KR920007014B1 - Preparation method of reddish crystalized glass - Google Patents

Preparation method of reddish crystalized glass Download PDF

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KR920007014B1
KR920007014B1 KR1019890017819A KR890017819A KR920007014B1 KR 920007014 B1 KR920007014 B1 KR 920007014B1 KR 1019890017819 A KR1019890017819 A KR 1019890017819A KR 890017819 A KR890017819 A KR 890017819A KR 920007014 B1 KR920007014 B1 KR 920007014B1
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glass
red
crystallized glass
electric furnace
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KR910011668A (en
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조영환
신용규
정국진
김성건
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삼성코닝 주식회사
한형수
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00Nature of the non-vitreous component
    • C03C2214/20Glass-ceramics matrix

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The red crystallized glass for building material is manufactured by preparing the glass compsn. of 45-70 wt.% SiO2, 5- 10 wt.% Al2O3, 10-20 wt.% CaO, 5-12 wt.% ZnO, 1-5 wt.% B2O3, 0.5- 5 wt.% Na2O, 0.5-5 wt.% K2O and 0.1-3 wt.% Sb2O3, adding 0.1- 2.5 wt.% S7C12, 1.5-2.5 wt.% C and 0.1-2.5 wt.% Cu2O as the coloring agent, melting in a electric furnace, making a small body, taking in a refractory mold, heat-treating to color with their metal colloid in a electric furnace, and water-quenching.

Description

적색 결정화 유리의 제조방법Manufacturing method of red crystallized glass

본 발명은 건재용으로 적합한 적색결정화유리의 제조방법에 관한 것으로서, 더욱 상세하게는 특정조성의 유리원료혼합물에 염화주석(SnCl2)과 탄소(C) 및 산화구리를 첨가한 후 용융하여 물급냉으로 소체화시키고, 그 소체를 내화물 모울드에 집적시킨 다음 재가열시킴으로써, 유리중에 천연대리석모양의 결정을 생성시키는 과정에서 금속콜로이드에 의해 적색으로 착색되도록 하는 적색 결정화 유리의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing red crystallized glass suitable for building materials, and more particularly, to adding glass of a specific raw glass mixture to tin chloride (SnCl 2 ), carbon (C) and copper oxide, followed by melting and quenching. The present invention relates to a method for producing red crystallized glass which is colored by red metal by colloid in the process of forming a natural marble crystal in glass by integrating the body into a refractory mold and then reheating the body.

일반적으로 건축물의 내, 외장등의 건재로서 천연석 모양의 포스터라이트(Forsterite)계 결정화유리, 휘석계(輝石系) 결정화유리, 울라스토나이트(Wollastonite)계 결정화 유리등의 제조방법이 제안되고 있다.In general, manufacturing methods such as natural stone-shaped Forsterite-based crystallized glass, whisker-based crystallized glass, and wollastonite-based crystallized glass have been proposed as building materials for interior and exterior of buildings.

그중에서는 울라스토나이트계 결정화유리의 착색방법에는 2가지가 있다.Among them, there are two kinds of coloring methods for the urastonite-based crystallized glass.

첫째는, 원료배치(batch)상에 착색제를 투입하여 용융한 것을 소체화하고 열처리시켜서 제조하는 것이고, 둘째는, 일단 흰소체를 제조한 후에 착색제를 투입하여 열처리함으로써 특유의 고유색을 만들어내는 방법이 있다.First, the colorant is added to a batch of material to melt the melted material and heat-treat it. Secondly, after the white body is manufactured, the colorant is added and heat-treated to produce a unique color. have.

이러한 방법에 있어서 결정화 유리에서의 착색은 유색이온에 의해 착색이 되는 것인데, 결정화 유리에 착색시키는 이온은 2가지 이상의 서로다른 원자가를 갖는 이온이 대부분이고, 그 원가가의 다름에 의해 서로 다른색으로 착색되는 경우가 있다.In this method, the coloration in the crystallized glass is colored by colored ions. Most of the ions to be colored in the crystallized glass are ions having two or more different valences, and the color is different depending on the cost. It may be colored.

이는 유리를 용융시킬때 주위의 분위기가 산화성 분위기인가 환원성 분위기인가에 크게 영향을 받는 것이고, 또한 같은 원자가라도 그 유색이온을 둘러싸고 있는 산소이온의 수에 의해서도 착색이 달라지는 경우가 발생되며, 기초유리의 조성차이에 의해서도 착색이 달라지는 등 제약조건이 많기 때문에, 특히 적색 결정화 유리를 제조하기는 매우 어려운 것으로 알려져 있다.This is because when the glass is melted, the surrounding atmosphere is greatly influenced by the oxidizing atmosphere or the reducing atmosphere, and even when the same valence is changed depending on the number of oxygen ions surrounding the colored ions, the color of the base glass is changed. It is known that it is very difficult to manufacture red crystallized glass especially because there are many constraint conditions, such as a coloring which changes also by composition difference.

최근에 들어서는 울라스토나이트 결정화유리의 제조시 흰소체에 착색제를 투입하여 자색을 띠게하는 방법이 개발되어 있으나, 이 방법에 있어서도 건재용 결정화유리에 있어서의 중요한 문제라 할 수 있는 천연석 모양의 자연스러운 패턴(pattern)이 나타나지 않게 되고, 표면에 깊은 질감을 나타내는 막이 형성되지 않을 뿐아니라, 전반적으로 조잡한 느낌을 주기때문에 상품가치가 현저히 떨어지는 문제는 여전히 남아있었다.Recently, a method of making purple color by adding a colorant to a white body during the manufacture of urastonite crystallized glass has been developed, but also in this method, a natural pattern of natural stone shape, which is an important problem in crystallized glass for building materials There was still a problem of not having a pattern, not forming a deep textured film on the surface, and giving a rough feeling overall, so that the value of the product was significantly reduced.

따라서, 본 발명은 유색이온에 의한 착색 결정화 유리의 제조시 상기와 같은 여러 난점을 해소하고 적색 결정화유리를 제조하기 위해, 유리 원료 혼합물중에 염화주석(SnCl2), 탄소(C) 및 산화구리를 일정량 첨가한 유리를 성형하여 소정의 재열처리를 시행함으로서, 유리중에 균일하게 분산되어 있는 미세한 금속콜로이드에 의해 적색으로 착색되도록 하는 개선된 적색 결정화 유리 제조방법을 제공하는데 그 목적이 있다.Therefore, the present invention solves the above-mentioned difficulties in the production of colored crystallized glass by colored ions and to prepare tin crystal (SnCl 2 ), carbon (C) and copper oxide in the glass raw material mixture in order to produce red crystallized glass. It is an object of the present invention to provide an improved method for producing red crystallized glass in which a predetermined amount of glass is formed and subjected to a predetermined reheat treatment, thereby allowing the glass to be colored red by fine metal colloids uniformly dispersed in the glass.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 결정화 유리를 제조함에 있어서, SiO245∼70중량%, Al2O35∼10중량%, CaO 10∼20중량%, ZnO 5∼12중량%, B2O31∼5중량%, Na2O 0.5∼5중량%, K2O 0.5∼5중량% 및 Sb2O30.1∼3중량%의 조성을 갖는 유리원료혼합물에다 염화주석(SnCl2), 탄소(C) 및 산화구리를 첨가시키고 전기로에서 용융시켜서 소체화시킨후, 전기로에서 열처리시키고 냉각시켜서 금속콜로이드에 의해 적색으로 착색되도록 하는 것을 특징으로 하는 적색 결정화 유리에 제조방법이다.In manufacturing the crystallized glass, the present invention, 45 to 70% by weight of SiO 2 , 5 to 10% by weight of Al 2 O 3, 10 to 20% by weight of CaO, 5 to 12% by weight of ZnO, 1 to 5% by weight of B 2 O 3 Tin chloride (SnCl 2 ), carbon (C) and copper oxide in a glass raw material mixture having a composition of%, Na 2 O 0.5-5 wt%, K 2 O 0.5-5 wt% and Sb 2 O 3 0.1-3 wt% The method for producing a red crystallized glass, which is added to and melted in an electric furnace to be elementary, and then heat treated and cooled in an electric furnace to be colored red by a metal colloid.

이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 상기와 같은 조성을 갖는 유리원료 혼합물에다 염화주석(SnCl2)와 탄소(C) 및 Cu2O 또는 CuO와 같은 산화구리를 첨가시키되 그 유리원료 혼합물에 대해 각각 염화주석 0.01∼4.0중량% 바람직하기로는 0.1∼2.5중량%, 탄소 0.01∼3.0중량% 바람직하기로는 1.5∼2.5중량%, 그리고 산화구리 0.01∼4.0중량% 바람직하기로는 0.1∼2.5중량%로 첨가 혼합시키고, 이를 전기로에서 용융시킨후 특정온도에서 물급냉(Water-quenching)으로 소체화시키므로서 1∼20㎜크기의 소체를 얻고, 이를 내화물모울드(mold)에 넣어서 전기로에서 열처리시키므로서 적색으로 착색된 결정화 유리가 제조되는 것이다.In the present invention, tin chloride (SnCl 2 ) and carbon oxide (C) and copper oxide such as Cu 2 O or CuO are added to a glass raw material mixture having the composition as described above, and 0.01 to 4.0 wt% of tin chloride is added to the glass raw material mixture, respectively. Preferably, 0.1 to 2.5% by weight, carbon to 0.01 to 3.0% by weight, preferably 1.5 to 2.5% by weight, and 0.01 to 4.0% by weight of copper oxide, preferably 0.1 to 2.5% by weight, and the mixture is melted in an electric furnace. After the body at a specific temperature by water-quenching (Water-quenching) to obtain a body size of 1 ~ 20㎜, and put it in a refractory mold (heat) in the electric furnace to produce a crystallized glass colored in red.

이러한, 본 발명에 따르면 상기와 같은 방법에서 유리내부에 천연석 모양의 결정인 울라스토나이트가 석출되면서 성장됨은 물론, 열처리 과정에서 산화구리가 탄소와 염화주석에 의한 열적 환원을 받아서 금속원자로 되기때문에, 그 금속콜로이드에 의해 적색으로 착색된 결정화유리를 제조할 수 있게 된다.According to the present invention, as the above-described method is grown by precipitation of urastonite, which is a natural stone crystal in the glass, as well as copper oxide undergoes thermal reduction by carbon and tin chloride in the heat treatment process, so as to become a metal atom, It becomes possible to manufacture crystallized glass colored in red by the metal colloid.

다시말하면, 상기 방법에서 열처리 과정중 구리(Cu)가 Cu+상태로 유리중에 균질하게 분산되어 있다가 주석(Sn)과 탄소(C)에 의한 열적 환원을 받아 금속원자(Cu°)로 되는데, 이때의 반응식은 다음과 같이 표시될 수 있다.In other words, during the heat treatment process, copper (Cu) is uniformly dispersed in the glass in a Cu + state, and is thermally reduced by tin (Sn) and carbon (C) to form a metal atom (Cu °). The reaction scheme at this time may be expressed as follows.

2Cu++Sn2→ 2Cu°+Sn4 2Cu + + Sn 2 → 2Cu ° + Sn 4

이때 형성된 구리원자(Cu°)가 어느 농도 이상이 되면, 서로 응집하여 미세한 콜로이드 입자로 석출되므로서 적색으로 착색된 결정화 유리를 형성하게 되는 것이다.At this time, when the formed copper atom (Cu °) is more than a certain concentration, it is agglomerated with each other to precipitate as fine colloidal particles to form a crystallized glass colored in red.

이와같은 본 발명에서, 상기 전기로에서의 용융열처리는 1400∼1600℃까지 30∼600℃/hr로 승온시키면서 0.5∼4시간동안 유지시키고나서, 다시 약 1400℃에서 0.5∼2시간동안 유지시키는 방법으로 처리하며, 이를 물급냉시키서 소체를 제조한다.In the present invention as described above, the heat treatment of the melting in the electric furnace is maintained at 0.5 to 4 hours while raising the temperature to 30 to 600 ℃ / hr to 1400 to 1600 ℃, and then maintained at about 1400 ℃ for 0.5 to 2 hours It is treated and water-quenched to produce a body.

또한, 이렇게 제조된 소체를 내화모울드에 넣고 열처리로에서 열처리시키는데, 이때의 열처리는 전기로에서 30∼300℃/hr의 승온속도로 900∼1200℃까지 승온시켜서 0.5∼5시간 유지시키는 방법으로 열처리시키고, 그후 노냉시킨다.In addition, the thus prepared body is placed in a refractory mold and heat-treated in a heat treatment furnace, wherein the heat treatment is heat-treated in an electric furnace by raising the temperature to 900-1200 ° C. at a heating rate of 30-300 ° C./hr and maintaining it for 0.5 to 5 hours. After that, cool it.

이와같이 결정화된 본 발명에 따른 적색결정화 유리는 연마처리하여 최종제품을 제조하게 된다.The red crystallized glass according to the present invention crystallized as described above is polished to produce a final product.

상술한 바와같이 본 발명의 적색 결정화유리 제조방법에 의해 제조된 결정화 유리는 우수한 표면 패턴과 천연석 모양의 막을 형성함은 물론, 유리중에 분산되어 있는 미세한 금속콜로이드에 의해 착색되므로 적색의 미려한 결정화 유리를 손쉽게 제조할 수 있게 되며, 또다른 색깔의 결정화유리, 예컨대 울라스토나이트계 결정화유리와도 용이하게 융착이 가능하여 다양한 색깔을 한제품표면에 나타낼 수 있는 잇점이 있다. 또한 종래의 천연석보다 기계적 강도 및 화학적 내구성이 현저히 우수함으로서 건축물의 내.외장재로서 충분히 사용가능하다.As described above, the crystallized glass prepared by the red crystallized glass manufacturing method of the present invention forms an excellent surface pattern and a natural stone-like film, and is colored by fine metal colloids dispersed in the glass. It can be easily manufactured and can be easily fused with another colored crystallized glass, for example, an urastonite-based crystallized glass, so that various colors can be displayed on one product surface. In addition, mechanical strength and chemical durability are remarkably superior to conventional natural stone, so that it can be sufficiently used as interior and exterior materials of buildings.

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.

[실시예 1∼5]EXAMPLES 1-5

기본 유리조성물은 중량%로 SiO256.3%, CaO 16.4%, Al2O38.2%, ZnO 8.1%, B2O32.8%, Na2O 4%, K2O 1.4%, Sb2O32.8%의 조성이 되도록 유리원료를 혼합하였는바, 이때 사용한 원료는 규사, 석회석, 수산화알루미늄, 소다회, 붕산, 탄산칼륨, 탄산바륨등을 사용하였다.The basic glass composition is 56.3% SiO 2 , 16.4% CaO, 8.2% Al 2 O 3 , 8.1% ZnO, 2.8% B 2 O 3 , Na 2 O 4%, K 2 O 1.4%, Sb 2 O 3 Glass raw materials were mixed so as to have a composition of 2.8%. The raw materials used were silica sand, limestone, aluminum hydroxide, soda ash, boric acid, potassium carbonate, barium carbonate, and the like.

상기 원료혼합물에 다음 표 1의 조성으로 염화주석, 탄소 및 산화구리를 첨가시켜 조합시켰다. 이렇게 조합한 원료를 알루미늄 도가니에 넣고, 전기로에서 1500℃온도로 4시간동안 유지시킨후, 다시 1400℃에서 30분 유지시킨 상태에서 물급냉(Waterquenching)처리를 하여 제조된 3∼14㎜사이의 소체를 선별하였다.The raw material mixture was combined by adding tin chloride, carbon and copper oxide in the composition of Table 1 below. The combined raw materials were placed in an aluminum crucible, and maintained at 1500 ° C. for 4 hours in an electric furnace, followed by a waterquenching treatment at 1400 ° C. for 30 minutes. Were screened.

이 선별한 소체를 내화물 모울드(mold)에 집적시킨 후 소성로에서 약 1100℃로 2시간동안 유지시킨후 노냉시켜서 결정화 공정을 완료하였다.This sorted body was integrated in a refractory mold, and then maintained in a calcination furnace at about 1100 ° C. for 2 hours, followed by quenching to complete the crystallization process.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

표 1에서와 같이 염화주석, 탄소, 산화구리의 첨가함량에서는 적색착색의 농염 차이는 있지만 모두 건재용 결정화유리로 사용가능함을 확인하였다.As shown in Table 1, the addition of tin chloride, carbon, and copper oxide, but there was a difference in the red-colored thick salt, it was confirmed that all can be used as a crystallized glass for building materials.

여기서, 상기 염화주석의 사용량이 과다하면 흑색이 나타나고 너무 적으면 청색이 나타나며, 탄소를 너무 과량 사용하면 흑색 반점이 생기고, 너무 소량 사용하면 청색 반점이 나타난다. 또 산화구리를 소량 사용하면 적색과 청색이 모자이크 형태로 나타나고 과량 사용하면 흑색과 적색이 모자이크 형태로 나타나므로 품질이 저하된다.Herein, when the amount of the tin chloride is used excessively, black color appears, and when the amount is too small, blue color appears. When too much carbon is used, black spots are generated, and when too little is used, blue spots appear. In addition, when a small amount of copper oxide is used, red and blue appear in mosaic form, and when used in an excessive amount, black and red appear in mosaic form.

Claims (1)

기본 유리조성이 SiO245∼70중량%, Al2O35∼10중량%, CaO 10∼20중량%, ZnO 5∼12중량%, B2O31∼5중량%, Na2O 0.5∼5중량%, K2O 0.5∼5중량% 및 Sb2O30.1∼3중량%의 조성을 갖는 유리원료 혼합물을 전기로에서 열처리시켜서 소체화시킨후, 얻어진 소체를 전기로에서 열처리시켜서 금속콜로이드에 의해 적색으로 착색시켜서 건재용 결정화 유리를 제조함에 있어서, 착색제로서 염화주석을 상기 유리원료혼합물에 대해 0.1∼2.5중량%, 탄소를 1.5∼2.5중량%, 그리고 산화구리를 0.1∼2.5중량%로 첨가사용하는 것을 특징으로 하는 적색 결정화 유리의 제조방법.Basic glass composition is 45 to 70% by weight of SiO 2 , 5 to 10% by weight of Al 2 O 3, 10 to 20% by weight of CaO, 5 to 12% by weight of ZnO, 1 to 5% by weight of B 2 O 3 , Na 2 O 0.5 A glass raw material mixture having a composition of ˜5% by weight, K 2 O 0.5-5% by weight and Sb 2 O 3 0.1-3% by weight was subjected to heat treatment in an electric furnace, followed by firing in an electric furnace, followed by metal colloid by heat treatment in an electric furnace. In producing red crystallized glass by coloring red, tin chloride is added as a coloring agent in an amount of 0.1 to 2.5% by weight based on the glass raw material mixture, 1.5 to 2.5% by weight of carbon, and 0.1 to 2.5% by weight of copper oxide. The manufacturing method of red crystallized glass characterized by the above-mentioned.
KR1019890017819A 1989-12-02 1989-12-02 Preparation method of reddish crystalized glass KR920007014B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1985591A1 (en) * 2007-04-24 2008-10-29 Schott AG Metal colloid-coloured glass ceramic and non-coloured glass which can be converted into a metal colloid coloured glass ceramic

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1985591A1 (en) * 2007-04-24 2008-10-29 Schott AG Metal colloid-coloured glass ceramic and non-coloured glass which can be converted into a metal colloid coloured glass ceramic
DE102007020246A1 (en) 2007-04-24 2008-10-30 Schott Ag Metallkolloidgefärbte glass-ceramic and convertible into a metallkolloidgefärbte glass-ceramic colorless glass
EP1985591B1 (en) * 2007-04-24 2012-06-27 Schott AG Metal colloid-coloured glass ceramic and non-coloured glass which can be converted into a metal colloid coloured glass ceramic

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