201231682 六、發明說明： 【發明所屬之技術領域】 本發明係關於銀-氧化物系電接點材料之製造方法及由其 所得之電接點材料。 【先前技術】 習知’作為電接點材料之製造方法，有如下述後氧化法的 製造其係齡解料作作為細的合金，騎軋製加 工、壓製加I等而加工為接點形狀後，進行内部氧化處理。 另外，有如下述預備氧化法的製造方法，其係藉熔解法製 作作為素材的合金，加I為板材等後，藉磨切等而製造細 片，對細片進行内部氧化處理後，進行壓縮成形為既定形 狀將、’’二壓縮成形之材料藉擠出加工而加工為線材或板材 後’再加工為接點形狀(例如參照專利文獻1)。 另外，有如下述利用粉末燒結法之製造方法，其係將金屬 粉末壓縮成形為既定形狀後，進行燒結，於軋製加工後加工 成為接點形狀(例如參照專利文獻2)。 (專利文獻1)日本專利特開平7-258769號公報 (專利文獻2)日本專利特開平9-111364號公報 【發明内容】 (發明所欲解決之問題） 例如在欲使用含有Ag、Zn、Te、Cu、Sb之組成的合金製 造電接點的情況，含有Zn之銀合金的塑性加工性差，因此 100141777 201231682 難以進行接點製造中不<或缺的軋製加工等之加工，而難以 藉由屬於習知電接點製造方法的後氧化法或預備氧化法進 行製造。 另外，即使在可稍微進行塑性加工的情況，若於加工成接 點形狀後進行内部氧化處理，則因氧化膨脹而於結晶粒界發 生大量之細微破裂，故成為非常跪弱的狀態’難以直接使用 作為電接點。如此，含有Ζη之銀-氧化物系電接點材料，係 電接點製造中不可或缺的塑性加工性低，難以進行軋製加 工，故未實用化為電接點材料。 然而，若含有Ζη之銀合金能夠具備可實用作為電接點材 料的性能，則可使大量使用之接點材料的單價降低，可提供 適於大量生產的電接點讨料。 本發明即以解決此種問題作為課題。 (解決問題之手段） 因此，本發明為了製造含有Ζη之銀-氧化物系電接點材 料，著眼於由該組成而得之銀合金之特徵的低塑性加工性， 與於特定之内部氧化條件下於結晶粒界發生大量之細微破 裂而變得非常脆弱雜質。本發明係齡解法製作鎮 直接依鑄錠狀態騎㈣氧化處理，航使其於結晶粒界發 生大量細微破㈣作鱗常脆弱態，錢，藉由對轉旋 進行粉料理，㈣㈣氧化處理完紅銀合㈣細片或粉 末再將孩。金之細片或粉末壓縮成形為所需形狀，並: 100141777 5 201231682 燒結處理後’藉擠出加工料加玉成線材或板材之電接點材 料，而可加工成最終的接點形狀。 本發明係依氧分壓0.5〜5.0MPa、氧化溫度6〇〇〜9〇〇〇c進行 内部氧化處理。此係根據迄今為止的實驗，在内部氧化條: 以外’則内部氧化未進行’含有Zn^銀合金無法得到作為 内部氧化型接點所必要的性f，且無法使其於結晶粒界發生 大量細微破裂以成為非常脆弱的狀態，無法作成用於對材料 進行壓縮成形所必要的細片或粉末。 於此’針雜由本發明之内魏化處理而於結晶粒界發生 大量細微破裂的原因，表述藉實驗而明朗的要點。 習知，在對屬於電接點主流之Ag_Sn_In系材料進行内部 氧化處理時，雖然於材料内部生成氧化物時材料多少會發生 %/脹，但並未於結晶粒界發生大量細微破裂。 在對Ag-Sn-In系材料進行内部氧化處理時，為了消除因 從材料表面進行内部氧化所產生的銀合金中之如或“等之 濃度梯度，銀合金中之Sn或In會朝向材料表面擴散。此時， Sn或In之擴散速度較内部氧化時a由材料表面擴散出的 速度快，故於材料内部發生若干的氧化物凝集，產生氣化物 較多處與較少處。其中，氧化物濃度較低處係處於容易塑性 變形的狀態。在發生因内部氧化所伴隨之氧化物生成所造成 的膨脹時’該氧化物濃度較低且容易塑性變形處因叹收今膨 脹所造成的變形，故未發生細微破裂。 100141777 6 201231682 然而’在對本發明之含有Zn的銀緒料進行内部氧化處 理時’由於内部氧化時之Zn擴散速度較Sii或In慢，來自 料表面之〇2擴散速度較快，故銀合金巾之氧化物生成較 I*夬氧化物均勻地分散至整體，難以發生氧化物凝集。因此，201231682 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a silver-oxide-based electrical contact material and an electrical contact material obtained therefrom. [Prior Art] Conventionally, as a method of manufacturing an electrical contact material, a post-oxidation method is used to produce a system-age material as a fine alloy, which is processed into a contact shape by rolling, pressing, and the like. After that, internal oxidation treatment is performed. Further, there is a method for producing a preliminary oxidation method in which an alloy as a material is produced by a melting method, and after adding I as a plate material, a fine piece is produced by grinding or the like, and the fine piece is internally oxidized and then compressed. When it is formed into a predetermined shape, the material of the 'two-compression molding is processed into a wire or a sheet by extrusion processing, and is reprocessed into a contact shape (for example, see Patent Document 1). In addition, the production method of the powder sintering method is as follows. After the metal powder is compression-molded into a predetermined shape, it is sintered and processed into a contact shape after the rolling process (see, for example, Patent Document 2). (Patent Document 1) Japanese Patent Laid-Open No. Hei 9-258769 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei 9-111364 (Invention) The problem to be solved by the invention, for example, is to use Ag, Zn, Te. In the case of manufacturing an electrical contact with an alloy composed of Cu or Sb, the plastic workability of the silver alloy containing Zn is poor. Therefore, it is difficult to carry out the processing such as rolling processing in the joint manufacturing, and it is difficult to borrow. It is produced by a post-oxidation method or a preliminary oxidation method belonging to a conventional electric contact manufacturing method. In addition, even in the case where the plastic working can be performed slightly, if the internal oxidation treatment is performed after processing into a contact shape, a large amount of fine cracks occur at the crystal grain boundary due to oxidative expansion, so that it is in a very weak state. Used as an electrical contact. As described above, the silver-oxide-based electrical contact material containing Ζη is indispensable in the production of electrical contacts, and is difficult to be subjected to rolling processing, so that it has not been put into practical use as an electrical contact material. However, if the silver alloy containing Ζη can have practical performance as an electrical contact material, the unit price of the contact material which is used in a large amount can be lowered, and an electric contact which is suitable for mass production can be provided. The present invention has been made to solve such problems. (Means for Solving the Problem) Therefore, in order to produce a silver-oxide-based electrical contact material containing Ζη, the present invention focuses on the low plastic workability characteristic of the silver alloy obtained from the composition, and specific internal oxidation conditions. A large number of fine cracks occur at the grain boundary to become very fragile impurities. According to the invention, the town is directly oxidized according to the state of the ingot, and a large amount of fine breakage occurs in the grain boundary. (4) The scale is often fragile, and the money is processed by turning the powder, (4) (4) oxidation treatment Red silver (4) fine pieces or powder will be used again. The fine pieces or powder of gold are compression-molded into the desired shape, and: 100141777 5 201231682 After the sintering treatment, the extruded joint material and the electric contact material of the jade wire or sheet can be processed into the final joint shape. The present invention performs internal oxidation treatment according to an oxygen partial pressure of 0.5 to 5.0 MPa and an oxidation temperature of 6 Torr to 9 〇〇〇c. According to the experiments to date, in the case of internal oxide strips: "the internal oxidation is not carried out", the Zn-containing silver alloy is not required to obtain the property f necessary as an internal oxidation type contact, and it is impossible to cause a large amount of crystal grain boundaries. Finely broken to become a very fragile state, it is impossible to make a fine piece or powder necessary for compression molding of a material. Here, the reason why a large amount of fine cracking occurs at the crystal grain boundary by the internal Weihua treatment of the present invention is described. Conventionally, in the internal oxidation treatment of the Ag_Sn_In material which is the mainstream of the electric contact, although the material is somewhat % swollen when the oxide is formed inside the material, a large amount of fine cracking does not occur at the crystal grain boundary. In the internal oxidation treatment of the Ag-Sn-In material, in order to eliminate the concentration gradient in the silver alloy generated by internal oxidation from the surface of the material, Sn or In in the silver alloy faces the surface of the material. Diffusion. At this time, the diffusion speed of Sn or In is faster than the diffusion of a from the surface of the material during internal oxidation, so that a certain amount of oxide agglomeration occurs inside the material, resulting in a large amount of vaporization and less. The lower concentration of the substance is in a state of being easily plastically deformed. In the case of expansion due to the formation of oxides accompanying internal oxidation, the deformation of the oxide is low and the deformation is easy due to the expansion of the plastic deformation. Therefore, no fine cracking occurred. 100141777 6 201231682 However, 'in the internal oxidation treatment of the Zn-containing silver sulphate of the present invention, the diffusion rate of Zn from the surface of the material is slow due to the slow diffusion rate of Zn during internal oxidation compared to Sii or In. Faster, so the oxide formation of the silver alloy towel is uniformly dispersed to the whole as compared with the I*夬 oxide, and it is difficult to cause oxide aggregation.
Ag_Sn_In系材料’整體的延展性低，無法吸收内部 氧化日π所發生的氧化物膨脹，故於結晶粒界發生大量細微破 4尤其疋在本發明所示之内部氧化條件下，此現象可明顯 地確認。 根據本發明所示之製造方法，可使用習知難以製造電接點 的3 Zn之銀系材料來製造電接點，並可製造接點性能比習 知接點材料更優越的電接點。 康I 5為止的貫驗，可知作為含Zn之銀系材料，調配 有Ag 98.7〜5G質量％、Zn 1〜4G質量％、Te G.1〜3.0質量％、The Ag_Sn_In material has a low ductility and cannot absorb the oxide expansion occurring in the internal oxidation day π, so a large amount of fine breakage occurs at the grain boundary, especially under the internal oxidation conditions shown in the present invention. Confirmation. According to the manufacturing method of the present invention, it is possible to manufacture electrical contacts using a 3 Zn silver-based material which is conventionally difficult to manufacture electrical contacts, and to manufacture electrical contacts having superior contact performance than conventional contact materials. In the case of the Zn-containing silver-based material, it is known that Ag 98.7 to 5 G mass%, Zn 1 to 4 G mass%, and Te G.1 to 3.0 mass% are prepared.
Cu 0· 1 〜5 D 曰 η， .貝里/〇、Sb 0.1〜2.0質量％者，可製造成接點性能 優越的電接點。 已知在對銀添加Zn時，藉由一併添加Te、Cu、Sb之3 元素，可製造接點性能優越的電接點。已知此等3元素的調 配比例’在分別未滿上述最小值時，則對耐消耗性及耐熔接 性亚不具有效果。又，若分別超過上述最大值，則因氧化物 過多而接觸電阻增大、導致溫度上昇，而成為熔接現象發生 的要口將仏調配比例設為1〜4〇重量％的理由在於，未滿 1重罝％時，則無法得到氧化物所造成之所需效果，故添加 100141777 201231682 無意義；若超過40重量％，則難以製造成電接點。 另外，根據實驗，已知若於上述合金中進一步添加Sn 0.5〜8.0重量％、In lo〜6.0重量％、犯〇卜。3重量％的至少 1種’則可控龍使氧化物均勻析出，並有效地使結晶粒細 微化。 將Sn、In、Ni之調配比例規定如上述的理自，已知係如 未滿0.5重量％、In未滿u重量％,未滿〇」重量％時， 將無法控制成使氧化物料析出，未能得到使結晶粒細微化 的效果。又’若Sn超過8.〇重量％、In超過6 〇重量％，則 氧化物凝集而發生内部氧化不良，若Ni超過〇.3重量％ / 則難以均勻熔解。 另外’根據實驗’已知藉由依〇 稚田依0.01〜〇.3重量％之範圍添加Cu 0·1 ～5 D 曰 η, .Berry/〇, Sb 0.1 to 2.0% by mass, can be made into an electrical contact with excellent contact performance. It is known that when Zn is added to silver, an electric contact excellent in contact performance can be manufactured by adding three elements of Te, Cu, and Sb together. It is known that when the ratios of the three elements are less than the above minimum values, they have no effect on the wear resistance and the weld resistance. In addition, when the maximum value is exceeded, the contact resistance increases and the temperature rises due to excessive oxides, and the reason why the fusion ratio occurs is 1 to 4% by weight. When 1% 罝%, the desired effect due to the oxide cannot be obtained, so adding 100141777 201231682 is meaningless; if it exceeds 40% by weight, it is difficult to manufacture an electrical contact. Further, according to the experiment, it is known that Sn is added in an amount of 0.5 to 8.0% by weight and In Lo to 6.0% by weight in the above alloy. At least one kind of 3% by weight of the controllable dragon uniformly precipitates the oxide and effectively refines the crystal grains. The ratio of the ratio of Sn, In, and Ni is determined as described above, and if it is less than 0.5% by weight, In less than 5% by weight, and less than 5% by weight, it is not possible to control the precipitation of the oxide material. The effect of making the crystal grains fine is not obtained. Further, when Sn exceeds 8. 〇 by weight and In exceeds 6 〇 by weight, the oxide aggregates to cause internal oxidation failure, and if Ni exceeds 3% by weight / it is difficult to uniformly melt. In addition, the 'experimental' is known to be added by the range of 0.01 to 〇.3 wt%
Mn、Ga、Mg、Bi之至少1種，目丨丨：石 】可更加提升作為電接點的 性月包。其理由在於，藉由使细妈 稭由使，放之氧化物析出於結晶組織 内’可k升耐雜性或耐熔祕。又 0.01重量％時則無法得到其效果 、"』、、口里在未滿 超過0.3重量％則氧化物 凝集而於内部發生氧化不良。 」虱化物 (發明效果） 接點，已知耐熔接性、耐 電特性優越，於各種接點 由本發明之電接點材料所得的電 電弧消耗性、低接觸電阻等之各種 用途方面具有優越特性。 藉此，可作為於銀合金中含右 、 n、被大量使用的接點材 100141777 201231682 料，而提供單價低、適合大量生產的電接點材料。 【實施方式】 藉表1說明本發明之實施例。 將表1所示之各實施例的材料，藉由熔解而製造成厚 20mm、覓5〇mm、長5〇mm的鎢録;後，直接以鑄疑狀態依 800°C、氧壓力〇.5MPa進行内部氧化處理約12〇小時。 其後，使用粉碎機粉碎鑄錠，製造細片及/或粉末。將所 製造之細片及/或粉末壓縮成形為所需形狀後，予以燒結， 藉擠出加ji形成為直徑4mm的線材，再藉由伸線加工及熱 處理，作成直徑2mm的線材。此時之加工率為75%。 接著，將上述線材藉成形壓製而成形加工為厚〇.8mm、寬 及長2.5mm的角形後，依DC2〇〇、3〇〇、35〇v進行溶接試 驗。 尚且’為了比較’製造Ag_Sn4n系之預備氧化型接點2 例作為習知例，進行比較試驗。 100141777 201231682 【Id C »1 | 5 ? <3 ◎ 0 〇 ◎ 〇 ◎ ◎ 〇 < <1 〇 < 〇 < i ί 7t ί ϊ ? 〈 〇 〇 〇 〇 ◎ ◎ 〇 〇 〇 <3 <] ◎ <] <] ί ι Μ 〇 < ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ ◎ ◎ 〇 ◎ 組成(mass%) m 0.10 0.05 0.30 0.01 0.10 0.05 0.10 ' Λ Ο 0.30 0.20 0.01 0.15 0.20 1 0.30 0.05 c： S 0.10 m 〇 1—H o r〇 〇 m 〇 m 〇 m O m 〇 m 〇 m 〇 m O (N 〇 m 〇 m 〇 〇 o 〇 vd o — o o 1—H in 1-H o CN 〇 m p 〇 CN ΓΟ o 00 o T-H (N 0 01 yn o OO o to p-H 〇 o 〇 vo 〇 oo 〇 (N o o o r ' i *> o oo o oo o o cs m o ro 〇 oo oo o P U 〇 in o o o (N o oo o yn o o rsi in oo 〇 o 〇 o »—H o ΓΛ o o 〇 q in O oo o 0 1 __H O (S o cn 〇 N 40.0 o r· H o p 寸 o 00 o cs 〇 rn o cn 20.0 30.0 40.0 25.0 15.0 50.0 98.7 86.4 86.6 83.2 89.1 88.3 91.2 72.5 CN VO 51.6 60.7 72.4 90.2 88.0 ί iS i 1 K 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 _1 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 習知例1 習知例2 驾丨：V 磑：ο^噢：◎^0£4:^^讅紱 AOS , ge , 00GG :阖铖齑鉍* οι ζ,αΙΗΟΟΙAt least one of Mn, Ga, Mg, and Bi, and the target: stone can further enhance the sexual monthly package as an electrical contact. The reason for this is that by placing the fine mother straw, the oxide is deposited in the crystal structure, which is resistant to impurities or melt. When the amount is 0.01% by weight, the effect is not obtained, and if the amount is more than 0.3% by weight in the mouth, the oxide aggregates and oxidative degradation occurs inside.虱 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In this way, it can be used as a contact material 100141777 201231682 in the silver alloy containing the right, n, which is used in a large amount, and provides an electric contact material which is low in unit price and suitable for mass production. [Embodiment] An embodiment of the present invention will be described with reference to Table 1. The materials of the respective examples shown in Table 1 were produced by melting to form a tungsten having a thickness of 20 mm, a thickness of 5 mm, and a length of 5 mm. After that, the state of the casting was directly at 800 ° C and oxygen pressure. 5 MPa was subjected to internal oxidation treatment for about 12 hours. Thereafter, the ingot is pulverized using a pulverizer to produce a fine sheet and/or a powder. The prepared fine sheet and/or powder was compression-molded into a desired shape, sintered, and formed into a wire having a diameter of 4 mm by extrusion and nip, and then subjected to wire drawing and heat treatment to prepare a wire having a diameter of 2 mm. The processing rate at this time was 75%. Next, the wire was formed into a rectangular shape having a thickness of 8 mm, a width, and a length of 2.5 mm by press molding, and then subjected to a fusion test in accordance with DC 2 〇〇, 3 〇〇, and 35 〇 v. Further, in order to compare the two examples of the preparation of the Ag_Sn4n-based preliminary oxidation type contact, a comparative test was carried out. 100141777 201231682 [Id C »1 | 5 ? <3 ◎ 0 〇◎ 〇◎ ◎ 〇<<1〇<〇< i ί 7t ί ϊ ? 〇〇〇〇 〇〇〇〇 ◎ ◎ 〇〇〇 < 3 <] ◎ <] <] ί ι Μ 〇 < ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ ◎ ◎ 〇 ◎ composition (mass%) m 0.10 0.05 0.30 0.01 0.10 0.05 0.10 ' Λ Ο 0.30 0.20 0.01 0.15 0.20 1 0.30 0.05 c: S 0.10 m 〇1—H or〇〇m 〇m 〇m O m 〇m 〇m 〇m O (N 〇m 〇m 〇〇o 〇vd o — oo 1—H in 1- H o CN 〇mp 〇CN ΓΟ o 00 o TH (N 0 01 yn o OO o to pH 〇o 〇vo 〇oo 〇 (N ooor ' i *> o oo o oo oo cs mo ro 〇oo oo o PU 〇in ooo (N o oo o yn oo rsi in oo 〇o 〇o »—H o ΓΛ oo 〇q in O oo o 0 1 __H O (S o cn 〇N 40.0 or· H op inch o 00 o cs 〇 Rn o cn 20.0 30.0 40.0 25.0 15.0 50.0 98.7 86.4 86.6 83.2 89.1 88.3 91.2 72.5 CN VO 51.6 60.7 72.4 90.2 88.0 ί iS i 1 K Example 1 Example 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 _1 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Example 13 Conventional Example 1 Conventional Example 2 Driving: V 硙: ο^噢:◎^0£4:^^讅绂AOS , ge , 00GG :阖铖齑铋* οι ζ,αΙΗΟΟΙ