• Resources Recycling
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• v.32 no.1
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• pp.42-49
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• 2023

The glass ceramic secondary resource containing Li-Al-Si is used in inductor, fireproof glass, and transparent cookware and accounts for 14% of the total consumption of Li, which is the second most widely used after Li-ion batteries. Therefore, new Li resources should be explored when the demand for Li is exploding, and extensive research on Li recovery is needed. Herein, we recovered Li from fireproof Li-Al-Si glass ceramic, which is a new secondary resource containing Li. The fireproof glass among all Li-Al-Si glass ceramics was used as raw material that contained 1.5% Li, 9.4% Al, and 28.9% Si. The process for recovering Li from the fireproof glass was divided into two parts: (1) calcium salt roasting and (2) water leaching. In calcium salt roasting, a sample of fireproof glass was crushed and ground below 325 mesh. The leaching efficiency was compared based on the presence or absence of heat treatment of the fireproof glass. Moreover, the leaching rates based on the input ratios of calcium salt, Li-Al-Si glass, and ceramics and the leaching process based on calcium salt roasting temperatures were compared. In water leaching, the leaching and recovery rates of Li based on different temperatures, times, solid-liquid ratios, and number of continuous leaching stages were compared. The results revealed that fireproof glass ceramics containing Li-Al-Si should be heat treated to change phase to beta-type spodumene. CaCO₃ salt should be added at a ratio of 6:1 with glass ceramics containing Li-Al-Si, and then leached 4 times or more to achieve a recovery efficiency of Li over 98% from a solution containing 200 mg/L of Li.

• 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.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.32 no.4
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• pp.507-515
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• 1995

The monolithic dry gels of the Li2O-Al2O3-TiO2-SiO2 system were prepared by the sol-gel technique using metal alkoxides as starting materials to obtain monolithic glass-ceramics at low temperature without melting. Activation energy for the crystal growth of the gel with 6.05% TiO2, nucleating ageng, for the preparation of Li2O-Al2O3-TiO2-SiO2 system glass-ceramic was 101.14kcal/mol. As a result of the analysis of DTA & XRD, it was confirmed that the crytallization of Li2O-Al2O3-TiO2-SiO2 system glass-ceramic was the most efficient when 6.05% TiO2, nucleating agent, was added. $\beta$-eucryptite solid solution crystals and $\beta$-spodumene solid solution crystals were detected in the sample heat treated above 85$0^{\circ}C$. The sintered gel heat treated at 85$0^{\circ}C$ had the specific surface area of 185$m^2$/g, the pore volume of 0.19cc/g and the average pore radius of 20.8$\AA$. This shows that the sintered gel is also comparatively porous material. In temperature range of 25~85$0^{\circ}C$ thermal expansion coefficient of the specimen which was crystallized for 10hrs at 85$0^{\circ}C$ was 6.7$\times$10-7/$^{\circ}C$, which indicated that the crystallized specimen was turned out to be the glass-ceramic with low thermal expansion.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.29 no.4
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• pp.154-159
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• 2019

The glass-ceramic of $Li_2O-Al_2O_3-SiO_2$ system was fabricated by using yttrium oxide and iron oxide that it can reduce the melting temperature and affect the homogenization. Zirconium sulfate was used as a nucleation agent. Calcium phosphate was used to improve the flow the glass so as reduce the viscosity of the glass. The glass-ceramics met a thermal shock test of more than $750^{\circ}C$ and the temperature at which the coefficient of thermal expansion rapidly increased at over $800^{\circ}C$ was shifted by about the above $30^{\circ}C$. Therefore, it is concluded that the glass-ceramic of $Li_2O-Al_2O_3-SiO_2$ system with yttrium oxide and iron oxide was founded to have good melting conditions and excellent thermal expansion resistance at high temperature such as special field for kitchen utensils.

• 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 Ceramic Society
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• v.25 no.5
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• pp.431-436
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• 1988

The properties of scid-resistance to boiling HCl, thermal expansion coefficient and softening temperature of mother glass and glass-ceramic of LAS systems were investigated at the contents of SiO2 varing from 57 to 67wt%. The nucleation and growth of crystalline phase of LAS compositions were carried out at 50$0^{\circ}C$ and $700^{\circ}C$. The crystalline phase jconsists of lithium alumino silicate, lithum meta silicate, lithium disilicate, $\alpha$-crystobalite and $\alpha$-quartz. Lithium alumino silicate(virgilite) is the major crystalline phase in the glass ceramics. The degree of acid resistant property was increased in proportion with the silica content for both glass and ceramics. Glass-ceramic gives lower acid-resistance and thermal expansion coefficient while softening temperature shows higher for glass-ceramic than for mother glass.

• Journal of the Korean Ceramic Society
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• v.22 no.2
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• pp.3-10
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• 1985

In the study the characteristics change of crystallized $Li_2O$.$Al_2O_3$.$SiO_2$ glass-ceramics when varying RO ratio and increasing Al2O3 were investigated to produce a glass-ceramics with high mechanical strength and low thermal expansion. Parent glass was obtained by melting at 1,350~1,40$0^{\circ}C$ for 3 hours and annealing at 45$0^{\circ}C$ and the various physical characteristics were measured. Results were as follows; 1. When ZnO was replaced by MgO thermal expansion coefficient was lowered when increasing ZnO content. 2. Major crystal phase was $\beta$-spodumene the crystal growth mophology was the three dimensional sphere and the activation energy for crystallization was 54.6 Kcal/mol. 3. Parent glass heat-treated at 95$0^{\circ}C$ for 10 hours had ; a) thermal expansion coeff. of $23.2{\times}10^{-7}$/$^{\circ}C$ b)whiteness of 76 c) microhardness of 1,089kg/$mm^2$

• Journal of the Korean Ceramic Society
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• v.25 no.3
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• pp.251-260
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• 1988

Ion-exchange porous glasses were prepared by heat treatment and subsequently hydro thermalor acid leaching treatment $10Li_2O$.$(90-x)B_2O_3$.$xSiO_2$ base glasses containing various amount of $Al_2O_3$ or $MoO_3$. It was investigated how the phase separation and the cation exchange capacity(CEC) were affected by the addition of $Al_2O_3$ or $MoO_3$. The optimum condition of phase separation in these glasses was about 48$0^{\circ}C$ for 10 hrs. The degree of phase separation was rapidly suppressed by the addition of $Al_2O_3$ up to 10 mol% and thereafter suppression effect was decreased. The maximum value of CEC, about 252meq/100g, was observed with the $1OLi_2O$.$45B_2O_3$.$45SiO_2＋7.5Al_2O_3$ porous glass prepared by hydrothermal treatment and its mean pore radius was about 16.3A. The addition of $MoO_3$ accelerated phase separation and leaching rate. Looking at the remakable increment of pore diameter and pore volume of these porous glasses by the addition of $MoO_3$, the effect of $MoO_3$ may be ascribed to the lowering of silica concentration in the borate phase and to the forming of water-soluble complex with silica during the leaching treatment.

• Journal of the Korean Ceramic Society
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• v.30 no.7
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• pp.535-542
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• 1993

It was investigated in this study that a preparation method, activation energy, surface area, pore volume, pore size distribution and DTA analysis of the dry gel in process of producing monolithic porous gel in Li2O-Al2O3-TiO2-SiO2 system by the sol-gel technique using metal alkoxides. Activation energy for gellation according to the variation of water concentration and the kind of catalysts ranged from 10 to 20kcal/mole. Monolithic dry gels were prepared after drying at 9$0^{\circ}C$ when the amount of water for gellation was 4~8 times more than the stoichiometric amount, that was necessary for the full hydrolysis of the mixed metal alkoxide. The specific surface area, the pore volume, the average pore radius of the dried gel at 18$0^{\circ}C$ according to the various kinds of catalyst were about 348~734$m^2$/g, 0.35~0.70ml/g and 10~35$\AA$, respectively. It showed that the dry gels were porous body. As a result ofthe analysis of DTA, it was confirmed that the exothermaic peaks at 715$^{\circ}C$ and 77$0^{\circ}C$ was clue to the crystallization of dried gel.