Thermal stability of the structural features in the superhydrophobic boehmite films on austenitic stainless steels

Boehmite thin film with 50–100 nm surface flake structure has been synthesized on AISI 316 type austenitic stainless steel by immersing boehmite gel film into boiling water. When further coated with hydrolyzed (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (FAS), the boehmite film becomes superhydrophobic with a contact angle for water of 152°. The superhydrophobic property results from both the nanoscale surface flake structure and the low surface energy of the FAS top layer. The topography of such film was revealed by atomic force microscope (AFM) and a set of roughness parameters of such film was discussed. The degradation of superhydrophobicity of the surface was studied as a function of the heat-treatment temperatures. Below 600 °C, the surface remained to be superhydrophobic with the FAS top layer. Above 700 °C, the surface was not superhydrophobic anymore due to a gradual loss in surface roughness which was revealed by field emission scanning electron microscope (FESEM). A phase change from boehmite to γ-Al₂O₃ occurred during the heat-treatments from 700 to 900 °C which was studied by the selected area electron diffraction (SAED) patterns from the transmission electron microscope (TEM) measurement.     

Enhanced magnetic properties of Nd–Fe–B thin films crystallized by heat treatment

Nd₂Fe₁₄B Φ phase crystallites were formed in Nd_16.7Fe_65.5B_17.8 thin films prepared by RF sputtering with subsequent heat treatment. The 2 μm-thick films were deposited onto 0.1 mm Mo sheets at an average substrate temperature (T_s) of 365°C. The enhanced magnetic properties of the magnetically anisotropic thin films were investigated using different heating rates (h_r) of 10°C, 20°C, 50°C and 100°C/min in an annealing experiment. Transformation from the amorphous phase to the crystalline phase is clearly manifested by the formation of fine crystallites embedded as a columnar matrix of Nd₂Fe₁₄B phase. High-resolution scanning electron microscope data of the cross-section of the annealed films show columnar stacking of Nd₂Fe₁₄B crystallites with sizes <500 nm. Transmission electron microscope observations revealed that the microstructure of these films having out-of-plane magnetization consists of uniformly distributed Φ phase with grain size around 400 nm together with small Nd rich particles. This grain size of Φ phase is comparable to the single domain particle diameter of Nd₂Fe₁₄B. Significant change in _iH_c, 4πM_r and 4πM_s with h_r was confirmed. Annealing conditions with a heating rate of 50°C/min to an annealing temperature (T_a) of 650°C for 30 min was consequently found to give optimum properties for the NdFeB thin films. The resulting magnetic properties, considered to be the effect of varying h_r were _iH_c= 1307–1357 kA/m, 4πM_r=0.78–1.06 T and 4πM_s=0.81–1.07 T.     

Synthesis of PS colloidal crystal templates and ordered ZnO porous thin films by dip-drawing method

Polystyrene spheres (PS) were synthesized by an emulsifier-free emulsion polymerization technique and the PS colloidal crystal templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS. Porous ZnO thin films were prepared by filling the ZnO sol into the spaces among the close-packed PS templates and then annealing to remove the PS templates. The effects of ZnO precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed an ordered ZnO porous thin film with designed pore size that depended on the sol concentration and PS size could be obtained. And the shrinkage of pore diameter was about 30-43%. X-ray diffraction (XRD) spectra indicated the thin film was wurtzite structure. The transmittance spectrum showed that optical transmittance decreased with the decrease of wavelength, but kept above 80% optical transmittances beyond the wavelength of 550 nm. Optical band gap of the porous ZnO thin film (fired at 500 °C) was 3.22 eV.     

Phase transition and dielectric characteristics of nano-grained BaTiO3 ceramics synthesized from surface-coated nano-powders

Nano-grained BaTiO₃ (BTO) ceramics were synthesized by pressureless sintering BTO nano-powders coated with Mn materials. The BTO ceramics, which were prepared at 800 °C from nano-powders of 40 nm size, are of a cubic structure with a small fraction of tetragonal phase, similar to that of the starting BTO nano-powders of the same size. On the other hand, the BTO ceramics with about grains of 1300 nm size, which were prepared at sintering temperature ranging from 1100 to 1200 °C, have a mainly tetragonal phase. By increasing the sintering temperature and/or the amount of the coating materials, the crystallinity of the tetragonal phase was increased. The relation of the dielectric features of the nano-grained BTO ceramics with the structural variation is discussed in terms of process parameters.     

Magnetic properties in BaFe12O19 nanoparticles prepared under a magnetic field

It was observed that the nanocrystallites of BaFe₁₂O₁₉ formed at 140°C under a 0.25 T magnetic field exhibited a higher saturation magnetization (6.1 emu/g at room temperature) than that of the sample (1.1 emu/g) obtained under zero magnetic field. Both of the two approaches yielded plain-like particles with an average particle size of 12 nm. However, the Curie temperature (T_c), a direct measuring of the strength of superexchange interaction of Fe³⁺–O²⁻–Fe³⁺, increased from 410°C for the nanoparticles prepared without an external field applied to 452°C for the particles formed under a 0.25 T magnetic field, which indicates that external magnetic fields can improve the occupancy of magnetic ions and then increase the superexchange interaction. This was confirmed by electron paramagnetic resonance and Mössbauer spectrum analysis. The results present in this paper suggest that in addition to oxygen defects, surface non-magnetic layer and a fraction of finer particles in the superparamagnetic range, cation vacancies should be responsible for the decreasing of saturation magnetization in magnetic nanoparticles.     

Improving Epoxy Adhesives with Zirconia Nanoparticles

Zirconia nanoparticles were synthesized by a sol–gel route and dispersed into an epoxy base for structural adhesives. Nanoparticles were used as-synthesized or after calcination. Moreover, the effect of silane functionalization was also investigated. According to preliminary tensile mechanical tests on bulk nanocomposite samples, calcined and untreated zirconia nanoparticles were selected for the preparation of adhesives with various filler contents. The glass transition temperature increased up to a filler content of 1 vol% and then decreased, probably due to the concurrent and contrasting effects of chain blocking and reduction of the crosslinking degree. Also tensile modulus, stress at break and fracture toughness of bulk adhesives samples were positively affected by the presence of an optimal amount of zirconia nanoparticles. Mechanical tests on single lap aluminium bonded joints indicated that zirconia nanoparticles led to relevant enhancements of the shear strength of the joints. In particular, the shear strength increased by about 60% for an optimal filler content of 1 vol%, and an adhesive failure mechanism was evidenced for all the tested specimens. Concurrently, a significant decrease of the equilibrium contact angle with water was observed for adhesives containing zirconia nanoparticles. It can therefore be concluded that the addition of zirconia nanoparticles can effectively improve epoxy adhesives, both by increasing their mechanical properties and by enhancing the interfacial wettability with an aluminium substrate.     

Dispersion of Nano TiO2 in Ethylene Glycol and Poly(ethylene terephthalate)

Nano TiO₂ was dispersed in ethylene glycol (EG) by the replacement of dispersion medium from water sol. EG/TiO₂ suspension was well stabilized by the electrostatic repulsive force when pH value of suspension was less than 4.3. In situ polymerization starting from bis(2-hydroxyethyl) terephthalate (BHET) and EG/TiO₂ suspension was carried out to prepare a series of poly(ethylene terephthalate) (PET)/TiO₂ nanocomposites. Under highly acidic conditions, 97% particles dispersed in PET matrix had the size less than 100 nm. With the increase of pH value, aggregation occurred and larger size particles appeared. A tensile test showed that Young's modulus of PET was increased by the addition of nano TiO₂     

Electrical properties of nickel - YSZ composites prepared by a sol gel method

Composite materials containing metallic nickel and yttria stabilised zirconia (YSZ) have been prepared by a sol gel method. Microstructural investigations show that metal particles with a diameter of less than 300 nm still remain present after sintering. In the present work, the conductivity behaviour of such composites was investigated. Furthermore, ageing phenomena, in particular the influence of the nickel content, were studied. A possible application of such materials as anodes in solid oxide fuel cells will be discussed. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Hydrogen peroxide bleaching of cotton in ultrasonic energy

It is well known that, conventional hydrogen peroxide bleaching process is an important and a specific step for wet processors; however it has some problems such as long time, high energy consumption. On the other hand, using ultrasonic energy in bleaching is an alternative method for the conventional processes.

In this work, 100% cotton materials of different forms such as raw fibre, ring-spun yarns and knitted fabrics produced from these cottons, were treated with hydrogen peroxide in two different concentrations (5 mL/L and 10 mL/L), at three different temperatures (20 °C, 30 °C, 40 °C) and times (20 min, 30 min, 60 min). Whiteness Index of the samples were then measured spectrophotometrically and the overall results were compared.     

Excess molar heat capacity of isobutyric acid–water binary liquid mixtures near and far away from the critical temperature

The heat capacity of the liquid–liquid mixture isobutyric acid–water has been measured for the first time near and far away from its critical point using an adiabatic calorimeter. The measurements were performed at atmospheric pressure, in the one phase region as a function of three temperatures: (1) T − T_C = 0.055 °C, (2) T − T_C = 3.055 °C, (3) T − T_C = 8.055 °C and of the composition X in acid (IA). The heat capacity C_p decreases rapidly when X increases at the used temperatures. Near the critical composition, C_p is not affected by the correlation of the concentration fluctuations.

The molar excess heat capacity of the system under investigation was analysed along the phase diagram and considered as a structural transformation effect.     

Structural studies of nanocrystalline oxides

We report the results of structural studies of samples of nanocrystalline tin oxide, zirconia, magnesia, alumina and silica, prepared by sol–gel techniques (including the addition of silica to restrict grain growth) and high-energy ball milling. XRD, EXAFS/XANES and MAS-NMR analyses were used to characterise the materials. EXAFS showed that nanocrystals of ZrO₂ and SnO₂ prepared by sol–gel methods are highly crystalline, consistent with previous EXAFS studies of sol–gel prepared nanocrystalline oxides [A.V. Chadwick, M.J. Pooley, K.E. Rammutla, S.L.P. Savin, A. Rougier, J. Phys.: Condens. Matter, 15 (2003) 431.; A.V. Chadwick, G.E. Rush, in Nanocrystalline Metals and Oxides: Selected Properties and Applications, (Kluwer, New York), (2002), p.133.]. In contrast, the sol–gel prepared SiO₂ appeared amorphous, even after prolonged heating at 1200 °C. The EXAFS of the ball-milled samples showed clearly attenuated signals that cannot be attributed solely to particle size. Ball milling of quartz crystals (which have a simple Q₄) first broadens the NMR line and then generates Q₃ and then Q₂ lines indicating the generation of amorphous materials in the samples.     

Characteristics of thermal distortions of the laser mirror substrates filled with phase-change materials

Under irradiating of the laser power of 2 kW, the thermal deformations of the silicon mirror substrates with phase change materials are experimentally measured and numerically analyzed by using finite element methods, respectively. The experimental results show that when the absorbed laser power is 120 W and the laser irradiating time gets to three seconds, the thermal distortion of the silicon mirror substrates with paraffin/carbon powder is 0.25 μm, that of the paraffin/aluminum powder 0.33 μm, and that of the paraffin/copper powder 0.37 μm. The numerical calculation coincides with the experimental results.     

Designing Zwitterionic SiO2NH2‐Au Particles with Tunable Patchiness using Wrinkles

A facile template‐based approach toward zwitterionic SiO₂NH₂‐Au patchy particles is presented. Therefore, wrinkle templates prepared by stress release in a bilayer system comprised of an elastic PDMS fundament and a thin SiO_x top layer are used. After aligning positively charged, amine‐functionalized silica particles in wrinkle grooves, their surfaces are partially modified with negatively charged gold nanoparticles in an electrostatic adsorption step. Patchiness is precisely controlled by the degree of immersion of the initial particles into wrinkles of varying dimensions. By ultrasonication or wetting with a water droplet, patchy particles are easily released from the substrate‐yielding particles with two oppositely charged hemispheres. Interfacial tension measurements prove the surface activity of the SiO₂NH₂‐Au particles in an oil/water system and are explained in the view of the Janus‐type surface charges of the particles and the charge of the oil/water interface.     

Thin film coating of photocatalytics on ultra light ceramic tile by use of supercritical fluid

Abstract

Although sol-gel method is an easy procedure to form a thin film, it's extremely difficult to coat on the surface of small size particles, fibers, and fiber ceramics, because concentration occurs by capillary phenomena and causes peeling or breakage of film.

In order to solve this problem, we use supercritical CO₂ rapid expansion from supercritical solution (RESS), nano-sized particles of TiO₂ with high intensity can be sprayed out of a nozzle, then collected on the surface of substrates, but can be absorbed into fibers or porous materials, being not interfered by viscosity of a solution.

TiO₂ sol made by hydrolysis process is set in a pressure cell and mixed together with super-critical CO₂. Controlling the pressure and the temperature, we could obtain TiO₂ sol and super critical fluid mixture, and then discharge to the substrate. At this point, Titania sol viscosity is so low that a surface wettability of the substrate becomes negligible.

By the use of the characteristics of the supercritical fluid, without constraint condition of viscosity or capillarity, this sol can penetrate into the interstices of the substance's structure.

Thus, clearing obstruction of capillary phenomena, supercritical fluid coating method shows its capability to penetrate deep into inside of entangled fiber of the three-dimensional structure so as considered to be a heat resistant filter with 95% porosity.     

The effect of key process parameters on crystallographic texture and magnetic properties of PrFeB HD sintered magnets produced using high-energy milling

A combination of hydrogen decrepitation and planetary ball milling has been used to produce sintered Pr₁₆Fe₇₆B₈ magnets. The effects of key process parameters and texture have been studied. The alignment degree (cos Θ) has been investigated by X-ray pole figure analysis using the (0 0 4) reflection. Magnets prepared from the alloy decrepitated for 3.6 ks and milled for 1.8 ks exhibited a low degree of crystal alignment (0.71±0.02) due to polycrystalline particles. Increasing the milling time to 4.5ks has led to an improvement in cos Θ to 0.84±0.02. This has been ascribed to the smaller particle size with a narrower size distribution as well as a more favorable particle shape for orientation. Superior alignment degree (cos Θ=0.88±0.02) has been achieved for the sintered magnet from the alloy decrepitated for 120 s and milled for 5.4 ks. This particular processing condition has led to a magnet with (BH)_max=250±5 kJ m⁻³, value found in magnets produced using roller ball milling, with the advantage of a reduced milling time (about 90%).     

Triblock copolymer-templated synthesis of porous TiO2 and its photocatalytic activity

Mixed amorphous and anatase-type titania particles were synthesized using non-ionic triblock copolymer as surfactant template and TiOSO₄ as inorganic precursor through sol–gel process. The as-prepared materials were characterized by X-ray diffraction spectroscopy, scanning and transmission electron microscopy, specific surface area, Fourier-transformed infrared spectroscopy, and diffuse reflectance ultraviolet–visible spectroscopy. The template material could be easily removed by extracting with dichloromethane and was confirmed by infrared spectroscopy. X-ray diffraction pattern reveals the crystalline part of as-prepared product as a framework of anatase phase. From the N₂ adsorption–desorption analysis, the as-prepared sample has a surface area of 301 m²/g with pore size distribution narrowly centered around 6 nm. The photodegradation of indigo carmine including kinetics, effect of pH, and recyclability of the product were investigated. The photocatalytic results showed that the as-synthesized titania could efficiently degrade indigo carmine under ultraviolet irradiation and showed higher photocatalytic activity than the commercial Degussa P25–TiO₂.     

飞秒激光直写生物凝胶模板原位合成纳米粒子

为了制备具有可控复杂形状和特定化学性质的聚合物微结构,提出了一种飞秒激光直写生物凝胶模板原位合成纳米粒子的方法。首先,采用飞秒激光直写技术加工带有COOH基团的复杂三维结构的生物凝胶模板,用氢氧化钠处理使COOH基团离子化为COO^-基团;然后,用金属盐溶液处理,使金属离子与COO^-基团螯合,形成纳米粒子结晶核。通过多次循环盐溶液处理步骤,控制模板中纳米粒子的粒径与含量。实验结果表明：所制备的生物凝胶模板具有亚100 nm分辨率和10 μm量级尺寸,纳米粒子含量高达9%。该法简单高效,具有很好的应用前景。     

Ultrasound emulsification: effect of ultrasonic and physicochemical properties on dispersed phase volume and droplet size

Ultrasonic emulsification of oil and water was carried out and the effect of irradiation time, irradiation power and physicochemical properties of oil on the dispersed phase volume and dispersed phase droplet size has been studied. The increase in the irradiation time increases the dispersed phase volume while decreases the dispersed phase droplets size. With an increase in the ultrasonic irradiation power, there is an increase in the fraction of volume of the dispersed phase while the droplet size of the dispersed phase decreases. The fractional volume of the dispersed phase increases for the case of groundnut oil-water system while it is low for paraffin (heavy) oil-water system. The droplet size of soyabean oil dispersed in water is found to be small while that of paraffin (heavy) oil is found to be large. These variations could be explained on the basis of varying physicochemical properties of the system, i.e., viscosity of oil and the interfacial tension. During the ultrasonic emulsification, coalescence phenomenon which is only marginal, has been observed, which can be attributed to the collision of small droplets when the droplet concentration increases beyond a certain number and the acoustic streaming strength increases.     

Two-dimensional nanopatterning by PDMS relief structures of polymeric colloidal crystals

A new constructive method of fabricating a nanoparticle self-assembly on the patterned surface of a poly(dimethylsiloxane) (PDMS) relief nanostructure was demonstrated. Patterned PDMS templates with close-packed microwells were fabricated by molding against a self-assembled monolayer of polystyrene spheres. Alkanethiol-functionalized gold nanoparticles with an average particle size of 2.5 nm were selectively deposited onto a hydrophobic self-assembled monolayer printed on the substrate by the micro-contact printing (μCP) of the prepared PDMS microwell, in which the patterned gold nanoparticles consisted of close-packed hexagons with an average diameter of 370 nm. In addition, two-dimensional colloidal crystals derived from PMMA microspheres with a diameter of 380 nm and a negative surface charge were successfully formed on the hemispherical microwells by electrostatic force using positively charged PAH-coated PDMS as a template to produce multidimensional nanostructures.     

Tuning of the periodicity of stable self-organized metallic templates

The atomic and electronic structures of Pb bilayer/Pt(111) are investigated with two theoretical calculations.We find that the stable (2 × 2)/(3 × 3) Pb/Pt(111) structure is a promising candidate for being used as a template with self-organized ordered Pb semi-cluster array on the first Pb monolayer.This stable structure can realize the ordered Au single-atom array around the Pb semi-clusters that can cause selective adsorption of noble atoms.The size of Pb magic number semi-cluster plays a more important role in determining the periodicity of the template than the lattice constant misfit between the substrate and the overlayer.This leads to quite a different periodicity between the two stable templates,which are (2 × 2)/(3 × 3) Pb/Pt(111) and Pb/Cu(111).Therefore,by considering the size of the stable semi-clusters and carefully selecting different substrate materials,we can tune the density of Pb semi-clusters as the nucleation points and then tune the periodicity of the stable template.