₂ existed in all samples even the calcination temperature reached up to 1400 °C. The continuous and uniform structure of the composite nanofibers was kept after calcining at different temperatures, while rougher surface was evident due to the growth of the grain caused by the elevated temperature. An increase of elastic modulus of the samples from 9.47 ± 1.91 GPa to 27.30 ± 2.61 GPa was observed when calcination temperatures increased from 800 °C to 1400 °C.     

Synthesis of CaTiO3 and CaTiO3/TiO2 nanoparticulate compounds through Ca2+/TiO2 colloidal sols: Structural and photocatalytic characterization

CaTiO₃ and CaTiO₃/TiO₂ nanocompounds have been synthesized through a colloidal sol-gel route using Ca²⁺/TiO₂ nanoparticulate sols. The peptization time was determined so that as higher is the Ca²⁺ concentration, shorter is the peptization time. The obtained cryogels from the respective sols were calcined at different temperatures (300–900 °C) and the structural and morphological changes were characterized mainly by X-ray diffraction and transmission electron microscopy. In all cases, the formation of the CaTiO₃ phase was observed after calcination at temperatures as low as 500 °C. Mesoporous cryogels with nanoparticles with sizes below 50 nm were obtained and their photocatalytic activity changes as a function of the calcination temperature and the applied wavelength were determined. Quantum yield values revealed that either CaTiO₃ or the CaTiO₃/TiO₂ (0.4 M ratio) compound can be chosen as the most efficient photocatalyst at higher calcination temperatures and longer wavelengths, while TiO₂ is more effective at low calcination temperatures and shorter wavelengths.     

Effects of fine reactive alumina powders on properties of alumina-magnesia castables with TiO2 additions

The design of alumina-magnesia castables was optimized based on the action mechanism of raw materials. In this study, the effects of fine reactive alumina powders on the properties of alumina-magnesia castables with TiO₂ additions were investigated. The phase composition and microstructure of castables with different contents of TiO₂ and two fine reactive alumina powders were characterized by X-ray diffraction and scanning electron microscopy. The results of these studies showed that the Na₂O/SiO₂ ratio of reactive alumina affected on the phase evolution and properties of castables. The changes in the spinel and CA₆ content and their solid solubility could account for the comprehensive effect of TiO₂ and reactive alumina on the castables. The difference in the expansion of castables with 1 wt% TiO₂ addition after calcination at 1350 °C was significant. The permanent linear changes and the apparent porosity of castables first increased and then decreased with increasing the calcination temperature. Castables containing reactive alumina with lower Na₂O/SiO₂ ratio had higher cold moduli of rupture.     

Solid-phase combustion synthesis of calcium aluminate with CaAl2O4 nanofiber structures

Calcium aluminate with CaAl₂O₄ (CA) nanofiber structures was fabricated through a facile solid-phase combustion synthesis method with raw materials of CaO₂, CaCO₃, Al, and Al₂O₃ in Ar atomosphere at a pressure of 0.1 MPa. The results indicated that the relative content of CA decreased, but that of Ca₁₂Al₁₄O₃₃ (C₁₂A₇) increased with the increase of r-value from 0 to 0.5 (r is molar substitution coefficient of CaCO₃ for CaO₂). Interestingly, CA nanofibers with tens of micrometers in length and about 200 nm in diameter were observed in the combustion products with r = 0.2, 0.3, 0.4, respectively. The more nanofibers can be found in the products, as the content of CaCO₃ in raw material ratios increased. And the yield of nanofibers in the combustion product with r = 0.4 is the highest. The typical round droplet on head of nanofiber indicated that the growth process of nanofibers was governed by vapor-liquid-solid (VLS) mechanism with base growth mode. It is proposed that both higher reaction temperature and reducing atmosphere are requirements for the growth of CA nanofiber during the process of combustion synthesis. The nanofiber cannot be generated in the samples r0, and r5, because the gaseous Ca is absent due to oxidizing atmosphere and lower reaction temperature, respectively.     

Structural,photocatalytic, biological and catalytic properties of SnO2/TiO2 nanoparticles

TiO₂ and SnO₂/TiO₂ nanoparticles with different SnO₂ contents (0–20 wt%) were synthesized via surfactant-assisted sol-gel method using a cationic surfactant (cetyltrimethylammonium bromide, CTAB). The effects of SnO₂ content on the structural, optical, and catalytic activity of TiO₂ have been studied by X-ray diffraction (XRD), Transmission electron microscope (TEM), Scanning electron microscope (SEM), Fourier transformer infrared (FTIR) and UV–vis diffuse reflection spectroscopy (DRS). The total surface acidity of the prepared samples was measured by nonaqueous titration of n-butylamine in acetonitrile and the types of Brönsted and Lewis acid sites were distinguish using FTIR spectra of chemisorbed pyridine. XRD patterns analysis indicates that the crystallite size reduced remarkably and the transformation of anatase-to-rutile phase accelerated greatly with increasing the SnO₂ content. TEM images exhibit a spherical shape with an average particle size varying in the range 10–24 nm and high-resolution TEM images (HRTEM) show lattice fringes with interplanar spacing 0.35 nm and 0.32 nm which corresponding to anatase and rutile phases, respectively. SEM images show the amount of SnO₂ on the TiO₂ surface increases with increasing the SnO₂ content and the particles of SnO₂ were aggregated on TiO₂ surface with increasing SnO₂ content to 20% wt. The catalytic activity was tested by various applications: Photodegradation of Methylene Blue (MB) and Rhodamine B (RhB) under UV–vis irradiations and synthesis of xanthene (14-phenyl-14H-dibenzo [a,j] xanthene). Antibacterial and antioxidant activities were also studied. The antibacterial property test was carried out via agar disc diffusion method, and the results indicated that the prepared catalysts showed moderate antibacterial activity.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

Durable superhydrophobic Zn/ZnO/TiO2 surfaces on Ti6Al4V substrate with self-cleaning property and switchable wettability

Durable superhydrophobic (SHP) Zn/ZnO/TiO₂ surfaces with dendritic structures on Ti₆Al₄V substrate were obtained by chemical etching, electrodeposition and following annealing process. The resultant coatings electrodeposited at ?1.5 V for 10 min and annealed at 190 °C for 60 min showed fine superhydrophobicity with a water contact angle of 160° and a rolling angle less than 1°, showing excellent rolling-off and self-cleaning properties. The morphology, chemical components and growth mechanism of samples were investigated by scanning electron microscopy (SEM), X-ray diffraction pattern (XRD), Energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Surface tribological properties were characterized by a universal mechanical tester (UMT). The as-prepared Zn/ZnO/TiO₂ surface still kept excellent SHP stability after exposure to the air, buried in soil and cold storage at 5 °C in the fridge for one year, as well as excellent repellence to some daily-used liquids such as coke, coffee, red wine, milk and tea. The surface can be reversibly switched between superhydrophobicity and superhydrophilicity by alternating UV illumination and dark storage or heating, which offer possibilities to widen future applications.     

Functionalizing slag wool fibers with photocatalytic activity by anatase TiO2 and CTAB modification

Anatase TiO₂ coatings prepared by solvothermal process in a neutral ethanol solution of isopropyl titanate at 160 °C have been grown on slag wool fibers (SWF) which were modified by hexadecyltrimethylammonium bromide (CTAB) in advance. X-ray diffraction patterns confirmed the coatings are of a nanocrystalline anatase structure, and scanning electron microscopy observations and energy-dispersive X-ray spectrum revealed a continuous coverage of TiO₂ formed on the fiber surfaces. The photocatalytic activity of the samples was tested by the photocatalytic degradation of methylene blue (MB) solution. The results show that CTAB modified slag wool fibers (CMSWF) are not a suitable adsorbent for MB due to their weaker negative surface charges. Anatase TiO₂ coated CMSWF display higher photocatalyst activity than anatase TiO₂ coated SWF without CTAB modification, and Anatase TiO₂ coated CMSWF are relatively stable under UV-light irradiation.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Synthesis and electrical properties of lead-free piezoelectric Bi0.5Na0.5TiO3 thin films prepared by Sol-Gel method

Lead-free Bi_0.5Na_0.5TiO₃ (BNT) piezoelectric thin films were deposited on Pt/TiO_x/SiO₂/Si substrates by Sol-Gel method. A dense and well crystallized thin film with a perovskite phase was obtained by annealing the film at 700 °C in a rapid thermal processing system. The relative dielectric constant and loss tangent at 12 kHz, of BNT thin film with 350 nm thickness, were 425 and 0.07, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 9 μC/cm² and a coercive field of 90 kV/cm. Piezoelectric measurements at the macroscopic level were also performed: a piezoelectric coefficient (d_33effmax) of 47 pm/V at E = 190 kV/cm was obtained. The piezoresponse force microscopy data confirmed that BNT thin films present ferroelectric and piezoelectric behavior at the nanoscale level.     

Annealing impact on the structural and optical properties of electrospun SnO2 nanofibers for TCOs

Tin oxide (SnO₂) nanofibers were fabricated by electrospinning technique and subsequent annealed at different temperatures. The structure, morphology and optical properties of the annealed samples were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR),and optical absorption techniques. The phase of SnO₂ of all samples is rutile (tetragonal), and at higher annealing temperatures, good crystallinity and lower absorption were obtained. Annealing of the samples at 600 °C caused the lower absorption and higher optical band gap, and the decrease of the absorption was probably because the fiber structure changed from solid to hollow structure. From PL spectra, it was observed that the SnO₂ hollow nanofibers annealed at 600 °C revealed green emission at 530 nm.     

The evidence of phase separation droplets in the crystallization process of a Li2O-Al2O3-SiO2 glass with TiO2 as nucleating agent – An X-ray diffraction and (S)TEM-study supported by EDX-analysis

Lithiumalumosilicate glasses are of great importance for industrial applications, because they enable the preparation of glass ceramics with coefficients of thermal expansion close to zero. While detailed studies of the effect of ZrO₂ on nucleation and crystal growth have already been performed in recent years, the effect of TiO₂ was up to now not reported in detail. It is shown for the first time, that liquid/liquid phase separation is the initial step of nucleation in lithiumalumosilicate glasses containing TiO₂. During temperature treatment above the glass transition temperature, at 740 °C for 0.25–24 h, in the formed droplets, TiO₂ nanocrystals precipitate. The formed phases were investigated by XRD- and TEM and STEM-EDX to illustrate the phase developments as well as the resulting microstructures and the local enrichments of the respective components as a function of time.Longer crystallization times resulted in the formation of crystalline lithiumalumosilicate (LAS) with a high-quartz structure. These crystals are notably larger than the TiO₂ crystals and are growing with increasing treatment time and temperature. The evidence of anatase formation was obtained from high resolution TEM from the lattice spacings because it cannot be distinguished from the high quartz structure using XRD.     

Preparation of Pt-loaded TiO2 nanofibers by electrospinning and their application for WGS reactions

Preparation of Pt-loaded TiO₂ nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO₂ nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)_n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)_n/Pt due to the PEO degradation and oxidation of Ti(OH)_n to TiO₂. Diameters of the Pt-loaded TiO₂ nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO₂ nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO₂ nanofibers from a Ti(OH)_n nanoparticle slurry using electrospinning and its application to WGS reactions.     

Morphology,structure and photowettability of TiO2 coatings doped with copper and fluorine

The work reports synthesis, structure and properties of doubly doped titanium dioxide coatings activated by ultraviolet and visible light. Copper within a concentration range of 0.4–3.4 at% and fluorine within a concentration range of 1.7–9.4 at% were introduced as dopants. The coatings were prepared with the help of radiofrequency plasma enhanced chemical vapor deposition technique with a single precursor compound providing both dopants and titanium (IV) chloride being a source of titanium. Elemental composition and chemical bonding analyses of the coatings were carried out with the help of X-ray photoelectron spectroscopy. The results indicate that both admixtures are chemically bound to the TiO₂ matrix – a notion confirmed by Fourier transform infrared spectroscopy. Phase composition studies, performed with a low angle X-ray diffraction method, revealed a presence of a threshold concentration of the dopants affecting the coatings crystallinity. Surface morphology and its topography were studied with the help of scanning electron microscopy and atomic force microscopy. Several coatings exhibited a superhydrophilic effect upon relatively short time of illumination.     

Polyimide/nano-TiO2 hybrid films having benzoxazole pendent groups: In situ sol–gel preparation and evaluation of properties

Polyimide/titania (PI/TiO₂) nanocomposite films have been successfully fabricated through the in situ formation of TiO₂ within a PI matrix via sol–gel method. Poly(amic acid) (PAA), which is the precursor of PI, was successfully synthesized by mixing pyromellitic dianhydride (PMDA), with equimolar amount of a diamine monomer having a pendent benzoxazole unit and two flexible ether linkages in N,N-dimethylformamide (DMF) solvent. Tetraethyl orthotitanate [Ti(OEt)₄] and acetylacetone were then added to the resulted PAA. After imidization at high temperature, PI/TiO₂ hybrid films were formed. The structure and morphology of the hybrid nanocomposites with different titania contents (0 wt%, 5 wt%, 10 wt%, and 15 wt%) were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. The results indicate that the TiO₂ nanoparticles were homogeneously dispersed in the hybrid films. The thermogravimetric analysis of nanocomposites confirms the improvement in the thermal stability with the increase in the percentage of titania nanoparticle. Transmission electron microscopy showed that the nanoparticles with an average diameter of 25–40 nm were dispersed in the polymer matrix.     

Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al_2−xTi_xO₃)·2(SiO₂) and 2(Al_2−xTi_xO₃)·(SiO₂), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al₂TiO₅ as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of lattice parameters of mullite, processed at temperatures from the range between 1400 and 1600 °C, with the starting nominal amount of titanium oxide indicated that the solubility limit of titanium oxide was in ranges 3.8–4.1 and 4.1–4.4 wt% TiO₂ for 3:2 and 2:1 mullites series, respectively. The anisotropic growth of titanium-doped mullite crystalline grains was significant only when the nominal amount of titanium oxide exceeded the limit of solubility into the mullite structure (for both mullite series). Stronger anisotropy occurred for the 3:2 series specimens, i.e. for the SiO₂-richer mullites. In both series of mullites, the anisotropic grain growth was observed for the process temperatures higher than 1400 °C; the crystalline grains of mullites processed at lower temperatures were equiaxials and of almost the same size.