KR100750941B1 - Glass beads coated with nano sized silver particle and manufacturing method therefor - Google Patents

Glass beads coated with nano sized silver particle and manufacturing method therefor Download PDF

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KR100750941B1
KR100750941B1 KR1020040095328A KR20040095328A KR100750941B1 KR 100750941 B1 KR100750941 B1 KR 100750941B1 KR 1020040095328 A KR1020040095328 A KR 1020040095328A KR 20040095328 A KR20040095328 A KR 20040095328A KR 100750941 B1 KR100750941 B1 KR 100750941B1
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glass beads
nano
silver
manufacturing
minutes
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KR20060056065A (en
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이철재
이무상
이형우
박순화
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주식회사 신일
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment

Abstract

본 발명의 나노 은 코팅 글라스비드 제조방법은, 글라스비드와 나노 은 콜로이드용액을 N:1(N은 1∼10) 무게비로 혼합용기에 담아 혼합용기를 회전시키면서 수십 내지 수백 도씨로 수십분간 가열한 후 식히는 제1과정과, 제1과정을 거친 다음 전기로에서 수백도씨로 수십분간 재차 가열하는 제2과정으로 이루어진다.
In the method of manufacturing nano-silver coated glass beads of the present invention, the glass beads and the nano-silver colloidal solution are placed in a mixing container at a weight ratio of N: 1 (N is 1 to 10) and heated for several tens of minutes to several hundred degrees while rotating the mixing container. After cooling, it consists of a first process and a second process of heating again for several hundred minutes at several hundred degrees in an electric furnace after the first process.

나노 은 콜로이드, 글라스비드, Nano silver colloid, glass beads,

Description

나노 은 코팅 글라스비드 및 그 제조방법{GLASS BEADS COATED WITH NANO SIZED SILVER PARTICLE AND MANUFACTURING METHOD THEREFOR}Nano silver coated glass bead and manufacturing method thereof {GLASS BEADS COATED WITH NANO SIZED SILVER PARTICLE AND MANUFACTURING METHOD THEREFOR}

본 발명은 살균 및 항균에 대한 개량에 관한 것으로, 특히 강력한 살균 및 항균이 가능한 은나노입자 글라스비드 및 그 제조방법에 관한 것이다. The present invention relates to an improvement on sterilization and antibacterial, and in particular, to silver nanoparticle glass beads capable of strong sterilization and antibacterial and a method of manufacturing the same.

오래 전부터 인류는 광범위한 여러 가지 살균 작용을 발견하였으며 또 사용해 왔다. 고대 로마, 고대 페르시아보다도 더 일찍이 사람들은 은으로 된 기구로 액체를 담아두어 부패를 방지하였다. 근대에 들어서 와서도 질산은 용액은 신생아의 눈에 떨구어 결막염을 예방하는 크레드(crede) 예방법으로서 지금까지도 사용되고 있다.Humans have long discovered and used a wide variety of bactericidal activities. Earlier than ancient Rome and ancient Persia, people contained liquids with silver utensils to prevent corruption. Even in modern times, silver nitrate solution is still used as a creed prevention method to prevent conjunctivitis by dropping in the newborn's eyes.

합성 항생소(antibiotic)가 출현한 이후 이러한 항생소들은 보통 은(銀)으로 제작한 제제(製劑)보다 살균력이 강하고, 속도가 빨라 점차적으로 은을 대체하게 되었다. 나노기술의 출현은 보통 은 제제의 살균력이 약한 병목(bottleneck)을 해결하였다. 과학자들은 은이 나노 상태에서는 살균 능력이 질적인 변화를 일으키는 것을 발견하였는데 극히 적은 양의 나노 은이 매우 강력한 살균 작용을 한다는 것 이다. 이것은 나노 은을 사용하여 살균하고, 세균을 방지하는데 더없는 전망을 보여주었다. Since the emergence of synthetic antibiotic, these antibiotics are more sterilizing and faster than silver-made preparations, and have gradually replaced silver. The emergence of nanotechnology has solved the bottleneck, which is usually a weak sterilization of silver preparations. Scientists have found that silver has a qualitative change in its sterilization ability in the nano state, with a very small amount of nanosilver having a very strong bactericidal effect. This shows the prospect of sterilizing using nano silver and preventing bacteria.

전문가들은 나노 은 항균 분말이 환경보호, 방직복장, 과일의 신선도 보존, 식품위생 등의 영역에 광범위하게 사용될 것으로 전망하고 있으며, 실제로 나노 은은 항균/제균, 방취기능, 자외선차단 기능, 전자파 차폐 기능, 제전기능, 항온/단열기능 등으로 다양한 제품들에 응용되고 있다. Experts predict that nano silver antibacterial powder will be widely used in the areas of environmental protection, textile garments, fruit freshness preservation, food hygiene, etc. In fact, nano silver has antibacterial / antibacterial, deodorization function, UV protection function, electromagnetic shielding function, It is applied to various products with antistatic function and constant temperature / insulation function.

한편 글라스비드(grass beads)는 각 산업분야에 필수적인 산업재료로 알려져 있으며, 일반적으로 생활 속에서 접할 수 있는 글라스비드의 대표적인 활용 사례는 도로표지판이나 도로상의 차선과 같은 곳에 교통 안전제품 외에도 정수장, 연마공구, 스크린 등등에 다양하게 사용 내지 응용되고 있다. On the other hand, glass beads are known as an essential industrial material for each industry, and typical applications of glass beads that can be encountered in everyday life are water purification plants and polishing in addition to traffic safety products such as road signs and lanes on the road. Various uses or applications in tools, screens and the like.

만일 나노 은을 글라스 비드에 코팅을 할 수 있으면 글라스비드와 나노 은의 장점이 조화되면서도 강력한 살균 및 소독기능을 할 수 있고 다양한 응용이 가능한 것이지만, 글라스비드가 유리구슬인 관계로 나노 은 코팅이 결코 용이하지 않았다.
If nano silver can be coated on glass beads, the advantages of glass bead and nano silver can be harmonized and powerful sterilization and disinfection functions can be applied. However, nano silver coating is easy because glass beads are glass beads. Did not do it.

따라서 본 발명의 목적은 글라스비드에 나노 은을 코팅하기 위한 나노 은 코팅 글라스비드 제조방법 및 그 글라스비드를 제공하는데 있다. Accordingly, an object of the present invention is to provide a method for producing nano-silver coated glass beads for coating nano-silver on glass beads and glass beads.

본 발명의 다른 목적은 강력한 살균 및 소독작용이 가능한 나노은 코팅 글라스비드 및 그 제조방법을 제공함에 있다. Another object of the present invention is to provide a nano silver coated glass bead capable of strong sterilization and disinfection, and a method of manufacturing the same.

상기한 목적을 달성하기 위한 본 발명은, 나노은 글라스비드 제조방법에 있어서, 글라스비드와 나노은 콜로이드용액을 N:1(N은 1∼10) 무게비로 혼합용기에 담아 혼합용기를 회전시키면서 50∼100℃의 온도로 20∼40분간 가열한 후 식히는 제1과정과, 제1과정을 거친 다음 전기로에서 290∼310℃의 온도로 20∼40분간 재차 가열하는 제2과정으로 이루어짐을 특징으로 한다.In the present invention for achieving the above object, in the method of manufacturing nanosilver glass beads, the glass beads and the nanosilver colloidal solution is contained in a mixing container in a weight ratio of N: 1 (N is 1 to 10) by 50 to 100 while rotating the mixing container. It is characterized by consisting of a first process of cooling after 20-40 minutes at a temperature of ℃ and a second process of heating again for 20-40 minutes at a temperature of 290 ~ 310 ℃ in the electric furnace after the first process.

본 명세서에서는 나노미터 사이즈의 은입자를 "나노 은"으로 약칭하고, 그 나노은 입자를 포함한 콜로이드용액을 "나노 은 콜로이드용액"이라 칭한다.
In the present specification, nanometer-sized silver particles are abbreviated as "nano silver", and the colloidal solution containing the nanosilver particles is referred to as "nano silver colloidal solution".

이하 본 발명의 바람직한 실시 예들을 상세히 설명한다. 본 발명의 명세서에서 특정 용어, 특정 수치 및 범위는 본 발명을 특정하거나 한정하는 것이 아니며 본 발명의 범위를 벗어나지 않고서 다양하게 변경 및 변형될 수 있음을 유의하여야 한다. 또한 본 명세서에서는 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 상세한 설명은 생략한다.Hereinafter, preferred embodiments of the present invention will be described in detail. It should be noted that the specific terms, specific numerical values, and ranges in the specification of the present invention do not specify or limit the present invention, and various changes and modifications may be made without departing from the scope of the present invention. In addition, detailed descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.

먼저 본 발명의 실시 예에서는 30㎛ ∼ 4.5㎜직경의 공업용 글라스비드를 제조한다.First, in the embodiment of the present invention, industrial glass beads having a diameter of 30 μm to 4.5 mm are manufactured.

공업용 글라스 비드는, 분쇄 및 선별공정을 거쳐서 일정한 크기로 선별된 카레트(유리조각)를 얻고, 일정한 크기로 선별된 카레트를 비드제조용 노에 넣어 비드화시키는 비드화 공정을 거침으로서 얻어진다.Industrial glass beads are obtained by passing through a beading step in which a curry (glass pieces) sorted to a constant size is obtained through a crushing and sorting step, and the beads sorted into a bead manufacturing furnace are beaded.

하기 표 1은 본 발명의 실시 예에서 사용하는 공업용 글라스비드의 구성성분 일예이다. Table 1 below is an example of the components of the industrial glass bead used in the embodiment of the present invention.                     

성 분ingredient 중량비(%)Weight ratio (%) SiO2 SiO 2 70∼73%70-73% Al2O3 Al 2 O 3 1∼2%1 to 2% Na2ONa 2 O 10∼15%10-15% MgOMgO 1.0∼4.5%1.0 to 4.5% Ca2OCa 2 O 7∼13%7-13% K2OK 2 O 0.5∼1.5%0.5-1.5%

상기 공업용 글라스비드는 하기와 같은 일 예의 특성을 가진다. 비중(specific gravity)은 약 2.5, 용융점(softing point)은 약 730℃, 경도(hardness)은 약 550kgf/㎟, 마모율(abrasion) 약 4-5%, 압축강도(compressive strength)는 약 18-22kgf/㎟ 정도이다.The industrial glass beads have the following characteristics. Specific gravity is about 2.5, softening point is about 730 ℃, hardness is about 550kgf / mm2, abrasion is about 4-5%, compressive strength is about 18-22kgf / Mm2 or so.

따라서 본 발명의 실시 예에 따른 공업용 글라스비드는 페인트 혼합 등에 사용되는 일반용 글라스비드와는 달리 구형도가 95∼99%이며, 투명도가 매우 높아 글라스비드내에 기포가 거의 없는 특성이 있다. 이러한 공업용 글라스비드는 고품질의 글라스비드로서 단위표면적이 넓어서 정수 등도 가능하다. Therefore, the industrial glass bead according to the embodiment of the present invention has a spherical degree of 95 to 99%, unlike a general glass bead used for paint mixing, and has a very high transparency and almost no bubbles in the glass bead. These industrial glass beads are high quality glass beads, and the unit surface area is large, so that the purified water beads can be used.

아울러 본 발명의 실시 예에서는 상기한 글라스비드에 코팅할 나노 은 콜로이드(colloid)용액을 제조하되, 그 농도가 0.5몰(㏖)∼0.005몰(㏖)이 되도록 한다. 나노 은 콜로이드용액은 나노 은이 용액중에 분산된 상태로 있되, 응집하거나 침전하기 않고 일정하게 분포된 상태를 유지한다.In addition, in the embodiment of the present invention to prepare a nano-silver colloid (colloid) solution to be coated on the glass beads, so that the concentration is 0.5 mol (mol) to 0.005 mol (mol). The nano silver colloidal solution is in a state in which the nano silver is dispersed in the solution, but remains uniformly distributed without aggregation or precipitation.

나노 은 콜로이드 용액은 하기와 같은 일 예로 제조할 수 있다. 예컨대, 은염(sliver slat)의 일종인 질산 은(AgNO3), 과염소산 은(AgClO4) 혹은 염소산은(AgClO3)을 3차 증류수에 녹인 후, 중간 생성물 제거제를 유기용매(또는 알코올)를 첨가하고, 콜로이드 안정제로 소디윰 도데 실술페이트(sodium dodecyl sufate: SDS), 폴리비닐알콜(poly vinyl alcohol: PVA), 폴리비닐피로리돈(poly vinyl rrodlidone: PVP) 등을 넣고, 질소 치환 후, 적당량의 방사선을 조사하여 일정한 분포를 가진 나노미터 크기의 은 콜로이드를 제조한다. Nano silver colloidal solution can be prepared by the following example. For example, a type of nitric acid, silver salt (sliver slat) is (AgNO 3), perchloric acid is (AgClO 4) or the acid is a. Then, the intermediate product remover dissolved (AgClO 3) in deionized water in an organic solvent (or alcohol) was added Sodium dodecyl sufate (SDS), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), or the like is added as a colloidal stabilizer. Irradiation produces nanometer-sized silver colloids with uniform distribution.

이러한 나노 은 콜로이드용액은 예컨대, 발명자 이무상 등에 의해서 대한민국에 특허출원되어 등록된 특허 제10-0425976호 '방사선 조사에 의한 나노미터 크기의 은 콜로이드 제조방법 및 그 나노미터 크기의 은 콜로이드'를 이용하면 제조할 수 있다. Such a nano silver colloidal solution is, for example, using a patent application No. 10-0425976 registered in the Republic of Korea by the inventor Lee Mu-sang, etc. 'Method of preparing nanometer-sized silver colloid by radiation irradiation and its nanometer-sized silver colloid' It can manufacture.

이러한 방사선을 이용한 나노 은 콜로이드용액 제조방법은 나노 은 콜로이드를 대량 제조가 가능할 뿐만 아니라 실온에서 대량 제조가 가능한 이점이 있으며, 이렇게 제조된 나노 은 콜로이드는 표면증강 라만 증강제, 전도성 접착제, 잉크 첨가제, 전자파 차단제, 항균제, 항생제 등으로 다양하게 사용할 수 있다. The method of manufacturing a nano silver colloidal solution using radiation has the advantage that not only a large amount of nano silver colloid can be manufactured but also a large amount can be manufactured at room temperature. It can be used variously as a blocking agent, antibacterial agent, antibiotic, and the like.

본 발명의 실시 예에서는 전기와 같이 준비된 글라스비드와 나노 은 콜로이드용액을 이용하여 하기와 같은 제조방법으로 나노 은 코팅된 글라스비드를 제조한다. In the embodiment of the present invention by using a glass bead and nano silver colloidal solution prepared as described above to prepare a nano-silver coated glass bead by the following manufacturing method.

요컨대, 글라스비드와 나노은 콜로이드용액을 N:1(N은 1∼10) 무게비로 혼합용기에 담아 혼합용기를 회전시키면서 수십 내지 수백 도씨로 수십 분간 가열한 후 식히는 제1과정, 제1과정을 거친 다음 전기로에서 수백 도씨로 수십 분간 재차 가열하는 제2과정으로 나노 은 코팅된 글라스비드를 제조한다. In other words, the glass beads and the nano silver colloidal solution in a weight ratio of N: 1 (N is 1 to 10) in a mixing container, while rotating the mixing container and heating it for several tens of minutes to hundreds of degrees while cooling the first and first processes. After the roughing, the second process of heating again for several tens of minutes at several hundred degrees Celsius in an electric furnace produces nano-silver coated glass beads.

보다 구체적으로 설명하면 하기와 같다. More specifically, it is as follows.                     

먼저 직경 30㎛ ∼ 4.5㎜인 글라스비드 90∼110g, 바람직하게는 약 100g을 준비하고, 농도가 0.5몰(㏖) ∼ 0.005몰(㏖)인 나노 은 콜로이드용액 20∼30g, 바람직하게는 약 25g을 준비하여, 그 준비된 글라스비드 100g와 나노 은 콜로이드용액 25g을 원통형 혼합용기에 담는다. 이때 사용되는 원통형 혼합용기는 직경이 수백 밀리이고 높이는 직경의 약 두배 정도가 적당하다.First, 90 to 110 g of glass beads having a diameter of 30 µm to 4.5 mm, preferably about 100 g, are prepared, and 20 to 30 g of nano silver colloidal solution having a concentration of 0.5 mol (mol) to 0.005 mol (mol) is preferably about 25 g. Then, 100 g of the prepared glass beads and 25 g of the nano silver colloidal solution were put in a cylindrical mixed container. At this time, the cylindrical mixing container used is several hundred millimeters in diameter and the height is about twice the diameter is appropriate.

그 후 원통형 혼합용기를 소정 각도 경사지게 설치하고 설치된 혼합용기를 5∼15rpm(revolution per minute) 회전속도로 회전시키면서 하부에 설치된 가스버너를 이용하여 50∼100℃의 온도로 20∼40분간(바람직하기로는 30분간) 가열한다. Thereafter, the cylindrical mixing vessel was installed at an inclined angle, and the installed mixing vessel was rotated at a rotational speed of 5 to 15 rpm (revolution per minute) while using a gas burner installed at the bottom for 20 to 40 minutes at a temperature of 50 to 100 ° C (preferably Heat for 30 minutes).

그 다음으로는 혼합용기에서 혼합용액을 꺼내서 식히고, 그 후 전기로에 혼합용액을 다시 넣고 290∼310℃의 온도로 재차 가열하되, 20∼40분간(바람직하게는 30분간)을 지속시킨다. 그 후 전기로에서 꺼내면 나노 은 콜로이드가 코팅된 글라스비드를 얻을 수 있게된다. Then, the mixed solution is taken out of the mixed container and cooled, and then the mixed solution is put back into the electric furnace and heated again at a temperature of 290 to 310 ° C. for 20 to 40 minutes (preferably 30 minutes). Then, when taken out of the electric furnace, the glass beads coated with nano silver colloid can be obtained.

본 발명의 실시 예에서는 재차 가열하는 온도는 여러 가지 변수들을 고려해서 200에서 최대 600℃까지 설정될 수 있으나, 글라스비드의 용융점(730℃)을 고려해서 최대 600℃를 넘지 않는 것이 바람직하다. In the embodiment of the present invention, the temperature of heating again may be set from 200 to 600 ° C. in consideration of various variables, but preferably, the temperature does not exceed 600 ° C. in consideration of the melting point (730 ° C.) of the glass bead.

상술한 본 발명의 설명에서는 구체적인 실시 예에 관해 설명하였으나, 여러 가지 변형이 본 발명의 범위에서 벗어나지 않고 실시할 수 있다. 따라서 본 발명의 범위는 설명된 실시 예에 의하여 정할 것이 아니고 특허청구범위와 특허청구범위의 균등한 것에 의해 정해져야 한다.
In the above description of the present invention, specific embodiments have been described, but various modifications may be made without departing from the scope of the present invention. Therefore, the scope of the present invention should not be defined by the described embodiments, but should be determined by the equivalent of claims and claims.

상술한 바와 같은 본 발명은 나노 은 콜로이드가 코팅된 글라스비드를 이용하여 강력한 살균 및 소독 작용을 할 수 있는 장점이 있다. 또한 본 발명은 상수원 살균소독(염소 대체제품), 정수기의 물을 정수-살균하는 기능(정수필터 대체 제품), 농산물을 장기간 보관케 하는 기능, 의료분야의 소독 살균기능, 수출입 식품 및 한약재료의 살균 소독용 등등 매우 다양하게 응용할 수 있다. The present invention as described above has the advantage that can be a strong sterilization and disinfection using nano silver colloid-coated glass beads. In addition, the present invention is a sanitary disinfection (chlorine substitute product), water purification-sterilization (purity filter alternative product), water storage function for long-term storage, disinfection sterilization function in the medical field, import and export food and herbal materials For sterilization and disinfection, etc., it can be applied in various ways.

Claims (3)

나노 은 코팅 글라스비드 제조방법에 있어서, In the nano-silver coated glass beads manufacturing method, 글라스비드와 나노 은 콜로이드용액을 N:1(N은 1∼10) 무게비로 혼합용기에 담아 혼합용기를 회전시키면서 50∼100℃의 온도로 20∼40분간 가열한 후 식히는 제1과정과,The first step of cooling glass beads and nano silver colloidal solution in a mixing ratio of N: 1 (N is 1 to 10) in a weight ratio, while heating the mixing vessel and heating at a temperature of 50 to 100 ° C. for 20 to 40 minutes, followed by cooling; 제1과정을 거친 다음 전기로에서 290∼310℃의 온도로 20∼40분간 재차 가열하는 제2과정으로 이루어짐을 특징으로 하는 나노 은 코팅 글라스비드 제조방법.After the first process is a nano-silver coated glass bead manufacturing method comprising a second process of heating again for 20 to 40 minutes at a temperature of 290 ~ 310 ℃ in an electric furnace. 청구항 1의 제조방법으로 제조된 나노 은 코팅 글라스비드. Nano silver coated glass beads prepared by the manufacturing method of claim 1. 글라스비드 90∼110g과 나노은 콜로이드용액 20∼30g을 원통형 혼합용기에 담아 원통형 혼합용기를 회전시키면서 50∼100℃의 온도로 20∼40분간 가열한 후 식히는 과정을 거친 후, 20∼40분간 전기로에서 290∼310℃의 온도로 재차 가열하는 과정을 거쳐 글라스비드에 나노은 콜로이드를 코팅시킴을 특징으로 하는 나노 은 코팅 글라스비드 제조방법. 90 to 110 g of glass beads and 20 to 30 g of nanosilver colloidal solution were put in a cylindrical mixing container, and the mixture was heated at a temperature of 50 to 100 ° C. for 20 to 40 minutes while cooling, and then cooled in an electric furnace for 20 to 40 minutes. Nano-silver coated glass beads manufacturing method characterized in that the nano-silver colloid is coated on the glass beads through a process of heating again to a temperature of 290 ~ 310 ℃.
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KR101020566B1 (en) * 2009-12-02 2011-03-09 유문식 A pipe unit assemble structure foe rainwater management system

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KR100697401B1 (en) * 2005-05-26 2007-03-20 주식회사 두산 Method for manufacturing nano silver coated-glass vessel

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JPH11236241A (en) 1998-02-25 1999-08-31 Ishizuka Glass Co Ltd Antibacterial crystallized glass beads for building material
KR20040047154A (en) * 2002-11-29 2004-06-05 한국화학연구원 A method for producing ultrafine spherical nickel particles
KR20040066335A (en) * 2003-01-17 2004-07-27 주식회사 엘지생활건강 Impregnated multilayered mesoporous and microporus core-shell carbon nanoball for deodorising

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JPH11236241A (en) 1998-02-25 1999-08-31 Ishizuka Glass Co Ltd Antibacterial crystallized glass beads for building material
KR20040047154A (en) * 2002-11-29 2004-06-05 한국화학연구원 A method for producing ultrafine spherical nickel particles
KR20040066335A (en) * 2003-01-17 2004-07-27 주식회사 엘지생활건강 Impregnated multilayered mesoporous and microporus core-shell carbon nanoball for deodorising

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101020566B1 (en) * 2009-12-02 2011-03-09 유문식 A pipe unit assemble structure foe rainwater management system

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