Studies of the surface wettability and hydrothermal stability of methyl-modified silica films by FT-IR and Raman spectra

Fourier transform infrared (FT-IR) and Raman spectroscopy were employed to study the hydrothermal stability and the influence of surface functional groups on the surface wettability of methyl-modified silica films. The surface free energy parameters of the silica films were determined using the Lifshitz-van der Waals/acid–base approach. The thermal decomposition mechanisms of the CH₃ groups in the methyl-modified silica material are proposed. The results show that with the increase of methyltriethoxysilane (MTES)/tetraethylorthosilicate (TEOS) ratio, the surface free energy and surface wettability of the silica films decrease greatly. This is mainly because of the contribution of the acid–base term; the intensity of Si–CH₃ groups increases at the expense of the intensity of O–H groups in the samples. The surfaces of the methyl-modified silica films exhibited predominantly monopolar electron-donicity. The contact angle on the silica film surface reaches its maximum value when calcination is performed at 350 °C. Thermogravimetric analysis implies that some low molecular weight species, such as H₂, CH₄, and C, are eliminated upon thermal decomposition of the –CH₃ groups. The Si–CH₃ and –CH₃ vibrational bands diminish in intensity as the calcination temperature is increased, disappearing completely when the calcination temperature is increased to 600 °C. When the calcination temperature is increased to 750 °C, the free carbon and CSi₄ species will be formed.     

Research on Preparation Methods of Carbon Nanomaterials Based on Self-Assembly of Carbon Quantum Dots

Here, based on self-assembly of carbon quantum dots (CDs), an innovative method to prepare nanomaterials under the action of a metal catalyst was presented. CDs were synthesized by a one-step hydrothermal method with citric acid (CA) as the carbon source, ethylenediamine (EDA) as the passivator and FeSO₄•7H₂O as the pre-catalyst. In the experiment, it was found that the nano-carbon films with a graphene-like structure were formed on the surface of the solution. The structure of the films was studied by high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FT-IR), etc. The results demonstrated that the films were formed by the self-assembly of CDs under the action of the gas–liquid interface template and the metal catalyst. Meanwhile, the electrochemical performance of the films was evaluated by linear cyclic voltammetry (CV) and galvanostatic charge discharge (GOD) tests. In addition, the bulk solution could be further reacted and self-assembled by reflux to form a bifunctional magnetic–fluorescent composite material. Characterizations such as X-ray diffractometer (XRD), fluorescence spectra (FL), vibrating sample magnetometer (VSM), etc. revealed that it was a composite of superparamagnetic γ-Fe₂O₃ and CDs. The results showed that self-assembly of CDs is a novel and effective method for preparing new carbon nanomaterials.     

Preparation of iron oxides using ammonium iron citrate precursor: Thin films and nanoparticles

Ammonium iron citrate (C₆H₈O₇·nFe·nH₃N) was used as a precursor for preparing both iron-oxide thin films and nanoparticles. Thin films of iron oxides were fabricated on silicon (111) substrate using a successive-ionic-layer-adsorption-and-reaction (SILAR) method and subsequent hydrothermal or furnace annealing. Atomic force microscopy (AFM) images of the iron-oxide films obtained under various annealing conditions show the changes of the micro-scale surface structures and the magnetic properties. Homogenous Fe₃O₄ nanoparticles around 4 nm in diameter were synthesized by hydrothermal reduction method at low temperature and investigated using transmission electron microscopy (TEM).     

Photoresist Modification of Sol–Gel Solutions for Texturing of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> and Bi<Subscript>3</Subscript>TiNbO<Subscript>9</Subscript> Thin Films

Bismuth titanate (Bi₄Ti₃O₁₂) and bismuth titanium niobate (Bi₃TiNbO₉) c-axis textured thin films were fabricated using the sol–gel processing technique. Chemical modification of precursor solutions was performed using a proprietary photosensitive chemical (photoresist). Increases in crystallinity and texture of resulting films were seen over films that were made from unmodified solutions. Analysis by X-ray diffraction (XRD) revealed c-axis orientation factors for Bi₄Ti₃O₁₂ near 88% and Bi₃TiNbO₉ near 63% in “modified” films. Atomic force microscopy images of films show microstructural improvement between “modified” and “unmodified” films. Images generally show smaller randomly oriented grains in “unmodified” films, and larger oriented platelet structures related to growth due to crystal habit in “modified” films. Light scattering experiments show the addition of photoresist to the precursor solution initiates accelerated particle growth. AFM imaging of soft-baked films also suggests an enhancement of texture.     

Oxide films: low-temperature deposition and crystallization

Thin films of CeO₂ and (Ce,Sm)O₂ have been prepared by using the SILAR method of deposition in conjunction with hydrothermal and high-temperature annealing. Low-temperature, low-pressure hydrothermal annealing of amorphous Mn:Zn₂GeO₄ films has lead to the growth of grains having edge lengths near 1 μm. Thick films of crystalline Zn₂SiO₄ exhibiting limited cracking have been prepared by a doctor-blade method also in conjunction with hydrothermal dehydration and annealing.     

Hydrothermal synthesis of yttria stabilized ZrO2 nanoparticles in subcritical and supercritical water using a flow reaction system

Yttria stabilized zirconia nanoparticles have been prepared by hydrothermal flow reaction system under subcritical and supercritical conditions. ZrO(NO₃)₂/Y(NO₃)₃ mixed solutions were used as starting materials. Reaction temperature was 300–400 °C. Reaction time was adjusted to 0.17–0.35 s. Based on the residual Zr and Y concentrations, the complete conversion of zirconium was achieved irrespective of pH and hydrothermal temperature, whereas the conversion of yttrium increased with an increase in pH and hydrothermal temperature. Stoichiometric solid solution was achieved at pH>8. XRD results revealed that tetragonal zirconia can be formed regardless of yttrium content, where the tetragonality was confirmed by Raman spectroscopy. The average particle size estimated from BET surface area was around 4–6 nm. Dynamic light scattering particle size increased with the solution pH owing to the aggregation of primary particles. TG-DTA analyses revealed that weight losses for adsorbed water and hydroxyl groups decreased with hydrothermal temperature.     

Effect of Cation Arrangement on the Magnetic Properties of Lithium Ferrites (LiFeO2) Prepared by Hydrothermal Reaction and Post-annealing Method

The magnetic properties of several LiFeO₂polymorphs (different cation arrangements in a cubic close-packed oxygen structure) have been examined by magnetic susceptibility measurements and Mössbauer spectroscopy. Samples with relatively low ferromagnetic impurity levels have been obtained by hydrothermal reaction of FeCl₃·6H₂O or FeOOH with LiOH·H₂O and subsequent annealing in air.α-NaFeO₂with no detectable ferromagnetic impurity has been obtained by hydrothermal reaction ofα-FeOOH and NaOH. Whileα-NaFeO₂revealed only one anomaly at 11 K (Néel point) in the magnetic susceptibility–temperature curves, each LiFeO₂sample shows two anomalies (40–50 and 90–280 K). Mössbauer data confirm that iron is present in the high-spin 3+ state according to the values of the internal field at 4.2 K and isomer shifts at 300 K. The relationship between the cation arrangements and the Néel temperature is discussed for LiFeO₂.     

Electrochemical hydrogen evolution over MoO3 nanowires produced by microwave-assisted hydrothermal reaction

Molybdenum trioxide (MoO₃) nanowire with unprecedentedly high aspect ratios (>200) and good crystallinity was prepared via decomposition of (NH₄)₆Mo₇O₂₄·4H₂O under a microwave-assisted hydrothermal (MH) process. The nanowire was orthorhombic MoO₃ with 50 nm in diameter and 10–12 μm in length. The conventional hydrothermal (CH) reaction required higher temperature and longer reaction times to produce one-dimensional MoO₃, yet its quality was lower. In the electrochemical hydrogen evolution reaction in a H₂SO₄ solution, MoO₃ nanowire from MH process showed much higher electrocatalytic activity than MoO₃ prepared from CH method and commercial bulk MoO₃ particles. The facile vectorial electron transport along the nanowire axis was considered to be responsible for the excellent electrocatalytic activity of the MH–MoO₃ nanowire.     

Ultraviolet-Laser-Induced Crystallization of Sol-Gel Derived Inorganic Oxide Films

Structural changes stimulated by ultraviolet (UV) laser irradiations of sol-gel derived inorganic oxide films were investigated. Dried gel films of TiO₂, Nb₂O₅, Ta₂O₅, SrTiO₃ and Pb(Zr _x Ti_1–x )O₃ (PZT) were found to be crystallized by the laser irradiation. On the other hand, the photo-induced change in gel films of BaTiO₃, LiNbO₃ and LiTaO₃ was not observed although the laser beams were absorbed in the films. These sol-gel films were thermally crystallized at almost the same temperature around 600–700°C except TiO₂. Thus, the UV-laser-induced crystallization is not directly ascribed to a simple thermal effect with the irradiation. Photochemical properties of the cations are assumed to be important for the change in sol-gel films.     

Synthesis of magnetic nickel spinel ferrite nanospheres by a reverse emulsion-assisted hydrothermal process

Nickel ferrite nanospheres were successfully synthesized by a reverse emulsion-assisted hydrothermal method. The reverse emulsion was composed of water, cetyltrimethyl ammonium bromide, polyoxyethylene(10)nonyl phenyl ether, iso-amyl alcohol and hexane. During the hydrothermal process, β-FeO(OH) and Ni_0.75Fe_0.25(CO₃)_0.125(OH)₂·0.38H₂O (INCHH) nanorods formed first and then transformed into nickel spinel ferrite nanospheres. The phase transformation mechanism is proposed based on the results of X-ray powder diffraction, transmission electron microscopy and energy-dispersive X-ray spectroscopy, etc. Nickel ferrite may form at the end of the INCHH nanorods or from the solution accompanied by the dissolution of β-FeO(OH) and INCHH nanorods. The X-ray photoelectron spectroscopy analysis shows that a few Fe³⁺ ions have been reduced to Fe²⁺ ions during the formation of nickel ferrite. The maximum magnetization of the nickel ferrite nanospheres obtained after hydrothermal reaction for 30 h is 55.01 emu/g, which is close to that of bulk NiFe₂O₄.     

In situ study on the effects of Ni and Mo on the passive film formed on Fe–20Cr alloys by photoelectrochemical and Mott–Schottky techniques

Effects of alloying elements (Ni and Mo) on the structure of passive film formed on Fe–20Cr alloys in pH 8.5 buffer solution were explored by analyzing the in situ electronic properties measured using the photoelectrochemical technique and Mott–Schottky analysis. The passive film formed on Fe–20Cr–10Ni was found to be mainly composed of Cr-substituted γ-Fe₂O₃ from similarities in photocurrent response for the passive films formed on the alloy and Fe–20Cr. On the other hand, the photocurrent spectra for the passive films of Fe–20Cr–15Ni–(0, 4)Mo alloys exhibited the spectral components associated with NiO and Mo oxide (MoO₂ and/or MoO₃) in addition to that induced by Cr-substituted γ-Fe₂O₃. Mott–Schottky plots for the passive films formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo confirmed that the passive films on Fe–20Cr–(10, 15)Ni–(0, 4)Mo alloys have a base structure of Cr-substituted γ-Fe₂O₃ with variation of densities of shallow and deep donors depending on the Ni and Mo contents in the alloys. We suggest that the passive film formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo alloys are composed of (Cr, Ni, Mo)-substituted γ-Fe₂O₃ when the concentrations of Ni and Mo are below critical values. However, NiO and Mo oxide (MoO₂ and/or MoO₃) would be precipitated in the passive films when the concentrations of Ni and Mo exceed critical values.     

Synthesis and electrophoretic deposition of high-dielectric-constant SrTiO3 nanoparticles

We have investigated on the synthesis of SrTiO₃ nanoparticles whose bulk exhibits dielectric constant of 300, and their colloidal dispersion. As a result, we successfully synthesized SrTiO₃ nanoparticles with an average diameter of 134–485 nm measured by a scanning electron microscopic observation. The SrTiO₃ nanoparticles with a negative charge (ζ = −25 to −31 mV) can be dispersed as colloidal nanoparticles in water, and the average diameter in the dispersion were 138–356 nm measured by a dynamic light scattering technique. The colloidal dispersion of SrTiO₃ nanoparticles is promising for fabrication of low-voltage organic field-effect transistors (FETs) by a wet-processing fabrication. We have also successfully prepared SrTiO₃ films with a thickness of 1–10 μm on n-doped silicon substrates by an electrophoretic deposition technique. The SrTiO₃ films on the silicon substrates are likely used as dielectric gate insulator to low-voltage organic FETs after a sintering treatment.     

Ion and solvent transfer discrimination at a nickel hydroxide film exposed to LiOH by combined electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD) techniques

A combined electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD) instrument was used to monitor the mobile species transfers associated with the redox processes of thin (Γ100–150 nmol cm⁻²) α- and β-nickel hydroxide films exposed to aqueous LiOH solution. A comparison of the measured PBD signal with the predicted PBD profiles, calculated by temporal convolution analysis of the current and mass responses, enabled the contributions to redox switching of anion (OH⁻) and solvent (H₂O) transfers to be discriminated quantitatively. The responses from the combined instrument are reconciled in terms of H⁺ deintercalation/intercalation within the nickel hydroxide structure as OH⁻ ions enter/exit the film. Hydroxide ion movement is associated with a counterflux of water. Thin nickel hydroxide films show a gradual α→β phase transformation with continuous voltammetric cycling, especially when the films are exposed to high concentrations of electrolyte. α-Films are characterised by OH⁻ transfers that dominate the H⁺ and H₂O movements; β-films are characterised by an increased participation of water and protons to the exchange dynamics.     

Thin films of metal dibenzotetraaza [14] annulene complexes.: Part 3. Dimerization and alternated dimerizations of γ-substituted Ni complexes

The electrochemical behaviour of some Ni γ-monosubstituted dibenzotetraaza [14] annulene complexes has been investigated. The oxidation in CH₂Cl₂ of the complex containing a 4-carboxybenzyl group leads to the corresponding γ-γ dimer whose electrochemical properties have been studied. The electrode surface can be coated by thin films of this dimer using CH₃CN instead of CH₂Cl₂; however, the resulting modified electrode is poorly stable. The oxidation of the complex containing 1-(4-carboxybenzyl)pyrrole as γ substituent involves γ-γ dimer formation before the formation of a regular polypyrrole film. The film displays reversible electrochemical reduction of the metal centre (Ni(II)/Ni(I)) and two successive oxidations of the macrocycle (Mc/Mc^•+ and Mc^•+/Mc²⁺). The complex containing a bromo(4-carboxybenzyl) group offers an unusual feature in that polymeric films can be obtained following an original procedure based on alternated dimerizations. This is a consequence of the formation of two different dimers obtained by anodic and cathodic processes.     

Formation of α-Fe2O3/FeOOH nanostructures with various morphologies by a hydrothermal route and their photocatalytic properties

A series of α-Fe₂O₃/FeOOH nanostructures with different morphologies have successfully been synthesized based on K₄[Fe(CN)₆] at 140 °C by a novel hydrothermal method. The morphology and phase of α-Fe₂O₃/FeOOH can be controlled by adjusting the reaction time. UV–vis absorption spectrum, X-ray powder diffraction, and transmission electron microscopy analyses were used to characterize the resulting products. A detailed, rational mechanism is proposed for the formation of α-Fe₂O₃/FeOOH nanostructures. The potential applications of the as-synthesized α-Fe₂O₃/FeOOH nanoparticles with different morphologies on photocatalytic decomposition of salicylic acid were also investigated.     

Facile preparation of BiVO4 thin film by screen-printing technique for its photocatalytic performance in the degradation of tetracycline under simulated sunlight irradiation

BiVO₄ films were prepared by a screen-printing technique on Corning glass substrate. The material employed to prepare the films was synthetized by the hydrothermal method. For comparative purposes, the BiVO₄ was synthesized via solid state reaction and deposited in film form by the same technique. From the X-ray diffraction structural characterization it has been stated that BiVO₄ films crystallized in the monoclinic structure. The characterization of BiVO₄ films was complemented with scanning electron microscopy, which revealed a morphology of irregular form and dendritic type depending on the starting material. The thickness of the BiVO₄ films were determined by profilometry. The film obtained from the hydrothermal method showed minor photoluminescence, i.e., the sample showed low recombination of electron–hole pairs. The highest photocatalytic activity in the degradation of tetracycline (TC) was presented for the BiVO₄ films obtained from hydrothermal powders under simulated sunlight irradiation; attributed mainly to the surface area value, smaller particle size and lower recombination of electron–hole pairs. Mineralization degree of TC by BiVO₄ films was determined by the total organic carbon analysis, reaching 50% after 24 h of irradiation. The main oxidizing species that was most influenced in the degradation of TC was the hydroxyl radical (OH^·).

     

Dielectric and optical properties of BaTiO<Subscript>3</Subscript> thin films prepared by low-temperature process

Barium titanate (BaTiO₃) thin films have been prepared by low temperature processing on Pt/Ti/SiO₂/Si substrates using sol-gel-hydrothermal (SGHT) technique, which combined the conventional sol-gel process and hydrothermal method. X-ray diffraction analysis showed that the barium titanate thin films are polycrystalline. As-reacted barium titanate films grown on Pt(111)/Ti/SiO₂/Si(100) substrates had a dielectric constant (ε) and loss tangent (tanδ) of 80 and 0.05 at 1 MHz, respectively. The optical constants including refractive index n, extinction coefficient k, and absorption coefficient α of the barium titanate thin films in the wavelength range of 2.5–12.6 μm were obtained by infrared spectroscopic ellipsometry.     

Stability of Wetting Films of F108 Triblock Copolymer Aqueous Solutions on Quartz

Wetting films of nonionic F108 triblock copolymer aqueous solutions with concentrations below the CMC containing an electrolyte (NaCl) and formed on a quartz substrate are studied. Primary thick films are disclosed to be metastable. Their temporal stability is explained by the electrostatic repulsive forces. Film thinning and transition to a stable state occur slowly at low electrolyte concentrations (C _NaCl = 10^–5 and 10^–3 M, respectively) and instantly at its high concentrations (C _NaCl = 10^–2 and 10^–1 M, respectively). The stability of thin films is explained by the steric repulsive forces.     

Effects of Geomaterial-Originated Fillers on Microstructure and Mechanical/Physical Properties of α- and β-Chitosan-Based Films

Edible films and coatings with good mechanical/physical properties are highly required for carrying medical substances and food packaging. So, solvent-cast films of α- or β-chitosan filled with palygorskite, montmorillonite or geopolymer-containing material (GCM), were prepared, and the effects of their clay contents (up to 50 wt.%) on the mechanical/physical properties were assessed. The microstructure of the films was investigated using FT-IR spectroscopy, SEM and thermal analysis. The results showed that, except for the films composed of GCM and β-chitosan, the mechanical properties of the films with limited (up to 5 wt.%) to moderate (5–25 wt.%) amounts of fillers increased as a result of the attractive electrostatic forces formed between the fillers and chitosan functional groups (–NH₃⁺, CH₂OH and NHCOCH₃). However, due to the occurrence of coarse aggregates, the strength of filler-rich films declined. The addition of fillers led to an increase in porosity and water absorption of the films, but it had irregular effects on their wettability and water vapor transmission rate. These observations as well as the thermal stability of the films were discussed in relation to the characterization results.     

Hydrothermal synthesis of 2D ordered macroporous ZnO films

The ZnO films with two-dimensional ordered macroporous structure were successfully fabricated through hydrothermal crystal growth of ZnO on the ZnO substrate covered with a monolayer of polystyrene (PS) spheres as template. The precursor solution of hydrothermal crystal growth of ZnO were prepared by equimolar solution of Zn(NO₃)₂·6H₂O and hexamethylenetramine (HMT). The confinement effect of the PS spheres template on the growth of ZnO nanorods and the influence of sodium citrate on the crystal growth of ZnO had been studied. The film surface morphology and the preferential growth of ZnO crystal were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Also, the photoluminescence spectrum of ZnO films had been measured, and the corresponding mechanism was discussed. __________ Translated from Chemistry, 2007, 70 (8): 587–592 [译自: 化学通报]