KR20000026488A - Method of manufacturing electric contact containing high sn content using inner oxidation - Google Patents
Method of manufacturing electric contact containing high sn content using inner oxidation Download PDFInfo
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- KR20000026488A KR20000026488A KR1019980044023A KR19980044023A KR20000026488A KR 20000026488 A KR20000026488 A KR 20000026488A KR 1019980044023 A KR1019980044023 A KR 1019980044023A KR 19980044023 A KR19980044023 A KR 19980044023A KR 20000026488 A KR20000026488 A KR 20000026488A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
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Abstract
Description
본 발명은 고함량의 주석(Sn)이 포함된 전기접점제를 내부산화를 이용하여 제조하기 위한 것이다.The present invention is to prepare an electrical contact agent containing a high content of tin (Sn) using internal oxidation.
통상 600[A] 이하의 중전류 영역에서 전기 접점 재료로써, Ag-CdO가 많이 사용된다.Usually, Ag-CdO is widely used as an electrical contact material in the medium current region of 600 [A] or less.
하지만 Ag-CdO의 공해 및 인체의 유해성으로 인하여 사용이 불가능해짐에 따라 대체 재료로써 Ag-SnO2가 사용되고 있다.However, due to the pollution of Ag-CdO and the harmfulness of the human body, the use of Ag-SnO 2 is being used as an alternative material.
Ag-SnO2합금은 분말야금법과 내부산화법으로 제조할 수 있는데 내부산화법으로 제조된 재료가 접점으로써의 성질이 우수하다.Ag-SnO 2 alloy can be manufactured by powder metallurgy and internal oxidation method, and the material produced by internal oxidation method has excellent properties as a contact point.
이하, 종래 기술에 따른 전기접점제를 설명하면 다음과 같다.Hereinafter, the electrical contact agent according to the prior art will be described.
내부산화는 순금속에서는 일어나지 않고 합금에서만 일어난다. Au, Ag, Pt등과 같이 내산화성이 높은 귀금속과 Cd, In, Sn, Zn등과 같이 산화가 잘되는 비금속이 합금을 이루고 있을 때 산소 분위기에서 열처리하면 산화 경향의 차이로 인해 비금속 원소들만 선택적으로 산화되어 석출물을 형성하는데 이를 일컬어 내부산화라 한다.Internal oxidation does not occur in pure metals but only in alloys. When alloys are composed of precious metals such as Au, Ag, Pt, etc. and highly oxidized nonmetals such as Cd, In, Sn, and Zn, heat treatment in an oxygen atmosphere selectively oxidizes only nonmetal elements due to differences in oxidation tendencies. It forms a precipitate, also called internal oxidation.
전기 접점 재료에서는 주로 전기전도도와 내부식성이 높은 Ag에 산화가 잘 되는 Cd, In, Sn, Zn, Ga, Mg 등의 금속원소들을 고용시켜 합금을 만들고 내부산화에 의해 이들 원소들을 산화물 형태로 Ag에 분산시켜 내마멸성, 내용착성, 내아크성들을 향상시켜 사용한다.In electrical contact materials, alloys are made of metal elements such as Cd, In, Sn, Zn, Ga, and Mg, which are easily oxidized to Ag, which has high electrical conductivity and corrosion resistance. Disperses in and improves abrasion resistance, welding resistance and arc resistance
내부산화가 잘 안되는 Ag-Sn 합금을 산화하기 위한 종래의 방법은 3원계 혹은 4원계의 합금 원소 첨가를 통한 효과이다.The conventional method for oxidizing Ag-Sn alloy which is not easily internally oxidized is an effect through the addition of ternary or quaternary alloying elements.
첨가원소를 통한 연구가 종래 연구의 대부분을 차지하고 있다.Research through additive elements makes up the bulk of conventional research.
즉, Ag-Sn 합금에 Bi를 0.2~0.5% 첨가한 경우가 가장 효과적인 것으로 알려져 있다.In other words, it is known that 0.2 to 0.5% of Bi is added to the Ag-Sn alloy.
지금까지는 상기 Bi를 0.5% 정도 첨가하여 Ag-Sn(8.5%) 합금까지 내부산화에 성공하였다.Until now, 0.5% of Bi was added to successfully internalize the Ag-Sn (8.5%) alloy.
이외에 3원계 및 4원계의 다양한 합금 원소를 첨가하여 실험하였으나, Sn의 최대 함량은 8.5%를 넘지 못하였다.In addition, experiments were carried out by adding various alloy elements of the ternary and quaternary systems, but the maximum content of Sn did not exceed 8.5%.
3원계의 합금의 경우, Ag-Sn-In 3원계 합금을 산화시켜 SnO2와 In2O3가 Ag내에 석출되도록하여 산화물의 총량이 13~14%가 되도록 하는 방법등이 있다.In the case of the ternary alloy, there is a method of oxidizing the Ag-Sn-In ternary alloy so that SnO 2 and In 2 O 3 precipitate in Ag so that the total amount of oxide is 13 to 14%.
이와 같은 종래 전기접점제는 다음과 같은 문제점이 있었다.Such a conventional electrical contact agent has the following problems.
첫째, Ag-Sn합금을 충분히 활용하기 위해서는 Ag내의 Sn함량이 10% 이상인 고함량 Ag-Sn 합금을 산화할 수 있어야하지만 종래에는 Sn 의 함량이 8.5%를 초과하지 못하였다.First, in order to fully utilize the Ag-Sn alloy, it should be possible to oxidize the high content Ag-Sn alloy having a Sn content of 10% or more in Ag, but conventionally, the Sn content did not exceed 8.5%.
둘째, Ag-Sn-In 3원계의 합금을 이용한 경우, 산화를 통한 석출 산화물의 균일성이나, 공정조건, 미세화의 측면에서 볼 때 SnO2단일상을 10% 이상 석출시키는 것이 보다 효과적이지만, 8.5% 이상의 Sn을 함유한 Ag-Sn합금을 내부산화할 수 있는 기술이 없다.Second, in the case of using Ag-Sn-In ternary alloy, it is more effective to precipitate more than 10% of SnO 2 single phase in terms of uniformity of oxides precipitated through oxidation, process conditions, and miniaturization. There is no technology to internally oxidize Ag-Sn alloy containing more than% Sn.
내부산화를 할 수 없는 이유는 Ag내내의 Sn함량이 증가함에 따라 산화속도가 감소하게 되고, Sn이 5%이상 첨가되면 Ag-Sn합금의 산화속도가 동일 온도에서의 Sn의 확산계수보다 작아지기 때문이다.The reason that internal oxidation is not possible is that the oxidation rate decreases as the Sn content in Ag increases, and when 5% or more of Sn is added, the oxidation rate of Ag-Sn alloy becomes smaller than the diffusion coefficient of Sn at the same temperature. Because.
합금의 산화속도가 용질 Sn의 확산속도보다 느려지면, 시편 내부쪽에서 확산해 온 Sn원자들이 산화진행선단에 편석되고, 산화/미산화 경계에서 집중적으로 산화물을 형성하게 된다.If the oxidation rate of the alloy is slower than the diffusion rate of the solute Sn, Sn atoms diffused from the inside of the specimen segregate at the oxidation progression tip and form oxides concentrated at the oxidation / unoxidized boundary.
산화물들이 산화경계에 밀집되면 시편 내부로 확산하던 산소의 통로를 제한하게 되고, 병목현상으로 인해 산화속도는 더욱 느려지게 된다.When the oxides are concentrated in the oxidative boundary, they limit the passage of oxygen diffused into the specimen and the oxidation rate becomes slower due to the bottleneck.
산화속도의 감소는 다시 Sn의 편석을 가중시키고, Sn의 편석은 산화물의 밀집을 가속시켜 결국 옥사이드 잼(oxide jam)상태에 이르게 된다.The reduction in oxidation rate in turn increases the segregation of Sn, and the segregation of Sn accelerates the density of oxides and eventually leads to an oxide jam state.
이 상태에서는 산소가 더 이상 시편의 내부로 침투할 수 없어 실질적으로 내부산화는 중단하게 된다.In this state, oxygen can no longer penetrate the inside of the specimen, effectively stopping internal oxidation.
본 발명은 상기한 종래의 문제점을 해결하기 위해 안출한 것으로써, 새로운 합금원소를 이용한 내부산화를 통해 10%이상의 고함량의 Sn을 함유한 전기접점제를 제조하여 Ag-Sn(8.5%)보다 월등한 전기접점제를 제공하는데 그 목적이 있다.The present invention has been made in order to solve the above-mentioned conventional problems, by producing an electrical contact agent containing a high content of Sn of more than 10% through internal oxidation using a new alloy element than Ag-Sn (8.5%) The aim is to provide superior electrical contact systems.
도 1은 본 발명의 고함량의 Sn을 함유한 전기접점제 제조방법에 따른 순서도1 is a flow chart according to the manufacturing method of the electrical contact agent containing a high content of Sn of the present invention
상기의 목적을 달성하기 위한 본 발명의 내부산화를 이용한 고함량의 Sn을 함유한 전기접점제 제조방법은 Ag-Sn-Te합금을 진공밀봉하여 고주파 유도로에서 용해시키는 단계, 진공분위기에서 균질화를 위한 1차 열처리를 실시하는 단계, 압연을 통해 결정립을 미세화시키는 단계, 압연된 합금을 일정크기로 절단하여 시편을 제조한 후, 표면을 연마하는 단계, 산화용 퍼니스내에 시편을 넣고 진공상태로 2차 열처리를 실시하는 단계, 상기 퍼니스내의 온도가 일정온도가 되면 상기 퍼니스내에 고순도의 산소를 공급하는 단계를 포함하여 이루어지는 것을 특징으로 한다.In order to achieve the above object, a method for preparing an electrical contact agent containing a high amount of Sn using internal oxidation of the present invention is to seal the Ag-Sn-Te alloy by vacuum sealing and dissolving it in a high frequency induction furnace, and homogenizing in a vacuum atmosphere. Performing a first heat treatment for the step, refining the grains by rolling, cutting the rolled alloy to a certain size to prepare a specimen, and then polishing the surface, placing the specimen in an oxidation furnace and placing it in a vacuum state. And performing a differential heat treatment, and supplying high purity oxygen into the furnace when the temperature in the furnace reaches a predetermined temperature.
이하, 본 발명의 내부산화를 이용한 고함량의 Sn을 함유한 전기접점제 제조방법을 상세히 설명하면 다음과 같다.Hereinafter, the method for producing an electrical contact agent containing a high content of Sn using the internal oxidation of the present invention will be described in detail.
먼저, 본 발명에 사용된 합금의 조성은 Ag-Sn(10.2at%)-Te(0.4%at) 또는 Ag-Sn(12.2at%)-Te(0.4at%)이다.First, the composition of the alloy used in the present invention is Ag-Sn (10.2at%)-Te (0.4% at) or Ag-Sn (12.2at%)-Te (0.4at%).
본 발명에 사용되는 합금은 용해 도중에 산화되는 것을 피하기 위해 석영관에 진공밀봉하여 고주파 유도로에서 용해하였다.The alloy used in the present invention was melted in a high frequency induction furnace by vacuum sealing the quartz tube in order to avoid being oxidized during melting.
용해 도중에 충분한 교반이 이루어졌을 것으로 예상되나, 혹시 있을 Sn의 편석을 피하기 위해 700℃ 이상의 온도에서 진공 분위기로 24시간 동안 균질화 열처리를 실시한다.Sufficient stirring is expected during the dissolution, but homogenization heat treatment is carried out for 24 hours in a vacuum atmosphere at a temperature of 700 ° C. or higher to avoid any segregation of Sn.
열처리가 끝난 후, 주조 조직을 제거하고 결정립 미세화를 위해 Ag-Sn(10.2at%)-Te(0.4at%) 합금은 냉간압연을 하고, Ab-Sn(12.2at%)-Te(0.4at%) 합금은 700℃ 이상에서 열간압연을 한다.After the heat treatment, the Ag-Sn (10.2at%)-Te (0.4at%) alloy was cold rolled and the Ab-Sn (12.2at%)-Te (0.4at%) to remove the cast structure and refine the grain. ) The alloy is hot rolled at 700 ℃ or higher.
압연한 재료를 1cm×1cm의 크기로 절단하여 시편을 제조하고, 시편의 표면을 연마지로 스케일(scale)한다.The rolled material is cut to a size of 1 cm x 1 cm to prepare a specimen, and the surface of the specimen is scaled with abrasive paper.
여기서, 상기 시편의 표면을 연마지로 연마하지 않고 후속공정을 진행하여도 무방하다.Here, the subsequent steps may be performed without polishing the surface of the specimen with abrasive paper.
이와 같이, 시편을 스케일한 후, 상기 압연 도중에 시편에 가해진 응력을 제거하기 위해 어닐을 실시하는데 어닐방식은 산화용 퍼니스(Furnace)에 시편을 넣고 로터리 펌프로 진공을 유지하며 산화온도인 600~850℃까지 승온한다.As described above, after the specimen is scaled, annealing is performed to remove the stress applied to the specimen during the rolling. The annealing method puts the specimen in an oxidation furnace (furnace), maintains a vacuum with a rotary pump, and the oxidation temperature is 600 to 850. The temperature is raised to ℃.
이때, 진공을 유지하는 이유는 프리-옥시데이션(pre-oxidation)을 방지하기 위함이다.At this time, the reason for maintaining the vacuum is to prevent the pre-oxidation (pre-oxidation).
어닐 시간은 퍼니스내의 온도가 상온에서 산화온도인 600~850℃에 도달할 때까지 약 3 시간 정도한다.The annealing time is about 3 hours until the temperature in the furnace reaches 600-850 ° C, which is the oxidation temperature at room temperature.
퍼니스 온도가 목표치에 도달한 후, 진공펌프쪽의 밸브를 닫고 산소 용기로 연결된 밸브를 열어 고순도 산소를 공급한다.After the furnace temperature has reached the target value, the valve on the vacuum pump side is closed and the valve connected to the oxygen container is opened to supply high purity oxygen.
이때, 퍼니스내의 산소압은 3~5기압으로 유지하고, 산화가 진행되는 동안 퍼니스내의 산소압은 일정하게 유지한다.At this time, the oxygen pressure in the furnace is maintained at 3 to 5 atm, and the oxygen pressure in the furnace is kept constant while oxidation is in progress.
이와 같이, Te를 첨가한 Ag-Sn-Te합금의 산화속도는 1.94×10-7cm/sec인데, 이것은 Te가 첨가되지 않은 Ag-Sn합금이나 Sn의 확산속도에 비해 대략 60배 정도로 산화속도를 증가시킬 수가 있다.As such, the oxidation rate of the Ag-Sn-Te alloy containing Te is 1.94 × 10 −7 cm / sec, which is about 60 times higher than the diffusion rate of Ag-Sn alloy or Sn without Te. Can be increased.
즉, Te의 첨가로 인해 합금의 산화속도가 Sn의 확산속도에 비해 훨씬 빨라지므로 Sn의 편석 및 산화물의 밀집현상이 발생하지 않고 정상적으로 내부산화가 진행될 수 있다.That is, due to the addition of Te, the oxidation rate of the alloy is much faster than the diffusion rate of Sn, so that segregation of Sn and density of oxides do not occur and internal oxidation can proceed normally.
이상에서 상술한 바와 같이 본 발명의 내부산화를 이용한 고함량의 Sn을 함유한 전기접점제 제조방법은 다음과 같은 효과가 있다.As described above, the manufacturing method of the electrical contact agent containing a high content of Sn using the internal oxidation of the present invention has the following effects.
10%이상의 고함량의 Sn을 함유한 전기접점제를 내부산화를 이용하여 제조함으로써, 양질의 전기접점제를 제조할 수 있다.By producing an electrical contact agent containing a high content of Sn of 10% or more by internal oxidation, a good electrical contact agent can be produced.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100921704B1 (en) * | 2007-10-31 | 2009-10-15 | 유창금속공업(주) | A manufacturing method of the planer electric contact |
CN110947977A (en) * | 2019-11-22 | 2020-04-03 | 江苏博迁新材料股份有限公司 | Production method of submicron AgSnTe alloy powder |
KR20220132251A (en) | 2021-03-23 | 2022-09-30 | 엘에스일렉트릭(주) | Electrical contact composites and Manufacturing method thereof |
-
1998
- 1998-10-20 KR KR1019980044023A patent/KR20000026488A/en not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100921704B1 (en) * | 2007-10-31 | 2009-10-15 | 유창금속공업(주) | A manufacturing method of the planer electric contact |
CN110947977A (en) * | 2019-11-22 | 2020-04-03 | 江苏博迁新材料股份有限公司 | Production method of submicron AgSnTe alloy powder |
KR20220132251A (en) | 2021-03-23 | 2022-09-30 | 엘에스일렉트릭(주) | Electrical contact composites and Manufacturing method thereof |
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