• 자원리싸이클링
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• 제32권1호
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• pp.42-49
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• 2023

Li-Al-Si를 함유한 유리세라믹 순환자원은 인덕션, 방화유리, 비젼냄비 등 리튬의 전체 소비량 중 14%로 리튬이온전지 다음으로 많이 쓰인다. 따라서 리튬의 수요가 폭발하고 있는 현재 새로운 리튬 자원을 찾아야 하고 이로부터 리튬의 회수 연구가 필요하다. 본 연구는 이러한 맥락하에 Li을 함유한 새로운 순환자원인 Li-Al-Si 유리세라믹으로부터 리튬을 회수하기 위한 연구를 수행하였다. 본 연구에서는 1.5% Li, 9.4% Al, 28.9% Si를 함유한 Li-Al-Si 유리세라믹 중 방화유리를 원료물질로 사용하였다. 방화유리로부터 리튬을 회수하기 위한 공정은 크게 칼슘 염을 투입한 건식 배소 공정과 수침출 공정으로 나뉜다. 325 mesh 이하로 분쇄된 방화유리 시료를 열처리 전과 열처리 후 칼슘 염을 투입하여 침출 실험을 비교 진행하였고 칼슘 염과 Li-Al-Si 유리세라의 투입비율에 따른 침출율, 칼슘 염 배소 온도에 따른 침출 연구도 비교 수행하였다. 수침출 연구에서는 온도, 시간, 고액비, 그리고 연속 침출횟수에 따라 리튬의 침출율 및 회수율을 비교하였다. 그 결과 Li-Al-Si를 함유한 유리세라믹 방화유리는 열처리를 반드시 수행하여 베타 형태의 스포듀민으로 상변화 시켜야 하며 이로부터 CaCO₃ 염을 Li-Al-Si를 함유한 유리세라믹 방화유리와 6:1의 비율로 투입하여 1000℃이상에서 배소한 후 4회 이상 연속 침출하여 리튬의 회수율을 98% 이상 획득하였고 이때 리튬의 농도는 200mg/L였다.

• 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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• 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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• 제32권4호
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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.

• 한국결정성장학회지
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• 제29권4호
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• pp.154-159
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• 2019

용융 온도를 낮추고 균질화에 영향을 줄 수 있는 yttrium oxide(산화 이트륨)과 iron oxide(산화철)를 사용하여 $LI_2O-Al_2O_3-SiO_2$ 계 결정화 유리를 제조하였다. 조핵제는 Zirconium sulfate(황산지르코늄)을 사용했고, 유리 점도를 낮추기 위해 calcium phosphate(인산칼슘)을 사용해 유리 유동성을 원활하게 하였다. 결정화 유리는 열충격 $750^{\circ}C$ 이상을 만족했고, $800^{\circ}C$ 이상에서 열팽창계수가 급격하게 상승하는 온도를 약 $30^{\circ}C$ 이상 시프트 하였다. 따라서 yttrium oxide와 iron oxide 포함하는 LAS 계 유리는 고온에서 양호한 용융 상태와 우수한 열팽창 저항성을 확인하였고 특수 주방용 재료 분야에 충분히 활용이 가능하리라 판단되었다.

• 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.

• 한국세라믹학회지
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• 제25권5호
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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.

• 한국세라믹학회지
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• 제22권2호
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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/$mm^2$

• 한국세라믹학회지
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• 제25권3호
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• pp.251-260
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• 1988

$10Li_2O$.$(90-x)B_2O_3$.$xSiO_2$ 기초유리에 $Al_2O_3$ 또는 $MoO_3$를 첨가한 유리를 열처리한 후 열수 또는 산처리하여 이온교환성 다공질 유리를 제조하였다. 그리고 $Al_2O_3$ 또는 $MoO_3$ 첨가가 분상과 양이온교환능(CEC)에 미치는 영향을 조사하였다. 이들 유리의 분상최적조건은 48$0^{\circ}C$, 10시간 열처리하였다. 분상은 $Al_2O_3$ 10mol%까지는 급격히 억제되고 그 이후에는 분상억제 효과가 완화되었다. 양이온교환능의 최대값은 $1OLi_2O$.$45B_2O_3$.$45SiO_2＋7.5Al_2O_3$ 조성유리를 열수처리한 다공질유리에서 약 252meq/100g을 나타냈으며 이 유리의 세공평균반경은 약 16.3A이었다. $MoO_3$ 첨가는 분상과 용출속도를 증가시켰다. $MoO_3$첨가에 의해 다공질유리의 세공반경과 세공용적이 크게 증가하는 것으로 보아 $MoO_3$는 유리의 붕산염상중의 실리카 농도를 낮추고 용출처리중 실리카를 수용성 착체로 형성시키는 효과가 있다고 생각된다.

• 한국세라믹학회지
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• 제30권7호
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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.