KR100408647B1 - Manufacturing Process of alloyed and composite nano-metal powder of a high degree of purity - Google Patents
Manufacturing Process of alloyed and composite nano-metal powder of a high degree of purity Download PDFInfo
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- KR100408647B1 KR100408647B1 KR10-2000-0064779A KR20000064779A KR100408647B1 KR 100408647 B1 KR100408647 B1 KR 100408647B1 KR 20000064779 A KR20000064779 A KR 20000064779A KR 100408647 B1 KR100408647 B1 KR 100408647B1
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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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
- B22F1/054—Nanosized 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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
- B22F2201/013—Hydrogen
Abstract
본 발명은 고기능성 분말야금 제품용 원료분말로 사용되는 고순도의 합금 및 복합상 나노금속분말의 제조방법에 관한 것으로 금속산화물을 볼과 알코올계 용매와 함께 용기에 장입한 후 초음파 발생기에서 초음파 볼밀을 하여 분쇄혼합하는 단계와, 상기의 분쇄혼합된 금속산화물을 건조한 후 수소환원하는 단계로 구성되는 제조방법을 제공함으로써 불순물 혼입이 전혀 없는 합금 및 복합상의 나노금속분말의 제조가 가능하며 나노결정립을 갖는 벌크재료등을 제조할 수 있을 뿐만 아니라 고기능성 재료의 제조에 유용하게 사용될 수 있다.The present invention relates to a method for producing high purity alloy and composite nanometal powders used as raw material powders for high functional powder metallurgy products. By pulverizing and mixing, and drying the pulverized mixed metal oxide and then hydrogen reduction to prepare an alloy and a composite nanometal powder having no impurity mixed therein, and having nanocrystal grains. Not only the bulk material can be manufactured, but also can be usefully used for the production of high functional materials.
Description
본 발명은 고순도의 합금 및 복합상 나노금속분말의 제조방법에 관한 것으로써, 특히 불순물혼입이 없는 고기능성 분말야금 제품용 원료분말의 제조방법에 관한 것이다.The present invention relates to a method for producing high purity alloys and composite nanometal powders, and more particularly to a method for producing raw powders for high functional powder metallurgy products without impurity incorporation.
일반적으로 분말의 최종제품이 구조용으로 사용되는 경우 미량의 불순물 혼입은 요구성질에 따라 허용될 수 있으나, 전자재료 및 자성재료와 같이 불순물에 의해 특성이 크게 영향을 받는 기능재료용의 경우에 불순물 혼입은 크게 제한된다. 일례로 고출력 IC(Integrated Circuit)용 방열재료로 사용되는 텅스텐(W)-구리(Cu, 15wt%미만)분말의 경우 볼밀링 과정에서 혼입되는 철(Fe), 크롬(Cr) 또는 니켈(Ni)은 기지상인 구리와 합금을 형성하여 전기 및 열전도도를 크게 저하시킨다. 동시에 기지상을 강화시켜 구리 기지상의 동적 소성변형특성이 요구되는 응용분야에 사용이 제한된다.In general, when the final product of the powder is used for structural purposes, incorporation of trace amounts of impurities may be acceptable depending on the required properties, but incorporation of impurities in the case of functional materials whose properties are greatly affected by impurities such as electronic materials and magnetic materials Is greatly limited. For example, in the case of tungsten (W) -copper (Cu, less than 15wt%) powder used as a heat dissipating material for high-output integrated circuits, iron (Fe), chromium (Cr), or nickel (Ni) mixed in the ball milling process It forms an alloy with copper which is silver matrix phase, and greatly reduces electrical and thermal conductivity. At the same time, the base phase is reinforced to limit its use in applications requiring dynamic plastic deformation properties on copper matrix.
복합분말의 제조방법에 관한 구체적인 예로 대한민국 공고특허 제 97-1558호는 고에너지 볼밀에 의해 분쇄혼합된 금속산화물을 수소환원하여 W-Cu, Fe-Cu등의 나노복합분말을 제조하는 방법에 관한 것으로서 금속산화물을 분쇄혼합한 후 수소환원하여 제조한 나노금속분말은 혼합균일성, 입자미세화등과 같은 우수한 분말특성을 가지고 있어 단시간 저온 소결공정만으로도 완전치밀화에 이르는 우수한 소결특성을 나타낸다. 또한 수소환원공정을 포함한 전 분말제조과정에서 생산되는 주요부산물이 물이기 때문에 타 분말제조공정에 비해 환경친화적이라는 장점을 가진다.As a specific example of a method for manufacturing a composite powder, Korean Patent Publication No. 97-1558 relates to a method for preparing nanocomposite powders such as W-Cu, Fe-Cu by hydrogen reduction of a metal oxide pulverized and mixed by a high energy ball mill. Nanometal powders prepared by pulverizing and mixing metal oxides and then hydrogen-reducing have excellent powder characteristics such as mixing uniformity and particle fineness, and thus exhibit excellent sintering characteristics up to complete densification even in a short time of low temperature sintering process. In addition, since the main by-products produced during the entire powder manufacturing process including hydrogen reduction process is water, it has the advantage of being more environmentally friendly than other powder manufacturing processes.
그러나 상기한 금속산화물의 분쇄혼합공정에서 고에너지 볼밀을 사용하기 때문에 짧은 볼밀공정에서도 용기와 볼에서부터 미량의 불순물이 분말에 혼입되는 것을 피할 수 없다. 특히 분말특성을 개선하기 위해 볼밀에너지를 증가시키는 경우에는 불순물 혼입도 아울러 증가하게 된다.However, since the high-energy ball mill is used in the pulverization-mixing step of the metal oxide, the incorporation of a small amount of impurities from the container and the ball into the powder cannot be avoided even in a short ball mill step. In particular, when the ball mill energy is increased in order to improve the powder characteristics, impurities are also increased.
본 발명은 상기한 종래 기술의 문제점을 해결하기 위해 제안된 것으로써, 본 발명의 목적은 종래의 금속산화물의 분쇄 및 혼합과정을 개선하여 불순물의 혼입을 배제할 뿐만 아니라 환경친화적이며 저가의 설비를 이용하는 우수한 특성의 합금 및 복합상 나노금속분말의 제조방법을 제공하기 위한 것이다.The present invention has been proposed in order to solve the above problems of the prior art, the object of the present invention is to improve the grinding and mixing process of the conventional metal oxide to eliminate the incorporation of impurities, as well as environmentally friendly and inexpensive equipment An object of the present invention is to provide a method for producing an alloy and a composite nanometal powder having excellent properties.
도 1은 실시예 1의 W-15중량%Cu 산화물을 초음파 볼밀링한 후의 주사전자현미경사진(배율: 70,000).1 is a scanning electron micrograph (magnification: 70,000) after ultrasonic ball milling of the W-15 wt% Cu oxide of Example 1. FIG.
도 2는 실시예 1의 W-15중량%Cu 산화물을 초음파 볼밀링한 다음 수소환원한 후의 주사전자현미경 사진(배율: 20,000).Figure 2 is a scanning electron micrograph (scaling ratio: 20,000) after ultrasonic ball milling and hydrogen reduction of the W-15% by weight Cu oxide of Example 1.
도 3은 실시예 1의 W-15중량%Cu 분말을 1200℃에서 2시간 소결한 시편의 미세구조 사진(배율: 5,000배).3 is a microstructure photograph of a specimen obtained by sintering the W-15 wt% Cu powder of Example 1 at 1200 ° C. for 2 hours (magnification: 5,000 ×).
도 4는 실시예 1의 W-15중량%Cu 분말을 1200℃에서 소결한 후 Cu 기지만을 EDS를 이용하여 성분분석한 그래프.Figure 4 is a graph of the component analysis using EDS only Cu base after sintering the W-15% by weight Cu powder of Example 1 at 1200 ℃.
도 5는 실시예 1과 비교예 1의 전기전도도를 측정한 그래프.5 is a graph measuring the electrical conductivity of Example 1 and Comparative Example 1.
도 6은 실시예 2의 Fe-50중량%Ni 분말을 주사전자현미경(배율: 50,000)으로 관찰한 사진.Figure 6 is a photograph of the Fe-50% by weight Ni powder of Example 2 observed with a scanning electron microscope (magnification: 50,000).
도 7은 실시예 2의 Fe-50중량%Ni 분말을 850℃에서 1시간 소결한 시편의 투과전자현미경 사진(배율: 200,000배).7 is a transmission electron micrograph (magnification: 200,000 times) of a specimen obtained by sintering Fe-50 wt% Ni powder of Example 2 at 850 ° C. for 1 hour.
도 8은 실시예 3의 W 중합금분말을 1460℃에서 20분 소결한 시편의 파면을 주사전자현미경(배율: 1,000)으로 관찰한 사진.FIG. 8 is a photograph of a wavefront of a specimen obtained by sintering the W polymerized gold powder of Example 3 at 1460 ° C. for 20 minutes using a scanning electron microscope (magnification: 1,000). FIG.
상기한 목적을 달성하기 위해 본 발명은 금속산화물을 볼과 알코올계 용매와 함께 용기에 장입한 후 초음파 발생기에서 초음파 볼밀을 하여 분쇄혼합하는 단계와, 상기의 분쇄혼합된 금속산화물을 건조한 후 수소환원하는 단계를 포함하여 이루어짐을 특징으로 하는 고순도의 합금 및 복합상 나노금속분말의 제조방법을 제공하는 것이다.In order to achieve the above object, the present invention is to charge the metal oxide in a container with a ball and an alcohol solvent and then pulverized and mixed by an ultrasonic ball mill in an ultrasonic generator, and the hydrogen ring after drying the pulverized mixed metal oxide It is to provide a method for producing a high purity alloy and composite nano-metal powder characterized in that it comprises a desired step.
본 발명은 불순물 혼입을 배제할 수 있는 분쇄방법으로 초음파분쇄와 볼밀분쇄를 결합한 혼합형을 이용함으로써, 금속산화물을 미세화한 후 수소환원하여 최종의 합금/복합상 나노분말로 제조하는 방법에 관한 것이다.The present invention relates to a method of producing a final alloy / composite nanopowder by miniaturizing a metal oxide and then hydrogen reduction by using a mixed type combining ultrasonic and ball milling as a grinding method to exclude impurities.
초음파 볼밀 분쇄는 금속산화물과 강, 스테인리스강 또는 기타 재질의 볼을알콜계 용매와 함께 초음파 발생기에서 분쇄혼합하는 기술로서, 초음파만으로 분쇄하는 방법에 의한 분쇄효율이 10% 미만인데 반하여 볼첨가에 의해 분쇄효율은 100%로 크게 증가한다. 이것은 초음파진동에 의해 볼이 진동하면서 동시에 금속산화물을 미세하게 분쇄하기 때문이다. 이 경우 볼이 진동할 때 볼간에 일어나는 충격 및 마찰에 의해 볼표면에서 발생할 수 있는 불순물의 유입은 없는 것으로 나타났다. 초음파 발생기의 진동수는 15-300 kHz 범위에서 선택될 수 있으며, 초음파볼밀 분쇄는 10-200 시간 동안 한다. 분쇄혼합후에는 금속산화물분말을 증류건조방법등을 이용하여 건조한 후 수소환원하여 나노금속분말을 제조한다. 수소환원 공정은 1분당 5-100℃의 승온속도로 200-1000℃ 온도범위로 가열한 후 1 단계 또는 2 단계로 1-5시간 등온 유지한후 냉각하는 방법이 사용된다.Ultrasonic ball mill grinding is a technology of grinding and mixing metal oxide and steel, stainless steel, or other materials with an alcohol-based solvent in an ultrasonic generator, and the grinding efficiency by the method of grinding only with ultrasonic waves is less than 10%. Grinding efficiency greatly increases to 100%. This is because the balls vibrate by ultrasonic vibration and finely pulverize the metal oxide. In this case, it is shown that there is no inflow of impurities that may occur on the surface of the ball due to the impact and friction between the balls when the ball vibrates. The frequency of the ultrasonic generator can be selected in the range of 15-300 kHz, and the ultrasonic ball mill grinding is performed for 10-200 hours. After the pulverized mixing, the metal oxide powder is dried using a distillation drying method and then hydrogen reduced to prepare a nano metal powder. In the hydrogen reduction process, a method of heating to a temperature range of 200-1000 ° C. at a temperature increase rate of 5-100 ° C. per minute and then isothermally holding it for 1-5 hours in one or two steps is used.
복합상 나노금속 분말을 제조하기 위하여 금속산화물로서 텅스텐산화물과 구리 산화물을 사용할 수 있으며 각 분말조성을 텅스텐 50-95%, 구리 5-50%의 중량비로 한다. 텅스텐-구리 복합재료는 상기의 함량범위내에서 각각 전극재료, 방열재료, 로켓노즐재료등으로 응용되며 상기의 함량범위를 벗어나면 산업적으로 응용 가치가 없어진다. 예를 들어 구리가 5% 이하이면 이론적으로 완전치밀화가 매우 어려우며, 50% 이상이면 전극재료로서 요구되는 내아크성과 같은 요구성질을 만족시키지 못한다. 수소환원 공정조건은 분당 5-100℃의 승온속도로 200-400℃의 온도까지 상승시킨 후 상기 온도에서 30분-2시간 유지하고, 1분당 5-100℃의 승온속도로 500-1000℃까지 승온시킨 다음 1-5시간 유지한 후 상온으로 냉각하는 방법을 사용한다.여기에서, 온도범위 200-400℃는 구리 산화물의 환원이 주로 이루어지는 온도범위이고, 온도범위 500~1000℃는 텅스텐산화물의 환원이 주로 이루어지는 온도범위이며, 이는 당업자에게 잘 알려져 있다. 또한, 승온속도가 5℃ 미만일 경우 환원공정이 너무 길어지고, 환원된 금속입자의 응집, 성장 편성의 문제점이 야기되며, 승온속도가 100℃보다 클 경우, 금소산화물의 환원이 제대로 이루어지지 않을 뿐 더러 급격한 수증기의 발생으로 환원되는 금속입자의 성장이 야기된다(수증기 분압이 높을수로 금속입자의 크기가 증가됨).To prepare a composite nanometal powder, tungsten oxide and copper oxide may be used as metal oxides, and each powder composition has a weight ratio of 50-95% tungsten and 5-50% copper. Tungsten-copper composite materials are applied as electrode materials, heat-radiating materials, rocket nozzle materials, etc. within the above-described content ranges, and if they fall outside the above-described content ranges, there is no industrial value. For example, when copper is 5% or less, perfect densification is very difficult in theory, and when 50% or more, it does not satisfy requirements such as arc resistance required as an electrode material. Hydrogen reduction process conditions are raised to a temperature of 200-400 ℃ at a temperature increase rate of 5-100 ℃ per minute and maintained at the temperature for 30 minutes-2 hours, to 500-1000 ℃ at a temperature increase rate of 5-100 ℃ per minute After raising the temperature and maintaining for 1-5 hours, a method of cooling to room temperature is used. Here, the temperature range of 200-400 ° C. is a temperature range in which the reduction of copper oxide is mainly performed, and the temperature range of 500-1000 ° C. is used for tungsten oxide. It is the temperature range in which reduction occurs primarily, which is well known to those skilled in the art. In addition, if the temperature increase rate is less than 5 ℃, the reduction process is too long, causing the problems of aggregation and growth of the reduced metal particles, and if the temperature increase rate is higher than 100 ℃, the reduction of the gold oxide is not made properly In addition, the rapid generation of water vapor causes the growth of reduced metal particles (the higher the partial pressure of water vapor, the larger the size of the metal particles).
또한, 복합상 나노금속 분말을 제조하기 위하여 금속산화물로서 텅스텐산화물, 니켈 산화물 및 철산화물을 사용할 수 있으며 각 분말조성은 텅스텐 85-97%, 니켈 2.1-10%, 철 0.9-5% 중량비로 한다. 상기의 텅스텐 중합금 재료는 운동에너지탄의 관통자소재등으로 응용되는데 텅스텐 함량이 85% 이하이면 관통자로서 요구되는 높은 밀도 및 인장강도를 만족시키지 못하며 97% 이상이면 완전치밀화 및 높은 연신율을 만족시키지 못한다. 수소환원 공정조건은 1분당 5-100℃의 승온속도로 500-1000℃까지 승온시켜 1-5시간 유지한 후 상온으로 냉각하는 방법으로 구성된다.여기에서, 온도범위 500~1000℃는 텅스텐 산화물의 환원이 주로 이루어지는 온도범위이며, Ni-Fe 산화물의 환원은 500℃ 미만의 승온과정에서 충분히 이루어질 수 있다. 또한, 승온속도가 5℃ 미만일 경우 환원공정이 너무 길어지고, 환원된 금속입자의 응집, 성장 편성의 문제점이 야기되며, 승온속도가 100℃보다 클 경우, 금소산화물의 환원이 제대로 이루어지지 않을 뿐 더러 급격한 수증기의 발생으로 환원되는 금속입자의 성장이 야기된다(수증기 분압이 높을수로 금속입자의 크기가 증가됨).In addition, tungsten oxide, nickel oxide, and iron oxide may be used as metal oxides to prepare the composite nanometal powder, and each powder composition has a weight ratio of 85-97% tungsten, 2.1-10% nickel, and 0.9-5% iron. . The above-mentioned tungsten polymer alloy material is applied as a penetrator material of kinetic energy coal. If the tungsten content is 85% or less, it does not satisfy the high density and tensile strength required as the penetrator, and if it is more than 97%, it does not satisfy the perfect densification and high elongation. . The hydrogen reduction process conditions consist of a method of heating up to 500-1000 ° C. at a heating rate of 5-100 ° C. per minute, maintaining the temperature for 1-5 hours, and then cooling to room temperature. The reduction is mainly in the temperature range, the reduction of the Ni-Fe oxide can be made sufficiently in the temperature increase process below 500 ℃. In addition, if the temperature increase rate is less than 5 ℃, the reduction process is too long, causing the problems of aggregation and growth of the reduced metal particles, and if the temperature increase rate is higher than 100 ℃, the reduction of the gold oxide is not made properly In addition, the rapid generation of water vapor causes the growth of reduced metal particles (the higher the partial pressure of water vapor, the larger the size of the metal particles).
합금상 나노금속 분말을 제조하기 위하여 금속산화물로서 철산화물과 니켈 산화물을 사용할 수 있으며 각 분말조성은 철 15-80%, 니켈 20-85%의 중량비로 한다. 연자성 재료로 응용되는 철-니켈 재료는 상기의 함량범위를 벗어나면 연자성 특성이 나타나지 않는다. 수소환원 공정조건은 분당 5-100℃의 승온속도로 400-800℃의 온도까지 승온시킨 다음 1-5시간 유지한 후 상온으로 냉각하는 과정으로 이루어진다.여기에서, 온도범위 400-800℃는 철산화물의 환원이 주로 이루어지는 온도범위이며, 니켈산화물의 환원은 400℃ 미만의 승온과정에서 충분히 이루어진다. 또한, 승온속도가 5℃ 미만일 경우 환원공정이 너무 길어지고, 환원된 금속입자의 응집, 성장 편성의 문제점이 야기되며, 승온속도가 100℃보다 클 경우, 금소산화물의 환원이 제대로 이루어지지 않을 뿐 더러 급격한 수증기의 발생으로 환원되는 금속입자의 성장이 야기된다(수증기 분압이 높을수로 금속입자의 크기가 증가됨).Iron oxides and nickel oxides may be used as metal oxides to prepare alloyed nanometal powders, and each powder composition has a weight ratio of 15-80% iron and 20-85% nickel. Iron-nickel materials applied as soft magnetic materials do not exhibit soft magnetic properties outside the above content ranges. The process of hydrogen reduction consists of raising the temperature to 400-800 ° C at a heating rate of 5-100 ° C per minute and maintaining it for 1-5 hours, then cooling it to room temperature. The reduction of the cargo is mainly in the temperature range, the reduction of the nickel oxide is sufficiently made in the temperature increase process below 400 ℃. In addition, if the temperature increase rate is less than 5 ℃, the reduction process is too long, causing the problems of aggregation and growth of the reduced metal particles, and if the temperature increase rate is higher than 100 ℃, the reduction of the gold oxide is not made properly In addition, the rapid generation of water vapor causes the growth of reduced metal particles (the higher the partial pressure of water vapor, the larger the size of the metal particles).
본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 한정되는 것은 아니다.If the present invention will be described in detail based on the Examples as follows, the present invention is not limited to the Examples.
<실시예 1> 고출력 IC용 방열재료분말Example 1 Heat Dissipating Material Powder for High Power IC
유리나 플라스틱 또는 금속용기에 강 및 스텐리스강 재질의 볼을 한 층으로 넣은 후 평균입도가 30㎛ 인 텅스텐 산화물과 평균입도가 2㎛인 구리산화물을 85중량%-15중량%(W-Cu)의 조성이 되도록 용기에 넣는다. 이때 분말의 무게는 볼의 1/10이다. 상기의 용기에 분말 1g 당 1.7 ㎖의 알콜을 첨가한 후 초음파 발생기에서 50시간 초음파 볼밀링을 한다. 사용된 초음파 발생기의 용기는 400 mm(가로)×390 mm(너비)×200 mm(높이)의 크기를 하고 있으며 출력은 1200W이다. 초음파 발생기의진동수는 28 kHz이다. 초음파에 의해 볼밀링된 금속산화물 분말은 건조후 스폰지 케이크(cake) 형태를 하고 있으며 100 메쉬의 체질을 통해 분말상태로 만든다. 상기의 금속 산화물 분말을 200℃에서 1시간, 800℃에서 1시간동안 관상로에서 수소(노점: -76℃)분위기에서 환원하여 W-15중량%Cu 나노복합분말을 제조한다. 이때 승온속도는 분당 30℃ 이었다.85% by weight to 15% by weight of tungsten oxide with an average particle size of 30 μm and copper oxide with an average particle size of 2 μm after putting balls of steel and stainless steel in a single layer in glass, plastic or metal container. Put in a container so that the composition of. At this time, the weight of the powder is 1/10 of the ball. After adding 1.7 ml of alcohol per gram of powder to the container, ultrasonic ball milling was performed for 50 hours in an ultrasonic generator. The vessel of the ultrasonic generator used is 400 mm (width) x 390 mm (width) x 200 mm (height) and the output is 1200W. The frequency of the ultrasonic generator is 28 kHz. The metal oxide powder ball milled by ultrasonication is in the form of a sponge cake after drying and is made into a powder state through a sieve of 100 mesh. The metal oxide powder is reduced in a hydrogen (dew point: -76 ° C) atmosphere in a tubular furnace for 1 hour at 200 ° C and 1 hour at 800 ° C to prepare a W-15 wt% Cu nanocomposite powder. The temperature increase rate was 30 ℃ per minute.
<비교예 1>Comparative Example 1
평균입도가 30㎛인 텅스텐 산화물과 평균입도가 2㎛인 구리산화물을 85중량%-15중량%(W-Cu)의 조성으로 마찰기(attritor)에서 1시간 동안 알콜을 사용하여 습식 볼밀링을 한 후 실시예 1과 동일한 방법으로 제조한다.Wet ball milling was carried out using alcohol for 1 hour in an attritor with a composition of 85 wt% -15 wt% (W-Cu) of tungsten oxide having an average particle size of 30 μm and a copper oxide having an average particle size of 2 μm. After the preparation in the same manner as in Example 1.
도 1은 실시예 1의 초음파 볼밀링한 W-15중량%Cu 산화물을 주사전자현미경으로 배율 70,000배의 조건에서 관찰한 사진으로, W 산화물과 Cu 산화물이 초음파볼밀링에 의해 극미세하게 분쇄되어 10-30nm 크기 입자를 형성하고 있어 분쇄효과가 매우 우수한 것을 알 수 있다.1 is a photograph of the ultrasonic ball milling W-15% by weight of the Cu oxide of Example 1 under the condition of 70,000 times magnification with a scanning electron microscope, where W oxide and Cu oxide are extremely finely ground by ultrasonic ball milling. 10-30nm size particles are formed, it can be seen that the grinding effect is very excellent.
도 2는 실시예 1의 초음파 볼밀링한 W-15중량%Cu 산화물을 200℃에서 1시간, 800℃에서 1시간 수소환원하여 주사전자현미경으로 배율 20,000배의 조건에서 관찰한 사진으로 W-Cu 응집체가 300nm 크기를 가지며, 엑스레이(X-ray) 회절분석결과 응집분말은 20-30nm의 W 과 Cu 입자로 구성되어 있음을 알 수 있다. 비교예 1의 W-Cu 응집분말은 수 마이크론의 크기를 갖는데 비해 실시예 1의 W-Cu 응집분말이 매우 균일하고 미세화되었음을 알 수 있다.FIG. 2 is a photograph of the ultrasonic ball milling W-15% by weight of Cu oxide of Example 1 at 200 ° C. for 1 hour and at 800 ° C. for 1 hour, and observed by scanning electron microscope at 20,000 times magnification. The aggregate has a size of 300 nm, and X-ray diffraction analysis shows that the aggregate powder is composed of 20-30 nm W and Cu particles. The W-Cu aggregated powder of Comparative Example 1 has a size of several microns, but it can be seen that the W-Cu aggregated powder of Example 1 is very uniform and fine.
도 3은 소결특성을 평가하기 위하여 실시예 1의 W-15중량%Cu 분말을 상대밀도 50%로 성형한후 10℃/min로 승온하여 1200℃에서 2시간 소결한 시편의 미세구조 사진(배율: 5,000배)으로서 W 입자와 Cu 기지가 매우 균일하게 분포하며 완전 치밀화한 것을 알 수 있다. 이는 초음파 볼밀링된 분말의 Cu 혼합도 및 소결성이 매우 우수한 것을 의미한다.3 is a microstructure photograph of a specimen sintered at 1200 ° C. for 2 hours at a temperature of 10 ° C./min after molding the W-15 wt% Cu powder of Example 1 to a relative density of 50% to evaluate sintering characteristics. : 5,000 times), the W particles and the Cu matrix are very uniformly distributed and are found to be completely densified. This means that the Cu mixing degree and the sinterability of the ultrasonic ball milled powder are very excellent.
도 4는 실시예 1의 분말을 1200℃에서 소결한 후 불순물 혼입정도를 조사하기 위해 Cu 기지만을 EDS로 성분분석한 결과이다. W, Cu 성분이외에 다른 성분의 피이크는 나타나지 않으며 초음파 볼밀링시 불순물 혼입이 전혀 없다는 것을 알 수 있다.FIG. 4 shows the results of component analysis of only Cu base with EDS to investigate the degree of impurity incorporation after sintering the powder of Example 1 at 1200 ° C. It can be seen that the peaks of other components other than the W and Cu components do not appear, and no impurities are mixed in the ultrasonic ball milling.
도 5는 실시예 1과 비교예 1의 전기전도도를 측정한 결과이다. 본 실시예 1은 30% IACS(International Annealed Copper Standard)의 값을, 그리고 비교예 1은 21% IACS를 나타낸다. 비교예 1은 산화물 분쇄과정에서 불순물이 혼입되었기 때문에 낮은 전기전도도를 나타내며, 반면에 실시예 1은 초음파 볼밀링과정에서 불순물의 혼입이 없고 소결후 완전치밀화와 균일한 미세조직이 형성되었기 때문에 높은 전기전도도를 나타낸다.5 is a result of measuring the electrical conductivity of Example 1 and Comparative Example 1. Example 1 shows a value of 30% IACS (International Annealed Copper Standard), and Comparative Example 1 shows a 21% IACS. Comparative Example 1 shows low electrical conductivity because impurities are mixed in the oxide grinding process, whereas Example 1 shows high electrical conductivity because no impurities are mixed in the ultrasonic ball milling process and perfect densification and uniform microstructure are formed after sintering. Indicates conductivity.
<실시예 2> 연자성 재료 분말Example 2 Soft Magnetic Material Powder
산화철분말과 Ni 산화물 분말을 환원시킨 다음 Fe-50중량%Ni의 조성으로 준비한 후 실시예 1과 동일한 방법으로 초음파 볼밀링을 150시간 실시한다. 상기의Fe-50중량%Ni 분말을 600℃에서 1시간 수소환원시켜 나노합금분말을 제조한다.After reducing the iron oxide powder and Ni oxide powder, and prepared in a composition of Fe-50% by weight Ni, ultrasonic ball milling is carried out in the same manner as in Example 1 for 150 hours. The Fe-50 wt% Ni powder is hydrogen-reduced at 600 ° C. for 1 hour to prepare nanoalloy powder.
도 6은 실시예 2의 Fe-50중량%Ni 분말을 주사전자현미경을 이용하여 배율 50,000배로 관찰한 사진으로서 100-300nm 크기의 응집분말을 형성하고 있었으며 엑스레이(X-ray) 회절분석결과 결정립 크기가 40nm이었다.6 is a photograph of the Fe-50% by weight Ni powder of Example 2 observed at 50,000 times magnification using a scanning electron microscope to form agglomerated powder having a size of 100-300 nm, and the grain size as a result of X-ray diffraction analysis. Was 40 nm.
도 7은 1250 MPa의 압력으로 상대밀도 80%의 성형체를 850℃에서 1시간 소결한 시편의 미세구조를 투과전자현미경을 이용하여 배율 200,000배로 관찰한 사진으로 소결밀도는 99%이상이었으며 결정립 크기가 50 nm 미만의 나노결정립 구조를 유지함을 알 수 있다.7 is a photograph of the microstructure of a specimen obtained by sintering a molded article having a relative density of 80% at 1850 MPa at 850 ° C. for 1 hour at a magnification of 200,000 times using a transmission electron microscope. The sintered density was greater than 99%. It can be seen that the nanocrystalline structure is maintained below 50 nm.
<실시예 3> 중합금 분말Example 3 Polymeric Gold Powder
텅스텐 산화물 분말, 산화철분말, 니켈산화물 분말을 환원시킨 다음 W-4.9중량%Fe-2.1중량%Ni이 되도록 준비한 후 실시예 1과 동일한 방법으로 초음파 볼밀링을 50시간 실시한다. 상기의 W-4.9중량%Fe-2.1중량%Ni 분말을 800℃에서 1시간 수소환원시켜 나노 중합금분말을 제조한다.After tungsten oxide powder, iron oxide powder and nickel oxide powder were reduced and prepared to be W-4.9% by weight Fe-2.1% by weight Ni, ultrasonic ball milling was carried out in the same manner as in Example 1 for 50 hours. The W-4.9 wt% Fe-2.1 wt% Ni powder was hydrogen-reduced at 800 ° C. for 1 hour to prepare a nano-polymerized gold powder.
도 8은 실시예 3의 W 중합금분말을 1460℃에서 20분 소결한 시편의 파면을 주사전자현미경을 이용하여 배율 1,000배로 관찰한 사진으로서 소결체가 완전치밀화된 것을 알 수 있다. 특징적인 것은 W 입자크기가 약 5 ㎛로 비교적 미세하면서 균일한 분포를 유지한다는 것이다. 또한 W 과 기지상이 매우 균일하게 분포되어 있으며 비교적 짧은 소결시간에도 불구하고 완전치밀화된 소결체를 얻을 수 있음을 알 수 있다.8 is a photograph of the wavefront of a specimen obtained by sintering the W polymerized gold powder of Example 3 at 1460 ° C. for 20 minutes at a magnification of 1,000 times using a scanning electron microscope, showing that the sintered compact was completely densified. Characteristic is that the W particle size is about 5 μm, maintaining a relatively fine and uniform distribution. In addition, it can be seen that W and matrix phases are very uniformly distributed, and a sintered compact can be obtained despite a relatively short sintering time.
상술한 바와 같이, 본 발명에 의해 불순물의 혼입이 전혀 없는 합금 및 복합상의 나노금속분말의 제조가 가능할 뿐만 아니라 나노결정립을 갖는 벌크재료의 제조가 가능하다. 또한 선진국에서 조차 나노구조재료의 기술부족으로 박막이나 코팅형태에 제한되고있는 실정에서 본 발명에 의해 나노구조의 벌크재료의 제조가 현실화됨에 따라 고기능성 재료시장에서 우위를 차지할 있다.As described above, the present invention enables not only the production of alloy and composite nanometal powders free of impurities, but also the preparation of bulk materials having nanocrystal grains. In addition, even in developed countries, due to the technical shortage of nanostructured materials, the present invention is limited to thin films or coating forms, and according to the present invention, the nanostructured bulk material is realized in the high functional materials market.
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| JPS6227506A (en) * | 1985-07-26 | 1987-02-05 | Sumitomo Special Metals Co Ltd | Production of alloy powder for rare earth-boron-ferrous permanent magnet |
| JPS63120404A (en) * | 1986-11-10 | 1988-05-24 | Mitsui Toatsu Chem Inc | Manufacture of magnetic iron powder |
| JPH10317020A (en) * | 1997-05-16 | 1998-12-02 | Korea Inst Of Mach & Metals | Production of fine grained wc(tungsten carbide)/co (cobalt) composite powder by mechanochemical method |
| JPH1180818A (en) * | 1997-09-08 | 1999-03-26 | Sumitomo Metal Mining Co Ltd | Production of metal powder, and metal powder produced by the method |
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| JPS6227506A (en) * | 1985-07-26 | 1987-02-05 | Sumitomo Special Metals Co Ltd | Production of alloy powder for rare earth-boron-ferrous permanent magnet |
| JPS63120404A (en) * | 1986-11-10 | 1988-05-24 | Mitsui Toatsu Chem Inc | Manufacture of magnetic iron powder |
| JPH10317020A (en) * | 1997-05-16 | 1998-12-02 | Korea Inst Of Mach & Metals | Production of fine grained wc(tungsten carbide)/co (cobalt) composite powder by mechanochemical method |
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