• Journal of the Korean Ceramic Society
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• v.31 no.1
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• pp.104-114
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• 1994

ZrO2 fibers were fabricated by means of the Sol-Gel process using Zr(O-nC3H7)4-H2O-C2H5OH-HNO3 solution as a starting material. The optimum experimental parameters such as molar ratio of starting materials, concentration, temperature, viscosity, the amounts of stabilizer and the pH of solution were determined. The experimentally determined optimum variables which produce good ZrO2 fibers were used to manufacture the Y2O3-and CaO-ZrO2 fibers. The amounts of Y2O3 and CaO were varied within the range from 1.5~5 mol% and 3~15 mol% respectively. The phase transformation and microstructural evolution of the fabricated ZrO2 gel fibers were investigated after heat treatments up to 120$0^{\circ}C$ by X-ray diffraction, Raman microprobe spectroscopy, SEM, and specific surface area and pore volume measurements. From the analysis of X-ray diffraction and Raman spectra, the phase of heat treated Y2O3-and CaO partially stabilized ZrO2 gel fibers(Y2O3:2.5~3 mol%, CaO:6~9 mol%) were identified as a tetragonal phase up to 100$0^{\circ}C$. The maximum tensile strength of 2.5Y2O3-97.5ZrO2 and 6CaO-94ZrO2 (in mol%) fibers heat treated at 100$0^{\circ}C$ for 1 hr was found be 1.3~2 GPa with diameters of 10~20 ${\mu}{\textrm}{m}$.

• Korean Journal of Materials Research
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• v.13 no.9
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• pp.572-580
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• 2003

Synthesizing behavior and microstructural evolution of $CaZrO_3$and $m-ZrO_2$in a thermal reaction process of $ZrSiO_4$-$xCaCO_3$mixtures, where x is 7 and 19, were investigated to determine the addition amount of CaO in CaO:$ZrO_2$:$SiO_2$ternary composition. CaZrO$_3$-Ca$_2$SiO$_4$precursor prepared by the mixture of $ZrSiO_4$and CaCO$_3$in aqueous suspending media was controlled to the acidic (pH=4.0) condition with HCI solution to enhance the thermal reaction. The addition amount of dispersant into the $ZrSiO_4$-$xCaCO_3$slip increased with increasing mole ratio of $CaCO_3$, which was associated with the viscosity of slip. Decarbonation reaction was activated with an increase of the addition amount of $CaCO_3$, showing different final temperatures in $ZrSiO_4$-$7CaCO_3$and $ZrSiO_4$-$19CaCO_3$mixtures as about 980 and 116$0^{\circ}C$, respectively, for finishing decarbonation reaction. The grain morphology was changed to spherical shape for all samples with an increase of sintering temperature. The grain size and phase composition of the synthesized composites depended on the mixture ratio of Zrsi04 and CacO3 powders, indicating that the main crystals were m-ZrO2 ($\leq$3 $\mu\textrm{m}$) and $CaZrO_3$ ($\leq$ 7 $\mu\textrm{m}$) in $ZrSiO_4$$>-7CaCO_3$and $ZrSiO_4$-$19CaCO_3$mixtures, respectively.

• Journal of the Korean Ceramic Society
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• v.34 no.2
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• pp.145-156
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• 1997

ZrO2 phase transformations depending on the type and amount of dopants and the sintering temperatures were studied for the 2 components (CaO-, Y2O3-, MgO-ZrO2) and the 3 components(MgO-ZrO2-Al2O3)ZrO2 powder by X-ray diffraction and Raman spectroscopy. In the CaO- and Y2O3-ZrO2 systems, as the CaO and Y2O3 contents increased to 6~15mol% and 3~15mol% respectively, we were not able to identify between tetragonal and cubic in the X-ray diffraction patterns. On the other hand, all Raman modes shifted to lower wavenumbers, decreasing in intensity and the number of bands, markedly. These phenomena were caused by tetragonallongrightarrowcubic phase transformation and interpreted by the breakdown of the wave vector selection rule(k=0) and the structural disorder associated with the formation of oxygen sublattice which was caused by the substitution between Zr4+ ion and Ca2+ or Y3+ ion in ZrO2 matrix. The monoclinic to cubic phase transformation occurred in 10mol% MgO-ZrO2 system. As the Al2O3 content increased from 0 to 20mol% in the MgO-ZrO2-Al2O3 systems, cubic phase transformed to monoclinic phase, this is because the MgO didn't play a role in a stabilizer because of the formation of the spinel(MgAl2O4) by the reaction between MgO and Al2O3, Also, the ZrO2 phase transformation was explained by the change of it's lattice parameters depending on the type and amount of dopants. Namely, as the amount of dopant increased to 10~13mol%, the axial ra-tio c/a came close to unity with increasing the lattice parameter a and decreasing the lattice parameter c. At that time, the tetragonallongrightarrowcubic phase transformation occurred.

• Journal of the Korean Ceramic Society
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• v.30 no.8
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• pp.635-642
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• 1993

To obtain a higher dielectric constant material, we investigated Ca substitution for Pb in PbZrO3. In this study, the four mixtures of (Pb0.68Ca0.32)ZrO3, (Pb0.65Ca0.37)ZrO3, (Pb0.63Ca0.37)ZrO3, and (Pb0.60Ca0.40)ZrO3 were prepared by coprecipitation reaction of Pb(NO3)2, ZrOCl2, and CaCl2 with (NH4)2CO3 and NH4OH in aqueous solution. The (Pb1-xCax)ZrO3 with different x mole fractions (x=0.35, 0.37) showed not only high dielectric constant, but also high Q values and low temperature coefficient of the capacitance.

• Journal of the Korean Ceramic Society
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• v.37 no.12
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• pp.1178-1186
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• 2000

타일의 내마모성과 내산성을 향상시키기 위해 결정화유리가 최근에 새로운 유약 재료로서 소개되고 있다. 신 유약의 연구에 사용된 조성은 $Ca_2$ZrSi$_4$O$_{12}$ 상에 근접하는 CaO-ZrO$_2$-SiO$_2$계의 유리조성의 분말로, 마이크로파 가열 (2.45 GHz)에 의해서 900-120$0^{\circ}C$의 0-20분간 소성되어 평가되었다. 그 결과, 100$0^{\circ}C$ 이상에서 소성한 시편은 내부 결정화를 나타내었으며, 결정상은 미세(5$mu extrm{m}$)한 크기를 갖는 $Ca_2$ZrSi$_4$O$_{12}$가 주 결정상이며, $Ca_2$ZrSi$_4$O$_{12}$, CaSiO$_3$, SiO$_2$의 세 상이 나타났다. 소결체의 미세구조는 사용한 유리분말의 입도의 영향을 받았다. 미세분말 (<38$\mu\textrm{m}$)을 이용한 소결체의 조직이 조세분말 (45-150$\mu\textrm{m}$)의 경우보다 수축율면에서 높았으며 낮은 기공도를 갖는 미세구조를 가졌다. 마이크로파에 의한 유리분말의 소성은 1000-120$0^{\circ}C$ 구간에서 10분 이내 결정화가 완료되는 급속 가열 공정이었으며 CaO-ZrO$_2$-SiO$_2$계 결정화 유리 제조에 균일한 체적가열을 할 수 있었다.

• Journal of the Korean Ceramic Society
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• v.33 no.5
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• pp.563-571
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• 1996

In order to fabricate solid electrolyte CaO-stabilized ZrO2 of high density sintered body economically 13 mol% CaO-stabilized ZrO2 powders were synthesized by the coprecipitation method. The characteristics and sintering behavior of fine powder were investigated. The precipitates has the specific surface area of 193 m2/g and apperaed to be fine and spherical primary particles with a size of approximately 5nm. The crystalliza-tion temperture of CaO-stabilized ZrO2 was 462$^{\circ}C$. The tetragonal phase was stable in the low calcining tempe-rature regions and the cubic zirconia solid solution was formed from above 120$0^{\circ}C$ through an intermediate stage of formation of CaZrO3 By introducing fine powders washed with alcohol and ball-milling process after calcination the sintered body was possible to attain the value of above 92% of the theoretical density at low temperature of 120$0^{\circ}C$.

• Journal of the Korean Institute of Telematics and Electronics A
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• v.30A no.5
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• pp.30-35
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• 1993

We have investigated microwave dielectric properties of TiO$_{2}$ added (Pb$_{1-x}$Ca$_{x}$)ZrO$_{3}$ Ceramics with x=0.33, 0.35, and 0.37 sintered at 1400$^{\circ}C$ for 2 h. For additions of up to 3wt% of TiO$_{2}$ in (Pb$_{0.63}$ Ca$_{0.37}$)ZrO$_{3}$ (x=0.37), TiO$_{2}$ was completely soluble in (Pb, Ca)ZrO3 phase and did not affect the grain size of ceramics. Dielectric constant and temperature coefficient of resonant frequency increased due to the formation of solid solution, whereas Q value decreased linearly as TiO$_{2}$ increased up to 1 wt%. However, the dielectric loss was very high as TiO$_{2}$ exceeded 2 wt%. It was also shown that as Ca ion content in 0.5 wt% TiO$_{2}$ added (Pb$_{1-x}$,Ca$_{x}$)ZrO$_{3}$ decreased from x=0.37 to x=0.33, dielectric constant increased and Q value decreased.

• Journal of the Korean Ceramic Society
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• v.16 no.4
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• pp.213-224
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• 1979

The present work was undertaken: (1) to determine if CaO-partially stabilized $ZrO_2$ prepared by Hot Petroleum Drying Method would show better ionic conductor as an oxygen sensor in molten metals than that prepared by Oxide Wet Mixing Method and than CaO-fully stabilized $ZrO_2$, and (2) to understand the nature of conduction mechanism of CaO-partially stabilized $ZrO_2$ by a comparison of measured electrical conductivity data with theory on defect structure of pure monoclinic $ZrO_2$ and fully stabilized cubic $ZrO_2$. The DC electrical conductivity was measured by 3-probe technique and the AC electrical conductivity by 2-probe technique as a function of temperature in the range 973-1373 K and oxygen partial pressure in the range 10-1-10-25Mpa. The results of the experiments were as follows: 1. CaO-partially stabilized $ZrO_2$ prepared by Hot petroleum Drying Method showed at T=1094-1285 K and $Po_2$=10-7-10-25 MPa a nearly ionic conduction with 4 times higher conductivity than that prepared by Oxide Wet Mixing Method. 2. High-oxygen pressure conductivity tends toward a Po_2^{+1/5}-Po_2^{+1/6}$dependence. An analysis of possible defect structures suggests that CaO-partially stabilized $ZrO_2$ has an anti-Frenkel defect in which singly or doubly ionized oxygen interstitials and defect electrons predominate at T=1094-1285 K and $Po_2$=10-1-10-7MPa. 3. The activation energy for pure electron hole-conduction and ionic conduction of CaO-partially stabilized $ZrO_2$ was found to be 130 KJ/mol at T=973-1373 K, $Po_2$=2, 127 10-2 MPa(air) and 153KJ/mol at T=1094-1285 K respectively.

• Korean Journal of Materials Research
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• v.30 no.4
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• pp.176-183
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• 2020

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 ℃. 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.

• Resources Recycling
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• v.21 no.6
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• pp.32-38
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• 2012

In this study, direct reduction of $ZrO_2$ using liquid calcium was investigated. The influence of molar ratio of Ca and $ZrO_2$, reaction time and temperature on the reduction behavior of $ZrO_2$ was studied. Experiments were conducted in a closed stainless steel chamber under Ar atmosphere during 5 to 60 minutes. Most of the $ZrO_2$ was reduced to Zr in 5 minutes at 1223 K and 3 Ca/$ZrO_2$ molar ratio. The minimum oxygen content in reduced metal Zr was obtained about 0.66 wt% at 1373 K after 30 minutes and 4 Ca/$ZrO_2$ molar ratio. The morphology of zirconium powder obtained was highly affected by the reaction temperature and reaction time.