The development of the electronics industry has led to an increased demand for the manufacture of MLCC (Multilayer Ceramic Capacitors), which in turn is expected to result in a rise in MLCC waste. The MLCC contains various metals, notably barium, titanium, and nickel, whose disposal is anticipated to increase correspondingly. Recently, recycling technologies for electronic waste have garnered attention as they address waste management and raw material supply challenges. This paper investigates the recovery of barium, nickel, and titanium from the MLCC by a hydrometallurgical process. Using citric acid, which is an organic acid, the metal inside the MLCC was leached. Additionally, metal materials were recovered through precipitation and complexing processes. As a result, barium and titanium were recovered from the leachate of the waste MLCC, and 93% of the nickel-based powder was recovered. Furthermore, the optimal recovery process conditions for recycling these metal elements were investigated.
Cu-Ti thin films were fabricated using a combinatorial sputtering system to realize highly sensitive surface acoustic wave (SAW) devices. The Cu-Ti sample library was grown with various chemical compositions and electrical resistivity, providing important information for selecting the most suitable materials for SAW devices. Considering that acoustic waves generated from piezoelectric materials are significantly affected by the resistivity and density of interdigital transducer (IDT) electrodes, three types of Cu-Ti thin films with different Cu contents were fabricated. The thickness of the Cu-Ti thin films used in the SAW-IDT electrode was fixed at 150 nm. As the Cu content of the Cu-Ti films was increased from 31.2 to 71.3 at%, the resistivity decreased from 10.5 to 5.8 × 10-5 ohm-cm, and the density increased from 5.5 to 7.3 g/cm3, respectively. A SAW device composed of Cu-Ti IDT electrodes resonated at exactly 143 MHz without frequency shifts, but the full width at half maximum (FWHM) values of the resonant frequency gradually increased as the Cu content increased. This means that although the increase in Cu content in the Cu-Ti thin film helps to improve the electrical properties of the IDT electrode, the increased density of the IDT electrode deteriorates the acoustic performance of SAW devices.
The surface of titanium (Ti) dental implants was modified by applying a zinc (Zn)-doped titanium dioxide (TiO2) coating. Initially, the Ti surfaces were etched with NaOH, followed by a hydrolysis co-condensation using tetrabutyl titanate (TBT, Ti(OC4H9)4) and zinc nitrate hexahydrate (Zn(NO3)2 ‧ 6H2O), with ammonia water (NH3 ‧ H2O) acting as a hydroxide anion source. The morphology and chemical composition of the Zn-doped TiO2-coated Ti plates were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and scanning electron microscopy (SEM). Synthesis temperatures were carefully adjusted to produce anatase Zn-doped TiO2 nanoparticles with a bipyramidal structure and approximate sizes of 100 nm. Wettability tests and cell viability assays demonstrated the biomedical potential of these modified surfaces, which showed high biocompatibility with a survival rate of over 95 % (p < 0.05) and improved wettability. Corrosion resistance tests using potentiodynamic polarization reveal that Zn-TiO2-treated samples with an anatase crystal structure exhibited a lower corrosion current density and more noble corrosion potential compared to samples coated with a rutile structure. This method offers a scalable approach that could be adapted by the biomaterial industry to improve the functionality and longevity of various biomedical implants.
This study is to manufacture a titanium dioxide (TiO2) photocatalyst by recycling sludge generated using titanium tetrachloride (TiCl4) as a coagulant. Compared to general sewage, a TiCl4 coagulant was applied to dyeing wastewater containing a large amount of non-degradable organic compounds to evaluate its performance. Then the generated sludge was dried and fired to prepare a photocatalyst (TFS). Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX), X-ray diffraction (XRD), and nitrogen oxide reduction experiments were conducted to analyze the surface properties and evaluate the photoactive ability of the prepared TFS. After using titanium tetrachloride (TiCl4) as a coagulant in the dyeing wastewater, the water quality characteristics were measured at 84 mg/L of chemical oxygen demand (COD), 10 mg/L of T-N, and 0.9 mg/L of T-P to satisfy the discharge water quality standards. The surface properties of the TFS were investigated and the anatase crystal structure was observed. It was confirmed that the ratio of Ti and O, the main components of TiO2, accounted for more than 90 %. As a result of the nitric oxide (NO) reduction experiment, 1.56 uMol of NO was reduced to confirm a removal rate of 20.60 %. This is judged to be a photocatalytic performance similar to that of the existing P-25. Therefore, by applying TiCl4 to the dyeing wastewater, it is possible to solve the problems of the existing coagulant and to reduce the amount of carbon dioxide generated, using an eco-friendly sludge treatment method. In addition, it is believed that environmental and economic advantages can be obtained by manufacturing TiO2 at an eco-friendly and lower cost than before.
In this study, we introduce a novel TiN/Ag embedded TiO2/FTO resistive random-access memory (RRAM) device. This distinctive device was fabricated using an environmentally sustainable, solution-based thin film manufacturing process. Utilizing the peroxo titanium complex (PTC) method, we successfully incorporated Ag precursors into the device architecture, markedly enhancing its performance. This innovative approach effectively mitigates the random filament formation typically observed in RRAM devices, and leverages the seed effect to guide filament growth. As a result, the device demonstrates switching behavior at substantially reduced voltage and current levels, heralding a new era of low-power RRAM operation. The changes occurring within the insulator depending on Ag contents were confirmed by X-ray photoelectron spectroscopy (XPS) analysis. Additionally, we confirmed the correlation between Ag and oxygen vacancies (Vo). The current-voltage (I-V ) curves obtained suggest that as the Ag content increases there is a change in the operating mechanism, from the space charge limited conduction (SCLC) model to ionic conduction mechanism. We propose a new filament model based on changes in filament configuration and the change in conduction mechanisms. Further, we propose a novel filament model that encapsulates this shift in conduction behavior. This model illustrates how introducing Ag alters the filament configuration within the device, leading to a more efficient and controlled resistive switching process.
Titanium, which has excellent strength and toughness characteristics, is increasingly used in the aerospace field. Among the titanium alloys used for body parts, more than 80 % are Ti-6Al-4V alloys with a tensile strength of 931 MPa. The spark plasma sintering (SPS) method is used for solidification molding of powder manufactured by the mechanical milling (MM) method, by sintering at low temperature for a short time. This sintering method avoids coarsening of the fine crystal grains or dispersed particles of the MM powder. To improve the mechanical properties of pure titanium without adding alloying elements, stearic acid was added to pure titanium powder as a process control agent (PCA), and MM treatment was performed. The properties of the MM powder and SPS material produced by solidifying the powder were investigated by hardness measurement, X-ray diffraction, density measurement and structure observation. The processing deformation of the pure titanium powder depends on the amount of stearic acid added and the MM treatment time. TiN was also generated in powder treated by MM 8 h with 0.50 g of added stearic acid, and the hardness of the powder was higher than that of Ti-6Al-4V alloy when treated with MM for 8 h. When the MM-treated powder was solidified in the SPS equipment, TiC was formed by the solid phase reaction. The SPS material prepared as a powder treated with MM 8 h by adding 0.50 g of stearic acid also formed TiN and exhibited the highest hardness of Hv1253.
Lithium lanthanum titanium oxide (LLTO) is a promising ceramic electrolyte because of its high ionic conductivity at room temperature, low electrical conductivity, and outstanding physical properties. Several routes for the synthesis of bulk LLTO are known, in particular, solid-state synthesis and sol-gel method. However, the extremely low ionic conductivity of LLTO at grain boundaries is one of the major problems for practical applications. To diminish the grain boundary effect, the structure of LLTO is tuned to nanoscale morphology with structures of different dimensionalities (0D spheres, and 1D tubes and wires); this strategy has great potential to enhance the ion conduction by intensifying Li diffusion and minimizing the grain boundary resistance. Therefore, in this work, 0D spherical LLTO is synthesized using ultrasonic spray pyrolysis (USP). The USP method primarily yields spherical particles from the droplets generated by ultrasonic waves passed through several heating zones. LLTO is synthesized using USP, and the effects of each precursor and their mechanisms as well as synthesis parameters are analyzed and discussed to optimize the synthesis. The phase structure of the obtained materials is analyzed using X-ray diffraction, and their morphology and particle size are analyzed using field-emission scanning electron microscopy.
The function of coolant in machining is to reduce the frictional force in the contact area in between the tool and the material, and to increase the precision by cooling the work-piece and the tool, to make the machining surface uniform, and to extend the tool life. However, cutting oil is harmful to the human body because it uses chlorine-based extreme pressure additives to cause environmental pollutants. In this study, the effect of cutting temperature and surface roughness of titanium alloy for medical purpose (Ti-6Al-7Nb) in eco-friendly ADL slot shape machining was investigated using the response surface analysis method. As the design of the experiment, three levels of cutting speed, feed rate, and depth of cut were designed and the experiment was conducted using the central composite planning method. The regression expressions of cutting temperature and surface roughness were respectively obtained as quadratic functions to obtain the minimum value and optimal cutting conditions. The values from this formula and the experimental values were compared. As a result, this study makes and establishes the basis to prevent environmental pollution caused by the use of coolant and to replace it with ADL (Aerosol Dry Lubricant) machining that uses a very small amount of vegetable oil with high pressure.
The low-temperature sinterability of TiO2-CuO systems was investigated using a solid solution of SnO2. Sample powders were prepared through conventional ball milling of mixed raw powders. With the SnO2 content, the compositions of the samples were Ti1-xSnxO2-CuO(2 wt.%) in the range of x 0.08. Compared with the samples without SnO2 addition, the densification was enhanced when the samples were sintered at 900oC. The dominant mass transport mechanism seemed to be grain-boundary diffusion during heat treatment at 900oC, where active grain-boundary diffusion was responsible for the improved densification. The rapid grain growth featured by activated sintering was also obstructed with the addition of SnO2. This suggested that both CuO as an activator and SnO2 dopant synergistically reduced the sintering temperature of TiO2.
Anderson-type polyoxometalate (POM) with general formula of [Hy(XO6)M6O18]n- (y=0-6, n=2-8, M=addenda atom, X=heteroatom) represents one of the basic topological structures among POM-type family. Anderson-type POMs have a planar arrangement and two terminal oxygen atoms attached to each addenda metal atom unlike other type. Thus, the Anderson-type POMs have high reactivity and various coordination modes. The various multifunctional organic-inorganic hybrid materials can be synthesized using the Anderson-type POMs as an inorganic building block. Another important feature of the Anderson-type POMs is the incorporation of the heteroatoms with various sizes and oxidation states, which can lead to tune chemical properties. No Anderson-type POMs with early transition metal ions in the heteroatom site have been reported previously. Recently, we reported the synthesis of titanium-containing Anderson-type POM, Na2K6Ti0.92W6.08O24∙12H2O (Ti-POM), which consists of pure inorganic framework built from a central Ti atom surrounded by six WO6 inorganic scaffold. Herein, in-depth studies were conducted to find optimal synthesis conditions such as composition and pH. The success of synthesis was confirmed with Powder X-ray Diffraction that the Ti-POM has a rhombohedral structure with space group of R-3m (No. 166) when the TiOSO4·xH2SO4∙yH2O/ Na2WO4∙2H2O molar ratio is in the range of 0.07 to 0.33. But outside of this range, other unwanted phases coexist. In a basic condition (pH=12), a single-phase Ti-POM with good crystallinity can be obtained, while a Keggin-type POM, NaxK10-x(H2W12O42), was formed through the decomposition of Ti-POM at pH lower than 7.
The magnetic Cs adsorbent functionalized with hierarchical titanium-ferrocyanide were fabricated for the highly efficient magnetic removal of radioactive cesium from water. The new magnetic Cs adsorbent has a core–shell structure that comprises a Fe3O4 core, an interlayer of SiO2, and a titanium-ferrocyanide-shell with hierarchical nanostructure. At first, the magnetic Fe3O4 nanoparticles synthesized via a hydrothermal reaction were coated with SiO2. Then, TiO2 were coated on the surface of SiO2 coated magnetic nanoparticles. Finally, the hierarchical titanium-ferrocyanide composed of 2-dimensional TiFC flakes was fabricated on the surface of core-shell MNP@SiO2@TiO2 microparticles using a TiO2 sacrificial template via a simple reaction with potassium ferrocyanide (FC) based on the Kirkendall-type diffusion. The resulting magnetic Cs adsorbent shows higher adsorption capacity of 416 mg/g than other magnetic Cs adsorbents (below 200 mg/g) because of the increased effective surface area of hierarchical titanium-ferrocyanide. Therefore, our Magnetic Cs adsorbent functionalized with hierarchical titanium-ferrocyanide has excellent potential for the treatment of various 137Cs-contaminated sources.
A spin coating process for RRAM, which is a TiN/TiO2/FTO structure based on a PTC sol solution, was developed in this laboratory, a method which enables low-temperature and eco-friendly manufacturing. The RRAM corresponds to an OxRAM that operates through the formation and extinction of conductive filaments. Heat treatment was selected as a method of controlling oxygen vacancy (VO), a major factor of the conductive filament. It was carried out at 100 oC under moisture removal conditions and at 300 oC and 500 oC for excellent phase stability. XRD analysis confirmed the anatase phase in the thin film increased as the heat treatment increased, and the Ti3+ and OH- groups were observed to decrease in the XPS analysis. In the I-V analysis, the device at 100 oC showed a low primary SET voltage of 5.1 V and a high ON/OFF ratio of 104. The double-logarithmic plot of the I-V curve confirmed the device at 100 oC required a low operating voltage. As a result, the 100 oC heat treatment conditions were suitable for the low voltage driving and high ON/OFF ratio of TiN/TiO2/FTO RRAM devices and these results suggest that the operating voltage and ON/OFF ratio required for OxRAM devices used in various fields under specific heat treatment conditions can be compromised.
The purpose of using coolant in machining is both to increase a tool life and also to prevent product deformation and thus, stabilize the surface quality by lubricating and cooling the tool and the machining surface. However, a very small amount of cutting mist should be used because chlorine-based extreme pressure additives are used to generate environmental pollutants in the production process and cause occupational diseases of workers. In this study, medical titanium alloy (Ti-6Al-7Nb) was subjected to a processing experiment by selecting factors and levels affecting cutting power in the processing of the Aerosol Dry Lubrication (ADL) method using vegetable oil. The machining shape was a slot to sufficiently reflect the effect of the cutting depth. As for the measurement of cutting force, the trend of cutting characteristics was identified through complete factor analysis. The factors affecting the cutting force of ADL slot processing were identified using the reaction surface analysis method, and the characteristics of the cutting force according to the change in factor level were analyzed. As the cutting speed increased, the cutting force decreased and then increased again. The cutting force continued to increase as the feed speed increased. The increase in the cutting depth increased the cutting force more significantly than the increase in the cutting speed and the feed speed. Through the reaction surface analysis method, the regression equation for predicting cutting force was identified, and the optimal processing conditions were proposed. The cutting force was predicted from the secondary regression equation and compared with the experimental value.
This study compares the characteristics of a compact TiO2 (c-TiO2) powdery film, which is used as the electron transport layer (ETL) of perovskite solar cells, based on the manufacturing method. Additionally, its efficiency is measured by applying it to a carbon electrode solar cell. Spin-coating and spray methods are compared, and spraybased c-TiO2 exhibits superior optical properties. Furthermore, surface analysis by scanning electron microscopy (SEM) and atomic force microscopy (AFM) exhibits the excellent surface properties of spray-based TiO2. The photoelectric conversion efficiency (PCE) is 14.31% when applied to planar perovskite solar cells based on metal electrodes. Finally, carbon nanotube (CNT) film electrode-based solar cells exhibits a 76% PCE compared with that of metal electrodebased solar cells, providing the possibility of commercialization.
Polyoxometalates (POMs) are nanoclusters composed of transition metals with high oxidation states. Owing to their redox properties and structural diversity, POMs have been applied to broad fields, such as catalysis, materials, and medicine. Among various fields of application, POMs play an important role in radiochemistry. POMs can form complexes with tri- and tetravalent lanthanides and actinides (radioactive elements), which may be good sequestrators or agents for separating nuclear wastes. Among the most prominent POM structures, Anderson-type POMs with a general formula of [Hy(XO6)M6O18]n− (y=0–6, n=2–8, M=addenda atom, X=heteroatom) represent one of the basic topological structures of the POM family. An important feature of Anderson type POMs is incorporating a large number of various heteroatoms with different size and oxidation states, which can lead to tune chemical properties. Interestingly, no example of Anderson type POMs with early transition metal ions in the heteroatom site has been reported to date. Herein, we discovered that the Anderson POM Na2K6Ti0.92W6.08O24·12H2O, which consists of pure inorganic framework built from a central Ti core supported by six WO6 inorganic scaffold, and the crystal structure was confirmed and refined using single-crystal X-ray diffraction (SC-XRD). In addition, structural characterizations, including, Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and Inductively coupled plasma-optical emission spectroscopy (ICP-OES) were performed.
In this study, phase-pure titanium dioxide TiO2 ceramics are sintered using standard high-temperature solid-state reaction technique at different temperatures (1,000, 1,100, 1,200, 1,300, 1,400 oC). The effect of sintering temperature on the densification and impedance properties of TiO2 ceramics is investigated. The bulk density and average grain size increase with the increase of sintering temperature. Impedance spectroscopy analysis (complex impedance Z * and complex modulus M *), performed in a broad frequency range from 100 Hz to 10 MHz, indicates that the TiO2 ceramics are dielectrically heterogeneous, consisting of grains and grain boundaries. The complex impedance Z *-plane indicates the resistance of grains of the TiO2 ceramics increases with increasing sintering temperature, while that of grain boundaries develops in the opposing direction. The complex modulus M *-plane shows a grain capacitance that seems to be independent of the sintering temperature, while that of the grain boundaries decreases with increasing sintering temperature. These results suggest that different sintering temperatures have effects on the microstructure, leading to changes in the impedance properties of TiO2 ceramics.
The physicochemical properties of crystalline titanium dioxide nanoparticles (TiO2 NPs) were investigated by comparing amorphous (amTiO2), anatase (aTiO2), metaphase of anatase-rutile (arTiO2), and rutile (rTiO2) NPs, which were prepared at various calcination temperatures (100℃, 400℃, 600℃, and 900℃). X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses confirmed that the phase-transformed TiO2 had the characteristic features of crystallinity and average size. The surface chemical properties of the crystalline phases were different in the spectral analysis. As anatase transformed to the rutile phase, the band of the hydroxyl group at 3,600–3,100 cm–1 decreased gradually, as assessed using Fourier transform infrared spectroscopy (FT-IR). For ultraviolet-visible (UVVis) spectra, the maximum absorbance of anatase TiO2 NPs at 309 nm was blue-shifted to 290 nm at the rutile phase with reduced absorbance. Under the electric field of capillary electrophoresis (CE), TiO2 NPs in anatase migrated and detected as a broaden peak, whereas the rutile NPs did not. In addition, anatase showed the highest photocatalytic activity in an UV-irradiated dye degradation assay in the following order: aTiO2 > arTiO2 > rTiO2. Overall, the phases of TiO2 NPs showed characteristic physicochemical properties regarding size, surface chemical properties, UV absorbance, CE migration, and photocatalytic activity.
This study aims to investigate the effect of an aluminum chromium nitride (AlCrN) coating on tool wear and hole quality in the conventional drilling process of carbon fiber-reinforced plastic (CFRP) composites, titanium alloy (Ti), and CFRP–Ti stack workpieces popular in the aerospace industry. The advanced arc plasma acceleration (APA) method of physical vapor deposition (PVD) was used for all AlCrN coatings. The drilling experiments were conducted with uncoated drills as well as AlCrN-coated drills. When drilling CFRP only, the AlCrN coating was removed at the drill cutting edges and the margin area, which suggests the carbon fibers abraded the coatings. When drilling Ti only, the AlCrN-coated drill mitigated the Ti adhesion formation, which resulted in less tool wear. In addition, hole quality for both CFRP and Ti was improved when the coating was used versus the uncoated tool. The machinability of CFRP–Ti stacks in the drilling process was improved by utilizing the advanced AlCrN coating on the WC tool in terms of drilling forces and hole quality parameters such as average hole size, average hole roundness, hole surface roughness, and Ti exit burr height.