KR0181572B1 - Method of manufacturing silver powder - Google Patents
Method of manufacturing silver powder Download PDFInfo
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- KR0181572B1 KR0181572B1 KR1019950039324A KR19950039324A KR0181572B1 KR 0181572 B1 KR0181572 B1 KR 0181572B1 KR 1019950039324 A KR1019950039324 A KR 1019950039324A KR 19950039324 A KR19950039324 A KR 19950039324A KR 0181572 B1 KR0181572 B1 KR 0181572B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
Abstract
본 발명은 은과 타 금속과의 소결합금시 사용되는 은 분말의 제조기술에 관한 것으로서 특히 유동성 및 혼합성이 우수한 은 분말을 제조하는 제조공정시의 화학반응조건에 관한 것이다. 본 발명의 은 분말 제조공정 중 화학 반응 조건을 정확히 명시하여 일정크기의 분말을 얻어내고, 개미산처리공법으로 입자도를 성장시켜 유동도 및 혼합성을 향상시키고, 알칼리의 양을 줄이고 환원제로 사용되는 포르말린을 첨가하여 최종액을 산성으로 만듬으로써 유동도 및 혼합성이 우수하게 되는 은분말제조공정을 제공하고 있다. 본 발명에 따르면 반응조건을 화학양론적으로 조절하여 최종반응의 pH 를 알칼리로 유지하여 평균입도 0.3∼2μm인 분말을 제조하고 이 분말에 개미산을 처리하여 입자의 크기를 3∼8μm으로 성장시키는 방법과, 반응조건을 화학양론적으로 조절하여 최종반응의 pH를 알칼리로 유지하여 평균입도 0.3∼2μm인 분말을 제조하는 방법을 사용하여 은 분말의 유동도 및 혼합성을 증대시키고 있다.The present invention relates to the production technology of silver powder used in the small bonds of silver and other metals, and more particularly to the chemical reaction conditions in the manufacturing process for producing silver powder with excellent flowability and mixing properties. The chemical reaction conditions of the silver powder manufacturing process of the present invention accurately specify the powder to obtain a certain size, by increasing the particle size by the formic acid treatment method to improve the flow and mixing properties, reduce the amount of alkali and formalin used as a reducing agent It is added to make the final solution acidic to provide a silver powder manufacturing process that is excellent in flowability and mixing properties. According to the present invention, by adjusting the reaction conditions stoichiometrically, maintaining a pH of the final reaction as an alkali to prepare a powder having an average particle size of 0.3 to 2 μm and treating the powder with formic acid to grow the particle size to 3 to 8 μm. The flow and mixing properties of the silver powder are increased by using a method of producing a powder having an average particle size of 0.3 to 2 μm by controlling the reaction conditions stoichiometrically and maintaining the pH of the final reaction as an alkali.
Description
제1도는 종래의 은 분말 제조공정을 단계적으로 도시한 도면.1 is a step-by-step view of a conventional silver powder manufacturing process.
제2도는 본 발명의 제1실시예에 따른 은 분말의 제조공정을 단계적으로 도시한 도면.2 is a diagram showing step by step a manufacturing process of silver powder according to the first embodiment of the present invention.
제3도는 본 발명의 제 2실시예에 따른 은 분말의 제조공정을 단계적으로 도시한 도면.3 is a diagram showing step by step a manufacturing process of silver powder according to a second embodiment of the present invention.
본 발명은 은과 타금속과의 소결합금시 사용되는 은 분말의 제조기술에 관한 것으로서 특히 유동성 및 혼합성이 우수한 은 분말을 제조하는 제조방법에 관한 것이다.The present invention relates to a production technique of silver powder used in the small bonding gold of silver and other metals, and more particularly to a manufacturing method for producing a silver powder excellent in flowability and mixing properties.
은 분말을 다이아몬드, 세라믹분말, WC, W분말, Gr분말, Ni분말 등과 혼합하여 소결합금할 경우에 사용되던 종래 소결합금용 은 분말 제조방법에 의해 제조된 은 분말은, 은 분말의 불균일성으로 인하여 소결합금이 불완전하게 되는 문제가 있었다.The silver powder prepared by the conventional method for producing silver powder for small binders, which is used when the silver powder is mixed with diamond, ceramic powder, WC, W powder, Gr powder, Ni powder, etc., due to the nonuniformity of silver powder There was a problem that the small bonds were incomplete.
소결합금의 원료로 사용되는 은 분말의 종래 제조방법으로는 화학적 방법과 기계적 방법이 함께 사용되었는데, 이를 도식적으로 나타내면 제1도에 도시한 바와 같다. 화학적 방법으로는 질산은 수용액을 알칼리 용액으로 중화시키는 중화반응을 거쳐 생성된 산화은이나 수산화은의 침전물에 히드라진이나 과산화수소, 포르말린 등의 환원제를 사용하여 환원시키는 방법과, 상기 중화반응에 의해 생성된 수산화은의 침전에 수소, 일산화탄소 등의 환원력이 강한 가스를 흡입시켜 환원시키는 방법, 또는 알칼리성 아민착체 수용액에 포르말린, 수산 등의 환원제를 첨가하여 환원시키는 방법을 거쳐 은 분말로 석출시키는 방법 등이 주로 사용되었고, 상기 화학적 방법를 통해 생성된 불균일한 은 분말을 분쇄하기 위한 기계적 방법으로는 볼밀(ball mill), 스탬프밀(stamp mill)을 이용한 은분 분쇄방법 등이 널리 행하여지고 있다.As a conventional method for preparing silver powder used as a raw material for sintered alloy, a chemical method and a mechanical method were used together, which is as shown in FIG. 1. Chemically, a method of reducing silver oxide or silver hydroxide produced by neutralization reaction of neutralizing an aqueous solution of silver nitrate with an alkaline solution using a reducing agent such as hydrazine, hydrogen peroxide or formalin, and precipitation of silver hydroxide produced by the neutralization reaction A method of precipitating a gas having strong reducing power, such as hydrogen or carbon monoxide, to reduce it, or a method of precipitating it into silver powder by adding a reducing agent such as formalin or oxalic acid to an aqueous solution of an alkaline amine complex and reducing the same. As a mechanical method for grinding non-uniform silver powder produced through a chemical method, a ball mill, a silver powder grinding method using a stamp mill, and the like are widely used.
이러한 종래의 제조공정에 의하면, 중화반응에 의해 형성된 수산화은 또는 산화은에 단순히 과산화수소 또는 히드라진, 포름알데히드(포르말린)등의 환원제를 첨가하여 생성되는 은 분말은, 입자가 0.3∼ 2μm 내지 3∼8μm 범위까지 존재하는 등 입자의 크기가 매우 불균일하며 입자크기 분포가 매우 크다. 또한 입자끼리 뭉쳐 있어 그 유동성도 매우 나쁘다. 따라서 타금속 분말과 혼합할 경우 혼합이 균일하게 되지 않고, 특히 타금속과 밀도 등의 차이가 클 경우에는 은 분말이 타금속 성분과 섞이지 않고 뭉쳐있게 되어 우수한 소결합금을 만들 수가 없었다.According to such a conventional manufacturing process, the silver powder produced by simply adding a hydrogen peroxide or a reducing agent such as hydrazine and formaldehyde (formalin) to the silver hydroxide or silver oxide formed by the neutralization reaction has particles ranging from 0.3 to 2 µm to 3 to 8 µm. The particle size is very non-uniform, such as present, and the particle size distribution is very large. In addition, the particles are aggregated together, the fluidity is also very bad. Therefore, when mixed with other metal powder, the mixing is not uniform. Especially, when the difference between the other metal and the density is large, the silver powder does not mix with other metal components and aggregates, thereby making it impossible to make an excellent small binder.
따라서 본 발명은 상기와 같은 종래의 은 분말의 제조에 있어서의 문제점을 해결하기 위하여, 은 분말 제조공정 중 반응용액을 알칼리성으로 엄격히 조절하여 일정크기의 분말을 얻어낸 후, 개미산 처리공법으로 입도(입자크기)를 성장시켜 유동도 및 혼합성을 향상시키는 방법과, 알칼리의 양을 줄이고 환원제로 사용되는 포르말린을 일정과량 첨가하여 최종액을 산성으로 조절함으로써 은 분말의 유동도 및 혼합성을 우수하게 하는 방법의 은 분말 제조공정을 제공하는 것을 목적으로 한다.Therefore, the present invention, in order to solve the problems in the conventional production of the silver powder as described above, after obtaining a certain size of powder by strictly adjusting the reaction solution to alkaline in the silver powder manufacturing process, the particle size (particles by the formic acid treatment method) Size) to improve the flowability and mixing properties, and to reduce the amount of alkali and add a certain amount of formalin used as a reducing agent to adjust the final liquid to acidity to improve the flowability and mixing properties of the silver powder. It is an object to provide a silver powder manufacturing process of the method.
본 발명은, 질산은 수용액을 수산화나트륨 또는 수산화칼륨 등의 알칼리 용액으로 중화하여 수산화은 또는 산화은의 침전이 형성된 상태에서 과산화수소, 포르말린 등의 환원제로 환원하는 종래의 제조공정에서, 반응공정시의 pH의 조건을 화학양론적으로 자세히 명시함으로써 입자의 크기를 조절할 수 있으며, 또한 환원된 분말을 개미산으로 처리함으로써 입자의 성장과 유동성을 크게 향상시켜 우수한 소결성을 지닌 은 분말의 제조가 가능하도록 하였다.The present invention, in the conventional manufacturing process of neutralizing the aqueous solution of silver nitrate with an alkaline solution such as sodium hydroxide or potassium hydroxide to reduce with a reducing agent such as hydrogen peroxide, formalin in the form of precipitation of silver hydroxide or silver oxide, conditions of the pH at the reaction step By specifying the stoichiometric details, the size of the particles can be controlled, and the reduced powder is treated with formic acid to greatly improve the growth and fluidity of the particles, thereby enabling the production of silver powder having excellent sinterability.
본 발명의 제1실시예에 의하면, 질산은(AgNO3) 수용액에 수산화나트륨(NaOH) 또는 수산화칼륨(KOH)등의 알칼리 용액을 화학양론적으로 첨가하여 생성된 수산화은 또는 산화은(Ag2O)의 침전에 포르말린(HCHO)를 환원제로 사용하여 최종반응의 pH를 알칼리(pH 10 이상)가 되도록 조절한다. 반응용액을 화학량론적으로 조절하여 pH 10 이상의 알칼리 용액으로 조절하면, 은 분말의 평균입도는 0.3∼2μm로 균일하게 되도록 제조할 수 있다. 또한 생성된 은 분말을 세척한 후 개미산(HCOOH)처리하면 평균입도가 3∼8μm인 균일한 입자로 성장되는데, 이렇게 제조된 은 분말은 타금속과의 소결합금시 유동도와 혼합성이 우수해진다.According to the first embodiment of the present invention, silver hydroxide or silver oxide (Ag 2 O) produced by stoichiometric addition of an alkaline solution such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) to an aqueous solution of silver nitrate (AgNO 3 ) Formalin (HCHO) is used as a reducing agent in the precipitation to adjust the pH of the final reaction to alkali (pH 10 or higher). When the reaction solution is adjusted stoichiometrically to an alkaline solution of pH 10 or more, the average particle size of the silver powder can be prepared to be uniform at 0.3 to 2 μm. In addition, the produced silver powder is washed and then formic acid (HCOOH) treatment to grow into a uniform particle having an average particle size of 3 ~ 8μm, the silver powder thus prepared is excellent in flowability and miscibility in small bonds with other metals.
본 발명의 제2실시예에 의하면 최종 반응액을 알칼리가 아닌 산성이 되도록 조정한 후, 산성 분위기에서 침적함으로써 평균입도가 3∼8μm인 균일한 분말이 제조되며, 이 또한 유동도와 혼합성이 우수하다.According to the second embodiment of the present invention, after adjusting the final reaction solution to be acid rather than alkali, it is deposited in an acidic atmosphere to produce a uniform powder having an average particle size of 3 to 8 μm, which is also excellent in fluidity and mixing property. Do.
본 발명의 은 분말 제조방법을 도면을 참고하여 상세히 설명하면 다음과 같다.Referring to the silver powder manufacturing method of the present invention in detail as follows.
본 발명의 제1실시예에 따른 은 분말의 제조공정은 제2도에 도시된 바와 같다.The manufacturing process of the silver powder according to the first embodiment of the present invention is as shown in FIG.
우선, 반응식 1과 같이 질산은(AgNO3) 수용액에 수산화나트륨(NaOH)이나 수산화칼륨 등의 알칼리 용액으로 중화반응을 한 후, 반응식 2와 같이, 환원제인 포르말린(HCHO)을 사용하여 환원반응하여 수산화나트륨을 첨가하여 알칼리성으로 유지한다.First, as shown in Scheme 1, a neutralization reaction is performed with an aqueous solution of silver nitrate (AgNO 3 ) with an alkaline solution such as sodium hydroxide (NaOH) or potassium hydroxide, and then, as shown in Scheme 2, reduction reaction is performed using formalin (HCHO) as a reducing agent. Maintain alkaline by adding sodium.
이때, 최종 반응액의 pH를 알칼리로 조정하기 위하여는 수산화나트륨(또는 수산화칼륨)과 포르말린의 양을 반응식 1 및 2에서와 같이 엄격하게 화학양론적으로 조정관리하는 것이 필요하다. 이 과정의 반응식을 화학양론적으로 표시하면 다음과 같다.At this time, in order to adjust the pH of the final reaction solution to an alkali, it is necessary to strictly control stoichiometrically the amount of sodium hydroxide (or potassium hydroxide) and formalin as in Schemes 1 and 2. The stoichiometry of this process is as follows.
2AgNO3+2NaOH→Ag2O+2NaNO3+H2O ………… (1)2AgNO 3 + 2NaOH → Ag 2 O + 2NaNO 3 + H 2 O... … … … (One)
Ag2O+HCHO+2NaOH→2Ag+NaCOOH+NaOH+H2O ………… (2)Ag 2 O + HCHO + 2NaOH → 2Ag + NaCOOH + NaOH + H 2 O... … … … (2)
반응식 1과 반응식 2를 연산하면, 다음의 반응식 3을 얻는다.Computing Scheme 1 and Scheme 2 yields the following Scheme 3.
2AgNO3+4NaOH+HCHO→2Ag+2NaNO3+NaCOOH+NaOH+2H2O ……… (3)2AgNO 3 + 4NaOH + HCHO → 2Ag + 2NaNO 3 + NaCOOH + NaOH + 2H 2 O... … … (3)
이와 같은 반응식에 의하여 최종 반응액은 pH가 10 이상으로 유지되며, 그에 의해 입자는 0.3∼2μm으로 균일하게 유지된다. 또한 이 분말을 세척한 후 10∼20%의 농도의 개미산(HCOOH)에 약 24시간 정도 침적시키면 입자가 성장하여 3∼8μm 정도의 균일한 입자가 된다. 입자의 성장속도는 개미산의 농도와 처리시간의 조정으로 제어가 가능하다.By such a reaction formula, the final reaction solution is maintained at a pH of 10 or more, thereby keeping the particles uniformly 0.3 ~ 2μm. After washing the powder, the powder is deposited in formic acid (HCOOH) at a concentration of 10 to 20% for about 24 hours to grow the particles into uniform particles of about 3 to 8 μm. The growth rate of the particles can be controlled by adjusting the concentration of formic acid and the treatment time.
본 발명의 제2실시예에 따른 은 분말의 제조공정은 제3도에 도시된 바와 같다.The manufacturing process of the silver powder according to the second embodiment of the present invention is as shown in FIG.
반응식 4와 같이 질산은(AgNO3) 수용액에 수산화나트륨(NaOH)이나 수산화칼륨 등의 알칼리 용액으로 중화반응한 후, 반응식 5와 같이 환원제인 포르말린(HCHO)을 첨가하여 환원반응한다. 이 제2실시예에 의한 최종의 반응액을 산성으로 조정하기 위하여, 수산화나트륨과 포르말린 등의 양을 반응식 4 및 반응식 5와 같이 화학양론적으로 관리하는 것이 필요하다.As shown in Scheme 4, the solution is neutralized with an aqueous solution of silver nitrate (AgNO 3 ) with an alkaline solution such as sodium hydroxide (NaOH) or potassium hydroxide, and then reacted with a reducing agent, formalin (HCHO), to reduce the reaction. In order to adjust the final reaction solution according to the second embodiment to acidity, it is necessary to stoichiometrically manage the amounts of sodium hydroxide, formalin and the like as in Schemes 4 and 5.
2AgNO3+2NaOH→Ag2O+2NaNO3+H2O …………(4)2AgNO 3 + 2NaOH → Ag 2 O + 2NaNO 3 + H 2 O... … … … (4)
Ag2O+HCHO→2Ag+HCOOH ……… (5)Ag 2 O + HCHO → 2Ag + HCOOH. … … (5)
반응식 4와 반응식 5를 연산하면, 다음의 반응식 6를 얻는다.By calculating Reaction Scheme 4 and Reaction Scheme 5, the following Reaction Scheme 6 is obtained.
2AgNO3+2NaOH+HCHO→2Ag+2NaNO3+HCOOH+H2O …………(6)2AgNO 3 + 2NaOH + HCHO → 2Ag + 2NaNO 3 + HCOOH + H 2 O... … … … (6)
이와 같은 반응에 의하면 최종 반응액의 pH가 산성으로 유지되며 산성 분위기에서 침적시키면 입자는 3∼8μm로 균일하게 되어 유동성 및 혼합성이 우수해진다.According to such a reaction, the pH of the final reaction solution is kept acidic, and when deposited in an acidic atmosphere, the particles are uniformized to 3 to 8 µm, thereby improving fluidity and mixing properties.
본 발명의 우수성을 증명하기 위한 실험데이터를 종래의 일반적 공정에 의한 결과와 비교하면 다음과 같다.Experimental data for demonstrating the superiority of the present invention is as follows when compared with the results of the conventional general process.
상기와 같이, 본래의 방법에 의해, 0.3∼2μm 크기의 입자와 3∼8μm 크기의 입자가 함께 존재하는 불균일한 입자가 제조된다. 그러나, 본 발명에 의하면 80% 이상이 3∼8μm로 균일한 입자가 제조된다.As described above, by the original method, non-uniform particles in which particles of 0.3 to 2 μm and particles of 3 to 8 μm are present together are produced. However, according to the present invention, 80% or more of uniform particles are produced at 3 to 8 µm.
본 발명의 우수성을 증명하기 위하여 본 발명의 제조방법에 의해 제조된 은 분말과 종래의 제조방법에 의해 제조된 은 분말을 타금속과 소결합금하여 그 특성을 비교해 본 데이터는 다음의 표에 도시된 바와 같다.In order to prove the superiority of the present invention, the silver powder prepared by the manufacturing method of the present invention and the silver powder prepared by the conventional manufacturing method were compared with the other metal by small-bonding, and the characteristics thereof are shown in the following table. As shown.
상기 표에서 비교된 바와 같이, 본 발명의 제조방법에 의하여 제조된 은 분말은 입자의 크기가 크고 균일하므로, 소결합금시 혼합이 용이하고 높은 비중의 소결체를 얻을 수 있다.As compared with the above table, since the silver powder produced by the production method of the present invention is large and uniform in particle size, it is easy to mix in small bonds and a high specific gravity sintered body can be obtained.
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Cited By (9)
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KR100473478B1 (en) * | 2002-11-20 | 2005-03-11 | (주)나눅스 | Silver colloid and preparation method thereof |
KR100490678B1 (en) * | 2002-11-29 | 2005-05-24 | (주)창성 | Method for manufacturing nano-scale nickel powders by wet reducing process |
KR100490668B1 (en) * | 2002-11-29 | 2005-05-24 | (주)창성 | Method for manufacturing nano-scale silver powders by wet reducing process |
KR100551979B1 (en) * | 2002-03-16 | 2006-02-20 | (주)나눅스 | Method for preparing high concentration silver colloid |
KR100713241B1 (en) * | 2006-06-28 | 2007-05-02 | 주식회사 씨에라인더스트리 | Method of manufacturing silver powder by chemical reduction |
KR100765192B1 (en) * | 2006-05-08 | 2007-10-09 | 주식회사 엔피케이 | Synthesis of organic silver solution |
KR20170038466A (en) | 2015-09-30 | 2017-04-07 | 엘에스니꼬동제련 주식회사 | The manufacturing method of silver powder |
KR20180121190A (en) | 2017-04-28 | 2018-11-07 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
KR20180133043A (en) | 2017-06-05 | 2018-12-13 | 대주전자재료 주식회사 | Silver particle and method of manufacture thereof |
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KR20200061193A (en) * | 2018-11-23 | 2020-06-02 | 엘에스니꼬동제련 주식회사 | Method for producing monodispersed Ag powder |
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1995
- 1995-11-02 KR KR1019950039324A patent/KR0181572B1/en not_active IP Right Cessation
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100551979B1 (en) * | 2002-03-16 | 2006-02-20 | (주)나눅스 | Method for preparing high concentration silver colloid |
KR100473478B1 (en) * | 2002-11-20 | 2005-03-11 | (주)나눅스 | Silver colloid and preparation method thereof |
KR100490678B1 (en) * | 2002-11-29 | 2005-05-24 | (주)창성 | Method for manufacturing nano-scale nickel powders by wet reducing process |
KR100490668B1 (en) * | 2002-11-29 | 2005-05-24 | (주)창성 | Method for manufacturing nano-scale silver powders by wet reducing process |
KR100765192B1 (en) * | 2006-05-08 | 2007-10-09 | 주식회사 엔피케이 | Synthesis of organic silver solution |
KR100713241B1 (en) * | 2006-06-28 | 2007-05-02 | 주식회사 씨에라인더스트리 | Method of manufacturing silver powder by chemical reduction |
KR20170038466A (en) | 2015-09-30 | 2017-04-07 | 엘에스니꼬동제련 주식회사 | The manufacturing method of silver powder |
KR20180121190A (en) | 2017-04-28 | 2018-11-07 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
KR20180133043A (en) | 2017-06-05 | 2018-12-13 | 대주전자재료 주식회사 | Silver particle and method of manufacture thereof |
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