Thin films of yttria-stabilized zirconia (YSZ) nanoparticles were prepared using a low-temperature deposition and crystallization process involving successive ionic layer adsorption and reaction (SILAR) or SILAR-Air spray Plus (SILAR-A+) methods, coupled with hydrothermal (175 °C) and furnace (500 °C) post-annealing. The annealed YSZ films resulted in crystalline products, and their phases of monoclinic, tetragonal, and cubic were categorized through X-ray diffraction analysis. The morphologies of the as-prepared films, fabricated by SILAR and SILAR-A+ processes, including hydrothermal dehydration and annealing, were characterized by the degree of surface cracking using scanning electron microscopy images. Additionally, the thicknesses of the YSZ thin films were compared by removing diffusion layers such as spectator anions and water accumulated during the air spray plus process. Crack-free YSZ thin films were successfully fabricated on glass substrates using the SILAR-A+ method, followed by hydrothermal and furnace annealing, making them suitable for application in solid oxide fuel cells.

지르코니아 복합체는 지르코니아 전구체, 알루미나 전구체, 그리고 유기 실란의 혼합물을 플라 스틱 기판 위에 코팅하여 졸 겔 공정과 저온의 광경화 과정, 그리고 열처리 공정 등 세 단계를 거쳐 합성하 였고, FT-IR과 XPS 분석을 통하여 지르코니아 전구체와 알루미나 전구체의 비율에 따라 합성된 복합체 내 Zr 원소와 Al 원소 비율이 일치함을 확인하였다. 코팅된 복합체는 파장이 420 nm 이상인 가시광선 영 역에서 96 % 이상의 투과도를 보였고, 기계적 강도는 연필 강도 9H 이상을 나타내었다. 특히 지르코니아 와 알루미나의 몰 비가 1:4의 비율의 복합 코팅제의 나노 압입 경도가 1.212 GPa로 가장 높은 것으로 확 인되었다.

3 mol% yttria-doped stabilized zirconia (3YSZ) is synthesized by a solvothermal process, and its characteristics are investigated using various methods. Also, the dispersibility of synthesized 3YSZ nanoparticles is observed with the species of surface modifier. The 3YSZ nano sol prepared with an optimum condition is employed in prism coating and its properties are evaluated. The synthesized 3YSZ nanoparticles show a globular shape with about 10 to 20 nm crystallite size. The mixed phases with the nano sol show a high specific surface of 178 m2/g. The prism sheet coated with the 3YSZ nano sol present an excellent refractive index, transmittance, and luminance; refractive index is 1.603, transmittance is 90.2 %, and luminance of coating film is improved by 5.9 % compared to that of the film without 3YSZ nano sol. It is verified that the surface modified 3YSZ is suitable as the prism sheet for optical displays.

The high-temperature stability of YSZ specimens fabricated by die pressure and cold isostatic press (CIP) is investigated in CaCl2-CaF2-CaO molten salt at 1,150 °C. The experimental results are as follows: green density 46.7 % and 50.9 %; sintering density 93.3 % and 99.3 % for die press and CIP, respectively. YSZ foremd by CIP exhibits higher stability than YSZ formed by die press due to denseness dependency after high-temperature stability test. YSZ shows peaks mainly attributed to CaZrO3, with a small t-ZrO2 peak, unlike the high-intensity tetragonal-ZrO2 (t-ZrO2) peak observed for the asreceived specimen. The t-ZrO2 phase of YSZ is likely stabilized by Y2O3, and the leaching of Y2O3 results in phase transformation from t-ZrO2 to m-ZrO2. CaZrO3 likely forms from the reaction between CaO and m-ZrO2. As the exposure time increases, more CaZrO3 is observed in the internal region of YSZ, which could be attributed to the inward diffusion of molten salt and outward diffusion of the stabilizer (Y2O3) through the pores. This results in greater susceptibility to phase transformation and CaZrO3 formation. To use SOM anodes for the electroreduction of various metals, YSZ stability must be improved by adjusting the high-density in the forming process.

This study analyzes the mechanical properties, including the attrition rate, of 50 μm size yttria-stabilized zirconia (YSZ) beads with different microstructures and high-energy milling conditions. The yttria distribution in the grain and grainboundary of the fully sintered beads relates closely to Vickers hardness and the attrition rate of the YSZ beads. Grain size, fractured surfaces, and yttrium distribution are analyzed by electronic microscopes. For standardization and a reliable comparison of the attrition rate of zirconia beads with different conditions, Zr content in milled ceramic powder is analyzed and calculated by X-ray Fluorescence Spectrometer(XRF) instead of directly measuring the weight change of milled YSZ beads. The beads with small grain sizes sintered at lower temperature exhibit a higher Vickers hardness and lower attrition rate. The attrition rate of 50 μm YSZ beads is measured and compared with the various materials properties of ceramic powders used for high-energy milling. The attrition rate of beads appears to be closely related to the Vickers hardness of ceramic materials used for milling, and demonstrates more than a 10 times higher attrition rate with Alumina(Hv ~1650) powder than BaTiO3 powder (Hv ~315).

최근 우수한 유연성과 화학적 안정성 등을 가진 고분자 수지와 우수한 기계적 성질 등을 나타내는 무기 재료로 이루어진 나노 복합 시스템으로써 유-무기 하이브리드 코팅 필름에 관한 연구가 활발히 진행되고 있다. 아크릴레이트 단량체로써 사용된 o-phenylphenoxyethyl acrylate (OPPEA)는 1.576의 높은 굴절률을 나타내고, Bisphenol A ethoxylate diacrylate (BAEDA)는 굴절률은 낮지만 경화된 고분자의 경도를 향상시킨다. 또한, 무기 소재로써 사용된 지르코니아는 산화지르코늄으로써 우수한 내구성과 광학특성 등을 나타낸다. 본 연구에서는 광학 특성을 향상시키기 위한 목적으로 아크릴레이트 단량체 중 BAEDA의 함량을 조절하여 필름을 제조한 뒤 연필 경도계와 아베굴절계를 이용하여 광학 특성 변화를 확인하였고, UV-vis spectrophotometer을 이용해 투과도를 비교하여 최적의 조건을 확립하였다. 그리고 실란 커플링제인 γ-methacryloxypropyltrimethoxysilane (MPS)를 사용하여 지르코니아를 소수화 처리하여 아크릴레이트 단량체에 대한 분산성을 향상시키고, 개질 전후의 물에 대한 분산성 변화를 조사하여 물에 대한 친화력이 감소하였음을 확인하였고, FT-IR ATR spectrophotometer를 통해 MPS에 의해 도입된 1716 cm-1에서의 에스터 C=O 결합 peak의 존재를 통해 MPS에 의한 지르코니아 표면의 개질 반응이 진행되었음을 확인하였다. 또한, 지르코니아의 표면에 도입된 규소 원자의 존재는 X 선 형광법을 이용하여 확인하였다. 그리고 화학적으로 개질된 지르코니아를 아크릴레이트 단량체에 도입하여 광경화 필름을 제조하였을 때, 굴절률은 아크릴레이트 자체 필름보다 1.2% 향상되었음을 확인하였고, SEM/EDS mapping 분석을 통해 PET 필름에 코팅된 개질 후 지르코니아가 아크릴레이트 코팅층에 균일하게 분포되어 있음을 알 수 있었다.

Particle size reduction is an important step in many technological operations. The process itself is defined as the mechanical breakdown of solids into smaller particles to increase the surface area and induce defects in solids, which are needed for subsequent operations such as chemical reactions. To fabricate nano-sized particles, several tens to hundreds of micron size ceramic beads, formed through high energy milling process, are required. To minimize the contamination effects during highenergy milling, the mechanical properties of zirconia beads are very important. Generally, the mechanical properties of Y2O3 stabilized tetragonal zirconia beads are closely related to the mechanism of phase change from tetragonal to monoclinic phase via external mechanical forces. Therefore, Y2O3 distribution in the sintered zirconia beads must also be closely related with the mechanical properties of the beads. In this work, commercially available 100μm-size beads are analyzed from the point of view of microstructure, composition homogeneity (especially for Y2O3), mechanical properties, and attrition rate.

Stable slurries of YSZ in aqueous suspension with added polymer dispersants, namely, poly-methacrylic acid ammonium salt (PMMA), poly-acrylic acid (PAA) and poly-acrylic-co-maleic acid (PAMA), were mixed with the monomolecular dispersants citric acid and oxalic acid. The dispersion properties of the suspension were investigated using PSA, viscosity, sedimentation, and FT-IR. The polymer dispersants and monomolecular dispersants were attached to the YSZ surface by the carboxylic group, as shown by the FTIR results. A stabilized aqueous suspension was obtained when the polymer dispersant and citric acid were mixed and compared to the use of citric acid alone as a dispersant agent. When the polymer dispersant and citric acid were mixed and milled through attrition milling, there was a smaller particle size compared to when the polymer dispersant alone was used as a dispersant agent. This study determined that the particle size of the mixed dispersant was affected by the properties of the monomolecular dispersant and that the stability of the suspension was affected by the polymer dispersant. However, when slurries of YSZ were mixed with oxalic acid, the particle bridging behavior was the result of the high degree of viscosity and the small sedimentation height.

본 연구에서는 고투과성 Ni-ZiO2 모세관 지지체를 NIPS 방법에 의해서 제조되었으며, 기체분리용 고투과성 분리막 제조에 사용하고자 하였다. 이때 Ni:ZrO2 비율을 각각 100:0, 70:30, 50:50, 30:70으로 섞어 만든 도프용액을 이용하여 모세관 지지체를 제조한 후 소결온도를 950, 1000, 1100, 1200, 1300, 1400, 1500°C으로 달리하여 Ni:ZrO2 비율과 소결온도가 Ni-ZiO2 모세관 지지체의 기계적 안정성, 기공구조 및 단일기체투과도에 미치는 영향을 분석하고자 하였다.

백색을 띄고 물리적·화학적으로 안정한 지르코니아는 열전도도가 낮고 강도와 인성, 내식성이 우수하여 단열재, 내화물과 같은 고온 재료와 각종 산업용 구조세라믹스에 사용되고 있다. 이러한 지르 코니아를 낮은 경도 및 굴절률 등과 같은 단점을 가진 고분자 코팅제에 도입하게 되면 화학적, 전기적, 광학적인 특성이 향상된다. 이와 같이 유기 소재에 무기 소재를 혼합하여 사용하는 유-무기 하이브리드 코팅을 목적으로 본 연구에서는 지르코니아 표면에 trimethylchlorosilane(TMCS)과 hexamethyldisilazane(HMDZ)을 사용하여 실릴화반응을 통한 -CH3기를 도입하여 소수성을 나노지르코 니아 표면에 도입하였다. 소수화된 지르코니아 표면에서의 TMCS와 HMDZ에 의해 도입된 Si-CH3의 존재는 FT-IR ATR spectroscopy를 통해 확인하였고, silicon 원소의 존재를 FE-SEM/EDS와 ICP-AES 를 통해 확인하였다. 또한, 개질 전후의 지르코니아를 아크릴레이트 단량체에 분산하여 침강속도를 확인 하여 분산성이 향상되는 것을 확인하였다. 지르코니아 입자의 크기 및 분포는 입도 분석기를 통해 확인 하였으며, BET 분석을 통해 개질 반응 전후의 비표면적은 18 m2/g 정도로 큰 변화가 없었다.

Spherical-type zirconia granules are successfully fabricated by a spray-drying process using a water solvent slurry, and the change in the green density of the granule powder compacts is examined according to the organic polymers used. Two organic binders, polyvinyl alcohol (PVA) and 2-hydroxyethyl methacrylate (HEMA), which are dissolved in a water solvent and have different degrees of polymerization, are applied to the slurry with a plasticizer (polyethylene glycol). The granules employing a binder with a higher degree of polymerization (PVA) are not broken under a uniaxial press; consequently, they exhibit a poor green density of 2.4 g/cm3. In contrast, the granule powder compacts employing a binder with a lower degree of polymerization (HEMA) show a higher density of 2.6 g/cm3 with an increase in plasticizer content. The packing behavior of the granule powders for each organic polymer system is studied by examining the microstructure of the fracture surface at different applied pressures.

Zirconia nanoparticles were widely used as filler in order to get high refractive index layer. However, dispersion of nanoparticles is difficult due to their agglomeration in solvent. In this study, the dispersibility of the zirconia suspension is promoted by controlling the steric hindrance and electrostatic interactions through the adsorption of PEI according to alkali treatment time. Also, to induce improved dispersibility on suspension, we changed the dispersion conditions variously and fabricated an ink formulation method for the coating layer. Zirconia suspension was characterized by dynamic light scattering (DLS), Zeta potential measurement, Transmission Electron Microscope (TEM) and FT-IR. We were able to confirm that good dispersion of zirconia suspension by alkali treatment and PEI led to high refractive index.

마이크로지르코니아는 높은 내약품성, 높은 전기저항성 등의 우수한 열적 기계적 성질을 가지 므로 다양한 분야에 사용되어 진다. 또한 지르코니아 표면을 친수화시키면, 물에 대한 분산성이 우수하 여 분산이 용이할 뿐만 아니라 대부분의 오염물질은 소수성을 띄기 때문에 오염물질에 대한 저항성을 높일 수도 있다. 본 연구에서는 지르코니아 표면에 γ-aminopropyltrimethoxysilane (APS)을 사용하여 서로 다른 pH 조건에서의 가수분해와 축합반응을 통한 친수성기의 도입과 물에 대한 분산성을 조사하 고 γ-ureidopropyltrimethoxysilane (UPS)을 사용한 결과와도 비교하였다.친수화로 개질된 마이크로지르코니아에의 지르코니아 표면의 수산기와 가수분해된 실란의 수산기와의 공유결합의 존재는 FT-IR ATR spectroscopy 및 ninhydrin 반응을 통해 확인하였다. 그러나, SEM/EDS의 결과로는 지르코니아 표면에 도입된 Si의 존재는 확인할 수 없었다. 또한, 입도 분석 결과 마이크로지르코니아는 개질 반응 중 일부 입자의 파쇄 및 aggregation이 일어남을 알 수 있었다. APS 로 개질한 경우 pH가 중성일 때 수분산성이 향상되었으나, 0.5~2% 농도의 UPS로 개질된 경우는 모든 경우 수분산성이 향상되며 분산안정성도 우수하였다.

본 연구에서는 기공의 크기가 큰 다공성 지지체를 3~4 μm, 150 nm의 크기를 갖는 α-알루미나 입자를 물과 실 리카-지르코니아 용액에 각각 분산시키는 방법으로 표면 개질을 하였다. 3~4 μm 크기의 알루미나 입자가 분산된 용액을 이 용하여 금속 지지체 및 알루미나 지지체에 코팅하였을 때, 코팅횟수가 증가할수록 지지체의 표면의 큰 기공이 감소하였고, 여 기에 150 nm 크기의 알루미나 입자가 분산된 용액으로 추가 코팅을 하면 작은 크기의 알루미나 입자가 기공 사이사이에 들 어가면서 지지체를 좀 더 매끄럽게 개질하는 역할을 하는 것을 확인하였다. 특히 실리카-지르코니아 용액을 분산매로 하여 표면 개질을 한 경우, 알루미나 입자가 실리카-지르코니아 층에 촘촘하게 박힌 모양으로 고정이 되어 지지체 개질에 효과적 임을 확인하였다. 이러한 방법으로 제조된 실리카-지르코니아 분리막의 기체투과도는 상온에서 각각 1.8 - 8.4 × 10-4 mol⋅m-2 ⋅s-1⋅Pa-1, 3.3 - 5.0 × 10-5 mol⋅m-2⋅s-1⋅Pa-1이며 수소/질소 선택도는 Knudsen 분포를 보였다. 표면 개질된 지지체에 다양 한 분리층을 형성하는 방법으로 무기 분리막 응용에 이용할 수 있을 것으로 예상된다.

To increase the mechanical property of zirconia, we have investigated the phase change and the resulting hardness of zirconia ceramics by hydroxyapatite (HA) powder bed sintering. It was observed using X-ray diffraction that the cubic zirconia phase, which has a higher hardness value than that of the tetragonal phase, was obtained at the surface of 3 mol% Y2O3 doped tetragonal zirconia polycrystal (3Y-TZP) ceramics during the sintering process; in our experimental conditions, the phase change at the surface increased as the sintering time increased. We believe that the observed crystalline phase change originated from the decomposition of HA and the diffusion of CaO, as follows. CaO, which was derived from the decomposition of HA at high temperature (1400˚C), diffused into the surface of 3Y-TZP and acted as a stabilizer. As a result, the Vickers hardness value of the treated specimens was higher than that of the non-treated specimen due to the formation of the cubic phase on the surface of 3Y-TZP.

The purpose of this study was to investigate the microstructures and mechanical properties of zirconia toughened alumina (ZTA) ceramics prepared from two kinds of 3Y-TZP powders. ZTA composites were prepared by adding two kinds of 3Y-TZP powders, 3YEH (BET = 7m2/g) and 3YEM (BET = 16m2/g), to α-alumina in the range of 5-25 wt%. It was found that the microstructure photographs of the ZTA composites showed that the average grain size of alumina decreased as the content of zirconia increased. In our present study, specimens containing 3YEM zirconia exhibited smaller grain sizes compared to those of 3YEH zirconia. The Vickers hardness of the ZTA composites that were sintered at 1600˚C for 2 hrs was found to smoothly decrease with increasing zirconia content because of the low Young modulus in zirconia. The Vickers hardness of the ZTA containing 3YEH zirconia was greater than that of the 3YEM zirconia. In substance, the fracture toughness (K1c) of the ZTA composites increased as the content of zirconia increased. The fracture toughness (K1c) of ZTA containing 3YEM zirconia was greater than that of 3YEH zirconia.

Yttria-stabilized zirconia (YSZ) coatings are fabricated via suspension plasma spray (SPS) for thermal barrier applications. Three different suspension sets are prepared by using a planetary mill as well as ball mill in order to examine the effect of starting suspension on the phase evolution and the microstructure of SPS prepared coatings. In the case of planetary-milled commercial YSZ powder, a deposited thick coating turns out to have a dense, vertically-cracked microstructure. In addition, a dense YSZ coating with fully developed phase can be obtained via suspension plasma spray with suspension from planetary-milled mixture of Y2O3 and ZrO2.

In this study, intermediate-mixed powders were prepared by loading zirconia powders initially in a ball-mill jar and loading alumina powders afterward; the initial-mixed powders were produced by loading zirconia and alumina powders together in the ball-mill jar. The effect of such differences in mixing method on the mechanical properties was investigated. In intermediate-mixed powders, the volume fraction of large particles slightly increased and, simultaneously, zirconia particles formed agglomerates that, due to early ball-mill loading of the zirconia powders only, were more dispersed than were the initial-mixed powders. For the intermediate-mixed powders, zirconia agglomerates were destroyed more quickly than were initial-mixed powders, so the number of dispersed zirconia particles rose and the inhibitory effect of densification due to the addition of a second phase was more obvious. In the microstructure of intermediate-mixed powders, zirconia grains were homogeneously dispersed and grain growth by coalescence was found to occur with increasing sintering temperature. For the initial-mixed powders, large zirconia grains formed by localized early-densification on the inside contacts of some zirconia agglomerates were observed in the early stages of sintering. The intermediate-mixed powders had slightly lower hardness values as a whole but higher fracture toughness compared to that of the initial-mixed powders.

The purpose of this paper was to investigate the effect of a high-energy milling (HEM) process on the particle morphology and the correlation between a thermal treatment and tetragonal/monoclinic nanostructured zirconia powders obtained by a precipitation process. To eliminate chloride residue ions from hydrous zirconia, a modified washing method was used. It was found that the used washing method was effective in removing the chloride from the precipitated gel. In order to investigate the effect of a pre-milling process on the particle morphology of the precipitate, dried Zr(OH)4 was milled using a HEM machine with distilled water. The particle size of the Zr(OH)4 powder exposed to HEM reduced to 100~150 nm, whereas that of fresh Zr(OH)4 powder without a pre-milling process had a large and irregular size of 100 nm~1.5 μm. Additionally, modified heat treatment process was proposed to achieve nano-sized zirconia having a pure monoclinic phase. It was evident that two-step calcining process was effective in perfectly eliminating the tetragonal phase, having a small average particle of ~100 nm with good uniformity compared to the sample calcined by a single-step process, showing a large average particle size of ~300 nm with an irregular particle shape and a broad particle size distribution. The modified method is considered to be a promising process for nano-sized zirconia having a fully monoclinic phase.