200427848 玖、發明說明： 【發明所屬之技術領域】 本發明係關於用於各種電氣開關、接觸器、斷路器等之 接觸可靠性、耐溶劑性及耐電弧耗損性皆優異之銀-氧化物 系電接點材料及其製造方法。 【先前技術】 電接點材料，有各種材料被使用著，其中，尤以銀一氧 化編（A g - C d 0 )系，由於在作為電接點材料所要求之耐熔著 性、耐電弧耗損性、低接觸電阻等之諸電氣特性方面皆優 異，故於各方面有廣泛的需要，長年來，材料的改良也不 斷進行著，學術研究亦多，可說是對於此系的材料，於製 造技術上可謂是已達到極限之狀態。 然而，近來，如眾所周知者，鎘（C d )，如同在各國的排 放基準之規定或歐洲共同體（EC)的廢家電（WEEE)法令等可 查知者，其係朝向廢止使用的方向進展著。 在此種情況下，具備可代替銀一氧化鎘系電接點材料之 諸項優異電氣特性的不含鎘之接點材料受到殷切的期盼。 因此，銀-(錫、銦、銻）係内部氧化接點材料，作為具備 諸特性之中負荷接點一路被開發過來，然而，最近的機器 之小型化的速度非常快速，尤其是對於接點之特性的要求 已日益嚴苛。 【發明内容】 (發明所欲解決之課題） 經由對銀（A g )添加錫（S η )、銦（I η )、錄（S b )、M ( B i )等 6 3 26\總檔\91 \9 111 9543\TF93 8011 (分割) 200427848 所成之合金施行内部氧化處理，雖可得到氧化物為分散析 出之内部構造，惟，就接點的製造條件、内部氧化條件、 接點特性評價試驗後的損耗狀況加以研究之結果，發現： 於接點製作時，形成於表面之銀富有層與其正下方之氧化 物凝縮層，於接點開閉時會招致熔著及接點溫度上昇等之 不良結果。 因此，本發明之目的在於，解決鎘的使用廢止問題，且 具有可與銀-氧化鎘系電接點材料相匹敵的特性，抑制銀 -(錫、銦、鉛）系的不含鎘接點材料之内部氧化處理時特有 之銀富有層與其正下方之氧化物凝集層的生成，並解決添 加元素氧化物粒子的濃度分布的不均一及粒子的粗大化以 及其凝集等之諸問題之解決。 (解決課題之手段） 本發明者，就内部氧化機構之溫度·氧氣壓·添加元素 之影響氧化組織的變化之諸要因加以分析，並就製造條件 擴大分析範圍做了檢討。並就鎘以外的各種元素對於氧化 物之接點特性所關聯之作用進行再檢討，電接點的表面之 清淨作用及對電弧之諸現象（例如添加之氧化物的特性，尤 其是其蒸汽壓的溫度特性及銀中的分散狀態與開閉時所發 生之電弧中的消弧作用現象）之間的關係加以解析，藉此， 於耐熔著性、耐電弧耗損性、低接觸電阻等之諸電氣特性 方面，含有能與銀-氧化鎘系電接點材料相匹敵之添加元素 及複合氧化物其氧化物在銀中的分散狀態之最適的關係得 以確認得知。 7 326V總檔\91\91119543VTF938011(分割) 200427848 在如此的確認之基礎上，著眼於約1 5 0 0〜4j〇 0 0 °C的 圍中較氧化鎘有高的蒸汽壓之毒性小之錫氧化物及 物，確認得知其等可發揮與氧化鎘系同等以上的接 清淨化作用。200427848 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a silver-oxide system having excellent contact reliability, solvent resistance, and arc wear resistance for various electrical switches, contactors, circuit breakers, etc. Electric contact material and manufacturing method thereof. [Prior art] Various materials have been used for electrical contact materials. Among them, silver monoxide (Ag-C d 0) series is used because of the resistance to fusion and resistance required as electrical contact materials. The electrical properties such as arc depletion and low contact resistance are excellent, so there is a wide range of needs in all aspects. Over the years, materials have been continuously improved, and there have been many academic studies. It can be said that for this series of materials, It can be said that it has reached the limit in terms of manufacturing technology. However, recently, as it is well known, cadmium (C d), as can be found in the emission standards of various countries or the European Community (EC) Waste Electrical Appliances (WEEE) Act, can be identified, which is progressing towards the abolition of use. . Under such circumstances, cadmium-free contact materials having excellent electrical properties that can replace silver cadmium oxide-based electrical contact materials have been eagerly expected. Therefore, silver- (tin, indium, antimony) based internal oxidation contact materials have been developed all the way as load contacts with various characteristics. However, the recent miniaturization of machines has been extremely rapid, especially for contacts. The requirements for its characteristics have become increasingly stringent. [Summary of the Invention] (Problems to be Solved by the Invention) By adding tin (S η), indium (I η), (S b), M (B i), etc. to silver (A g) 6 3 26 \ \ 91 \ 9 111 9543 \ TF93 8011 (split) 200427848 The alloy formed is subjected to internal oxidation treatment. Although the internal structure of the oxide is dispersed and precipitated, the manufacturing conditions, internal oxidation conditions, and contact characteristics of the contacts are obtained. As a result of the evaluation of the loss after the test, it was found that, during the production of the contact, the silver-rich layer formed on the surface and the oxide condensation layer directly below it would cause fusion and increase in temperature of the contact when the contact was opened and closed. Bad results. Therefore, the purpose of the present invention is to solve the problem of the abolition of cadmium, and have characteristics comparable to silver-cadmium oxide-based electrical contact materials, and to suppress silver- (tin, indium, lead) -based cadmium-free contacts. During the internal oxidation treatment of the material, the formation of a unique silver-rich layer and the oxide agglomeration layer directly below it, and solved the problems of uneven concentration distribution of the element oxide particles, coarsening of the particles, and its agglomeration. (Means for Solving the Problems) The present inventor analyzed the factors that influence the temperature of the internal oxidation mechanism, the oxygen pressure, and the added elements to influence the change of the oxidized structure, and reviewed the manufacturing conditions and expanded the analysis range. And review the effects of various elements other than cadmium on the contact characteristics of the oxide, the cleaning effect of the surface of the electrical contact and the phenomena of the arc (such as the characteristics of the added oxide, especially its vapor pressure It analyzes the relationship between the temperature characteristics and the state of dispersion in silver and the arc extinguishing effect in the arc that occurs during opening and closing, and thus, it can be used for various properties such as resistance to welding, arc loss, and low contact resistance. In terms of electrical characteristics, the optimum relationship between the dispersed state of silver and cadmium oxide-based electrical contact materials and the complex oxide in silver was confirmed. 7 326V total file \ 91 \ 91119543VTF938011 (divided) 200427848 Based on such confirmation, the focus is on tin with a lower vapor pressure than cadmium oxide in the range of about 1 500 0 ~ 4j 0 0 ° C, which is less toxic than tin. It has been confirmed that the oxides and substances can perform a cleaning and purifying effect equal to or higher than that of a cadmium oxide system.
再者，亦可確認得知，藉由使錫以外的添加元素 自的複合氧化物使其分散於銀中，可發揮此等之相I 因此，本發明乃基於上述確認之内容而完成者， 由對錫氧化物，於約5 0 0〜4 0 0 0 °C的溫度範圍下，使 鎘蒸汽壓低的銦之氧化物分散於其中，藉此，使此 複合氧化物形態的組合之合成蒸汽壓的行為更加近 化鎘之行為，可使其相乘作用發揮優異的接點特性 作為抑制導致接點的接觸可靠性不安定之接點最表 富有層之生成的手段，係在銀中之由錫1〜5重量％、 重量％、及鐵、鎳、鈷中之1種或2種0 . 0 5〜1重量％、 銀所構成之合金，使其進行内部氧化，且於内部組 添加元素之錫·銦複合氧化物與鐵、鎳、姑中之1涛 的氧化物，係均一且微細地分散析出，是其特徵。 還有，本發明之又一實施形態，係對錫、鉍氧化 約5 0 0〜4 0 0 0 °C的溫度範圍下，使較氧化鎘蒸汽壓低 氧化物分散於其中，藉此，使此等金屬複合氧化物 組合之合成蒸汽壓的行為更加近似於氧化鎘之行為 其相乘作用發揮優異的接點特性，又，作為抑制導 的接觸可靠性不安定之接點最表面的銀富有層之生 段，係在銀中之由錫1〜5重量％、銦3〜1 0重量％、鉍（ 326\總檔\91 \91119543VTF93 8011 (分割) 8 溫度範 銻氧化 點用面 以其各 I效果。 其係藉 較氧化 等金屬 似於氧 ，又 ， 面的銀 钢3〜1 0 其餘為 織中， I或2種 物，於 的銦之 形態的 ，可使 致接點 成的手 .05 〜2 200427848 重量％、及鐵、鎳、鈷中之1種或2種0.05〜1重量％、其餘為 銀所構成之合金，使其進行内部氧化，且於内部組織中， 添加元素之錫·銦複合氧化物、銦·絲複合氧化物、錫· 鉍複合氧化物、及錫·銦·鉍複合氧化物，與鐵、鎳、鈷 中之1種或2種的氧化物，係均一且微細地分散析出，是其 特徵。 還有，本發明之又另一實施形態，係對錫、銻氧化物， 於約5 0 0〜4 0 0 0 °C的溫度範圍下，使較氧化鎘蒸汽壓低的銦 之氧化物分散於其中，藉此，使此等金屬複合氧化物形態 的組合之合成蒸汽壓的行為更加近似於氧化鎘之行為，可 使其相乘作用發揮優異的接點特性，又，作為抑制導致接 點的接觸可靠性不安定之接點最表面的銀富有層之生成的 手段，係在銀中之由錫1〜5重量％、銦3〜1 0重量％、銻0. 0 5〜2 重量％、及鐵、鎳、鈷中之1種或2種0 . 0 5〜1重量％、其餘為 銀所構成之合金，使其進行内部氧化，且於内部組織中， 添加元素之錫·銦複合氧化物、銦·銻複合氧化物、錫· 銻複合氧化物、及錫·銦·銻複合氧化物，與鐵、鎳、鈷 中之1種或2種的氧化物，係均一且微細地分散析出，是其 特徵。 還有，本發明之一又另一實施形態，係對錫、絲、録氧 化物，於約5 0 0〜4 0 0 0 °C的溫度範圍下，使較氧化鎘蒸汽壓 低的銦之氧化物分散於其中，藉此，使此等金屬複合氧化 物形態的組合之合成蒸汽壓的行為更加近似於氧化鎘之行 為，可使其相乘作用發揮優異的接點特性，又，作為抑制 9 326\總檔\91 \91119543VTF93 8011 (分割) 200427848 導致接點的接觸可靠性不安定之接點最表面的銀富有 生成的手段，係在銀中之由錫1〜5重量％、銦3〜1 0重量％ 0 . 0 5〜2重量％、銻0 · 0 5〜5重量％，及鐵、鎳、鈷中之1潜 種0 . 0 5〜1重量％、其餘為銀所構成之合金，使其進行内 化，且於内部組織中，添加元素之錫·銦複合氧化物、 鉍複合氧化物、錫·鉍複合氧化物、錫、銻複合氧化 銦·銻複合氧化物及錫·銦·鉍·銻複合氧化物，與 鎳、鈷中之1種或2種的氧化物，係均一且微細地分散析 是其特徵。 如上述般，於銀中，固溶有錫、銦、及鐵、錄、始中 種或2種，以及必要時所須之鉍與銻之1種以上之合金 其以加工率5 0〜9 5 %的條件下製作成所要的接點形狀， 壓下以純氧置換後，在氧氣壓5kg/cm2〜50kg/cm2的氧ΐ 中，自2 0 0 °C昇溫以7 0 0 °C為上限之溫度作為内部氧化 度，藉此，於使用習用的製程中之因於内部氧化之進 發生之銀富有層及其正下方之氧化物凝集層之生成可 抑制，且，藉由上述的高加工率之加強加工，可提高 轉位密度，藉由使其產生多數的結晶及氧化物粒子生 核之相互作用，可使添加元素的複合氧化物均一且微 分散析出，藉此，可作成对炫著性、对電弧耗損性、 觸電阻等之諸電氣特性方面皆優異之不含鎘之電接點 料。 又，於上述中，將加工率的上限定為9 5 %之理由在於 過此限度之加工，於材料的加工性有其界限，又未滿 326V總檔\91 \91119543VTF93 8011 (分割) 10 層之 、银 [或2 部氧 銦· 物、 鐵、 出， r之1 ，將 於常 歡境 溫 行所 付以 内部 成的 細地 低接 材 ，超 5 0% 200427848 的加工，會無法充分達到賴以充分發揮效果之加工變形。 又，於常溫下置換成純氧，將氧氣壓定為 5kg/cm2〜50kg/cm2之理由在於，藉由置換，可將内部氧化 爐中的非氧化性氣體（即空氣中的氮與氫）除去，並且提高 爐内的氧化環境，於氧氣壓未滿5 k g / c m2下，則添加元素的 複合氧化物不易均一且微細地分散析出到材料内部之深層 處，而若高於5 0 k g / c m2，則爐體設備須作成甚龐大，無法 得到與製造成本之增加之相稱的特性上之改進效果。 再者，於加壓氧環境中，自2 0 0 °C昇溫以7 0 0 °C為上限之 溫度作為内部氧化溫度之理由在於，2 0 0 °C為内部氧化溫度 的下限，而7 0 0 °C以上，則於内部氧化中，自材料表面之溶 質元素的擴散速度會較氧的擴散速度大，會在組織表層分 散析出強固的凝集物，而妨礙到其後的内部氧化之進行。 又，據推測，於昇溫前，經加壓的氧之供給有延遲，則 與上述同樣地，於氧的擴散不充分的狀態下溶質元素即開 始擴散，氧的供給延遲致發生在組織表層之氧化物生成反 應，故會於最表層堆積成銀富有層。 再者，對於銀之錫的成分範圍的上限定為5重量％的理由 在於，超過此範圍之添加，無法使該氧化物微細地析出， 在氧化組織内部分散析出層狀的強固的凝集，使得其後的 内部氧化之進行變得困難，致引起氧化後的組織之嚴重的 脆化之故。又，未滿1重量％之添加時，則無法充分達成與 多元素之複合氧化，無法得到對於諸電氣特性之充分的添 加效果。 11 326\總檔\91 \91119543VTF93 8011 (分割) 200427848 其次，將銦的成分範圍的上限定為l 〇重量％之理由在於 此範圍以上的添加，在與其他元素之組合下，於内部氧 時會於表面分散析出緻密的氧化膜，致氧難以自表面進 之故。若未滿3重量％，則無法發揮作為較上述氧化鎘低 蒸汽壓的效果，即抑制因於電弧之揮發損耗之效果。 再者，將鉍的成分範圍的上限定為2重量％的理由在於 於超過此範圍之添加量的情況，會引起熱脆性，由於要 成本發明之要素之氧化物的微細化之緣故，欲將合金以 工率5 0 %〜9 5 %製作會變得困難，而且，於内部氧化時，會 氧化物.的顯著的凝集發生，致使其後的内部氧化之進行 得困難。若未滿0 . 0 5重量％，則無法顯現使複合氧化物粒 微細地分散之效果。 又，將銻的成分範圍的上限定為5重量％之理由在於， 範圍以上的添加，於内部氧化時會於表面分散析出緻密 氧化皮膜，致氧難以自表面進入之故。若未滿0 · 0 5重量9 則無法發揮作為較氧化鎘高的蒸汽壓的效果之接點用面 淨作用。 再者，鐵、鎳、鈷中之1種或2種之添加，主要用以發 使結晶之結晶粒微細化及氧化物粒子大小的均一化之效 果，此時，以1重量％作為上限的理由在於，即使超過此 圍添加，欲經由熔融法使其合金化是極為困難的，若未 0 . 0 5重量％，則無法發揮結晶粒微細化等之效果。 【實施方式】 以下，就本發明之實施形態例加以說明。 326\總檔\91 \91119543VTF93 8011 (分割) 12 化 入 的 達 加 使 變 子 此 的 /〇， 清 揮 範 滿 200427848 以具有9 9 . 5重量％以上的純度之錫、銦、鉍、銻，及鐵、 鎳、鈷中之1種或2種作為原料，以下述的程序製作表1所示 之組成的合金。 用高頻誘導熔解爐，將經熔解、鑄造之合金塊進行熱軋 後，於其一面上，以銀板進行熱壓合，形成焊接用之銀層。 接著，將該素材，以表1所示之實施形態例1〜9之各加工 率進行冷軋作成厚度2mm的板之後，衝壓成直徑6mm的圓盤 狀。 此試料，於實施形態例1中，係在氧氣壓5 0 k g / c m2的氧環 境中昇溫至2 0 0 °C〜6 0 0 °C ，使其進行内部氧化。 於實施形態例2中，係在氧氣壓3 0 k g / c m2的氧環境中昇溫 至2 0 0 °C〜6 3 0 °C ，使其進行内部氧化。 於實施形態例3中，係在氧氣壓5 k g / c m2的氧環境中昇溫 至2 0 0 °C〜5 5 0 °C ，使其進行内部氧化。 於實施形態例4中，係在氧氣壓5 0 k g / c m2的氧環境中昇溫 至2 0 0 °C〜7 0 0 °C ，使其進行内部氧化。 於實施形態例5中，係在氧氣壓5kg/cm2的氧環境中昇溫 至2 0 0 °C〜6 7 0 °C ，使其進行内部氧化。 於實施形態例6中，係在氧氣壓2 0 k g / c m2的氧環境中昇溫 至2 0 0 °C〜6 5 0 °C ，使其進行内部氧化。 於實施形態例7中，係在氧氣壓1 0 k g / c m2的氧環境中昇溫 至2 0 0 °C〜6 0 0 °C ，使其進行内部氧化。 於實施形態例8中，係在氧氣壓8kg/cm2的氧環境中昇溫 至2 0 0 °C〜6 8 0 °C ，使其進行内部氧化。 13 326V總檔\91\91119543VTF93 8011 (分割) 200427848 於實施形態例9中，係在氧氣壓4 0 k g / c m2的氧環境中昇溫 至2 Ο 0 °C〜4 5 0 °C ，使其進行内部氧化。 作為用以比較的習知例，作成之習知例1為銀-1 2重量％ 鎘，習知例2為銀-6重量％錫-3重量％銦，習知例3為銀-7重 量％銦的合金，分別以5 0 %以下的加工率作成同樣的形狀之 後，在氧氣壓3kg/cm2的氧化環境中固定於780 °C之溫度 下，作成經内部氧化者。接點試驗，係以施行接觸電阻與 熔合試驗機（6 Ο A定值用）及市售接觸器之實機測試 (A C 2 Ο Ο V，2 0 A )，就其電氣特性作評價。 表1 試料 組成（重量°/〇) 加工率(％) 接觸電阻ΟηΩ) 熔合次數(次） 電弧消耗量(mg) 編號 開閉前 ΙΟ4開閉後 60Α，104次開閉 103開閉後 習 1 Ag-12Cd 34 0.52 0.80 10 35 〜51 知 2 Ag-6Sn-3In 30 0.55 0.98 2 30 〜46 例 3 Ag-7In 35 0.48 0.77 19 59 〜72 1 Ag-1. 2Sn-9.8In-0. IBi-0.2Ni 87 0.53 0.71 0 22 〜27 2 Ag-5Sn-5In~0.8Bi-0. 9Co 52 0.56 0.72 1 23 〜30 實 3 Ag-lSn-10In-0. 07Sb-0.3Fe 70 0.55 0.70 0 18〜25 施 4 Ag-3Sn-3.2In-l.9Bi-0.8Ni 89 0.49 0.67 0 21-28 形 5 Ag-4Sn-3In-lBi-0. 5Ni-0. 5Co 76 0.51 0.69 1 27 〜33 態 6 Ag-2Sn-7In-0.5Sb-0.1Co 67 0.48 0.68 0 24 〜30 例 7 Ag-3Sn-4In-0.3Bi-5Sb-0.05Ni 63 0. 56 0.70 0 17 〜24 8 Ag-5Sn-10In-2Bi~0. 8Sb-lFe 95 0.50 0.74 0 20 〜26 9 Ag-2Sn-6In-0.05Bi-lSb-0.lNi 73 0.48 0.68 1 25 〜33 14 326\總檔\91\91119543VTF938011(分割) 200427848 (發明之效果） 依據上述所詳細說明之本發明，顯示出，於耐熔著性、 耐電弧耗損性、低接觸電阻等之諸電氣特性方面皆優異， 而且，於圖1中所示之實施形態例4所顯示之氧化組織與圖2 中所示之習知例1之氧化組織中所可見到般，由氧化物粒子 及結晶粒徑的觀點來看，亦顯示出理想的效果。 又，於最表面可見到之銀富有層的除去方面，亦有優異 的效果。Furthermore, it can also be confirmed that such a phase I can be exhibited by dispersing a composite oxide of an additive element other than tin in silver, so that the present invention was completed based on the content of the above confirmation, The indium oxide with low cadmium vapor pressure is dispersed in the tin oxide at a temperature range of about 500 to 4 0 ° C, thereby making the composite steam in the form of a composite steam The behavior of pressing is closer to the behavior of cadmium, which can make its multiplicative effect exhibit excellent contact characteristics. As a means to suppress the formation of the richest layer of the contact, which causes the contact reliability of the contact to be unstable. An alloy composed of 1 to 5% by weight of tin, 5% by weight, and one or two of iron, nickel, and cobalt, 0.5 to 5% by weight, and silver, which are internally oxidized, and added to the internal group The elemental tin-indium composite oxide and the oxides of iron, nickel, and Zhongtao are characterized by uniform and fine dispersion and precipitation. Also, according to another embodiment of the present invention, tin and bismuth are oxidized at a temperature range of about 500 to 400 ° C, and oxides are dispersed therein with a lower vapor pressure than cadmium oxide. The composite vapor pressure behavior of the combination of equal metal composite oxides is more similar to the behavior of cadmium oxide. Its multiplicative effect exhibits excellent contact characteristics, and it is the silver-rich layer on the top surface of the contact that suppresses unstable contact reliability. The life section is made of silver 1 ~ 5% by weight of tin, 3 ~ 10% by weight of indium, bismuth (326 \ total file \ 91 \ 91119543VTF93 8011 (divided) 8 temperature range antimony oxidation point surface with each The effect of I. It is similar to oxygen by oxidizing and other metals, and the surface of silver steel 3 ~ 10. The rest is weaving, I or 2 kinds of indium, which can make the contact point into a hand. .05 to 2 200427848 wt%, and one or two of iron, nickel, and cobalt 0.05 to 1 wt%, and the rest are made of silver, and the alloy is internally oxidized, and the element is added to the internal structure Tin · indium composite oxide, indium · wire composite oxide, tin · bismuth composite oxide, The characteristics of tin, indium, and bismuth composite oxides are that they are uniformly and finely dispersed and precipitated with one or two oxides of iron, nickel, and cobalt. In still another embodiment of the present invention, For tin and antimony oxide, disperse the oxide of indium with a vapor pressure lower than that of cadmium oxide in a temperature range of about 500 ~ 400 0 ° C, thereby making these metal composite oxides The combined vapor pressure behavior of the combination of forms is more similar to the behavior of cadmium oxide, which can make its multiplication effect exhibit excellent contact characteristics, and it is the silver on the outermost surface of the contact that suppresses the unstable contact reliability of the contact. The means for forming the rich layer are 1 to 5 wt% of tin, 3 to 10 wt% of indium, 0.5 to 2 wt% of antimony, and one or 2 of iron, nickel, and cobalt in silver. 0.5 to 1% by weight of the alloy, the rest of which is made of silver, is internally oxidized, and an elemental tin-indium composite oxide, indium-antimony composite oxide, and tin-antimony are added to the internal structure. Composite oxides, and tin · in · antimony composite oxides with one or two of iron, nickel, and cobalt The oxide is characterized by uniformly and finely dispersed and precipitated. In addition, another embodiment of the present invention is for tin, wire, and oxide, at about 5 0 ~ 4 0 0 ° C In the temperature range, the oxide of indium having a vapor pressure lower than that of cadmium oxide is dispersed therein, so that the behavior of the combined vapor pressure of these metal composite oxide forms is more similar to that of cadmium oxide, which can make it The multiplying effect exhibits excellent contact characteristics, and it is a means to suppress the formation of silver on the surface of the contact, which is 9 326 \ total file \ 91 \ 91119543VTF93 8011 (split) 200427848. Among silver, 1 to 5 wt% of tin, 3 to 10 wt% of indium, 0.5 to 2 wt%, 0.5 to 5 wt% of antimony, and 1 latent species of iron, nickel, and cobalt. 0.5 ~ 1% by weight, the rest is made of an alloy made of silver, and internal elements are added with tin-indium composite oxide, bismuth composite oxide, tin-bismuth composite oxide, Tin and antimony composite indium oxide · antimony composite oxide and tin · in · bismuth · antimony composite oxide , Nickel, cobalt, one or two kinds of oxides, uniformly and finely dispersed system is further analysis. As mentioned above, in silver, tin, indium, and iron, aluminum, aluminum, or two kinds are solid-solved, and if necessary, one or more alloys of bismuth and antimony are processed at a processing rate of 50 to 9 The desired contact shape is made under the conditions of 5%, and after replacement with pure oxygen, the temperature is increased from 20 ° C to 70 ° C in an oxygen pressure of 5 kg / cm2 to 50 kg / cm2. The temperature is used as the internal oxidation degree, thereby suppressing the formation of the silver-rich layer and the oxide agglomerate layer directly underneath the internal oxidation in the conventional manufacturing process, and by the above-mentioned high processing The enhanced processing rate can increase the translocation density. By making it produce a large number of crystals and the interaction of nucleation of oxide particles, the compound oxide with added elements can be uniformly and finely dispersed and precipitated, thereby making it possible to make a pair Cadmium-free electrical contact materials that are excellent in electrical properties such as adhesion, arc loss, and contact resistance. In the above, the reason why the upper limit of the processing rate is 95% is because of the processing beyond this limit, and there is a limit on the processability of the material, and it is less than the total 326V file \ 91 \ 91119543VTF93 8011 (divided) 10 layers Zhi, silver [or 2 indium oxides, iron, iron, iron, and 1 of r, will be a fine, low-profile material made by Changhuanjing Wenxing in-house, exceeding 50% of the processing of 200427848, will not be sufficient To achieve processing deformation on which full effect is achieved. In addition, the reason for replacing with pure oxygen at normal temperature and setting the oxygen pressure to 5 kg / cm2 to 50 kg / cm2 is that the non-oxidizing gas in the internal oxidation furnace (ie, nitrogen and hydrogen in the air) can be replaced by replacement. It is removed and the oxidation environment in the furnace is improved. If the oxygen pressure is less than 5 kg / c m2, the compound oxide of the added element is not easy to be uniformly and finely dispersed and precipitated into the deep layer inside the material, and if it is higher than 50 kg / c m2, the furnace body equipment must be made very large, and the improvement effect on the characteristics commensurate with the increase in manufacturing cost cannot be obtained. Furthermore, in a pressurized oxygen environment, the reason why the temperature rises from 200 ° C with an upper limit of 700 ° C as the internal oxidation temperature is that 200 ° C is the lower limit of the internal oxidation temperature, and 70 Above 0 ° C, during internal oxidation, the diffusion rate of solute elements from the surface of the material will be greater than that of oxygen, and strong aggregates will be dispersed and precipitated on the surface of the tissue, which hinders the subsequent internal oxidation. In addition, it is presumed that the supply of pressurized oxygen is delayed before the temperature is raised. As described above, the solute element starts to diffuse in a state where the diffusion of oxygen is insufficient, and the delayed supply of oxygen occurs in the surface layer of the tissue. Oxide formation reaction, so the silver-rich layer will be deposited on the outermost layer. The reason why the upper limit of the composition range of silver tin is 5% by weight is that addition beyond this range does not allow fine precipitation of the oxide and disperses and deposits layered strong agglomeration in the oxidized structure, so that Subsequent internal oxidation becomes difficult to cause severe embrittlement of the oxidized structure. In addition, when the content is less than 1% by weight, the composite oxidation with a plurality of elements cannot be sufficiently achieved, and a sufficient additive effect for various electrical characteristics cannot be obtained. 11 326 \ Total file \ 91 \ 91119543VTF93 8011 (divided) 200427848 Secondly, the reason for limiting the upper limit of the composition range of indium to 10% by weight is due to the addition above this range, in combination with other elements, when the internal oxygen It will disperse and deposit a dense oxide film on the surface, which makes it difficult for oxygen to enter from the surface. If it is less than 3% by weight, the effect of lowering the vapor pressure than the above-mentioned cadmium oxide, that is, the effect of suppressing volatilization loss due to an arc, cannot be exhibited. The reason why the upper limit of the composition range of bismuth is 2% by weight is that the addition of an amount exceeding this range may cause hot brittleness. Because of miniaturization of the oxide of the element of the invention, it is desired to It is difficult to produce the alloy at a working rate of 50% to 95%, and during internal oxidation, significant agglomeration of oxides occurs, making it difficult to perform internal oxidation thereafter. If it is less than 0.05% by weight, the effect of finely dispersing the composite oxide particles cannot be exhibited. The reason why the upper limit of the antimony component range is 5% by weight is that the addition of the above range may cause a dense oxide film to be dispersed and precipitated on the surface during internal oxidation, and it is difficult for oxygen to enter from the surface. If the weight is less than 0 · 0 5 and 9 weight, the surface effect of the contact as a vapor pressure effect higher than that of cadmium oxide cannot be exhibited. In addition, the addition of one or two of iron, nickel, and cobalt is mainly used for the effect of miniaturizing crystal grains and uniformizing the size of oxide particles. At this time, the upper limit is 1% by weight. The reason is that even if it is added beyond this range, it is extremely difficult to alloy it by a melting method. If it is less than 0.05% by weight, effects such as miniaturization of crystal grains cannot be exhibited. [Embodiment] An embodiment of the present invention will be described below. 326 \ Total file \ 91 \ 91119543VTF93 8011 (divided) 12 of the Daga made by the //, Qing Man Fan 200427848 to have tin, indium, bismuth, antimony with a purity of 99.5 wt% or more And one or two of iron, nickel, and cobalt as raw materials, and an alloy having the composition shown in Table 1 was prepared by the following procedure. In a high-frequency induction melting furnace, the melted and cast alloy block is hot-rolled, and a silver plate is hot-pressed on one side to form a silver layer for welding. Next, the material was cold-rolled into a plate having a thickness of 2 mm at each processing rate of Embodiment Examples 1 to 9 shown in Table 1, and then punched into a disc shape having a diameter of 6 mm. This sample was heated to 200 ° C to 60 ° C in an oxygen environment with an oxygen pressure of 50 kg / cm2 in Embodiment 1 to perform internal oxidation. In Embodiment 2, the temperature was raised to 200 ° C to 63 ° C in an oxygen environment with an oxygen pressure of 30 kg / cm2, and internal oxidation was performed. In the embodiment 3, the temperature was raised to 200 ° C to 55 ° C in an oxygen environment with an oxygen pressure of 5 kg / cm2, and internal oxidation was performed. In Embodiment 4, the temperature was raised to 200 ° C to 700 ° C in an oxygen environment with an oxygen pressure of 50 kg / cm2, and internal oxidation was performed. In Example 5, the temperature was raised to 200 ° C to 67 ° C in an oxygen environment with an oxygen pressure of 5 kg / cm2, and internal oxidation was performed. In Embodiment 6, the temperature was raised to 200 ° C to 65 ° C in an oxygen environment with an oxygen pressure of 20 kg / cm2, and internal oxidation was performed. In Embodiment 7, the temperature was raised to 200 ° C to 600 ° C in an oxygen environment with an oxygen pressure of 10 kg / cm2, and internal oxidation was performed. In Embodiment 8, the temperature was raised to 200 ° C to 680 ° C in an oxygen environment with an oxygen pressure of 8 kg / cm2, and internal oxidation was performed. 13 326V total file \ 91 \ 91119543VTF93 8011 (divided) 200427848 In Embodiment 9, the temperature was raised to 2 0 0 ° C ~ 4 5 0 ° C in an oxygen environment with an oxygen pressure of 40 kg / c m2. Internal oxidation is performed. As a conventional example for comparison, the prepared conventional example 1 is silver-12% by weight cadmium, the conventional example 2 is silver-6% by weight tin-3% by weight indium, and the conventional example 3 is silver-7 weight % Indium alloys were made into the same shape at a processing rate of 50% or less, and then fixed at a temperature of 780 ° C in an oxidizing environment with an oxygen pressure of 3 kg / cm2 to form internally oxidized ones. The contact test is based on the contact resistance and fusion tester (for a fixed value of 〇 A) and the actual test of a commercially available contactor (A C 2 〇 0 V, 20 A) to evaluate its electrical characteristics. Table 1 Sample composition (weight ° / 〇) Processing rate (%) Contact resistance 〇ηΩ) Number of fusions (times) Arc consumption (mg) Number before opening and closing 10 104 after opening and closing 60A, 104 opening and closing 103 After opening and closing 1 Ag-12Cd 34 0.52 0.80 10 35 to 51 2 Ag-6Sn-3In 30 0.55 0.98 2 30 to 46 Example 3 Ag-7In 35 0.48 0.77 19 59 to 72 1 Ag-1. 2Sn-9.8In-0. IBi-0.2Ni 87 0.53 0.71 0 22 ～ 27 2 Ag-5Sn-5In ~ 0.8Bi-0. 9Co 52 0.56 0.72 1 23 ～ 30 solid 3 Ag-lSn-10In-0. 07Sb-0.3Fe 70 0.55 0.70 0 18 ~ 25 Shi 4 Ag- 3Sn-3.2In-l.9Bi-0.8Ni 89 0.49 0.67 0 21-28 Shape 5 Ag-4Sn-3In-lBi-0. 5Ni-0. 5Co 76 0.51 0.69 1 27 to 33 State 6 Ag-2Sn-7In- 0.5Sb-0.1Co 67 0.48 0.68 0 24 ～ 30 Example 7 Ag-3Sn-4In-0.3Bi-5Sb-0.05Ni 63 0. 56 0.70 0 17 ～ 24 8 Ag-5Sn-10In-2Bi ~ 0. 8Sb-lFe 95 0.50 0.74 0 20 to 26 9 Ag-2Sn-6In-0.05Bi-lSb-0.lNi 73 0.48 0.68 1 25 to 33 14 326 \ Total file \ 91 \ 91119543VTF938011 (division) 200427848 (Effect of the invention) According to the above The present invention described in detail shows electrical characteristics such as resistance to welding, resistance to arc wear, and low contact resistance. Both of them are excellent in terms of properties, and the oxidized structure shown in Embodiment Example 4 shown in FIG. 1 and the oxidized structure of Conventional Example 1 shown in FIG. 2 can be seen from oxide particles and crystal particles. From the perspective of trails, it also shows ideal results. In addition, it has an excellent effect in removing the silver-rich layer that can be seen on the outermost surface.
【圖式簡單說明】 圖1為實施形態例4之内部組織的顯微鏡照相。 圖2為習知例1之内部組織的顯微鏡照相。[Brief Description of the Drawings] FIG. 1 is a microscope photograph of the internal structure of Example 4. FIG. 2 is a photomicrograph of the internal tissue of Conventional Example 1. FIG.
15 326\總檔\91 \9 111 9543VTF93 8011 (分割)15 326 \ total file \ 91 \ 9 111 9543VTF93 8011 (split)