In this study, a new type of composite material combined with carbonyl iron, a relatively strong ferromagnetic material, was prepared to overcome the current application limitations of Prussian blue, which is effective in removing radioactive cesium. The surface of the prepared composite was analyzed using SEM and XRD, and it was confirmed that nano-sized Prussian Blue was synthesized on the particle surface. In order to evaluate the cesium removal ability, 0.2 g of the composite prepared for raw cesium aquatic solution at a concentration of 5 μg was added and reacted, resulting in a cesium removal rate of 99.5 %. The complex follows Langmuir’s adsorption model and has a maximum adsorption amount (qe) of 79.3 mg/g. The Central Composite Design (CCD) of the Response Surface Method (RSM) was used to derive the optimal application conditions of the prepared composite. The optimal application conditions achieved using Response optimization appeared at a stirring speed of pH 7, 17.6 RPM. The composite manufactured through this research is a material that overcomes the Prussian Blue limit in powder form and is considered to be excellent economically and environmentally when applied to a cesium removal site.
Tungsten carbide is widely used in carbide tools. However, its production process generates a significant number of end-of-life products and by-products. Therefore, it is necessary to develop efficient recycling methods and investigate the remanufacturing of tungsten carbide using recycled materials. Herein, we have recovered 99.9% of the tungsten in cemented carbide hard scrap as tungsten oxide via an alkali leaching process. Subsequently, using the recovered tungsten oxide as a starting material, tungsten carbide has been produced by employing a self-propagating high-temperature synthesis (SHS) method. SHS is advantageous as it reduces the reaction time and is energy-efficient. Tungsten carbide with a carbon content of 6.18 wt % and a particle size of 116 nm has been successfully synthesized by optimizing the SHS process parameters, pulverization, and mixing. In this study, a series of processes for the highefficiency recycling and quality improvement of tungsten-based materials have been developed.
Solid state grain growth (SSCG) is a method of growing large single crystals from seed single crystals by abnormal grain growth in a small-grained matrix. During grain growth, pores are often trapped in the matrix and remain in single crystals. Aerosol deposition (AD) is a method of manufacturing films with almost full density from nano grains by causing high energy collision between substrates and ceramic powders. AD and SSCG are used to grow single crystals with few pores. BaTiO3 films are coated on (100) SrTiO3 seeds by AD. To generate grain growth, BaTiO3 films are heated to 1,300 oC and held for 10 h, and entire films are grown as single crystals. The condition of grain growth driving force is ΔGmax < ΔGc ≤ ΔGseed. On the other hand, the condition of grain growth driving force in BaTiO3 AD films heat-treated at 1,100 and 1,200 oC is ΔGc < ΔGmax, and single crystals are not grown.
Predicting the quality of materials after they are subjected to plasma sintering is a challenging task because of the non-linear relationships between the process variables and mechanical properties. Furthermore, the variables governing the sintering process affect the microstructure and the mechanical properties of the final product. Therefore, an artificial neural network modeling was carried out to correlate the parameters of the spark plasma sintering process with the densification and hardness values of Ti-6Al-4V alloys dispersed with nano-sized TiN particles. The relative density (%), effective density (g/cm3), and hardness (HV) were estimated as functions of sintering temperature (oC), time (min), and composition (change in % TiN). A total of 20 datasets were collected from the open literature to develop the model. The high-level accuracy in model predictions (>80%) discloses the complex relationships among the sintering process variables, product quality, and mechanical performance. Further, the effect of sintering temperature, time, and TiN percentage on the density and hardness values were quantitatively estimated with the help of the developed model.
Effective control of the heat generated from electronics and semiconductor devices requires a high thermal conductivity and a low thermal expansion coefficient appropriate for devices or modules. A method of reducing the thermal expansion coefficient of Cu has been suggested wherein a ceramic filler having a low thermal expansion coefficient is applied to Cu, which has high thermal conductivity. In this study, using pressureless sintering rather than costly pressure sintering, a polymer solution synthesis method was used to make nano-sized Cu powder for application to Cu matrix with an AlN filler. Due to the low sinterability, the sintered Cu prepared from commercial Cu powder included large pores inside the sintered bodies. A sintered Cu body with Zn, as a liquid phase sintering agent, was prepared by the polymer solution synthesis method for exclusion of pores, which affect thermal conductivity and thermal expansion. The pressureless sintered Cu bodies including Zn showed higher thermal conductivity (180 W/m·K) and lower thermal expansion coefficient (15.8×10−6/℃) than did the monolithic synthesized Cu sintered body.
Lead free (Ba0.7Ca0.3) TiO3 thick films with nano-sized grains are prepared using an aerosol deposition (AD) method at room temperature. The crystallinity of the AD thick films is enhanced by a post annealing process. Contrary to the sharp phase transition of bulk ceramics that has been reported, AD films show broad phase transition behaviors due to the nanosized grains. The polarization-electric hysteresis loop of annealed AD film shows ferroelectric behaviors. With an increase in annealing temperature, the saturation polarization increases because of an increase in crystallinity. However, the remnant polarization and cohesive field are not affected by the annealing temperature. BCT AD thick films annealed at 700 ℃/2h have an energy density of 1.84 J/cm3 and a charge-discharge efficiency of 69.9%, which is much higher than those of bulk ceramic with the same composition. The higher energy storage properties are likely due to the increase in the breakdown field from a large number of grain boundaries of nano-sized grains.
In2O3 doped WO3 powders were prepared by a polymer solution route and their NO2 gas sensing properties were analyzed. The synthesized powders showed nano-sized particles with specific surface areas of 6.01~21.5 m2/g and the particle size and shape changed according to the content of In2O3. The gas sensors fabricated with the synthesized powders were tested at operating temperatures of 400~500 oC and 100~500 ppm concentrations of NO2 atmosphere. The particle size and In2O3 content affected on the initial sensor resistance in an air atmosphere. The highest sensitivity (8.57 at 500 oC), which was 1.77 higher than the sensor consisting of the pure WO3 sample, was measured in the 0.5 mol% In2O3 doping sample. In addition, the response time and recovery time were improved by the addition of In2O3.
Nano-sized Zinc selenide (ZnSe) powder was successfully synthesized using Zn and Se precursors in a hydrothermal process. Temperature for the synthesis was varied from 95 oC to 180 oC to evaluate its influence on the microstructural properties of the synthetic particles. ZnSe powder thus fabricated was characterized using various analytical tools such as SEM, XRD, TEM and UV-Vis methods. Two types of ZnSe particles, that is, the precipitated particle and the colloidal particles, were identified in the analysis. The precipitated particles were around 100 nm in average size, whereas the average size of the colloidal particles was around 20 nm. The precipitated particles made at 150 oC and 180 oC were found to be a single phase of ZnSe; however, an inhomogeneous phase was obtained at the lower synthesis temperature of 95 oC, suggesting that the temperature for the synthesis should be over 100 oC. The precipitated particles were inactive in the UV-Vis absorption investigation, whereas the colloidal particles showed that absorptions occurred at 380 nm in the UV-Vis spectrum.
2ZrO2·P2O5 powder, which is not synthesized by solid reaction method, was successfully synthesized through PVA solution method. In this process, the firing temperature and the PVA content strongly affected the crystallization behavior and final particle size. A stable α-phase 2ZrO2·P2O5 was synthesized at a firing temperature of 1200 oC and holding time of 4 h. β-phase 2ZrO2·P2O5 was observed, with un-reacted ZrO2 phases, for firing temperatures lower than 1200 oC. In terms of the PVA content effect, the powder prepared with a PVA mixing ratio of 12:1 showed stable α-phase 2ZrO2·P2O5; however, the β-phase was found to co-exist at relatively higher PVA content. The synthesized α-phase 2ZrO2·P2O5 powder showed an average particle size of 100~250 nm and an average thermal expansion coefficient of −2.5 × 10−6/oC in the range of room temp. ~800 oC.
In order to identify changes in the nature of the particles due to changes in the inflow rate of the raw material solution, the present study was intended to prepare nano-sized cobalt oxide (Co3O4) powder with an average particle size of 50 nm or less by spray pyrolysis reaction using raw cobalt chloride solution. As the inflow rate of the raw material solution increased, droplets formed by the pyrolysis reaction showed more divided form and the particle size distribution was more uneven. As the inflow rate of the solution increased from 2 to 10 ml/min, the average particle size of the formed particles increased from about 25 nm to 40 nm, while the average particle size did not show significant changes when the inflow rate increased from 10 to 50 ml/min. XRD analysis showed that the intensity of the XRD peaks increased remarkably when the inflow rate of the solution increased from 2 to 10 ml/min. On the other hand, the peak intensity stayed almost constant when the inflow rate increased from 10 to 50 ml/min. With the increase in the inflow rate from 2 to 10 ml/min, the specific surface area of the particles decreased by approximately 20 %. On the contrary, the specific surface area stayed constant when the inflow rate increased from 10 to 50 ml/min.
Iron-overload can cause harmful effects such as cancer and aging via promoting the production of free radicals. The effect of orally administered nano-Fe overload with ascorbic acid on colon carcinogenesis was investigated in male ICR mice. After a 1-week acclimation, 5-week-old mice received three intraperitoneal injections (experimental week 0-2) of azoxymethane (AOM, 10 mg/kg body weight) weekly, followed by 2% dextran sodium sulfate (DSS) in drinking water for the next 1 week to induce aberrant crypt foci (ACF). Animals were divided into four groups; carboxymethylcellulose (CMC) alone (control), CMC + ascorbic acid (AA), CMC + nano-Fe (NFe), and CMC + NFe + AA groups. Animals were fed an AIN-76A purified rodent diet and daily administrated oral doses of 450 ppm each of nano-Fe and AA combination for 6 weeks. The colonic mucosa was stained with 0.5% methylene blue, and then the ACF and polyps were counted. Lipid peroxidation in the serum and liver was evaluated using the thiobarbituric acid-reactive substances (TBARS) assay. Iron concentration in the liver was measured using Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). Iron concentration in the liver of the NFe-overloaded groups was higher than that of the control (p<0.05). AA treatment increased the iron concentration in the liver. The number of ACF was not significantly different among all the groups. The number of polyps in all the NFe-treated groups was slightly higher than that in the control group and AA only-treated group. The serum TBARS was not significantly different among all the groups, but that in the liver was higher in all the NFe-treated groups than it was in the control group (p<0.05). These results indicate that the additional NFe treatment did not affect the experimental colon carcinogenesis in mice regardless of the presence of ascorbic acid.
Copper is an essential micronutrient whose deficiency is often seen to occur in humans. Although many biomedical studies have focused on the use of nanoparticles, the nutritional effects of nano-sized copper oxide particles are not well known. This aim of this study was to investigate the nutritional bioavailability of nano- and micro-sized copper oxide (CuO) particles in copper-deficient (CuD) mice. Copper deficiency was induced in mice by feeding a CuD diet (0.93 mg Cu/kg diet) for 7 weeks. After the induction of copper deficiency, nano- or micro-sized copper oxide particles were administered orally at two different doses (0.8 and 4.0 mg CuO/kg body weight) to mice in the following groups: (1) normal control (NC), (2) CuD, (3) low dose micro-sized CuO, (4) high dose micro-sized CuO, (5) low dose nano-sized CuO, and (6) high dose nano-sized CuO. The hepatic copper concentration in the CuD group was significantly lower than that in the NC group. Compared to the NC group, the CuD group exhibited lower serum ceruloplasmin (CP) activity and CP level. The copper/zinc-superoxide dismutase activity in the CuD group was significantly lower than that in the NC group. Treatment with nano- or micro-sized copper oxide particles for 2 weeks restored the hepatic copper levels and serum CP activities to values similar to those observed in the NC group. The CP levels and copper/zinc-superoxide dismutase activities in all the copper oxide treatment groups also recovered to normal values after 3 weeks of copper oxide treatment. These results show that oral administration of either nano- or micro-sized copper oxide particles for 2–3 weeks restored the normal condition in previously CuD mice.
Using the spray pyrolysis process, nano-sized cobalt oxide powder with average particle size below 50 nm was prepared from cobalt chloride solution. The influences of the raw material solution on the properties of the powder formed examined. When the concentration of Co was low(20 g/L), the average particle size of the powder formed was roughly 20 nm, and the cohesion between these particles was significantly strong. When the concentration of Co increased to 100 g/L, the droplets nearly failed to exist in circular form and reflected a severely divided form. Furthermore, the average size of the particles formed was roughly 40 nm, and the particles reflected a polygonal form. When the solution was increased to nearly saturation level (Co at 200 g/L), the particle size distribution reflected significant unevenness due to severe droplet division while the surface also reflected significant unevenness. Furthermore, the average size of the particles formed increased significantly to 70 nm. The results of XRD analysis showed that the strength of the peaks reflected very little change when the concentration of Co was increased from 20 g/L to 50 g/L. Alternatively, when the concentration was increased to 100 g/L, the strength of the peaks increased compared to when the concentration was 50 g/L. However, when the concentration was increased to 200 g/L, the strength of the peaks failed to reflect significant change compared to when the concentration was 100 g/L. The specific surface area dramatically decreased by 30 % when the concentration of Co was increased from 20 g/L to 50 g/L. Alternatively, when the concentration of Co the solution increased to 100 g/L, the specific surface area decreased by roughly 15 %. Furthermore, when the concentration of Co was increased to nearly saturation level(200 g/L), the specific surface area decreased by roughly 35%.
In this study, nano-sized cobalt oxide powder with an average particle size below 50 nm was prepared from a cobalt chloride solution by the spray pyrolysis process. The influences of reaction temperature on the properties of the generated powder were examined. The average particle size of the particles formed based on the spray pyrolysis process at a reaction temperature of 700˚C is roughly 20 nm. Moreover, most of these particles cannot appear with an independent type, thereby coexisting in a droplet type. When the reaction temperature increases to 800˚C, the average particle size not only increases to roughly 40 nm but also shows a more dense structure while the ratio of particles which shows a polygonal form significantly increases. As the reaction temperature increases to 900˚C, the distribution of the particles is from roughly 70 nm to 100 nm, while most of the particle surface is more intricately close and forms a polygonal shape. When the reaction temperature increases to 1000˚C, the particle size distribution of the powder shows an existing form from 80 nm to at least 150 nm in an uneven form. As the reaction temperature increases, the XRD peak intensity gradually increases, yet the specific surface area gradually decreases.
In this study, by using nickel chloride solution as a raw material, a nano-sized nickel oxide powder with an average particle size below 50 nm was produced by spray pyrolysis reaction. A spray pyrolysis system was specially designed and built for this study. The influence of nozzle tip size on the properties of the produced powder was examined. When the nozzle tip size was 1 mm, the particle size distribution was more uniform than when other nozzle tip sizes were used and the average particle size of the powder was about 15 nm. When the nozzle tip size increases to 2 mm, the average particle size increases to roughly 20 nm, and the particle size distribution becomes more uneven. When the tip size increases to 3 mm, particles with an average size of 25 nm and equal to or less than 10 nm coexist and the particle size distribution becomes much more uneven. When the tip size increases to 5 mm, large particles with average size of 50 nm partially exist, mostly consisting of minute particles with average sizes in the range of 15~25 nm. When the tip size increases from 1 mm to 2 mm, the XRD peak intensities greatly increase while the specific surface area decreases. When the tip size increases to 3 mm, the XRD peak intensities decrease while the specific surface area increases. When the tip size increases to 5 mm, the XRD peak intensities increase again while the specific surface area decreases.
In this study, using a tin chloride solution as the raw material, a nano-sized tin oxide powder with an average particle size below 50 nm is generated by a spray pyrolysis process. The properties of the tin oxide powder according to the nozzle tip size are examined. Along with an increase in the nozzle tip size from 1 mm to 5 mm, the generated particles that appear in the shape of droplets maintain an average particle size of 30 nm. When the nozzle tip size increases from 1 mm to 2 mm, the average size of the generated particles is around 80-100 nm, and the ratio of the independent particles with a compact surface structure increases significantly. When the nozzle tip size is at 3 mm, the majority of the generated particles maintain the droplet shape, the average size of the droplet-shaped particles increases remarkably compared to the cases of other nozzle tip sizes, and the particle size distribution also becomes extremely irregular. When the nozzle tip size is at 5 mm, the ratio of droplet-shaped particles decreases significantly and most of the generated particles are independent ones with incompact surface structures. Along with an increase in the nozzle tip size from 1 mm to 3 mm, the XRD peak intensity increases, whereas the specific surface area decreases greatly. When the nozzle tip size increases up to 5 mm, the XRD peak intensity decreases significantly, while the specific surface area increases remarkably.
Porous Al2O3 dispersed with nano-sized Cu was fabricated by freeze-drying process and solution chemistry method using Cu-nitrate. To prepare porous Al2O3, camphene was used as the sublimable vehicle. Camphene slurries with Al2O3 content of 10 vol% were prepared by milling at 50˚C with a small amount of oligomeric polyester dispersant. Freezing of the slurry was done in a Teflon cylinder attached to a copper bottom plate cooled to -25˚C while unidirectionally controlling the growth direction of the camphene. Pores were subsequently generated by sublimation of the camphene during drying in air for 48 h. The green body was sintered in a furnace at 1400˚C for 1 h. Cu particles were dispersed in porous Al2O3 by calcination and hydrogen reduction of Cu-nitrate. The sintered samples showed large pores with sizes of about 150μm; these pores were aligned parallel to the camphene growth direction. Also, the internal walls of the large pores had relatively small pores due to the traces of camphene left between the concentrated Al2O3 particles on the internal wall. EDS analysis revealed that the Cu particles were mainly dispersed on the surfaces of the large pores. These results strongly suggest that porous Al2O3 with Cu dispersion can be successfully fabricated by freeze-drying and solution chemistry routes.