• Journal of the Korean Ceramic Society
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• v.18 no.3
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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.

• Journal of the Korean Ceramic Society
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• v.13 no.1
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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$^{\circ}C$.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.6 no.2
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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.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.28 no.6
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• pp.229-234
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• 2018

The glass-ceramic of $Li_2O-Al_2O_3-SiO_2$ system was synthesized by using $ZrO_2$, $ZrSiO_4$, $ZrOCl_2$ and $Zr(SO_4)_2$, which is a raw material of Zr serving as a nucleation agent. It was confirmed that Avrami parameter of these four glasses is over 3 for bulk crystallization. The glass synthesized by $ZrOCl_2$, and $Zr(SO_4)_2$ showed high melting quality during the melting process. It is also observed that the Zr component is uniformly distributed in the glass. Various characterizations was evaluated, including composition analysis and bending strength.

• Journal of the Korean Ceramic Society
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• v.44 no.4 s.299
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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.

• Journal of the Korean Ceramic Society
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• v.31 no.6
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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.

• Journal of the Korean Ceramic Society
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• v.26 no.3
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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.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.2 no.2
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• pp.20-32
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• 1992

$Na_2O-CaO-MgO-Al_2O_3-SiO_2$ glass was taken as a basic glass and then $Li_2O$ O.5wt%, $K_2O$ 2.0wt% were substituted to $Na_2O$content, MgO 12.0wt %, ZnO 6.0wt % to CaO content. And also nucleation agent $ZrO_2 and $CaF_2$ were added to 1-2wt% respectively. The crystal according to the compositions appeared wollastonite, diopside and diopside.tremolite. The glasses substituted NazO by LizO was decreased thermal expansion coeffcient but substituted by ZnO was opposite direction and both of them increased bending strength. In the ratio of ZrOz to CaF, each 1: 1 and 1: 2 have shown considerable crystal growth at $1000^{circ}C~1050^{\circ}C$ and high bending strength, but the glass in the ratio 1: 2 have shown lowest thermal expansion coefficient. The activation energy was at the glass in the ratio of ZrO, to CaFz 1:2 evaluated 55.24kvsl/mol by Ozawa type and 53.05kal/mol by kissinger type.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.3 no.2
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• pp.176-184
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• 1993

The glasses, which the $\beta$-spodumene as the principal crystalline phase could be precipitated, were melted by adding >, $P_2O_5, TiO_2, ZrO_2 in the Li_2O-Al_2O_3-SiO_2$ system. In order to achieve the glass-ceramic body of near-theoritical density by sintering method, the optimum condition of heat treatment, the effect of glass powder size and the properties were investigated by DTA, XRD, bulk density, thermal expansion and SEM. Addition of $P_20_5$ imProved the tendency of sintering and the sample with 9wt% $P_20_5$ content was the most dense OOdy by sintering method. The optimum condition of heat treatmemt was sintered for densitification at $740^{\circ}C$ and crystallized at $950^{\circ}C$. In the optimum condition, the relative density was above 90% and the thermal expansion was negative about $-1{\times}10^{-7}/^{\circ}C$.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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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.