KR100713241B1 - Method of manufacturing silver powder by chemical reduction - Google Patents
Method of manufacturing silver powder by chemical reduction Download PDFInfo
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- KR100713241B1 KR100713241B1 KR1020060058469A KR20060058469A KR100713241B1 KR 100713241 B1 KR100713241 B1 KR 100713241B1 KR 1020060058469 A KR1020060058469 A KR 1020060058469A KR 20060058469 A KR20060058469 A KR 20060058469A KR 100713241 B1 KR100713241 B1 KR 100713241B1
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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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical 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
- 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
Abstract
본 발명은 칩 콘덴서, 세라믹 콘덴서, PDP 등의 전자부품의 전극형성에 사용되는 고정밀화, 고신뢰성의 도전성페이스트에 적합한 분산성이 우수하고, 입도분포가 좁은 구상 은 분말을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing spherical silver powder having excellent dispersibility and narrow particle size distribution suitable for high precision and high reliability conductive pastes used for forming electrodes of electronic components such as chip capacitors, ceramic capacitors, and PDPs. .
본 발명에서는 첫 번째, 환원제로 수소화붕소나트륨을 용해하고 분산제로 젤라틴을 첨가하여 만든 용액을 사용하고, 이 용액을 질산은이 용해된 용액에 혼합시켜서 단분산된 구형 은 분말을 제조하는 방법을 제공한다. 두 번째, 환원제로 하이드라진을 용해하고 분산제로 젤라틴을 첨가하여 만든 용액을 사용하고, 이 용액을 질산은과 수산화나트륨으로부터 제조된 은 산화물이 용해된 용액에 혼합시켜서 단분산된 구형 은 분말을 제조하는 방법을 제공한다.First, the present invention provides a method for preparing monodisperse spherical silver powder by dissolving sodium borohydride as a reducing agent and adding gelatin as a dispersant, and mixing the solution with a solution containing silver nitrate. . Second, using a solution made by dissolving hydrazine as a reducing agent and gelatin as a dispersant, and mixing the solution with a solution containing silver oxide prepared from silver nitrate and sodium hydroxide to prepare monodisperse spherical silver powder. To provide.
본 발명에 의하면, 상기 화학적 환원법으로 용이하게 구형의 은 분말을 만들 수 있으며, 더욱이 얻어지는 은 분말의 입도분포가 좁아 단분산된 은 분말을 얻을 수 있다. 또한 본 발명에 의하면, 은 분말의 제조공정이 단순하고, 상온에서 제조가 가능하여 효율성, 생산성 면에서 매우 우수한 은 분말을 제조하는 것이 가능하다.According to the present invention, the spherical silver powder can be easily produced by the above chemical reduction method, and the silver powder obtained by narrowing the particle size distribution of the silver powder obtained can be obtained narrowly. In addition, according to the present invention, the production process of the silver powder is simple, it is possible to manufacture at room temperature, it is possible to produce a very excellent silver powder in terms of efficiency and productivity.
화학환원법, 구형, 은 분말, 단분산, 수소화붕소나트륨, 하이드라진. 젤라틴 Chemical reduction, spherical, silver powder, monodisperse, sodium borohydride, hydrazine. gelatin
Description
도 1은 공지 방법에 따른 구형 은 분말의 주사전자 현미경 사진(3500 배율).1 is a scanning electron micrograph (3500 magnification) of spherical silver powder according to a known method.
도 2a, 2b는 본 발명에 사용된 은 분말 제조방법의 공정도Figure 2a, 2b is a process chart of the silver powder manufacturing method used in the present invention
도 3은 실시예1에 따른 구형 은 분말을 보여주는 주사전자 현미경 사진(3500 배율).3 is a scanning electron micrograph (3500 magnification) showing a spherical silver powder according to Example 1. FIG.
도 4는 실시예1에 따른 구형 은 분말의 입도분포도.4 is a particle size distribution diagram of the spherical silver powder according to Example 1. FIG.
도 5는 실시예2에 따른 구형 은 분말을 보여주는 주사전자 현미경 사진(7500 배율).FIG. 5 is a scanning electron micrograph (7500 magnification) showing a spherical silver powder according to Example 2. FIG.
도 6은 실시예2에 따른 구형 은 분말의 입도분포도.6 is a particle size distribution diagram of a spherical silver powder according to Example 2. FIG.
도 7는 실시예3에 따른 구형 은 분말을 보여주는 주사전자 현미경 사진(25000 배율).7 is a scanning electron micrograph (25000 magnification) showing a spherical silver powder according to Example 3. FIG.
도 8은 실시예3에 따른 구형 은 분말의 입도분포도.8 is a particle size distribution diagram of a spherical silver powder according to Example 3. FIG.
본 발명은 은 분말의 제조방법, 특히 화학환원법을 이용하여 구형의 은 분말 을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing silver powder, particularly a method for producing spherical silver powder using a chemical reduction method.
은(Ag)은 예로부터 순수한 금속의 형태로 공예품, 화폐, 미용의 용도 등에 사용되어 왔으며, 최근 들어서는 그 용도가 매우 다양해지고 있는 추세이다.Silver (Ag) has long been used in the form of pure metals in crafts, money, beauty, and the like, and in recent years, its use has become very diverse.
은의 연성·전성은 금 다음으로 커서 두께 0.0015mm의 박을 만들 수 있으며, 1g의 은으로 1800m의 선을 만들 수도 있다. 은은 화학적으로 매우 안정하여서 산소나 물과 반응하지 않으나, 질산이나 따뜻한 황산에는 용해된다. 또한 열·전기전도성은 금속 중 최대이고 미립자 분산기술로 제조된 초미세 은 분말은 미세한 선이나 패턴(pattern)을 제조하는데 적합하다. 이같은 은의 성질을 이용하여 콘덴서, 저항기, 압전소자 등의 전자부품의 전극제조에 사용되고 있으며, 도전성 접착제 또는 paste로 제조되어서 Micro Electronics 분야에 사용되고 있다.The ductility and malleability of silver is next to gold, making a foil of 0.0015mm thick, or 1800m of wire with 1g of silver. Silver is chemically very stable and does not react with oxygen or water, but dissolves in nitric acid or warm sulfuric acid. In addition, the thermal and electrical conductivity of the metal and the ultra fine silver powder produced by the fine particle dispersion technology is suitable for producing fine lines or patterns. It is used in the manufacture of electrodes for electronic parts such as capacitors, resistors, piezoelectric elements, etc. by using such a silver property, and is made of conductive adhesive or paste and used in the field of Micro Electronics.
전자부품의 급격한 소형화, 고정밀도화와 함께 고신뢰성의 요구가 증대하고 있으며, 초미세 은 분말을 이용한 도전성 접착제 또는 paste는 접착력과 내팽창성, 내수축성이 우수하고 불량률이 매우 낮으므로 미세 은 분말에 대한 사용분야는 계속 증대할 것으로 기대되며, 특히 입도분포가 좁아 균일하게 단분산된 은 분말이 요구된다.The demand for high reliability along with the rapid miniaturization and precision of electronic components is increasing.Conductive adhesives or pastes made of ultra fine silver powder have excellent adhesion, expansion resistance, shrinkage resistance and very low defect rate. The field of use is expected to continue to increase, in particular, a uniformly dispersed silver powder is required due to the narrow particle size distribution.
은 분말의 제조방법으로는 화학적인 방법과 물리적(기계적)인 방법이 사용되고 있다. Toivo T. Kodas등은 휘발성 용매에 열분해성 은 함유 화합물을 용해시켜서 캐리어 가스로 에어로졸을 만들고, 이 에어로졸을 은 화합물의 분해온도 이상으로 가열하여 은 분말을 만드는 방법을 개시하고 있다(미국 특허 제 5,439,502호).이 방법에 의할 경우 에어로졸을 만드는 과정이 필요하고 가열과정이 필요하여 많 은 에너지가 소모된다.As a method for producing silver powder, a chemical method and a physical (mechanical) method are used. Toivo T. Kodas et al. Disclose a method of dissolving a pyrolytic silver-containing compound in a volatile solvent to form an aerosol with a carrier gas and heating the aerosol above the decomposition temperature of the silver compound to produce a silver powder (US Pat. No. 5,439,502). This method requires aerosol-making process and heating process, which consumes a lot of energy.
한국특허공개 제 2002-0017490호에는 질산은을 증류수에 용해시킨 후 암모니아수를 첨가하여 pH를 11로 조정하고 하이드로퀴논으로 10~180분간 환원하여 구형 은 분말을 제조하는 방법을 개시하고 있다. 이 방법에 의하면 구형의 1~2㎛크기의 은 분말을 상온에서 단시간 내에 얻을 수 있다고 한다. 본 출원인들은 상기 문헌에 기재된 실시예에 따라 구형 은 분말을 제조한 결과 은 분말이 용이하게 얻어짐을 확인하였으나, 수회의 실험으로도 얻어진 은 분말은 만족할만한 구형은 아니었으며, 더욱이 도 1(상기 문헌의 실시예에 따른 방법으로 제조된 은 분말에 대한 주사전자 현미경 사진)에 나타낸 것처럼 입도분포가 균일하지 않은 은 분말이 얻어지는 것을 확인하였다. 이는 상기 문헌의 도 3(은 분말의 주사전자 현미경 사진)으로부터도 입도분포가 좁은 단분산된 은 분말이 아님을 확인할 수 있다.Korean Patent Laid-Open Publication No. 2002-0017490 discloses a method of preparing spherical silver powder by dissolving silver nitrate in distilled water, adjusting the pH to 11 by adding ammonia water, and reducing the hydrophobine for 10 to 180 minutes. According to this method, a spherical silver powder having a size of 1 to 2 µm can be obtained within a short time at room temperature. Applicants have confirmed that the silver powder is easily obtained as a result of preparing the spherical silver powder according to the embodiment described in the above document, the silver powder obtained by several experiments was not satisfactory spherical, furthermore, Figure 1 (the document It was confirmed that a silver powder having a uniform particle size distribution was obtained as shown in the scanning electron micrograph of the silver powder prepared by the method according to the Example. It can be seen from FIG. 3 (scanning electron micrograph of silver powder) of the above document that the particle size distribution is not monodisperse silver powder.
이처럼 개시된 기술에 의하면, 동일한 용액을 사용하여 단분산된 구형의 은 분말을 만드는 경제적인 방법은 알려져 있지 않다.According to the disclosed technique, an economical method for producing monodisperse spherical silver powder using the same solution is not known.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 동일한 용액을 사용하면서 몰농도를 조정함으로써 화학적 환원법으로 용이하게 구형의 은 분말을 만들 수 있으며, 더욱이 얻어지는 은 분말의 입도분포가 좁아 단분산된 은 분말을 얻을 수 있는 은 분말의 제조방법을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, it is possible to easily make a spherical silver powder by chemical reduction method by adjusting the molar concentration while using the same solution, and furthermore, the particle size distribution of the obtained silver powder is narrow It is to provide a method for producing silver powder in which dispersed silver powder can be obtained.
본 발명에서는 첫 번째, 화학적 환원법으로 구형의 은 분말을 제조하는 방법 에 있어서, 증류수에 환원제로 수소화붕소나트륨을 용해하고 분산제로 젤라틴을 첨가하여 제 1용액을 만드는 단계; 질산은을 증류수에 용해하여 제 2용액을 만드는 단계; 상기 제 1용액을 제 2용액에 혼합시키는 단계; 은 분말을 침전시키는 단계; 및 생성된 구형 은 분말을 채취하여 수세, 건조시키는 단계로 구성되는 것을 특징으로 하는 단분산된 구형 은 분말의 제조방법을 제공한다.In the present invention, first, a method for producing a spherical silver powder by chemical reduction method, the step of dissolving sodium borohydride as a reducing agent in distilled water and gelatin as a dispersant to make a first solution; Dissolving silver nitrate in distilled water to form a second solution; Mixing the first solution with a second solution; Precipitating silver powder; And collecting and washing the resulting spherical silver powder with water and drying to provide a method for producing the monodisperse spherical silver powder.
두 번째, 화학적 환원법으로 구형의 은 분말을 제조하는 방법에 있어서, 증류수에 환원제로 수소화붕소나트륨을 용해하고 분산제로 젤라틴을 첨가하여 제 1용액을 만드는 단계; 질산은의 수용액으로부터 수산화나트륨을 첨가하여 은 산화물을 제조하여 은 산화물을 증류수에 용해하여 제 2용액을 만드는 단계; 상기 제 1용액을 제 2용액에 혼합시키는 단계; 은 분말을 침전시키는 단계; 및 생성된 구형 은 분말을 채취하여 수세, 건조시키는 단계로 구성되는 것을 특징으로 하는 단분산된 구형 은 분말의 제조방법이 제공된다.A second method for producing spherical silver powder by chemical reduction method, comprising: dissolving sodium borohydride as a reducing agent in distilled water and adding gelatin as a dispersant to make a first solution; Preparing a silver oxide by adding sodium hydroxide from an aqueous solution of silver nitrate to dissolve the silver oxide in distilled water to form a second solution; Mixing the first solution with a second solution; Precipitating silver powder; And collecting and washing the resulting spherical silver powder with water, and providing a method for producing the monodisperse spherical silver powder.
세 번째, 화학적 환원법으로 구형의 은 분말을 제조하는 방법에 있어서, 증류수에 환원제로 하이드라진을 용해하고 분산제로 젤라틴을 첨가하여 제 1용액을 만드는 단계; 질산은의 수용액으로부터 수산화나트륨을 첨가하여 은 산화물을 제조하여 은 산화물을 증류수에 용해하여 제 2용액을 만드는 단계; 상기 제 1용액을 제 2용액에 혼합시키는 단계; 은 분말을 침전시키는 단계; 및 생성된 구형 은 분말을 채취하여 수세, 건조시키는 단계로 구성되는 것을 특징으로 하는 단분산된 구형 은 분말의 제조방법이 제공된다.Third, the method for producing the spherical silver powder by chemical reduction method comprising the steps of dissolving hydrazine in distilled water as a reducing agent and gelatin as a dispersing agent to form a first solution; Preparing a silver oxide by adding sodium hydroxide from an aqueous solution of silver nitrate to dissolve the silver oxide in distilled water to form a second solution; Mixing the first solution with a second solution; Precipitating silver powder; And collecting and washing the resulting spherical silver powder with water, and providing a method for producing the monodisperse spherical silver powder.
화학식 1 AgNO3+0.5NaBH4 -> Ag+0.5NaBO2+0.7HNO2+0.6H2O+0.1HN3
(NaBO2+H2O -> NaOH+HBO2) (NaBO 2 + H 2 O-> NaOH + HBO 2 )
화학식 2 2AgNO3 + 2NaOH -> Ag2O + 2NaNO3 + H2O Chemical Formula 2 2AgNO 3 + 2NaOH-> Ag 2 O + 2NaNO 3 + H 2 O
화학식 3 2Ag2O + NaBH4 -> 4Ag↓ + NaBO2 + H2
(NaBO2 +H2O -> NaOH +HBO2)(NaBO 2 + H 2 O-> NaOH + HBO 2 )
화학식 4 2Ag2O + N2H4 H2O + nH2O -> 4Ag↓ + N2 + (3+n)H2O + Q Formula 4 2Ag 2 O + N 2 H 4 H 2 O + nH 2 O-> 4Ag ↓ + N 2 + (3 + n) H 2 O + Q
상기 제조방법의 화학식1에 의하면, 질산은(1mole), 수소화붕소나트륨(0.5~3mole)이 상기 제 1용액과 제 2용액의 혼합용액 1리터당 각각 17g, 1.9~11.3g이 첨가되고, 질산은 무게의 10wt% 이하의 젤라틴이 첨가된다. 이때 구형 은 분말의 입도는 0.5㎛~5㎛정도였다. According to Chemical Formula 1 of the preparation method, silver nitrate (1 mole) and sodium borohydride (0.5 to 3 mole) are added in an amount of 17 g and 1.9 to 11.3 g per 1 liter of the mixed solution of the first and second solutions, respectively, Up to 10 wt% gelatin is added. At this time, the particle size of the spherical silver powder was about 0.5㎛ ~ 5㎛.
또한 상기제조 방법의 화학식2에 의하면, 질산은(1mole)의 수용액으로부터 수산화나트륨(1mole)을 첨가하여 은 산화물을 제조한다. 화학식3에 의해서 은산화물(1mole), 수소화붕소나트륨(0.5~3mole)이 상기 제 1용액과 제 2용액의 혼합용액 1리터당 각각 23.2g, 1.9~11.3g이 첨가되고, 은 산화물 무게의 10wt% 이하의 젤라틴이 첨가된다. 이때 구형 은 분말의 입도는 0.5㎛~3㎛정도였다.In addition, according to the formula (2) of the manufacturing method, a silver oxide is prepared by adding sodium hydroxide (1 mole) from an aqueous solution of silver nitrate (1 mole). According to Formula 3, 23.2 g and 1.9-11.3 g of silver oxide (1 mole) and sodium borohydride (0.5-3 mole) were added per 1 liter of the mixed solution of the first and second solutions, respectively, and 10wt% of the weight of the silver oxide. The following gelatin is added. At this time, the particle size of the spherical silver powder was about 0.5㎛ ~ 3㎛.
화학식4에 의해서 은산화물(1mole), 하이드라진(0.5~3mole)이 상기 제 1용액과 제 2용액의 혼합용액 1리터당 각각 23.2g, 2.5~15g이 첨가되고, 은 산화물 무게 의 10wt% 이하의 젤라틴이 첨가된다. 이때 구형 은 분말의 입도는 50nm~200nm 정도였다. 또한 수소화붕소나트륨에 대한 하이드라진의 비율이 0~50%일 때도 구형의 은분말을 제조 할수 있었다. According to Formula 4, 23.2 g and 2.5-15 g of silver oxide (1 mole) and hydrazine (0.5-3 mole) are added per liter of the mixed solution of the first and second solutions, respectively, and the gelatin of 10 wt% or less of the weight of silver oxide Is added. The particle size of the spherical silver powder was about 50nm ~ 200nm. In addition, spherical silver powder could be prepared even when the ratio of hydrazine to sodium borohydride was 0 to 50%.
이하에서는 본 발명의 바람직한 실시예를 설명한다. 본 실시예에서 사용된 모든 원료들은 시중에서 용이하게 구입할 수 있는 공업용 등급이다.Hereinafter, a preferred embodiment of the present invention will be described. All raw materials used in this example are of industrial grade which can be easily purchased on the market.
실시예Example 1 One
비이커에 증류수 1리터를 담고 환원제인 0.5몰의 수소화붕소나트륨 1.9g, 분산제인 젤라틴을 1g 넣어 용해하여 제 1용액을 만들었다. 다음에는 다른 비커에서 1몰의 질산은(AgNO3) 17g을 용해하여 제 2용액을 만들었다. 제 1용액에 제 2용액을 혼합하면서 교반(100~300rpm)시켜서 은 구형을 만들었다. 은 분말이 침전될 때까지 충분한 시간을 유지한 후 폐수를 버리고 은 분말을 회수하였다. 회수된 은 분말을 증류수로 수세하고 에틸알콜을 이용하여 세척하였다. 세척한 은 분말을 진공건조기에 넣고 건조하여 은 분말을 얻었다.1 liter of distilled water was placed in a beaker, and 1.9 g of 0.5 mol of sodium borohydride, a reducing agent, and 1 g of gelatin, a dispersant, were dissolved to prepare a first solution. Next, a second solution was prepared by dissolving 17 g of 1 mol of silver nitrate (AgNO 3 ) in another beaker. A silver sphere was formed by stirring (100-300 rpm) while mixing the second solution with the first solution. After sufficient time until the silver powder precipitated, the wastewater was discarded and the silver powder was recovered. The recovered silver powder was washed with distilled water and washed with ethyl alcohol. The washed silver powder was put into a vacuum dryer and dried to obtain a silver powder.
도 3은 이렇게 생성된 은 분말의 주사전자현미경 사진이다. 사진에서 보는 바처럼, 얻어진 은 분말은 모두 구형임을 알 수 있다.3 is a scanning electron micrograph of the silver powder thus produced. As shown in the photograph, it can be seen that the silver powders obtained are all spherical.
도 4는 레이저 입도분석기를 이용하여 생성된 구형 은의 입도분포를 측정한 것으로, 평균입도는 1.03㎛이었고 입자의 80%가 0.20~2.00㎛의 크기를 가져서 입도분포가 매우좁아 단분산된 은 구형임을 알 수 있다.4 is a particle size distribution of spherical silver produced using a laser particle size analyzer. The average particle size was 1.03 μm, and 80% of the particles had a size of 0.20 to 2.00 μm, indicating that the particle size distribution was very narrow. Able to know.
한편, 은의 회수율은 수회의 실험결과 평균 98%이상으로 나타났으며, 수세과정에서 손실되는 은을 고려할 때 화학반응만에 의한 은의 회수율은 거의 100%에 가까운 것으로 판단된다.On the other hand, the recovery rate of silver was more than 98% on average in several experiments, and considering the silver lost during the washing process, the recovery rate of silver by chemical reaction alone is nearly 100%.
실시예Example 2 2
1몰의 질산은 수용액으로부터 1몰의 수산화나트륨을 첨가하여 은 산화물을 제조하였다. 비이커에 증류수 1리터를 담고 환원제인 0.5몰의 수소화붕소나트륨 1.9g, 분산제인 젤라틴을 1g 용해하여 제 1용액을 만들었다. 다음에는 다른 비커에서 1몰의 은 산화물(Ag2O) 23.2g을 용해하여 제 2용액을 만들었다. 제 1용액에 제 2용액을 혼합하면서 교반(100~300rpm)시켜 은 구형을 만들었다. 은 분말이 침전될 때까지 충분한 시간을 유지한 후 폐수를 버리고 은 분말을 회수하였다. 회수된 은 분말을 증류수로 수세하고 에틸알콜을 이용하여 세척하였다. 세척한 은 분말을 진공건조기에 넣고 건조하여 은 분말을 얻었다.Silver oxide was prepared by adding 1 mol of sodium hydroxide from an aqueous solution of 1 mol of silver nitrate. 1 liter of distilled water was placed in a beaker, and 1.9 g of 0.5 mol of sodium borohydride, a reducing agent, and 1 g of gelatin, a dispersant, were dissolved to prepare a first solution. Next, a second solution was prepared by dissolving 23.2 g of 1 mol of silver oxide (Ag 2 O) in another beaker. The silver sphere was formed by stirring (100-300 rpm) while mixing the second solution with the first solution. After sufficient time until the silver powder precipitated, the wastewater was discarded and the silver powder was recovered. The recovered silver powder was washed with distilled water and washed with ethyl alcohol. The washed silver powder was put into a vacuum dryer and dried to obtain a silver powder.
도 5는 이렇게 생성된 은 분말의 주사전자현미경 사진이다. 사진에서 보는 바처럼, 얻어진 은 분말은 모두 구형임을 알 수 있다.5 is a scanning electron micrograph of the silver powder thus produced. As shown in the photograph, it can be seen that the silver powders obtained are all spherical.
도 6은 레이저 입도분석기를 이용하여 생성된 구형 은의 입도분포를 측정한 것으로, 평균입도는 1.39㎛이었고 입자의 80%가 0.50~2.70㎛의 크기를 가져서 입도분포가 매우좁아 단분산된 은 구형임을 알 수 있다.6 is a particle size distribution of spherical silver produced using a laser particle size analyzer. The average particle size was 1.39 μm, and 80% of the particles had a size of 0.50˜2.70 μm. Able to know.
한편, 은의 회수율은 수회의 실험결과 평균 98%이상으로 나타났으며, 수세과정에서 손실되는 은을 고려할 때 화학반응만에 의한 은의 회수율은 거의 100%에 가 까운 것으로 판단된다.On the other hand, the recovery rate of silver was more than 98% on average in several experiments. Considering the silver lost in the washing process, the recovery rate of silver by chemical reaction alone is almost 100%.
실시예Example 3 3
1몰의 질산은 수용액으로부터 1몰의 수산화나트륨을 첨가하여 은 산화물을 제조하였다. 비이커에 증류수 1리터를 담고 환원제인 0.5몰의 하이드라진 2.5g, 분산제인 젤라틴을 1g 용해하여 제 1용액을 만들었다. 다음에는 다른 비커에서 1몰의 은 산화물(Ag2O) 23.2g을 용해하여 제 2용액을 만들었다. 제 1용액에 제 2용액을 혼합하면서 교반(100~300rpm)시켜 은 구형을 만들었다. 은 분말이 침전될 때까지 충분한 시간을 유지한 후 폐수를 버리고 은 분말을 회수하였다. 회수된 은 분말을 증류수로 수세하고 에틸알콜을 이용하여 세척하였다. 세척한 은 분말을 진공건조기에 넣고 건조하여 은 분말을 얻었다.Silver oxide was prepared by adding 1 mol of sodium hydroxide from an aqueous solution of 1 mol of silver nitrate. 1 liter of distilled water was placed in a beaker, and 2.5 g of 0.5 mole hydrazine, a reducing agent, and 1 g of gelatin, a dispersant, were dissolved to prepare a first solution. Next, a second solution was prepared by dissolving 23.2 g of 1 mol of silver oxide (Ag 2 O) in another beaker. The silver sphere was formed by stirring (100-300 rpm) while mixing the second solution with the first solution. After sufficient time until the silver powder precipitated, the wastewater was discarded and the silver powder was recovered. The recovered silver powder was washed with distilled water and washed with ethyl alcohol. The washed silver powder was put into a vacuum dryer and dried to obtain a silver powder.
도 7는 이렇게 생성된 은 분말의 주사전자현미경 사진이다. 사진에서 보는 바처럼, 얻어진 은 분말은 모두 구형임을 알 수 있다.7 is a scanning electron micrograph of the silver powder thus produced. As shown in the photograph, it can be seen that the silver powders obtained are all spherical.
도 8은 레이저 입도분석기를 이용하여 생성된 구형 은의 입도분포를 측정한 것으로, 평균입도는 0.12㎛이었고 입자의 80%가 0.06~0.12㎛의 크기를 가져서 입도분포가 매우좁아 단분산된 은 구형임을 알 수 있다.FIG. 8 is a particle size distribution of spherical silver produced using a laser particle size analyzer. The average particle size was 0.12 μm, and 80% of the particles had a size of 0.06 to 0.12 μm. Able to know.
한편, 은의 회수율은 수회의 실험결과 평균 98%이상으로 나타났으며, 수세과정에서 손실되는 은을 고려할 때 화학반응만에 의한 은의 회수율은 거의 100%에 가까운 것으로 판단된다.On the other hand, the recovery rate of silver was more than 98% on average in several experiments, and considering the silver lost during the washing process, the recovery rate of silver by chemical reaction alone is nearly 100%.
본 발명에 의하면, 동일한 용액을 사용하면서 화학적 환원법으로 용이하게 구형의 은 분말을 만들 수 있으며, 더욱이 얻어지는 은 분말의 입도분포가 좁아 단분산된 은 분말을 얻을 수 있다. 또한 본 발명에 의하면, 은 분말의 제조공정이 단순하고, 상온에서 제조가 가능하며, 공업용 등급의 원료들만을 사용하여서도 은 분말을 제조할 수 있어서 효율성, 생산성 면에서 매우 우수한 은 분말을 제조하는 것이 가능하다.According to the present invention, spherical silver powder can be easily produced by the chemical reduction method while using the same solution. Furthermore, the silver powder obtained by narrowing the particle size distribution of the silver powder obtained can be obtained. In addition, according to the present invention, the production process of the silver powder is simple, can be produced at room temperature, and the silver powder can be produced using only industrial grade raw materials, thereby producing a silver powder having excellent efficiency and productivity. It is possible.
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Cited By (11)
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| CN102632248A (en) * | 2012-05-03 | 2012-08-15 | 中国人民解放军国防科学技术大学 | Spherical silver powder and preparation method thereof |
| CN102699345A (en) * | 2012-05-18 | 2012-10-03 | 西北稀有金属材料研究院 | Preparation method of micron-sized high-activity spherical silver powder |
| CN103769603A (en) * | 2014-01-23 | 2014-05-07 | 永新股份（黄山）包装有限公司 | Nanometer silver particle and synthetic method thereof |
| KR101397552B1 (en) | 2012-08-27 | 2014-05-20 | 강원대학교산학협력단 | Preparation method of silver nano-structure for surface enhanced Raman scattering substrate and silver nano-structure thereby |
| KR101456175B1 (en) * | 2014-01-28 | 2014-10-31 | 강원대학교산학협력단 | Silver nano-structure for surface enhanced Raman scattering substrate |
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| CN102632248A (en) * | 2012-05-03 | 2012-08-15 | 中国人民解放军国防科学技术大学 | Spherical silver powder and preparation method thereof |
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| KR20170038466A (en) | 2015-09-30 | 2017-04-07 | 엘에스니꼬동제련 주식회사 | The manufacturing method of silver powder |
| CN105436513A (en) * | 2015-11-17 | 2016-03-30 | 广西大学 | Preparation method for spherical water-based nano-silver paste |
| CN105436513B (en) * | 2015-11-17 | 2017-06-16 | 广西大学 | A kind of preparation method of spherical water nano silver paste |
| CN107971502A (en) * | 2017-11-01 | 2018-05-01 | 昆明理工大学 | A kind of preparation method of high dispersiveness spherical silver powder |
| CN107971502B (en) * | 2017-11-01 | 2020-07-31 | 昆明理工大学 | Preparation method of high-dispersity spherical silver powder |
| CN111804905A (en) * | 2020-09-02 | 2020-10-23 | 西安宏星电子浆料科技股份有限公司 | Micron-sized spherical hollow gold powder and preparation method thereof |
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