KR20190047950A - Crystallized glass composition and crystallized glass using waste glass for architecture interior and exterior material producing method thereof - Google Patents
Crystallized glass composition and crystallized glass using waste glass for architecture interior and exterior material producing method thereof Download PDFInfo
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- KR20190047950A KR20190047950A KR1020170142362A KR20170142362A KR20190047950A KR 20190047950 A KR20190047950 A KR 20190047950A KR 1020170142362 A KR1020170142362 A KR 1020170142362A KR 20170142362 A KR20170142362 A KR 20170142362A KR 20190047950 A KR20190047950 A KR 20190047950A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C10/00—Devitrified 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
- C03C10/0063—Devitrified 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 waste materials, e.g. slags
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/012—Tempering or quenching glass products by heat treatment, e.g. for crystallisation; Heat treatment of glass products before tempering by cooling
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C10/00—Devitrified 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
- C03C10/0036—Devitrified 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 SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified 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 SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2214/00—Nature of the non-vitreous component
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Abstract
Description
본 발명은 폐유리를 이용한 건축 내외장재용 결정화 유리 조성물에 관한 것으로, 보다 상세하게는 생활 폐기물인 폐유리와 해안에 폐기되는 패각을 재활용하여 베타-월라스토나이트(β-Wollastonite)를 함유하는 결정화 유리를 제조하기 위한 조성물, 제조된 결정화 유리 및 제조방법에 관한 것이다.The present invention relates to a crystallized glass composition for architectural interior and exterior materials using waste glass, and more particularly, to a glass composition for interior and exterior construction using waste glass, which comprises recycled waste glass as a municipal waste and a shell discarded on the shore to produce a crystallized glass containing beta-wollastonite , A crystallized glass prepared, and a manufacturing method thereof.
비결정질 유리는 강도가 약하지만, 결정화 유리, 특히 베타-월라스토나이트를 함유한 결정화 유리는 강도 및 단열성이 우수하여 건축용 자재로 사용하기에 적합한 것으로 알려져 있다.Amorphous glass is weak in strength, but crystallized glass, especially beta-wollastonite-containing crystallized glass, is known to be suitable for use as a building material because of its excellent strength and heat insulation.
종래 베타-월라스토나이트를 함유한 결정화 유리를 제조하는 방법으로는 주로 유리 용융물을 수쇄한 입상유리를 적재하고 소성로에서 열처리하는 방법, 또는 결정성 유리원료 성분과 핵 형성제를 용융하여 결정화시키는 방법이 사용되어 왔다. Conventionally, as a method for producing crystallized glass containing beta-wollastonite, there are a method in which granular glass which is mainly composed of a glass melt is loaded and heat-treated in a baking furnace, or a method in which a crystalline glass raw material component and a nucleating agent are melted and crystallized Has been used.
유리 용융물을 수쇄한 입상유리를 적재하고 소성로에서 열처리하여 베타-월라스토나이트를 함유한 결정화 유리를 제조하는 방법에서는, 결정화 유리 조성물을 혼합하여 전기저항로, 탱크로 및 도가니로에서 용융한 후 출탕과 동시에 냉각수를 흘려 수쇄하여 일정한 크기의 입상유리를 제조하고 이형제가 도포된 뮬라이트 혹은 SiC 붕판에 적재 성형한 후 소성로에서 열처리하여 결정화시킨다. 상기 방법은 결정화가 용이한 반면 소성과정에서 입자에 의한 기포가 발생하기 쉽고 내부에 폐기공이 잔류하게 되어 강도가 감소하며, 비용이 상승하는 단점이 있다. 이러한 방법의 예로 일본특허공개 제10152334호가 있다. In a method of producing a crystallized glass containing beta-wollastonite by loading granular glass with glass melt and heat-treating it in a sintering furnace, the crystallized glass composition is mixed and melted in a tank and a crucible by electric resistance, And cooling water is flowed thereon to prepare granular glass of a predetermined size, and the granulated glass is stacked on the mullite or SiC dabs coated with the releasing agent, and then heat-treated in a firing furnace to crystallize. This method is easy to crystallize, but bubbles due to particles are easily generated in the firing process, and the waste balls remain in the interior, resulting in a decrease in strength and an increase in cost. An example of such a method is Japanese Patent Laid-Open No. 10152334.
반면, 결정성 유리원료 성분과 핵 형성제를 용융하여 결정화시켜 베타-월라스토나이트를 함유한 결정화 유리를 제조하는 방법은, 규사정제부산물을 활용하여 자원의 효율성을 높인 장점이 있는 반면, 건축용 자재로 사용하기 위해서는 결정성 무늬와 강도를 나타내어야 하는데 결정성 무늬와 강도를 위해서는 핵 형성제를 사용하여 표면으로부터 결정화 유리 내부로 베타-월라스토나이트 결정상을 성장시켜야 하기 때문에 열처리에 장시간이 필요하고 고강도의 결정화 유리를 제조하기 어려운 단점이 있다. 이러한 방법의 예로 대한민국 특허등록 제10-0083082호가 있다.On the other hand, a method of producing a crystallized glass containing beta-wollastonite by melting a crystalline glass raw material component and a nucleating agent to crystallize the crystalline glass raw material component and the nucleating agent is advantageous in that the efficiency of the resource is improved by utilizing silica- It is necessary to show a crystalline pattern and strength. For the crystal pattern and strength, it is necessary to grow a beta-wollastonite crystal phase from the surface to the inside of the crystallized glass by using a nucleating agent, It is difficult to produce the crystallized glass of the present invention. An example of such a method is Korean Patent Registration No. 10-0083082.
상기 문제점을 해결하기 위하여, 본 발명은 생활 폐기물인 폐유리와 해안에 폐기되는 패각을 재활용하여 낮은 비용으로 베타-월라스토나이트를 함유하여 강도 및 단열성이 우수한 결정화 유리를 제조할 수 있는 유리 조성물을 제공하는 것을 목적으로 한다. In order to solve the above problems, the present invention relates to a glass composition capable of producing a crystallized glass having high strength and heat insulation property by containing waste glass as a municipal waste and a shell recycled on the shore and containing beta-wollastonite at low cost The purpose is to provide.
상기 목적을 달성하기 위하여, 본 발명은 폐유리분말과 패각분말을 2:1~4:1의 중량비로 포함하고, 조성물 중 이산화규소(SiO2)의 함량이 68~76중량%이고 산화칼슘(CaO)의 함량이 5~7중량%인, 폐유리를 이용한 건축 내외장재용 결정화 유리 조성물을 제공한다.In order to attain the above object, the present invention provides a method for producing a glass composition, which comprises a waste glass powder and a shell powder at a weight ratio of 2: 1 to 4: 1, wherein the composition contains silicon dioxide (SiO 2 ) CaO) of 5 to 7% by weight based on the total weight of the glass composition.
상기 결정화 유리 조성물은 SiO2 68~76중량%, CaO 5~7중량%, Na2O 10~17중량%, MgO 2~4중량%, Al2O3 2~4중량%, B2O3 1~2중량%, Fe2O3 0.03~0.08중량%, K2O 1~2중량%, SO3 0.1~0.3중량% 및 F 0.1~0.4중량%를 포함하는 것이 바람직하다.The crystallized glass composition SiO 2 68-76 wt%,
상기 조성물은 폐유리분말과 패각분말 혼합물의 중량을 기준으로 10~20중량%의 이산화티탄(TiO2) 분말을 더 포함하는 것이 바람직하다.The composition preferably further comprises 10 to 20 wt% of titanium dioxide (TiO 2 ) powder based on the weight of the waste glass powder and shell powder mixture.
또한 본 발명은 폐유리분말과 패각분말을 2:1~4:1의 중량비로 포함하고, 조성물 중 이산화규소(SiO2)의 함량이 68~76중량%이고 산화칼슘(CaO)의 함량이 5~7중량%이며, 베타-월라스토나이트가 주결정상인, 폐유리를 이용한 건축 내외장재용 결정화 유리를 제공한다.The invention also waste glass powder and shell powder 2: 1 to 4: the content of the first silicon dioxide (SiO 2) is 68-76% by weight and calcium oxide (CaO) content in a weight ratio, and the composition of the 5 To 7% by weight, and the beta-wollastonite is a main crystal phase.
상기 결정화 유리는 SiO2 68~76중량%, CaO 5~7중량%, Na2O 10~17중량%, MgO 2~4중량%, Al2O3 2~4중량%, B2O3 1~2중량%, Fe2O3 0.03~0.08중량%, K2O 1~2중량%, SO3 0.1~0.3중량% 및 F 0.1~0.4중량%를 포함하는 것이 바람직하다.The crystallized glass may be SiO 2 68-76 wt%,
또한 본 발명은 폐유리를 세척, 건조 및 볼밀분쇄하여 폐유리분말을 제조하는 단계; 패각을 세척, 건조 및 볼밀분쇄하여 패각분말을 제조하는 단계; 상기 폐유리분말과 패각분말을 2:1~4:1의 중량비로 혼합하는 단계; 상기 혼합된 폐유리분말과 패각분말을 전기로에서 1000~1200℃로 1~2시간 동안 용융시키는 단계; 상기 용융물을 냉수로 수쇄한 다음 유리입자를 회수하는 단계; 상기 회수된 유리입자를 100~140℃에서 건조시키는 단계; 상기 건조된 유리입자를 미분으로 분쇄하는 단계; 상기 유리 미분을 300~700kg/cm2의 압력으로 압축 및 성형하는 단계; 및 상기 성형된 유리를 전기로에서 700~1000℃로 2시간 동안 열처리하여 결정화 유리를 얻는 단계를 포함하는, 폐유리를 이용한 건축 내외장재용 결정화 유리의 제조방법을 제공한다.The present invention also relates to a method for producing waste glass powder, comprising the steps of washing, drying and ball milling waste glass to produce waste glass powder; Washing, drying and ball milling the shell to produce a shell powder; Mixing the waste glass powder and the shell powder at a weight ratio of 2: 1 to 4: 1; Melting the mixed waste glass powder and shell powder in an electric furnace at 1000 to 1200 ° C for 1 to 2 hours; Washing the melt with cold water and recovering the glass particles; Drying the recovered glass particles at 100 to 140 캜; Pulverizing the dried glass particles into fine particles; Compressing and molding the glass powder at a pressure of 300 to 700 kg / cm 2 ; And heat-treating the molded glass in an electric furnace at 700 to 1000 ° C for 2 hours to obtain a crystallized glass. The present invention also provides a method for manufacturing a crystallized glass for building interior and exterior materials using waste glass.
상기 방법은, 상기 폐유리분말과 패각분말을 혼합한 후, 폐유리분말과 패각분말 혼합물의 중량을 기준으로 10~20중량%의 이산화티탄(TiO2) 분말을 혼합하는 단계를 더 포함할 수 있다.The method may further comprise mixing 10 to 20 wt% of titanium dioxide (TiO 2 ) powder, based on the weight of the waste glass powder and the shell powder mixture, after mixing the waste glass powder and the shell powder have.
본 발명은 생활 폐기물로 폐기되는 폐유리와 바닷가에 폐기되고 있는 패각을 재활용하여 베타-월라스토나이트가 혼재된 강도가 높고 단열성이 우수한 건축 내외장재용 결정화 유리를 낮은 비용으로 제조할 수 있고, 폐기물을 재활용함으로써 환경문제를 해결할 수 있는 효과가 있다. 제조된 결정화 유리는 고강도와 고단열성이 요구되는 건축용 내,외장재에 사용하기에 적합하다.The present invention recycles waste glass discarded as municipal waste and shells discarded on the beach to produce crystallized glass for building interior and exterior materials having a high strength and high heat insulating property mixed with beta-wollastonite at low cost, There is an effect of solving environmental problems by recycling. The produced crystallized glass is suitable for use in interior and exterior materials for construction requiring high strength and high heat insulation.
도 1은 실시예 2의 시료를 X선 회절 분석한 결과이다.
도 2는 실시예 2의 시료를 전자현미경으로 관찰한 사진이다.
도 3은 실시예 2의 시료의 결정상 부분의 성분을 분석한 결과이다.
도 4는 실시예 1 내지 3의 시편에 대한 압축강도를 측정한 결과이다. Fig. 1 shows the results of X-ray diffraction analysis of the sample of Example 2. Fig.
2 is a photograph of the sample of Example 2 observed with an electron microscope.
Fig. 3 shows the result of analyzing the components of the crystalline phase portion of the sample of Example 2. Fig.
Fig. 4 shows the results of measurement of the compressive strength of the specimens of Examples 1 to 3. Fig.
본 발명은 결정화 유리를 형성하는 결정화 유리 조성물의 원료로 폐유리와 패각을 사용한다. The present invention uses waste glass and shell as raw materials for a crystallized glass composition forming a crystallized glass.
폐유리의 예로는 가정 등에서 폐기되는 폐유리등을 들 수 있으며, 패각은 어촌 등에서 폐기되는 패각을 사용하는 것이 바람직하다.Examples of the waste glass include waste glass discarded at home and the like, and the shell is preferably used at a fishing village or the like.
폐유리는 이산화규소(SiO2) 공급원으로 사용되며, 패각은 산화칼슘(CaO) 공급원으로 사용된다. 결정화 유리 조성물에서 바람직한 SiO2의 함량은 68~76중량%이고, CaO의 함량은 5~7중량%이다. SiO2와 CaO의 함량이 상기 범위보다 적으면 결정상이 감소하여 강도가 감소하며, 상기 범위를 초과하면 강도증가에 비해 결정화 온도가 상승하는 단점이 있다.Waste glass is used as a source of silicon dioxide (SiO 2 ), and the shell is used as a source of calcium oxide (CaO). The preferable content of SiO 2 in the crystallized glass composition is 68 to 76 wt%, and the content of CaO is 5 to 7 wt%. When the content of SiO 2 and CaO is less than the above range, the crystal phase decreases and the strength decreases. If the content exceeds the above range, the crystallization temperature rises as compared with the increase in strength.
폐유리와 패각은 깨끗이 세척하고 충분히 건조시킨 후 분쇄한 분말의 형태로 사용한다. 폐유리와 패각의 분쇄시 볼밀을 사용하는 것이 바람직하며, 볼밀로 분쇄함으로써 분쇄된 입자의 크기가 작아 이후 열처리 온도와 시간을 줄이면서도 더 높은 강도의 결정화 유리를 얻을 수 있다.Waste glass and shell should be thoroughly cleaned and thoroughly dried before use in the form of ground powder. It is preferable to use a ball mill for crushing waste glass and shell, and since the size of the crushed particles is small by crushing with a ball mill, a crystallized glass having a higher strength can be obtained while reducing the heat treatment temperature and time.
상기 폐유리분말과 패각분말은 2:1~4:1의 중량비로 혼합하는 것이 바람직하며, 4:1의 중량비로 혼합하는 것이 특히 바람직하다.The waste glass powder and the shell powder are mixed preferably in a weight ratio of 2: 1 to 4: 1, and particularly preferably in a weight ratio of 4: 1.
상기 혼합된 폐유리분말과 패각분말을 전기로에서 1000~1200℃로 1~2시간 동안 용융시킨다. 1000℃에서 1시간 동안 용융시키는 것이 보다 바람직하다. The mixed waste glass powder and shell powder are melted in an electric furnace at 1000 to 1200 ° C for 1 to 2 hours. It is more preferable to melt at 1000 DEG C for 1 hour.
상기 용융된 용융물에 냉수를 부어 수쇄한 다음 유리입자를 회수하여 100~140℃, 보다 바람직하게는 120℃에서 충분히 건조시키고, 건조된 유리입자는 미분으로 분쇄한다. 이때 분쇄는 유발에서 분쇄하는 것이 바람직하다.After cold water is poured into the molten melt to recover the glass particles, the glass particles are recovered and sufficiently dried at 100 to 140 ° C, more preferably at 120 ° C, and the dried glass particles are pulverized into fine particles. At this time, the pulverization is preferably pulverized in the induction.
상기 유리 미분을 300~700 kg/cm2의 압력으로 압축 성형하고, 성형품을 전기로에서 700~1000℃로 2시간 동안 열처리하여 결정화 유리를 얻는다.The glass powder is compression molded at a pressure of 300 to 700 kg / cm 2 , and the molded product is heat-treated in an electric furnace at 700 to 1000 ° C for 2 hours to obtain a crystallized glass.
상기 제조된 결정화 유리는 베타-월라스토나이트(CaSiO3)가 주결정상이고 소듐 칼슘 실리케이트(Sodium calcium silicate)와 겔레나이트(Gehlenite)가 부결정상인 고강도 결정화 유리이다. The crystallized glass thus prepared is a high strength crystallized glass in which beta-wollastonite (CaSiO 3 ) is the main crystal phase and sodium calcium silicate and gehlenite are in the normal state.
상기와 같은 본 발명의 결정화 유리는 SiO2 68~76중량%, CaO 5~7중량%, Na2O 10~17중량%, MgO 2~4중량%, Al2O3 2~4중량%, B2O3 1~2중량%, Fe2O3 0.03~0.08중량%, K2O 1~2중량%, SO3 0.1~0.3중량% 및 F 0.1~0.4중량%로 이루어지는 것이 보다 바람직하다.The above-mentioned crystallized glass of the present invention comprises 68 to 76 wt% of SiO 2 , 5 to 7 wt% of CaO, 10 to 17 wt% of Na 2 O, 2 to 4 wt% of MgO, 2 to 4 wt% of Al 2 O 3 , More preferably 1 to 2% by weight of B 2 O 3 , 0.03 to 0.08% by weight of Fe 2 O 3 , 1 to 2% by weight of K 2 O, 0.1 to 0.3% by weight of SO 3 and 0.1 to 0.4% by weight of F.
상기 Na2O는 망목형성제 역할을 함으로써 용융온도를 낮춘다. Na2O의 함량이 10중량%보다 낮으면 용융온도를 상승시키고, 17중량%를 초과하면 내화학성이 감소하는 단점이 있다. The Na 2 O acts as a networking agent to lower the melting temperature. If the content of Na 2 O is less than 10% by weight, the melting temperature is increased. If the content is more than 17% by weight, the chemical resistance is decreased.
상기 Fe2O3와 SO3는 서로 반응하여 FeS를 형성함으로써 베타-월라스토나이트 결정을 석출시키는 핵 형성제 역할을 한다.The Fe 2 O 3 and SO 3 react with each other to form FeS, which serves as a nucleating agent to precipitate beta-wollastonite crystals.
상기 MgO와 Al2O3는 결정화 속도를 증가시키는 결정화 촉진제의 역할을 한다. MgO와 Al2O3의 함량이 2중량%보다 낮으면 유리의 결정상이 감소하여 강도가 감소되고, 4중량%를 초과하면 유리의 용융온도가 증가하는 단점이 있다. The MgO and Al 2 O 3 serve as crystallization accelerators for increasing the crystallization rate. When the content of MgO and Al 2 O 3 is less than 2% by weight, the crystal phase of the glass decreases and the strength decreases. When the content of MgO and Al 2 O 3 exceeds 4% by weight, the melting temperature of the glass increases.
건조 및 분쇄된 폐유리분말과 패각분말의 혼합물에 혼합물 중량을 기준으로 이산화티탄(TiO2) 분말 10~20중량%를 혼합하고, 동일한 방법으로 처리하여 결정화 유리를 얻을 수도 있다. 이산화티탄을 함유한 결정화 유리는 항균기능이 우수하다. The crystallized glass may be obtained by mixing 10 to 20% by weight of titanium dioxide (TiO 2 ) powder based on the weight of the mixture with a mixture of dried and pulverized waste glass powder and shell powder and treating them in the same manner. The crystallized glass containing titanium dioxide is excellent in antibacterial function.
상기와 같은 본 발명의 결정화 유리는 강도가 높고 단열성이 우수하여 건축 내외장재로 사용하기에 적합하다.The above-mentioned crystallized glass of the present invention has high strength and excellent heat insulating property, and is suitable for use as a building interior and exterior material.
이하 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 하기 실시예는 본 발명을 예시하는 것으로서 본 발명의 범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples. The following examples illustrate the invention and are not intended to limit the scope of the invention.
<< 실시예Example 1~3> 1 to 3>
원료로는 폐유리등 조각과 패각을 사용하였다. 서로 다른 곳에서 수집한 각각 3가지 원료를 사용하여 하기와 같이 처리하여 실시예 1 내지 3의 고강도 결정화 유리를 얻었다.Scrap and shells such as waste glass were used as raw materials. The three kinds of raw materials collected at different places were used to obtain the high strength crystallized glass of Examples 1 to 3 as follows.
페유리등 조각을 물로 세척한 다음 120℃의 건조기에서 충분히 건조시켰다. 패각도 수집된 상태에서 깨끗한 물로 세척하고 120℃의 건조기에서 충분히 건조시켰다. 건조된 폐유리등 조각과 패각을 볼밀에서 분쇄하였다.The flakes were washed with water and dried thoroughly in a dryer at 120 ° C. The shell was washed with clean water in the collected state and sufficiently dried in a dryer at 120 ° C. Dried pieces of waste glass and the like were crushed in a ball mill.
분쇄된 폐유리등 분말과 패각분말을 4:1의 중량비로 혼합하였다. And pulverized waste glass powder and shell powder were mixed at a weight ratio of 4: 1.
상기 혼합된 폐유리등 분말과 패각분말을 전기로에서 1000℃로 1시간 동안 용융시켰다.The mixed powder such as waste glass and the shell powder were melted in an electric furnace at 1000 ° C for 1 hour.
용융된 용융물에 찬물에 부어 수쇄한 다음 유리입자를 회수하여 120℃에서 충분히 건조시켰고, 건조된 유리입자는 유발에서 미분으로 분쇄하였다.The molten melted material was poured into cold water to be polished, and then the glass particles were recovered and sufficiently dried at 120 ° C, and the dried glass particles were pulverized into fine particles at the induction.
상기 유리 미분을 300~700 kg/cm2의 압력으로 압축 성형하고, 성형품을 전기로에서 700~1000℃로 2시간 동안 열처리하여 베타-월라스토나이트가 주결정상인 고강도 결정화 유리를 얻었다.The glass powder was compression molded at a pressure of 300 to 700 kg / cm 2 , and the molded product was heat-treated in an electric furnace at 700 to 1000 ° C for 2 hours to obtain a high-strength crystallized glass having beta-wollastonite as a main crystal phase.
<< 비교예Comparative Example 1~3> 1 to 3>
상기 실시예 1 내지 3에서의 폐유리등 분말과 패각분말의 혼합물에 이들 총 중량의 20중량%의 이산화티탄(TiO2)을 혼합한 것을 제외하고는 상기 실시예 1~3에서와 동일하게 처리하여 비교예 1 내지 3의 결정화 유리를 얻었다.The same procedures as in Examples 1 to 3 were carried out except that 20% by weight of titanium dioxide (TiO 2 ) was added to a mixture of powders of waste glass and the like in Examples 1 to 3, To obtain the crystallized glasses of Comparative Examples 1 to 3.
<< 실험예Experimental Example 1> 1>
상기 실시예 1~3에서 얻어진 결정화 유리의 조성, 주결정상, 부결정상, 압축강도 및 표면상태를 확인하였다. 그 결과를 하기 표 1에 나타내었다. The composition of the crystallized glass obtained in Examples 1 to 3, the main crystal phase, the crushed crystal phase, the compressive strength and the surface state were confirmed. The results are shown in Table 1 below.
(2) CaO : 7%
(3) Na2O : 15%
(4) MgO : 3%
(5) Al2O3 : 3%
(6) B2O3 : 1.5%
(7) Fe2O3 : 0.04%
(8) K2O3 : 1.0%
(9) SO3 : 0.2%
(10) F : 0.26%(1) SiO 2 : 69%
(2) CaO: 7%
(3) Na 2 O: 15%
(4) MgO: 3%
(5) Al 2 O 3 : 3%
(6) B 2 O 3 : 1.5%
(7) Fe 2 O 3 : 0.04%
(8) K 2 O 3 : 1.0%
(9) SO 3 : 0.2%
(10) F: 0.26%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 188.2 MPa
(4) 표면상태: 기공없음 (1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 188.2 MPa
(4) Surface condition: No porosity
: X선회절분석,
전자현미경
(2) 표면상태
: 육안검사
(1) Crystal phase inspection
: X-ray diffraction analysis,
Electron microscope
(2) surface state
: Visual inspection
(2) CaO : 6 %
(3) Na2O : 11%
(4) MgO : 4%
(5) Al2O3 : 4%
(6) B2O3 : 1.5%
(7) Fe2O3 : 0.04%
(8) K2O3 : 1.0%
(9) SO3 : 0.2%
(10) F : 0.26%(1) SiO 2 : 72%
(2) CaO: 6%
(3) Na 2 O: 11%
(4) MgO: 4%
(5) Al 2 O 3 : 4%
(6) B 2 O 3 : 1.5%
(7) Fe 2 O 3 : 0.04%
(8) K 2 O 3 : 1.0%
(9) SO 3 : 0.2%
(10) F: 0.26%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 228.7 MPa
(4) 표면상태: 기공없음 (1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 228.7 MPa
(4) Surface condition: No porosity
(2) CaO : 7%
(3) Na2O : 11%
(4) MgO : 4%
(5) Al2O3 : 4%
(6) B2O3 : 1.5%
(7) Fe2O3 : 0.04%
(8) K2O3 : 1.0%
(9) SO3 : 0.2%
(10) F : 0.26%(1) SiO 2 : 71%
(2) CaO: 7%
(3) Na 2 O: 11%
(4) MgO: 4%
(5) Al 2 O 3 : 4%
(6) B 2 O 3 : 1.5%
(7) Fe 2 O 3 : 0.04%
(8) K 2 O 3 : 1.0%
(9) SO 3 : 0.2%
(10) F: 0.26%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 196.0 MPa
(4) 표면상태: 기공없음 (1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 196.0 MPa
(4) Surface condition: No porosity
또한, 실시예 2의 시료를 X선 회절분석한 결과를 도 1에, 전자현미경으로 관찰한 사진을 도 2에, 결정상 부분의 성분을 분석한 결과를 도 3에 나타내었다. 또한, 상기 실시예 1 내지 3의 시편에 대한 압축강도를 측정한 결과를 도 4에 나타내었다. The results of X-ray diffraction analysis of the sample of Example 2 are shown in Fig. 1, the photographs observed by an electron microscope are shown in Fig. 2, and the results of analysis of the components of the crystal phase portion are shown in Fig. The results of measuring the compressive strength of the specimens of Examples 1 to 3 are shown in FIG.
상기 표 1 및 도 4의 결과에서 알 수 있는 바와 같이, 폐유리등과 패각을 이용하여 제조한 실시예 1 내지 3의 결정화 유리 조성물로 제조된 유리는 압축강도가 188~229Mpa로 매우 높았다. As can be seen from the results of Table 1 and FIG. 4, the glass prepared from the crystallized glass compositions of Examples 1 to 3 prepared by using waste glass and shell has a very high compressive strength of 188 to 229 MPa.
<< 실험예Experimental Example 2> 2>
상기 비교예 1~3에서 얻어진 결정화 유리의 조성, 주결정상, 부결정상, 압축강도 및 표면상태를 확인하였다. 그 결과를 하기 표 2에 나타내었다. The composition of the crystallized glass obtained in Comparative Examples 1 to 3, the main crystal phase, the solidification state, the compressive strength and the surface state were confirmed. The results are shown in Table 2 below.
(2) CaO : 6%
(3) Na2O : 11%
(4) MgO : 4%
(5) Al2O3 : 4%
(6) B2O3 : 1.5%
(7) Fe2O3 : 0.01%
(8) K2O3 : 1.23%
(9) SO3 : 0.0%
(10) F : 0.26%
(11) TiO2 : 2%(1) SiO 2 : 72%
(2) CaO: 6%
(3) Na 2 O: 11%
(4) MgO: 4%
(5) Al 2 O 3 : 4%
(6) B 2 O 3 : 1.5%
(7) Fe 2 O 3 : 0.01%
(8) K 2 O 3 : 1.23%
(9) SO 3 : 0.0%
(10) F: 0.26%
(11) TiO 2: 2%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 120.1 MPa
(4) 표면상태: 기공없음(1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 120.1 MPa
(4) Surface condition: No porosity
: X선회절분석,
전자현미경
(2) 표면상태
: 육안검사
(1) Crystal phase inspection
: X-ray diffraction analysis,
Electron microscope
(2) surface state
: Visual inspection
(2) CaO : 6%
(3) Na2O : 11%
(4) MgO : 1%
(5) Al2O3 : 4%
(6) B2O3 : 2.5%
(7) Fe2O3 : 0.04%
(8) K2O3 : 1.0%
(9) SO3 : 0.2%
(10) F : 0.26%
(11) TiO2 : 2%(1) SiO 2 : 74%
(2) CaO: 6%
(3) Na 2 O: 11%
(4) MgO: 1%
(5) Al 2 O 3 : 4%
(6) B 2 O 3 : 2.5%
(7) Fe 2 O 3 : 0.04%
(8) K 2 O 3 : 1.0%
(9) SO 3 : 0.2%
(10) F: 0.26%
(11) TiO 2: 2%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 110.2 MPa
(4) 표면상태: 기공없음 (1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 110.2 MPa
(4) Surface condition: No porosity
(2) CaO : 6%
(3) Na2O : 11%
(4) MgO : 4%
(5) Al2O3 : 1%
(6) B2O3 : 2.5%
(7) Fe2O3 : 0.04%
(8) K2O3 : 1.0%
(9) SO3 : 0.2%
(10) F : 0.26%
(11) TiO2 : 2%(1) SiO 2 : 74%
(2) CaO: 6%
(3) Na 2 O: 11%
(4) MgO: 4%
(5) Al 2 O 3 : 1%
(6) B 2 O 3 : 2.5%
(7) Fe 2 O 3 : 0.04%
(8) K 2 O 3 : 1.0%
(9) SO 3 : 0.2%
(10) F: 0.26%
(11) TiO 2: 2%
베타-월라스토나이트
(2) 부결정상:
소듐 칼슘 실리케이트,
겔레나이트
(3) 압축강도: 113.3 MPa
(4) 표면상태: 기공없음 (1) Main crystalline phase:
Beta - Wollastonite
(2) Negative normal:
Sodium calcium silicate,
Gellenite
(3) Compressive strength: 113.3 MPa
(4) Surface condition: No porosity
Claims (7)
상기 결정화 유리 조성물은 SiO2 68~76중량%, CaO 5~7중량%, Na2O 10~17중량%, MgO 2~4중량%, Al2O3 2~4중량%, B2O3 1~2중량%, Fe2O3 0.03~0.08중량%, K2O 1~2중량%, SO3 0.1~0.3중량% 및 F 0.1~0.4중량%를 포함하는 것을 특징으로 하는, 폐유리를 이용한 건축 내외장재용 결정화 유리 조성물.The method according to claim 1,
The crystallized glass composition SiO 2 68-76 wt%, CaO 5 ~ 7 wt%, Na 2 O 10 ~ 17 wt%, MgO 2 ~ 4 wt%, Al 2 O 3 2 ~ 4 wt%, B 2 O 3 1 ~ 2 weight%, Fe Wherein the glass composition comprises 0.03 to 0.08% by weight of 2 O 3 , 1 to 2% by weight of K 2 O, 0.1 to 0.3% by weight of SO 3 and 0.1 to 0.4% by weight of F. .
상기 조성물은 폐유리분말과 패각분말 혼합물의 중량을 기준으로 10~20중량%의 이산화티탄(TiO2) 분말을 더 포함하는 것을 특징으로 하는, 폐유리를 이용한 건축 내외장재용 결정화 유리 조성물.3. The method according to claim 1 or 2,
Characterized in that the composition further comprises 10 to 20% by weight of titanium dioxide (TiO 2 ) powder based on the weight of the waste glass powder and the shell powder mixture.
상기 결정화 유리는 SiO2 68~76중량%, CaO 5~7중량%, Na2O 10~17중량%, MgO 2~4중량%, Al2O3 2~4중량%, B2O3 1~2중량%, Fe2O3 0.03~0.08중량%, K2O 1~2중량%, SO3 0.1~0.3중량% 및 F 0.1~0.4중량%를 포함하는 것을 특징으로 하는, 폐유리를 이용한 건축 내외장재용 결정화 유리.5. The method of claim 4,
The crystallized glass may be SiO 2 68-76 wt%, CaO 5 ~ 7 wt%, Na 2 O 10 ~ 17 wt%, MgO 2 ~ 4 wt%, Al 2 O 3 2 ~ 4 wt%, B 2 O 3 1 ~ 2 weight%, Fe Wherein the glass composition comprises 0.03 to 0.08% by weight of 2 O 3 , 1 to 2% by weight of K 2 O, 0.1 to 0.3% by weight of SO 3 and 0.1 to 0.4% by weight of F.
패각을 세척, 건조 및 볼밀분쇄하여 패각분말을 제조하는 단계;
상기 폐유리분말과 패각분말을 2:1~4:1의 중량비로 혼합하는 단계;
상기 혼합된 폐유리분말과 패각분말을 전기로에서 1000~1200℃로 1~2시간 동안 용융시키는 단계;
상기 용융물을 냉수로 수쇄한 다음 유리입자를 회수하는 단계;
상기 회수된 유리입자를 100~140℃에서 건조시키는 단계;
상기 건조된 유리입자를 미분으로 분쇄하는 단계;
상기 유리 미분을 300~700kg/cm2의 압력으로 압축 및 성형하는 단계; 및
상기 성형된 유리를 전기로에서 700~1000℃로 2시간 동안 열처리하여 결정화 유리를 얻는 단계를 포함하는, 폐유리를 이용한 건축 내외장재용 결정화 유리의 제조방법.Washing, drying and ball milling the waste glass to produce a waste glass powder;
Washing, drying and ball milling the shell to produce a shell powder;
Mixing the waste glass powder and the shell powder at a weight ratio of 2: 1 to 4: 1;
Melting the mixed waste glass powder and shell powder in an electric furnace at 1000 to 1200 ° C for 1 to 2 hours;
Washing the melt with cold water and recovering the glass particles;
Drying the recovered glass particles at 100 to 140 캜;
Pulverizing the dried glass particles into fine particles;
Compressing and molding the glass powder at a pressure of 300 to 700 kg / cm 2 ; And
And heat-treating the molded glass in an electric furnace at 700 to 1000 占 폚 for 2 hours to obtain a crystallized glass.
상기 폐유리분말과 패각분말을 혼합한 후, 폐유리분말과 패각분말 혼합물의 중량을 기준으로 10~20중량%의 이산화티탄(TiO2) 분말을 혼합하는 단계를 더 포함하는 것을 특징으로 하는, 폐유리를 이용한 건축 내외장재용 결정화 유리의 제조방법.
The method according to claim 6,
Further comprising the step of mixing the waste glass powder and the shell powder and then mixing 10 to 20 wt% of the titanium dioxide (TiO 2 ) powder based on the weight of the waste glass powder and the shell powder mixture. Process for the production of crystallized glass for building interior and exterior materials using waste glass.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10152334A (en) | 1996-11-21 | 1998-06-09 | Nippon Electric Glass Co Ltd | Construction material made of crystallized glass and its production |
| JP2000072487A (en) * | 1998-08-27 | 2000-03-07 | Nippon Electric Glass Co Ltd | Antibacterial crystallized glass article and its production |
| JP2000272959A (en) * | 1999-03-26 | 2000-10-03 | Fukui Prefecture | Crystallized glass complex ceramic and its production |
| KR20030047501A (en) * | 2001-12-11 | 2003-06-18 | 황규석 | Fabrication of glass-ceramics by waste fluorescent glass and shell |
| KR20100118398A (en) | 2009-04-28 | 2010-11-05 | 주식회사 인스나인 | Manufacturing method of high-strength glass-ceramics |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10152334A (en) | 1996-11-21 | 1998-06-09 | Nippon Electric Glass Co Ltd | Construction material made of crystallized glass and its production |
| JP2000072487A (en) * | 1998-08-27 | 2000-03-07 | Nippon Electric Glass Co Ltd | Antibacterial crystallized glass article and its production |
| JP2000272959A (en) * | 1999-03-26 | 2000-10-03 | Fukui Prefecture | Crystallized glass complex ceramic and its production |
| KR20030047501A (en) * | 2001-12-11 | 2003-06-18 | 황규석 | Fabrication of glass-ceramics by waste fluorescent glass and shell |
| KR20100118398A (en) | 2009-04-28 | 2010-11-05 | 주식회사 인스나인 | Manufacturing method of high-strength glass-ceramics |
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