• 한국세라믹학회지
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• 제18권3호
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• pp.187-191
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• 1981

The effect of additions, $TiO_2$ and $ZrO_2$ as nucleant on the base glass which composition was determined to 0.97 $Li_2O-Al_2O_3-SiO_2$ has been investigated by means of D.T.A., X-ray diffraction and dilatation. $TiO_2$ and $ZrO_2$ as nucleant were added 0.06mole, in which ratios of $TiO_2$/$ZrO_2$ were varied 1/0, 2/1, 1/1, 1/2 and 0/1. The crystalline phases were appeared to $\beta$-spodumene as principal, $\beta$-eucryptite and $ZrO_2$ as secondary, regardless of nucleant variations. The crystallinity of the crystallized glass added $TiO_2$, $ZrO_2$ mixture as nucleant was higher than that of the glass added $TiO_2$ or $ZrO_2$ only. The crystallinity of the glass added $TiO_2$/$ZrO_2$ =1/1 was highest. Increasing the addition of $ZrO_2$, it has been observed that the crystal growing temperature became higher.

• 한국세라믹학회지
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• 제13권1호
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• pp.30-34
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• 1976

In general the chemical composition of glass ceramics in Li2O-Al2O3-SiO2 system is similar to the composition of $\beta$-spodumene (Li2O-Al2O3-4SiO2). With the object to manufacture the glass ceramics which can be produced in the domestic pot the composition of glass was so settled at 1.0 Li2O.0.9Al2O3.6.0SiO2 in order to reduce the contents of Li2O, to prevent the corrosion of the pot and to decrease the cost of raw materials. 0.2 mole and 0.1 mole of the mixture of TiO2 and ZrO2 as nucleants were added to the basic composition of 1.0 Li2O-0.9Al2O3-6.0SiO2. Each sample was divided into two kinds with a TiO2/ZrO2 ratio of 2 to 1 and the other with a TiO2/ZrO2 ratio fo 1 to 1. Thermal expansion coefficient, the most important property of glass ceramics, was tested. The softening point and the melting point of the samples were observed by the use of a heating microscope. The results obtained were as follows. The manufacturing of glass ceramics seems to be possible in the industrial plant using the domestic pot. 1) The composition of the glass which can be melted in the domestic pot process was near 1.0 Li2O.0.9Al2O3.6.0SiO2. 2) The temperature range of crystal creation and crystal growth was between 850-94$0^{\circ}C$, and 5 hours holding the samples at the temperature range was enough to crystallize them. The major crystal was $\beta$-spdumene and there existed petalite partialy. 3) The thermal expansion coefficient fo the crystallized glass was negative. 4) The deforming point of the crystallized glass was 1435$^{\circ}C$.

• 한국결정성장학회지
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• 제6권2호
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• pp.275-285
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• 1996

The effect of heat-treatment on catalytic crystallization in $LI_2O-Al_2O_3-SiO_2$ glass system over its glass transition temperature was investigated. Glass composition $4Li_2O{cdot}22AL_2O_3{cdot}66SiO_2{cdot}2TiO_2{cdot}2.5ZrO_2{cdot}1.5P_2O_5{cdot}1.0Na_2O{cdot}1.0As_2O_3$ (wt%) was selected and heat-treated at different heating conditions to obtain transparent glass-ceramic. Nucleation and crystallization behaviour of this composition were estimated by differential thermal analysis (DTA) and X-ray diffractometer (XRD) and its thermal expansion coefficients were measured by Dilatometer. As a result, glass transition temperature was $730^{\circ}C$ and two maximum nucleation temperatures were estimated at $730^{\circ}C$ and 82$0^{\circ}C$ using JMA(Johson-Mehl-Avrami) equation by DTA. $ZrTiO_4$ $\beta$-Quartz solid solution and $\beta$-Spodumene crystals were identified by XRD. The optimum crystallization temperature was 92$0^{\circ}C$ and three step heating schedule was expected to be useful to obtain transparent glass-ceramic.

• 한국결정성장학회지
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• 제28권6호
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• pp.229-234
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• 2018

조핵제 역할을 하는 지르코늄의 원료로써 $ZrO_2$(지르코늄 옥사이드), $ZrSiO_4$(지르코늄 실리케이트), $ZrOCl_2$(지르코늄 옥시클로라이드), $Zr(SO_4)_2$(지르코늄 서페이트) 4종류의 원료를 사용하여 $Li_2O-Al_2O_3-SiO_2$계 결정화 유리를 제조하였다. 동일한 조성의 모든 유리에서 Avrami 상수는 3 이상으로 체적 결정화가 진행됨을 확인하였다. 또한 $ZrOCl_2$, $Zr(SO_4)_2$를 사용하여 제조한 유리는 용융 과정에서 미용융물이 발생하지 않으며 지르코늄 성분이 균일하게 분포되었음을 확인하였다. 이와 같은 결과를 성분 분석, 굽힘 강도를 연계하여 평가하였다.

• 한국세라믹학회지
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• 제44권4호
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• pp.219-223
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• 2007

The ionic conductivity of $Li_2O-ZrO_2-SiO_2$ glasses has been designed and analyzed on the basis of a mixture design experiment with constraints. Fitted models for the activation energy and the ionic conductivity are as follows: $Q(kJ/moi)=54.8565x_1+144.825x_2+133.846x_3-170.908x_1x_3-334.338x_2x_3$ $log{\sigma}(300K)=-5.00245x_1-1.17876x_2-15.5173x_3+17.4522x_1x_3$. The electrical properties are very sensitive to the ratio of $Li_2O/SiO_2$. The effect of $ZrO_2$ is less than that of this ratio but $ZrO_2$ component attributes to the reduction of the activation energy. The optimal composition for best ionic conduction based on these fitted models is $55Li_2O{\cdot}10ZrO_2{\cdot}35SiO_2$. Its activation energy and ionic conductivity at 300 K are 46.98 kJ/mol and $1.08{\times}10^{-5}{\Omega}^{-1}{\cdot}cm^{-1}$, respectively.

• 한국세라믹학회지
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• 제31권6호
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• pp.660-670
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• 1994

Transparent, crack-free dried gel monoliths with a composition of LiZr1.5Si2P2O12.5 have been synthesized by the low temperature polymerization of the Sol-Gel technique using metal alkoxides as starting materials. After initial reaction (20~40 min), each metal alkoxide closely paralleled each other during the hydrolysis reactions. The safe drying conditions of gels with no creaks the control of the shrinkage rate. The gels converted into the glass by heat treatment at 75$0^{\circ}C$. FTIR data indicated that the gels were phase separated into silicarich and phosphate-rich regions with the lithium. XRD results showed the formation of crystalline LiH2PO4. The gels dried at 15$0^{\circ}C$ or fired at 75$0^{\circ}C$ contained the residual water. The high ionic conductivity at room temperature for these gels was attributed to the motion of protons.

• 한국세라믹학회지
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• 제26권3호
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• pp.315-322
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• 1989

Li2O-Al2O3-SiO2 system glasses contained P2O5, TiO2 and ZrO2as the nucleating agents were melted and formed. The glass was subsequently heated first to nucleate and then to grow the crystals. At constant nucleating agent content the base glass compositions were varied and the influences of these variations on the crystallization behaviour were investigated. The study was made by measurement of thermal expansion coefficient, differential thermal analysis, X-ray diffraction analysis, scanning electron microscope observation and transmission measurement of crystallized glass specimen in visible region. It was shown that the content of crystalline phase decreased with increasing SiO2 content as well as decresing Li2O in the base glass compositions. As the result of X-ray diffrection analysis, the major crystal was $\beta$-quartz solid solution. The degree of crystallinity which was calculated using the noncrystalline scattering methods increased in S-shape with increasing heat treatment time. This change was similar to that in thermal expansion coefficient. The transmissions of 5mm thick samples were 80-90% in visible ray region.

• 한국결정성장학회지
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• 제2권2호
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• pp.20-32
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• 1992

$Na_2O-CaO-MgO-Al_2O_3-SiO_2$계를 기본조성으로 하여 $Na_2O$에 $Li_2O 0.05wt%, $K_2O$를, CaO에 MgO 12.0wt%, ZnO 6.0%를 각각 치환하여 조성을 선정하였다. 기본 유리조성의 결정상은 wollastonite이고, 치환된 조성들은 diopside, diopside.tremolite의 혼정이 나타났다. $Na_2O$를 $Li_2O$로 치환한 시편은 열팽창계수가 감소하였지만 CaO를 ZnO로 치환한 시편은 열팽창 계수가 증가하였다. 곡강도에 있어서는 치환에 따라 모두 증가시켰다. 핵행성제로 $ZrO_2와 $CaF_2$를 각각 1~2wt%의 변화를 시켜본 결과 핵형성제 $ZnO_2$와 $CaF_2$가 1:1, 1:2인 시편은 $1000~1050^{\circ}C$온도에서 급격한 결정성장을 보였으며 1:2시편이 가장 낮은 열팽창 계수값을 나타냈다. 곡강도는 모두 $1000~1050^{\circ}C$의 결정화 온도 범위에서 높은 강도를 나타내었다. 결정화에 필요한 활성화 에너지는 Ozawa와 Kissinger식으로 plot하여 각각 55.24kcal/mol과 53.05kcal/mol이다.

• 한국결정성장학회지
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• 제3권2호
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• pp.176-184
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• 1993

$Li_2O-Al_2O_3-SiO_2$계 유리조성에서, 특히 주결정상으로 $\beta$-spodumene을 석출시킬 수 있는 조성영역에서 $P_2O_5, TiO_2, ZrO_2$ 등을 첨가하여 용융한 후 소결법을 이용하여 이론밀도에 가까운 결정화 유리를 만들기 위한 최적 열처리 조건, 유리 분말의 입도 변화에 따란 영향과 그 때의 물성을 시차열분석, X-선 회절분석, 비중 측정, 열팽창 측정, 전자현미경 관찰 등을 통하여 연구하였다. $P_2O_5$를 첨가하여 소결법으로 결정화할 때 소결을 증진시키는 효과가 있었으며 9wt% 첨가한 경우가 가장 치밀한 것으로 나타났다. 최적의 열처리 조건은 $740^{\circ}C$에서 소결하여 치밀화를 시키고$ 950^{\circ}C$에서 결정화를 시켰을 때로서 상대밀도는 90% 이상이었으며 열팽창계수는 $-1{\times}10^{-7}/^{\circ}C$ 정도로서 부팽창인 것으로 나타났다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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• pp.98-98
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• 2003

초내열성 결정화유리는 전기전자부품, 천체만원경의 반사경, 직화용 조리기기, 군사용 부품 등에 광범위하게 이용되고 있는데 이중 LAS 계가 가장 오랫동안 알려진 조성 계이다. 이 결정화유리는 주입성형후 열처리에 의하여 결정상을 생성하여 사용되는데 표면이 매우 낮은 조도를 갖는 것으로 알려져 있으나 실제로는 제조상에 조도가 높게 나타나는 문제점이 제기되고 있다. 따라서 본 연구에서는 미세조직적인 측면에서 이러한 점을 연구하고자 Li$_2$O-AL$_2$O$_3$-SiO$_2$를 주성분으로 하고 소량의 MgO와 핵생성제로서 TiO$_2$, ZrO$_2$를 사용하여 시편을 제조하였다. 제조된 결정화유리의 결정화도의 차이에 따라 AFM, $\alpha$-STEP등으로 표면의 조도를 정량화였다. 결정상의 종류, 크기, 결정화도, 결정상간의 간격 등이 표면의 조도에 어떻게 영향을 주는가 에 대하여 연구한 결과를 제시하였다.