• 한국세라믹학회지
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• 제31권1호
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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 ${\mu}{\textrm}{m}$.

• 한국재료학회지
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• 제13권9호
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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.

• 한국세라믹학회지
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• 제34권2호
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• pp.145-156
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• 1997

2성분계(CaO-, Y2O3-, MgO-ZrO2) 및 3성분계(MgO-ZrO2-Al2O3)ZrO2분말의 안정화제 종류, 첨가량 및 열처리온도 변화에 따른 ZrO2의 상전이를 X-선 회절과 Raman분광법으로 연구하였다. CaO-, 및 Y2O3-ZrO2계에서 CaO와 Y2O3의 첨가량이 각각 6~15mol% 및 3~15mol%로 증가에 따른 정방정상에서의 입방정상으로의 상전이를 X-선회절 pattern으로는 판별하기 어려웠으나, Raman spectra에서는 모든 Raman band가 저파수쪽으로 이동하고 band의 수 및 그 세기가 현저히 감소함을 관찰할 수 있었다. 이것은 정방정$\longrightarrow$입방정의 상전이가 발생한 것으로 ZrO2 격자내에서 Zr4+ 이온과 Ca2+ 혹은 Y3+이온의 치환에 의해 산소이온의 빈자리 생성으로 인한 구조적 불규칙성과 선택규칙(k=0)의 파괴에 기인한 것으로 해석된다. MgO의 경우에는 10mol%에서 단사정에서 입방정으로 상전이가 발생하였다. MgO-ZrO2-Al2O3계에서는 Al2O3의 첨가에 의해 입방정$\longrightarrow$단사정의 상전이가 발생하는데 이것은 MgO와 Al2O3의 반응에 의해 spinel(MgAl2O4)의 형성으로 인하여 MgO가 충분히 안정화제로서의 역할을 하지 못하기 때문으로 판단된다. 또한, 안정화제의 종류와 첨가량 변화에 따른 ZrO2의 상전이를 ZrO2의 격자상수값의 변화와 관련하여 설명할 수 있는데, 즉, 안정화제의 첨가량이 증가할수록 격자상수 a값은 증가하고 c값은 감소하여 10~13mol%사이에서는 c/a의 축비가 1에 근접하고, 따라서 정방정$\longrightarrow$입방정의 상전이가 진행됨을 알 수 있었다.

• 한국세라믹학회지
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• 제30권8호
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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.

• 한국세라믹학회지
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• 제37권12호
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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.

• 한국세라믹학회지
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• 제33권5호
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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$0^{\circ}C$.

• 전자공학회논문지A
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• 제30A권5호
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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.

• 한국세라믹학회지
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• 제16권4호
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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.

• 한국재료학회지
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• 제30권4호
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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.

• 자원리싸이클링
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• 제21권6호
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• pp.32-38
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• 2012

본 연구에서는 액상 칼슘에 의한 $ZrO_2$의 직접환원에 대하여 조사하였다. $ZrO_2$의 직접환원에 미치는 Ca과 $ZrO_2$의 몰비, 반응시간, 그리고 반응온도의 영향에 대하여 검토하였다. 실험은 5분에서 60분까지 Ar 분위기의 밀폐된 스테인리스강제의 반응기에서 실시하였다. 반응온도 1223 K, Ca과 $ZrO_2$의 몰비가 3 이상인 조건에서 대부분의 $ZrO_2$는 5분만에 Zr으로 환원되었다. 반응온도가 1337 K이고 Ca을 이론적인 양의 2배를 첨가한 경우 금속 Zr 중의 산소농도는 최저 0.66 wt%를 나타내었다. 그리고 Zr 입자의 형상은 반응온도와 반응시간에 큰 영향을 받는 것으로 나타났다.