200422411 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種無氧銅合金，其中有改良加工切削 性，尤其係可衝孔性之合金化材料。此合金尤其適合使用 於需要良好導電性及良好加工切削性兩者的目的。 【先前技術】 最常使用之銅品質的氧含量，所謂的ETP銅（電解靭煉）200422411 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an oxygen-free copper alloy, which has improved machining machinability, especially an alloying material capable of being punched. This alloy is particularly suitable for purposes that require both good electrical conductivity and good machinability. [Previous technology] The most commonly used copper-quality oxygen content is the so-called ETP copper (electrolytic toughening)
I 典型上係銅重量之200-400 ppm。氧在一般的製程中會自 然結合於銅中。由於氧會與有害物質結合成較無害之氧化 物，因而亦可故意使氧含量維持於一期望值下。氧化物顆 粒亦會提高脆性，其可改良例如可衝孔性。 一般而言，銅之導電性始終係當銅愈純時愈高。銅之導 熱性係與其之導電性成比例。尤其為改良導電性、加工切 削性及熔接性，而製造具不高於1 0 ΡΡ1Ώ之氧含量之所謂的 無氧銅。在無氧銅之製造中，經由於溶體上方使用保護性 還原層（例如石墨），經由使用保護性氣體（例如氮）或經由 使用真空，而防止氧與熔融銅接觸。 然而，無氧銅之特性一般係具高拉伸性，其在一些情況 中會產生加工切削的問題，例如於衝孔中。 公告J P - A - 6 2 2 5 3 7 4 3中建議一種尤其供加工切削用之無 氧銅，此合金包含總量0 . 0 2 _ 1 · 0 %之以下材料的至少兩 者：硫、硒及碲。公告J P - A - 0 6 0 0 2 0 5 8中建議一種用於防 止晶粒成長之具0 . 0 0 0 6 - 0 . 0 0 1 5 %硫之無氧銅合金。 【發明内容】 5 312/發明說明書(補件)/93-06/931084% 200422411 發明人現發明一種如申請專利範圍第1項之無氧銅。本 發明之較佳具體例記述於其他之申請專利範圍中。 根據本發明，於無氧銅中將合金重量之50-300 ppm之 硫合金化成為唯一的合金成分。如此，加工切削性獲得改 良，同時導電性仍維持良好。 此合金尤其適合使用於需要良好導電性或導熱性及良 好加工切削性兩者的產品中。此種產品係例如各種經由衝 孔製得的導電性組件。 【實施方式】 根據本發明之無氧銅的硫含量係5 0 - 3 0 0 p p m，以 100 - 200 ppm較佳。合金之氧含量不高於10 ppm，以不高 於5ppm較佳，諸如1 - 3ppm。。 利用根據本發明之硫合金化，無氧銅之加工切削性，尤 其是可衝孔性，顯著地獲得改良。當加工切削性與ETP銅 為相同數量級時，可以根據本發明之銅取代E T P銅。 與ETP銅比較，無氧銅亦具有沒有氫脆性之危險的優 點。因此，無氧銅較適合於在高溫下加工，例如經由焊接 及炼接。 硫之脆性增加效果係基於其在銅基質中係以個別顆粒 存在。顆粒大小具有顯著的重要性，尤其係於可衝孔性行 為中：顆粒愈大，則衝孔性愈佳。顆粒大小會受鑄造小胚 之冷卻速率，及在高溫下進行之個別熱處理的影響。 合金可利用與其他品質之無氧銅類似的製造技術製 造，例如以板塊或桿鱗造，作為水平或垂直禱造。在一適 6 312/發明說明書(補件)/93-06/93108495 200422411 當的方法步驟中，例如於鑄造爐中，加入所需量的硫。經 由應用板塊/桿/熱軋/熱擠方法，對硫顆粒獲致較垂直 鑄造-熱擠方法大之尺寸。 可將合金加工成例如厚度例如為0 . 2 - 1 2毫米之條狀 物。可例如經由衝孔而由此種條狀物製得各種產品。該產 品例如為許多的導電性及導熱性組件。例如，可經由衝孔 製造空調孔洞（諸如於散熱片中）或固定孔洞。此種條狀物 尤其可經由使用板塊鑄造及熱軋路徑而製造。 另一可行的製造路徑為垂直鑄造-連續熱擠。以此方 式，可製得例如具在4 - 1 2毫米内之厚度範圍的扁鋼（f 1 a t b a r )或其他外形。 銅之硫含量並不會使例如可熔接性質減弱。硫亦不會於 例如再循環中產生問題。 (實施例） 製造無氧銅合金，其中將50、100、150、200、250及 3 0 0 p p m之硫合金化。材料係經由於真空爐中桿鑄造而製 得，將其熱擠成3 9 · 9 X 7 · 2毫米尺寸，並牽伸成3 8 . 9 6 X 6 · 1 7毫米尺寸（減少1 6 % )。所使用之參考材料係得自製造 之尺寸6 X 4 0毫米的牽伸扁鋼。其之變形程度大略與試驗 材料相同。在此等材料中，利用相同工具衝出細長孔洞（約 3 X 2 5毫米）。除了可衝孔性之外，亦測試試驗材料之導電 性及機械性質。 關於描述可衝孔性之大小，可使用整個切割表面之破裂 區域的比率。對於高拉伸性材料，拋光區域之比率甚大於 7 312/發明說明書(補件)/93-06/93108495 200422411 脆性材料。最終結果亦會顯著地受模頭餘隙（即模墊與切割 表面之間之距離）影響。材料愈具拉伸性，則必需使用以達 到相同最終結果之餘隙愈小。然而，切割餘隙愈小，則工 具的磨損愈強。當提高切割餘隙時，整個切割表面之破裂 比率增加。 在實驗中，研究0 · 5 5及0· 8 5毫米之模頭餘隙的可衝孔 性，當偵測到較大或較小值時，所得結果過度不均勻。使 用於實驗中之衝孔工具係水平頭（1 e v e 1 - h e a d e d )，且其具 有1毫米之後牽引（b a c k d r a f t)。利用材料及衝孑L參數之 各組合衝出三個孔洞。 試驗結果示於附表。 硫添加 模頭餘隙 同1 孔洞2 :同3 平均 平均散射 [ppm] [nun ] [破裂％ ] [破裂％ ] [破裂％ ] - 0.85 20. 75 24. 44 25. 48 23. 56 2. 48 50 0.85 23. 86 25. 00 25. 76 27. 87 0· 95 1 00 0.85 34. 88 33· 08 32. 20 33. 39 1 . 37 150 0.85 41 . 31 41 · 29 4 1 · 54 41 . 38 0. 14 200 0.85 43. 13 42· 64 44. 66 43. 48 1 · 05 250 0.85 41 · 60 40. 98 42. 91 41 · 83 0· 99 300 0.85 48. 46 47. 06 48. 5 1 48. 01 0. 82 50 0.55 23. 97 24. 62 23. 77 24. 12 0· 44 1 00 0.5 5 30. 15 3 1· 94 30. 65 30. 92 0· 92 1 50 0.55 35. 98 36. 68 37. 93 36. 86 0· 99 200 0.55 38. 64 38. 66 39. 54 38. 95 0.52 250 0.55 37· 88 38. 26 38· 26 38. 13 0· 22 300 0.55 44. 40 45· 49 46. 59 45. 49 1 . 09 當觀察衝孔結果時，發現含硫樣品之破裂區域相較於未 合金化銅相當均勻。 8 312/發明說明書(補件)/93-06/93108495 200422411 下表指示樣品之測量機械性質以及其之導電性。 硫添加 [ppm] 硬度 [Hv] 應變 [%] R〇. 2 [N/mm2] R"i [N/mm2 ] 晶粒大小 [mm] 導電性 [%IACS] 50 85 30.1 242 253 0.050 100.8 1 00 83 29.8 245 256 0.045 100.2 1 50 85 34.8 230 249 0.050 100.0 200 84 34.1 229 243 0.045 100.0 250 85 32 227 24 1 0.040 100.0 300 84 27.4 242 254 0.040 99.8 亦使部分的樣品進行彎曲試驗，其可毫無問題地進行。 312/發明說明書(補件)/93-06/93〗08495 9I is typically 200-400 ppm of copper. Oxygen is naturally incorporated into copper in normal processes. Since oxygen can be combined with harmful substances to form relatively harmless oxides, the oxygen content can also be intentionally maintained at a desired value. Oxide particles also increase brittleness, which can improve, for example, punchability. In general, the electrical conductivity of copper is always higher as the copper is more pure. The thermal conductivity of copper is proportional to its electrical conductivity. In particular, so-called oxygen-free copper having an oxygen content of not higher than 10 PP1Ώ is produced in order to improve electrical conductivity, processability, and weldability. In the production of oxygen-free copper, oxygen is prevented from contacting the molten copper by using a protective reducing layer (such as graphite) above the solution, by using a protective gas (such as nitrogen), or by using a vacuum. However, the characteristics of oxygen-free copper are generally high stretchability, which may cause machining cutting problems in some cases, such as in punching. Bulletin JP-A-6 2 2 5 3 7 4 3 proposes an oxygen-free copper especially for machining cutting. This alloy contains at least two of the following materials in a total amount of 0.0 2 _ 1 · 0%: sulfur, Selenium and tellurium. Announcement J P-A-0 6 0 0 2 0 5 8 proposes an oxygen-free copper alloy with 0. 0 0 6-0. 0 0 1 5% for preventing grain growth. [Summary of the Invention] 5 312 / Invention Specification (Supplement) / 93-06 / 931084% 200422411 The inventor now invents an oxygen-free copper such as the first item in the scope of patent application. Preferred specific examples of the present invention are described in other patent applications. According to the present invention, 50-300 ppm of sulfur in the oxygen-free copper is alloyed into the sole alloy composition. In this way, the machinability is improved, and the electrical conductivity is still maintained. This alloy is particularly suitable for products that require both good electrical or thermal conductivity and good machinability. Such products are, for example, various conductive components manufactured by punching. [Embodiment] The sulfur content of the oxygen-free copper according to the present invention is 50-3 0 0 p p m, preferably 100-200 ppm. The oxygen content of the alloy is not higher than 10 ppm, and preferably not higher than 5 ppm, such as 1-3 ppm. . With the sulfur alloying according to the present invention, the machinability of oxygen-free copper, especially the punchability, is significantly improved. When machining machinability is of the same order of magnitude as ETP copper, E T P copper can be replaced by copper according to the invention. Compared with ETP copper, oxygen-free copper also has the advantage of not having the danger of hydrogen embrittlement. Therefore, oxygen-free copper is more suitable for processing at high temperatures, such as welding and smelting. The effect of increasing the brittleness of sulfur is based on its existence as individual particles in the copper matrix. Particle size is of significant importance, especially in punchability: the larger the particles, the better the punchability. The particle size is affected by the cooling rate of the cast embryo and the individual heat treatments performed at high temperatures. Alloys can be made using similar manufacturing techniques to other qualities of oxygen-free copper, such as plates or rod scales, as a horizontal or vertical prayer. In a suitable method step of 6 312 / Invention Specification (Supplement) / 93-06 / 93108495 200422411, for example, in a casting furnace, a required amount of sulfur is added. By applying the plate / rod / hot rolling / hot extrusion method, the sulfur particles have a larger size than the vertical casting-hot extrusion method. The alloy can be processed into, for example, a strip having a thickness of, for example, 0.2 to 12 mm. Various products can be made from such bars, for example via punching. This product is, for example, many conductive and thermally conductive components. For example, air conditioning holes (such as in heat sinks) or fixed holes can be made via punching. Such bars can be manufactured in particular by using plate casting and hot rolling paths. Another feasible manufacturing path is vertical casting-continuous hot extrusion. In this way, flat steel (f 1 a t b a r) or other shapes having a thickness in the range of 4 to 12 mm can be produced, for example. The sulfur content of copper does not diminish, for example, weldability. Sulfur also does not cause problems in, for example, recycling. (Example) An oxygen-free copper alloy was produced in which 50, 100, 150, 200, 250, and 300 p p m of sulfur were alloyed. The material is made by casting in a vacuum furnace. It is hot extruded to a size of 3 9 · 9 X 7 · 2 mm and drawn to a size of 3 8. 9 6 X 6 · 17 mm (16% reduction). ). The reference material used was drawn from manufactured flat steel with dimensions of 6 x 40 mm. The degree of deformation is almost the same as that of the test material. In these materials, the same tool is used to punch out elongated holes (approximately 3 X 2 5 mm). In addition to punchability, the conductivity and mechanical properties of the test materials are also tested. Regarding the description of the punchability, the ratio of the fractured area of the entire cutting surface may be used. For highly stretchable materials, the ratio of polished areas is much greater than 7 312 / Invention Specification (Supplement) / 93-06 / 93108495 200422411 Brittle materials. The end result is also significantly affected by the die clearance (ie, the distance between the die pad and the cutting surface). The more stretchable the material, the smaller the clearance that must be used to achieve the same end result. However, the smaller the cutting clearance, the stronger the tool will wear. When the cutting clearance is increased, the fracture ratio of the entire cutting surface increases. In the experiments, the punchability of die clearances of 0.55 and 0.85 mm was studied. When larger or smaller values were detected, the results were excessively uneven. The punching tool used in the experiment was a horizontal head (1 e v e 1-h e a d e d), and it had a traction of 1 mm (b a c k d r a f t). Three holes were punched out using each combination of material and punching L parameters. The test results are shown in the attached table. Sulfur addition die clearance is the same as 1 hole 2: same as 3 average average scattering [ppm] [nun] [% of crack] [% of crack] [% of crack]-0.85 20. 75 24. 44 25. 48 23. 56 2. 48 50 0.85 23. 86 25. 00 25. 76 27. 87 0 · 95 1 00 0.85 34. 88 33 · 08 32. 20 33. 39 1.. 37 150 0.85 41. 31 41 · 29 4 1 · 54 41. 38 0. 14 200 0.85 43. 13 42 · 64 44. 66 43. 48 1 · 05 250 0.85 41 · 60 40. 98 42. 91 41 · 83 0 · 99 300 0.85 48. 46 47. 06 48. 5 1 48. 01 0. 82 50 0.55 23. 97 24. 62 23. 77 24. 12 0 · 44 1 00 0.5 5 30. 15 3 1 · 94 30. 65 30. 92 0 · 92 1 50 0.55 35. 98 36 68 37. 93 36. 86 0 99 200 0.55 38. 64 38. 66 39. 54 38. 95 0.52 250 0.55 37 · 88 38. 26 38 · 26 38. 13 0 · 22 300 0.55 44. 40 45 · 49 46. 59 45. 49 1. .09 When observing the punching results, it was found that the cracked area of the sulfur-containing sample was quite uniform compared to unalloyed copper. 8 312 / Invention Specification (Supplement) / 93-06 / 93108495 200422411 The following table indicates the measurement mechanical properties of the sample and its electrical conductivity. Addition of sulfur [ppm] Hardness [Hv] Strain [%] R〇. 2 [N / mm2] R " i [N / mm2] Grain size [mm] Electrical conductivity [% IACS] 50 85 30.1 242 253 0.050 100.8 1 00 83 29.8 245 256 0.045 100.2 1 50 85 34.8 230 249 0.050 100.0 200 84 34.1 229 243 0.045 100.0 250 85 32 227 24 1 0.040 100.0 300 84 27.4 242 254 0.040 99.8 Some of the samples were also subjected to bending tests. Problematic. 312 / Invention Specification (Supplement) / 93-06 / 93 〖08495 9