• Proceedings of the Korea Association of Crystal Growth Conference
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• 1996.06b
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• pp.55-85
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• 1996

지르코니아 분말은 ZrO2 결정상이 온도변화에 따라 부피변화를 수반하는 상전이변태를 나타낸다. 단사정 ZrO2가 110$0^{\circ}C$에서는 정방정으로, 2$700^{\circ}C$ 내외에서는 입방정으로 결정구조가 가역적으로 변한다. 이 ZrO2에 금속산화물을 고용시키면 형석 (CaF2:Florite)형의 입방정 결정구조가 실온에서도 안정하게 존재하게 된다. 안정화제 산화물은 caO, MgO등 2가 산화물외에 3가 또는 4가의 금속산화물로서 Sc2O3, Y2O3, Sm2O3, Nd2O3, Gd2O3, Y2O3, CeO2 등이며 이들은 금속이온의 원자가가 변하기 쉬운 희토류 산화물이다. 안정화 지르코니아는 형석형 결정구조이며 결정화학적으로 보면 금속양이온이 산소이온에 대해서 정육면체형의 8배위를 하고 있다. 이때 이온반경비(양이온/음이온)에 따라 Zr+4자리와 O-2자리의 격자위치와 모양이 형성되므로 비틀어진 정육면체구조이건 이상적인 정육면체 형석구조를 이룬다. 이는 지르코니아의 결정상의 2상-3상인 부분안정화 지르코니아다결정체(PSZ : partially stabilized zirconia)이거나 단일상-2상인 정방정 지르코니아다결정체(TZP : tetragonal zirconia polycrystal)의 결정구조를 가지는데 기인한다. PSZ는 주로 MgO, CaO를 안정화제로 고용시켜 입방정 영역에서 소결하고 이를 다시 입방정과 정방정의 상 영역에서 열처리하여 입방정 입자내부에 정방정을 석출 형성시킨 것이며 TZP는 Y2O3 및 CeO2를 고용시켜 PSZ와 다르게 일반적인 상압소결한 정방정 결정상의 미립자이다. 산화지르코늄 분말은 지르콘사에서 열분해시킨 지르코늄소결.융해괴(caustic fusion clinker)를 산처리하여얻어진 지르코늄산용액(zirconyl acid solution : cloride, sulfide, nitride 등)으로부터 제조된다. 고순도 산화지르코늄은 용액 결정석출법에 의해 ZrOCl2.8H2O, 5ZrO2.3SO3.15H2O, ZrO(NO3)2.xH2O 등의 지르코늄 수화물만을 재결정화시킨 것으로부터 얻을 수 있으며 이 지르코늄염 수용액으로부터 입자미세구조를 효과적으로 제어하여 산화지르코늄 및 안정화 지르코니아 분말제조가 가능하다. 안정화 지르코니아 분말은 ZrO2와 안정화산화물의 고용을위하여 가열처리를 필요로 하며 일정온도에서 최적상태로 숙성하므로서 2가지 상(phase) 이상의 고용체를 가지게 된다. 안정화 지르코니아 분말은 고용처리온도를 낮추고 효과적으로 생성시키기 위해서는 지르코늄 및 안정화제염을 혼합하고 습식 직접합성하여 저온에서 고용체의 합해진상 영역을 생성시키는 것이다. 이는 지르코니아 원료분말의 미세구조를 제어하므로서 가능하며 이때 화학성분조성과 크기형태가 균일하게 분포된 입자분말을 얻을 수 있다.

• Journal of the Korean Ceramic Society
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• v.25 no.3
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• pp.225-230
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• 1988

The strength and thermal shock resistance of $Al_2O_3-ZrO_2$ composites have been studied. The tetragonal $ZrO_2$ powder containing 1 mol.% $Y_2O_3$ and monoclinic $ZrO_2$ powder were prepared by coprecipitation method and subsequently mixed with $Al_2O_3$ powder and granulated by sieving. Duplex composites were prepared by dry mixing matrix agglomerate with 15 to 30 vol.% of dispersion agglomerate, followed by pressing and sintering at 1$600^{\circ}C$ for1 hr. These $Al_2O_3-ZrO_2$ 2 composites having heterogeneous structure showed improved thermal shock behaviors because of the microcracking and pores in dispersed granules, and compressive stresses around dispersed granules resulting from $ZrO_2$ transformation.

• Journal of the Institute of Electronics Engineers of Korea TE
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• v.39 no.1
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• pp.1-8
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• 2002

The effects of the addition of either monoclinic $ZrO_2$($ZrO_2$(m)) or tetragonal $ZrO_2$($ZrO_2$(t)) containing 5.35wt% $Y_2O_3$ on the physical properties and electrical conductivity of TEX>$Al_2O_3$ were investigated. The addition of $ZrO_2$(m) and $ZrO_2$(t) increased sintered density of $Al_2O_3$. The Vickers hardness also increased as addition of >($ZrO_2$(t) increased going through a maximum at 20wt% and the hardness of the specimens was found to be dependent on the sintered density. The addition of $ZrO_2$(t) improved the hardness of $Al_2O_3$-$ZrO_2$ systems and the $ZrO_2$(m) addition showed the better effect on the thermal shock property of $Al_2O_3$-$ZrO_2$ systems than that of the $ZrO_2$(t) addition. Above 15wt% addition of $ZrO_2$(t), the electrical conductivity is gradually increased with increasing applied voltage but not effects by addition of $ZrO_2$(m).

• Korean Journal of Materials Research
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• v.8 no.1
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• pp.3-9
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• 1998

40$0^{\circ}C$ H$_{2}$O, D$_{2}$O및 $O_{2}$분위기에서 Zr-2.5Nb합금의 부식거동을 분석하였다. Martensitic $\alpha$'-Zr상이나 $\alpha$-Zr과 $\beta$-Zr상의 Zr-2.5Nb합금인 경우, 부식분위기에 매우 민감하여, $O_{2}$속에서 가장 큰 부식속도를 보였다. 반면, $\alpha$-Zr나 $\beta$-Zr상의 경우, 부식 매질에 따른 별다른 차이없이 높은 부식저항성을 보였다. 이러한 Zr-2.5Nb 합금의 미세조직 및 부식 매질에 따른 부식거동변화는 Zr-2.5Nb 합금의 음극 지배 부식반응의 관점으로 해석되었으며, 이들 결과를 이용하여 CANDU 형및 RBMK 형 Zr-2.5Nb 압력관의 가동조건 차이를 설명할 수 있었다. Zr-2.5Nb 합금의 모든 조직에서 주로 단사정 ZrO$_{2}$산화물이 형성되었으며, 산화물내 정방정 ZrO$_{2}$비율은 산화물 두께가 증가함에 따라 감소하였다.

• Journal of the Korean Ceramic Society
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• v.37 no.11
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• pp.1058-1064
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• 2000

연속슬립캐스팅 및 상압소결법으로 $Al_2$O$_3$/ZrO$_2$적층복합체를 제조하였으며, 적층복합체에서 ZrO$_2$층을 단사정, 정방정 및 입방정으로 각각 달리 적층하여 균열생성 및 전파 거동에 미치는 ZrO$_2$상의 영향을 고찰하였다. 균열 생성은 냉각시 $Al_2$O$_3$층과 ZrO$_2$층 간의 열팽창 계수의 차이에 의한 열적불일치응력이 가장 큰 요인으로 작용하였다. 적층체 내에 존재하는 균열은 tetra-ZrO$_2$의 경우 적층두께 조절로 가능하였으며, cubic-ZrO$_2$의 경우는 냉각속도 조절로 균열밀도로 크게 낮출 수 있었다. $Al_2$O$_3$/ZrO$_2$적층체를 구성하는 세가지 ZrO$_2$상(mono, tetra, cubic)들 중에서 cubic-ZrO$_2$가 포함된 적층체의 경우 $Al_2$O$_3$와 ZrO$_2$계면에 형성된 잔류압축응력으로 인한 균열굴절 효과를 얻을 수 있었다.

• Journal of the Korean Ceramic Society
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• v.27 no.3
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• pp.361-368
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• 1990

The properties of the powder of ZrO2＋3m/o Y2O3 system prepared by co-precipitation method at the pH values of 7, 9, 10 and 11 were investigated. ZrOCl2.8H2O and YCl3.6H2O were used as starting materials and NH4OH as a precipitation agent. Zirconium hydroxide near by Zr(OH)4 structure showed more excellent crystallinity and lower formation temperature of tetragonal ZrO2. In the range of this study, cubic ZrO2 was not formed and stability of tetragonal ZrO2 prepared in the conditiion of pH 7 was most excellent. Average particle sizes and specific surface areas of tetragonal ZrO2 powders, prepared as calcining amorphous zirconium hydroxides at $600^{\circ}C$ for 1h, were 0.6-0.8${\mu}{\textrm}{m}$ and 45-70$m^2$/g, respectively.

• Journal of the Korean Ceramic Society
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• v.34 no.6
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• pp.645-651
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• 1997

Tetragonal zirconia polycrystals (TZPs) doped with $Y_{2}O_{3}$ and $Nb_{2}O_{5}$ were prepared by the conventional sintering to enhance fracture toughness and phase stability of TZPs without controlling the grain size. TZP composites were obtained by adding the transformable TZP to the non-transformable TZP in wt%. The monolithic tetragonal $ZrO_2$, same as the composite composition containing 15 wt% transformable TZP, sintered at $1550^{\circ}C$ for 10h in air, exhibited the fracture toughness of 9$MPam^{1/2}$ and no low-and high-temperature degradation at temperatures in the range of 220 to $1000^{\circ}C$ for 100h in air. The corresponding single composition was 90.24 mol% $ZrO_2$-5.31 mol% $Y_{2}O_{3}$-4.75 mol% $Nb_{2}O_{5}$. The microstructure observation revealed that the t-$ZrO_2$ grains grew grandually with sintering time and no microcraking and twinning were observed.

• Journal of the Korean Ceramic Society
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• v.31 no.5
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• pp.513-519
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• 1994

Alumina composite was fabricated by introducing tetragonal ZrO2 in alumina composite of $\alpha$-alumina reinforced with in-situ formed La-$\beta$-aluminate (LaAl11O18). The powder mixture of composition (100-x)[88 Al2O3+(La2O3+11 Al2O3)]+x vol% ZrO2 was prepared with x from 0 to 40. Dense composites fabricated by hot-pressing exhibited bending strength up to 1200 MPa. The gain growth inhibiting effect of ZrO2 grains and La-$\beta$-aluminate platelets, and possibly the stress-induced phase transformation of ZrO2 have resulted in the high bending strength. The fracture toughness of the composite also increased up to 8.5 MPa.m1/2. The enhancement in toughness can be explained by transformation and microcrack toughening of ZrO2 and by crack deflection and bridging of La-$\beta$-aluminate platelets and ZrO2.

• 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 Industrial Technology
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• v.20 no.A
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• pp.247-256
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• 2000

Precursor gels with the composition of $xZrO_2{\cdot}(100-x)SiO_2$ systems (x=10, 20 and 30 mol%) were prepared by the sol-gel method. Kinetic parameters, such as activation energy, Avrami's exponent, n, and dimensionality crystal growth value, m, have been simultaneously calculated from the DTA data using Kissinger and Matusita equations. The crystallite size dependence on tetragonal to monoclinic transformation of $ZrO_2$ was investigated using XRD, in relation to the fracture toughness. The crystallization of tetragonal $ZrO_2$ occurred through 3-dimensional diffusion controlled growth(n=m=2) and the activation energy for crystallization was calculated using Kissinger and Matusita equations, as about $310{\sim}325{\pm}10kJ/mol$. The growth of $t-ZrO_2$, in proportion to the cube of radius, increased with increasing heating temperature and heat-treatment time. It was suggested that the diffusion of Zr4+ions by Ostwald ripening was rate-limiting process for the growth of $t-ZrO_2$ crystallite size. The fracture toughness of $xZrO_2{\cdot}(100-x)SiO_2$ systems glass ceramics increased with increasing crystallite size of $t-ZrO_2$. The fracture toughness of $30ZrO_2{\cdot}70SiO_2$ system glass ceramics heated at $1,100^{\circ}C$ for 5 h was $4.84Mpam^{1/2}$ at a critical crystaliite size of 40 nm.