201042060 六、發明說明· 【發明所屬之技術領域】 本發明係關於一種以銅、鎳、錫、鉛為主的合金及 其製作方法。更特定言之，本發明係特別關於（但不限 於此）一種以銅、鎳、錫、鉛為主的合金，其可輕易地 進行車削、切割或碾磨加工。 【先前技術】201042060 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an alloy mainly composed of copper, nickel, tin and lead and a method for producing the same. More specifically, the present invention is particularly directed to, but not limited to, an alloy of copper, nickel, tin, and lead which can be easily turned, cut, or milled. [Prior Art]
以銅、鎳及錫為主的合金是目前已知且廣泛使用的 合金。它們提供了優異的機械性質’且在應變硬化 (strain-hardening )期間展現出很強的硬化性。它們的 機械性質可藉由已知的加熱老化處理（如離相分解 (spinodal decomposition))方式獲得進一步的改善。對含 有15%鎳及8%錫（重量％)的合金（標準合金ASTM C72900)來說，其機械阻力可達1500 MPa。這些合金 也提供良好的抗應力鬆弛性（stress relaxation resistance ) ’且在空氣中有高度抗蝕性（c〇rr〇si〇n resistance) ° 这空柯料的另一項優點是它們具有優異的成型 性，且結合了適宜的彈性，這是它們降伏應力 二钕生及優異的抗熱鬆弛性（resistanc 二 u-Ni-Sn彈耳也不會因為老 這些有利的性質盘良好的3 :們_力。 業之尚度可靠的連接器 ：：私業及車工 ，電裝置，或作為電子組件於鐘錶及電氣或 電荷的軸承摩擦表面。 又塚物或用以製作承受高 這些合金通常是藉由加入^獲得良好的可加工 201042060 性，其中鉛係作為精細分散之夾雜物而分布於該合金基 體中。然而，這類加入鉛的方式也會大大增加合金的熱 脆性（warm shortness )，而這在製程及使用上方面都會 引起問題。Alloys mainly composed of copper, nickel and tin are currently known and widely used alloys. They provide excellent mechanical properties' and exhibit strong hardenability during strain-hardening. Their mechanical properties can be further improved by known heat aging treatments such as spinodal decomposition. For alloys containing 15% nickel and 8% tin (% by weight) (standard alloy ASTM C72900), the mechanical resistance can reach 1500 MPa. These alloys also provide good stress relaxation resistance' and are highly resistant to air (c〇rr〇si〇n resistance). Another advantage of this empty material is that they are excellent. Formability, combined with suitable elasticity, which is their secondary stress and excellent thermal relaxation resistance (resistcic two u-Ni-Sn lugs are not good because of these favorable properties of the old 3: _ force. The industry's reliable connectors: private and car mechanics, electrical devices, or as electronic components on the surface of the watch and electrical or electric bearing friction surfaces. Also the materials or used to make high withstand these alloys are usually Good processability 201042060 is obtained by adding ^, in which lead is distributed as finely dispersed inclusions in the alloy matrix. However, this type of lead addition also greatly increases the thermal shortness of the alloy. This will cause problems in terms of process and use.
Cu基合金在中間溫度（300°C-700°C)會失去延展 性是一個長久以來的問題，R.V. Foulger與E. Nicholls (Metals Technology, 3, pages 366-369 (1976))及 V. Laporte 與 A. Mortensen ( International Materials Reviews，付印中(2009))都發表過評論。在這個溫度範 圍内開始發生的晶界滑移（grain boundary sliding )會在 晶界產生空隙及空腔，而且會使銅及其合金在正常情況 下的延性斷裂（normally ductile fracture )變成粒間脆性 破壞（intergranular brittle failure)。這個現象可以在純 銅觀察到，但當使合金脆化或合金中有不純元素時，這 個現象會更加顯著。而在超過這個關鍵範圍的更高溫度 下，動態再結晶（dynamic recrystallization)會使延展性 復原。 熔融的Pb夾雜物在這類Cu-合金中的存在可能會 引起液態金屬脆化（liquid metal embrittlement，LME )， 特別是在高應變率的情況下更是如此。同時，有報告顯 示船含量低到18 ppm仍可使Cu-Ni合金的晶界脆化， 而已暴露於於800°C之鉛氣當中的合金會以脆化的方式 破壞’顯示鉛亦可引起固體晶界脆化；與LME相反的 是，它在低應變率的時候會更加嚴重。其他已知會在Cu-合金中引起晶界脆化的元素是硫和氧。 【發明内容】 因此’本發明之一目的係提出一種由一 Cu-Ni-Sn-Pb-基合金所構成的金屬產物，其可克服至少部分先前技 術的限制。 201042060 本發明之另一目的係提供一種由一 Cu-Ni-Sn-Pb-基 合金所構成之金屬產物，其具有更強的拉伸性質及良好 的可加工性。 在本發明中，這些目的係藉由一包含獨立請求項之 技術特徵、獨立請求項及本文所指之較佳具體實施態樣 的系統及方法來達成。 這些目的也可藉由一種合金來達成，其中前述合金 係於Cu中含有在1重量％與20重量％之間的Ni、在1 重量％與20重量％之間的Sn、在0.5重量％與3重量％ 之間的Pb，且前述Cu占該合金之至少50重量％;而其 〇 特徵在於，該合金進一步含有在0.01重量％與5重量％ 之間的P或B或其組合。 在本發明之一具體實施態樣中，該合金進一步含有 在0.01重量％與0.5重量％之間的P或B或其組合。 在本發明之一較佳具體實施態樣中，該合金包含9 重量％的Ni、6重量％的Sn、1重量％的Pb。 本發明之合金之特徵在於，於800°C熱處理約1小 時、繼於水或空氣中淬火後，於400°C測量所得降伏強 度（yield strength ) Rp〇.2及最大應力Rm實質上分別高於 180 MPa及333 MPa。該合金亦具有下列特徵：於800° ^ C熱處理約1小時、繼於320°C老化約12小時後，測 量所得之Hv硬度實質上高於190。 這些目的也可藉由一種由本發明之合金所構成之 金屬產物的製作方法來達成，其包含下列步驟：取得前 述合金之第一金屬塊，其具有一均質構造（homogeneous structure);使前述合金於包含在690°C與880°C之間的 溫度退火，使之均質化並改善該合金之冷成型性質；以 在50°C/min與50000°C/min之間的冷卻速度進行冷 卻，其係取決於前述合金之產物及組合物的水平寬度； 以及冷成型。 5 201042060 本發明亦涵括一種由本發明之合金所構成之金屬 產物、以及用本發明之方法所製作之金屬產物，該產物The loss of ductility of Cu-based alloys at intermediate temperatures (300 ° C - 700 ° C) is a long-standing problem, RV Foulger and E. Nicholls (Metals Technology, 3, pages 366-369 (1976)) and V. Laporte Comments were made with A. Mortensen (International Materials Reviews, Fu Yinzhong (2009)). The grain boundary sliding that begins to occur in this temperature range creates voids and cavities at the grain boundaries, and causes the normally ductile fracture of copper and its alloys to become intergranular brittleness under normal conditions. Intergranular brittle failure. This phenomenon can be observed in pure copper, but this phenomenon is more pronounced when the alloy is embrittled or there are impure elements in the alloy. At higher temperatures above this critical range, dynamic recrystallization restores ductility. The presence of molten Pb inclusions in such Cu-alloys may cause liquid metal embrittlement (LME), especially at high strain rates. At the same time, reports indicate that the ship's content as low as 18 ppm can still embrittle the grain boundary of Cu-Ni alloy, and the alloy that has been exposed to lead gas at 800 °C will be destroyed by embrittlement. Solid grain boundary embrittlement; contrary to LME, it is more severe at low strain rates. Other elements known to cause grain boundary embrittlement in Cu-alloys are sulfur and oxygen. SUMMARY OF THE INVENTION Accordingly, one object of the present invention is to provide a metal product composed of a Cu-Ni-Sn-Pb-based alloy that overcomes at least some of the limitations of the prior art. 201042060 Another object of the present invention is to provide a metal product composed of a Cu-Ni-Sn-Pb-based alloy which has stronger tensile properties and good processability. In the present invention, these objects are achieved by a system and method comprising the technical features of the independent claims, the independent claims, and the preferred embodiments herein. These objects can also be achieved by an alloy in which Cu contains between 1% and 20% by weight of Ni, between 1% and 20% by weight of Sn, at 0.5% by weight and Pb between 3 wt%, and the aforementioned Cu accounts for at least 50 wt% of the alloy; and the niobium is characterized in that the alloy further contains between 0.01 wt% and 5 wt% of P or B or a combination thereof. In one embodiment of the invention, the alloy further comprises between 0.01% and 0.5% by weight of P or B or a combination thereof. In a preferred embodiment of the invention, the alloy comprises 9% by weight of Ni, 6% by weight of Sn, and 1% by weight of Pb. The alloy of the present invention is characterized in that after the heat treatment at 800 ° C for about 1 hour, after quenching in water or air, the measured yield strength Rp 〇 2 and the maximum stress R m are substantially higher at 400 ° C, respectively. At 180 MPa and 333 MPa. The alloy also has the following characteristics: after heat treatment at 800 ° C for about 1 hour, and after aging at 320 ° C for about 12 hours, the measured Hv hardness is substantially higher than 190. These objects can also be attained by a method for producing a metal product consisting of the alloy of the present invention, comprising the steps of: obtaining a first metal block of the foregoing alloy having a homogeneous structure; Annealing at a temperature between 690 ° C and 880 ° C to homogenize and improve the cold forming properties of the alloy; cooling at a cooling rate between 50 ° C / min and 50000 ° C / min, It depends on the product of the aforementioned alloy and the horizontal width of the composition; and cold forming. 5 201042060 The invention also encompasses a metal product consisting of the alloy of the invention, and a metal product produced by the process of the invention, the product
之特徵為·以標準ASTMC36000黃銅（standard ASTM C36000 brass)而言’其機械阻力包含在700_15〇〇N/mm2 之間，其Hv硬度包含在250與400之間，且其可加工 性指數大於70%。 ^ 該可加工性金屬產物可在中間溫度（3〇(rc_7〇(rc) 製得沒有裂隙、且具有優異的機械及拉伸性質的產物。 在本發明之說明書中，即使在文中並未特別提及， 所有的％均表示重量％。 【實施方式】 在本發明之一具體實施態樣中，CU基合金包含在j 重量％與20重量％之_1^、在i重量％與2()重量％ 之間的Sn、而Pb的比例則可在〇.丨重量％鱼4重量％之 間變動’剩下的部分實質上由CU所構成，而該cu其入 $所包含之無可避免的不純物質一般係在5〇〇 ppm二 錯本質上不溶於該合金中的其他金屬’所得產物將 包含分散在Cu-Ni-Sn基體中的热顆粒。在加工 鉛會有潤滑效果，並使裂片（slivers)碎裂。 ’、 引入合金中的鉛量係取決於想要達到多高的可加 工性。-般來說，可引人高達數個重量百分比_ 會改變合金在正常溫度下的機械性質。然而在鉛融點 ( 327 C)以上，液態錯會大大削弱合金。因此含船合 金製作不易，一方面是因為它們非常容易裂，另一 則是因為它們展現出一種含有一不理想的弱化相 (we^cening phase )的兩相晶體結構（tw〇 phased crystallographic structure)。所以，在本發明之人 錯含量較佳係在〇.5重量％與3重量％之間或在=〇 5重量 201042060 %與2重量％之間；又更佳者，係在0.5重量％與1.5重 量％之間。 該合金組合物可進一步選擇性包含一種引入該組 合物作為脫氧劑的元素（如Μη)，其量在0.1%與1%之 間。該Cu合金亦可包含其他元素來取代Μη、或在Μη 以外再加入其他元素，前述其他元素係如Al、Mg、Zr、 Fe、或這些元素當中至少兩種的組合。這些元素的存在 . 亦可改善Cu合金的離相硬化（spinodal hardening )。或 者，可以使用預防Cu合金氧化的裝置。 在另一具體實施態樣中，本發明之合金所含有的部 〇 分Cu可以被其他元素（如Fe或Zn)以一定比例所取 代，其中前述比例係如高達10%。 在本發明之又一另一具體實施態樣中，該Cu基合 金含有至少0.01重量％的另一種合金元素，其係選自 Al、Mn、Zr、P (石粪）或B (棚）。或者，本發明之Cu 基合金含有一至少兩種選自Al、Μη、Zr、P或B之其 他元素的混合物，其量為至少0.01重量％。 在本發明之一較佳具體實施態樣中，該Cu基合金 含有在0.01重量％與5重量％之間的P或B。 〇 在本發明之更佳具體實施態樣中，該Cu基合金含 ^ 有9重量％的Ni、6重量％的Sn、1重量％的Pb、以及 在0.02%與0.5%之間的P或B。 之前已有關於加入P及/或B對Cu-Ni-Sn-Pb合金於 中間溫度之機械性質有何影響的研究。為了達成此一目 的，由純的組成分（預合金(pre-alloy) Cu3P及CuZr: 99.5重量％，Al : 99.9重量％，其他所有的成分：99.99 重量％ )在半連續鑄造單元（semi-continuous casting unit)(容量：30 kg)及氬的保護之下製備一由Cu基合 金所構成的金屬產物，其中前述Cu基合約含：9重量％ 的Ni、6重量％的Sn、l重量％的Pb及約在0.02%與0.5% 201042060 之間的P或B。 本發明對不同合金的組合物進行研究，並運用感應 耦合電漿（inductively coupled plasma，ICP)分析進行 測量後，將結果列於表1，這些組合物的單位為重量％， 剩餘的部分是Cu。而Zr的值無法用ICP方法加以彳貞測。 201042060 ο ο 噶溴<^^- 一 ♦ 3 0.004 0.004 0.005 1- | 0.005 1- 0.005 0.18 I 0.004 d) tin 0.008 0.016 Oh 0.478 0.075 CQ 0.325 i I 0.02 1____— N 0.25 Mn 0.002 0.009 0.002 0.474 0.002 0.002 0.002 0.003 0.027 0.515 0.020 £ Γ^Γ 0.997 0.968 0.995 0.963 0.997 0.890 0.920 ! 1 6.230 6.083 6.104 1_ 5.979 ! 6.300 6.096 6.259 6.250 6.300 1 1 8.907 9.231 8.810 1_ 1 1 8.960 8.917 8.950 1_ 8.915 1 9.480 9.170 I 1 CuNi9Sn6 CuNi9Sn6Pbl CuNi9Sn6Pbl + 0.5 A1 1_ 1 1 CuNi9Sn6Pbl + 0.5 Mn CuNi9Sn6Pbl + 0.25 Zr CuNi9Sn6Pbl +0.3 B 1_ CuNi9Sn6Pbl + 0.5 P CuNi9Sn6Pbl + 0.03 B CuNi9Sn6Pbl +0.1 P < (N < r—^ CQ PQ CQ IT) CQ u <N u 201042060 ^該金屬產物鑄造成直徑12 mm的圓棒，之後 的模鱗，做成直# 7.5 mm。將這些標準尺^ 直徑4顏的81棒狀拉伸賴樣本進行加工 將樣^空氣中於刪。C均質化丨小時，並在水中泮火。 入，&1及C2合金加人這項清單，以檢驗低含量的合 金加入，是否也可以達到可加工性及高強度這樣的特 性。”私不為B的合金不同的是，C1及C2合金樣本於 800T退火1小時後，是在空氣中冷卻。 、 第一圖及第二圖分別顯示本發明之含B (B4)及含 P (B5)合金之金相切片的SEM顯微照片。B4及B5兩 種合金顯示富含Ni、Sn、以及B或p當中之一的硬質 第二相顆粒1，其係分別在將B或p加入Cu基合金時 形成。當把Zr加入Cu基合金中時，也會形成富含Ni、 Sn及Zr的硬質第二相顆粒！（未顯示）。第二相i要比 該Cu基合金基體其餘部分來得硬。B4及B5合金也用 晶粒大小來界定特徵，此處平均直徑實質上為35 μπ1， 與其他不g Β*ρ的合金相較之下，小了幾近兩倍。含 較少Β或Ρ量的C1及C2合金也分別呈現第二相顆粒 1 ’不過量較少（顯微照片未顯示）。第二相顆粒1係平 均分布在微結構中，大小是幾微米。在第一圖及第二圖 中，Pb夾雜物2顯示為白色。 表2報告了對B1至B5合金於80(TC熱處理約1 小時、繼於320°C老化約10及12小時後，測量所得的 維氏硬度（Vickers hardness) (HV10)測試值。將這些 測試值與A2合金所得之值進行比較，在硬度方面增加 最多的是本發明之B4及B5合金。 201042060 表2 -以Hv表示的維氏硬度（HvlO) 時間[h] A2 B1 B2 —-~~- B3 B4 B5 0 98 105 99 102 114 114 10 177 137 161 179 167 190 12 160 138 160 177 ----—1 188 208 表3報告了 A1至B5合金樣本的降伏強度（Rp〇2) 及最大應力（Rm)值。這些值是藉由熱拉伸測試得出， 即於800 C熱處理約1小時、繼於水或空氣中泮火後所 得出的。拉伸測試是使用伺服液壓測試儀（serv〇_ O hydraulic testing machine )( MFL 1 〇〇 kN )於 400。C 及應 變率1(Γ2^的條件下進行。將這些樣本在燈爐（丨amp furnace) (Research Inc.，Model 4068-12-10)上快速加 熱’在2分鐘内達到穩定的測試溫度，將加熱期間相變 (phase transformation )的發生減到最低。因為快速加 熱及高應變率的關係，於4 00。C維持不超過三分鐘後所 得之樣本會有裂痕。It is characterized by the standard ASTM C36000 brass (standard ASTM C36000 brass) whose mechanical resistance is between 700_15〇〇N/mm2, its Hv hardness is between 250 and 400, and its processability index is greater than 70%. ^ The processable metal product can be produced at an intermediate temperature (3 〇(rc_7〇(rc)) without cracks and having excellent mechanical and tensile properties. In the specification of the present invention, even if it is not particularly It is mentioned that all % represent % by weight. [Embodiment] In one embodiment of the invention, the CU-based alloy is contained in j% by weight and 20% by weight, in i% by weight and 2 ( The ratio of Sn between the weight % and the ratio of Pb can be changed between 〇.丨% by weight and 4% by weight. The remaining part is essentially composed of CU, and the cu is included in the $include. The impurities that are avoided are generally 5 〇〇ppm, and the other metals that are insoluble in the alloy are essentially containing the hot particles dispersed in the Cu-Ni-Sn matrix. The processing of lead has a lubricating effect, and The sliver is shattered. 'The amount of lead introduced into the alloy depends on how much workability is desired. - Generally speaking, it can be as high as several weight percentages _ will change the alloy at normal temperature. Mechanical properties. However, above the lead melting point (327 C), the liquid is wrong. The alloy is greatly weakened. Therefore, the alloys containing the ship are not easy to manufacture, on the one hand because they are very easy to crack, and the other because they exhibit a two-phase crystal structure containing an undesired weak phase (tw^phased). Therefore, the human error content in the present invention is preferably between 5% by weight and 3% by weight or between 〇5 by weight: 201042060% and 2% by weight; more preferably, it is Between 0.5% by weight and 1.5% by weight. The alloy composition may further optionally comprise an element (such as Μη) which is introduced into the composition as a deoxidizing agent in an amount of between 0.1% and 1%. Other elements are included in place of Μη, or other elements are added in addition to Μη, such as Al, Mg, Zr, Fe, or a combination of at least two of these elements. The presence of these elements can also improve the Cu alloy. Spinodal hardening. Alternatively, a device for preventing oxidation of the Cu alloy may be used. In another embodiment, the alloy of the present invention may contain a portion of Cu which may be other elements. (such as Fe or Zn) is substituted in a proportion, wherein the aforementioned ratio is as high as 10%. In still another embodiment of the present invention, the Cu-based alloy contains at least 0.01% by weight of another alloying element, It is selected from the group consisting of Al, Mn, Zr, P (stone manure) or B (shed). Alternatively, the Cu-based alloy of the present invention contains a mixture of at least two other elements selected from the group consisting of Al, Mn, Zr, P or B. The amount is at least 0.01% by weight. In a preferred embodiment of the invention, the Cu-based alloy contains between 0.01% and 5% by weight of P or B. In a more preferred embodiment of the present invention, the Cu-based alloy contains 9 wt% of Ni, 6 wt% of Sn, 1 wt% of Pb, and P between 0.02% and 0.5%. B. Previous studies have been conducted on the effect of the addition of P and/or B on the mechanical properties of Cu-Ni-Sn-Pb alloys at intermediate temperatures. In order to achieve this, the pure composition (pre-alloy Cu3P and CuZr: 99.5% by weight, Al: 99.9% by weight, all other components: 99.99% by weight) in semi-continuous casting units (semi- Continuous casting unit) (capacity: 30 kg) and a metal product composed of a Cu-based alloy under the protection of argon, wherein the aforementioned Cu-based contract contains: 9% by weight of Ni, 6% by weight of Sn, and 1% by weight Pb and P or B between about 0.02% and 0.5% 201042060. The present invention studies various alloy compositions and measures them by inductively coupled plasma (ICP) analysis. The results are shown in Table 1. The units of these compositions are % by weight, and the remaining part is Cu. . The value of Zr cannot be guessed by the ICP method. 201042060 ο ο 噶 噶 &<^^- 一♦ 3 0.004 0.004 0.005 1- | 0.005 1- 0.005 0.18 I 0.004 d) tin 0.008 0.016 Oh 0.478 0.075 CQ 0.325 i I 0.02 1____— N 0.25 Mn 0.002 0.009 0.002 0.474 0.002 0.002 0.002 0.003 0.027 0.515 0.020 £ Γ^Γ 0.997 0.968 0.995 0.963 0.997 0.890 0.920 ! 1 6.230 6.083 6.104 1_ 5.979 ! 6.300 6.096 6.259 6.250 6.300 1 1 8.907 9.231 8.810 1_ 1 1 8.960 8.917 8.950 1_ 8.915 1 9.480 9.170 I 1 CuNi9Sn6 CuNi9Sn6Pbl CuNi9Sn6Pbl + 0.5 A1 1_ 1 1 CuNi9Sn6Pbl + 0.5 Mn CuNi9Sn6Pbl + 0.25 Zr CuNi9Sn6Pbl +0.3 B 1_ CuNi9Sn6Pbl + 0.5 P CuNi9Sn6Pbl + 0.03 B CuNi9Sn6Pbl +0.1 P < (N < r -^ CQ PQ CQ IT) CQ u <N u 201042060 ^The metal product was cast into a round rod of 12 mm in diameter, and the subsequent scale was made straight #7.5 mm. These 81 rod-shaped stretched samples of standard size ^ 4 diameters were processed. C homogenizes for 丨 hours and bonfires in water. Add, & 1 and C2 alloys to add this list to test whether low levels of alloys can be added, and whether they can achieve the characteristics of workability and high strength. The difference between the alloys that are not B is that the C1 and C2 alloy samples are cooled in air after annealing at 800T for one hour. The first and second figures show the B (B4) and P containing of the present invention, respectively. (B5) SEM micrograph of metallographic section of alloy. B4 and B5 alloys show hard second phase particles 1 rich in Ni, Sn, and B or p, respectively, which are in B or P, respectively. Formed when a Cu-based alloy is added. When Zr is added to a Cu-based alloy, hard second phase particles rich in Ni, Sn, and Zr are also formed! (not shown). The second phase i is more than the Cu-based alloy matrix. The rest is hard. B4 and B5 alloys are also characterized by grain size, where the average diameter is essentially 35 μπ1, which is nearly twice as small as other alloys that are not g Β*ρ. The lesser or ruthenium C1 and C2 alloys also exhibited the second phase particles 1', respectively, but the amount was less (micrographs are not shown). The second phase particles 1 were evenly distributed in the microstructure and were a few microns in size. In the first and second figures, Pb inclusions 2 are shown in white. Table 2 reports that for B1 to B5 alloys at 80 (TC heat treatment is about 1 small) After the aging at 320 ° C for about 10 and 12 hours, the measured Vickers hardness (HV10) test value was measured. Comparing these test values with the value obtained by the A2 alloy, the most increase in hardness is B4 and B5 alloys of the invention 201042060 Table 2 - Vickers hardness in Hv (HvlO) Time [h] A2 B1 B2 —-~~- B3 B4 B5 0 98 105 99 102 114 114 10 177 137 161 179 167 190 12 160 138 160 177 ----—1 188 208 Table 3 reports the drop strength (Rp〇2) and maximum stress (Rm) values for the A1 to B5 alloy samples. These values are obtained by hot tensile testing. , which is obtained by heat treatment at 800 C for about 1 hour, followed by bonfire in water or air. The tensile test is performed using a servo hydraulic tester (MFL 1 〇〇kN) at 400. C and strain rate 1 (Γ2^). These samples were rapidly heated in a 丨 furnace (Research Inc., Model 4068-12-10) to achieve a stable test temperature in 2 minutes. , minimizes the occurrence of phase transformation during heating because of rapid heating And the high strain rate relationship, there will be cracks in the samples obtained after 400 seconds of maintenance for no more than three minutes.
表UfPa,示的坪伏強度RDp與最大應力R A1 A2 Rp〇.2 [MPa] 229 161 Rm [MPa] 422 184 B1 158 B2 134 B3 166 B4 184 B5 190 198 333 334 在CuNi9Sn6合金中加入鉛會使該合金顯著地脆 化。與其他未加入P及/或B的含Pb合金A2至B3所得 之值相較，本發明之B4及B5合金所得之降伏強度 (RPo.2)及最大應力（Rm)值獲得改善。C1及C2合金 降低了 B ( 〇.〇3重量％)及p (〇1重量％)，其於4〇〇。 c所得之降伏強度及最大應力分別是16〇 MPa及約3〇〇 MPa，與A2至B3合金於該溫度所得之值相較，亦獲得 201042060 了改善。 在前述熱拉伸測試中出現裂痕（fracture)後，對C1 及C2合金的破碎樣本的縱切面進行SEM研究（未顯 示），顯現第二相顆粒1常位於鄰近Pb夾雜物2的地方 (見第一圖及第二圖），這是一項粒間破壞，表示裂痕 沒有在更大的第二相顆粒1處集結（nucleate )。 表4就品質層面報告了合金A2至B5對淬火-裂缝 形成的敏感性。在表4中，記號「+」代表出現了裂缝， 而從「+」到「+++」，其數目及深度都有增加；而「0」 代表沒有任何裂缝。淬火實驗係使用A2至B5合金之鑄 件（as-cast)樣本來進行，首先將樣本於800°C熱處理 || 1小時，並將樣本浸入室溫水浴、或者80°C或180°C 的油浴中。之後目視檢查合金樣本表面有無裂縫。表4 顯示本發明之B4及B5合金對淬火-裂缝形成是最不敏 感的。 表4 水 油 80oC 油 180oC A2 +++ ++ + B1 +++ + + B2 ++ + + B3 +++ + + B4 + 0 0 B5 + 0 0 C) 透過鑽孔測試（說明了切削速度、進料及晶片長 度），發現本發明之B4至C2合金的可加工性與其他不 含P或B的合金相似。與其他A1至C2合金相較之下， 發現B5合金的可加工性最佳。 前述結果顯示，該硬質第二相顆粒1不代表合金中 12 201042060Table UfPa, showing the flat strength RDp and maximum stress R A1 A2 Rp 〇 2 [MPa] 229 161 Rm [MPa] 422 184 B1 158 B2 134 B3 166 B4 184 B5 190 198 333 334 Adding lead to CuNi9Sn6 alloy The alloy is significantly embrittled. The values of the lodging strength (RPo.2) and the maximum stress (Rm) obtained by the B4 and B5 alloys of the present invention are improved as compared with the values obtained by other Pb-containing alloys A2 to B3 to which P and/or B are not added. The C1 and C2 alloys reduced B (〇.〇3 wt%) and p (〇1 wt%), which were 4〇〇. The fluctuating strength and maximum stress obtained by c are 16 MPa and about 3 MPa, respectively. Compared with the value obtained by the A2 to B3 alloy at this temperature, it is also improved by 201042060. After the occurrence of a crack in the aforementioned hot tensile test, an SEM study (not shown) was performed on the longitudinal section of the fractured sample of the C1 and C2 alloys, showing that the second phase particle 1 is often located adjacent to the Pb inclusion 2 (see First and second), this is an intergranular failure, indicating that the crack does not nucleate at the larger second phase particle 1. Table 4 reports the sensitivity of alloys A2 to B5 to quenching-crack formation on the quality level. In Table 4, the mark "+" indicates that a crack has occurred, and the number and depth of "+" to "+++" have increased; and "0" indicates that there is no crack. The quenching test was carried out using an A- to B5 alloy as-cast sample. The sample was first heat treated at 800 ° C for 1 hour and the sample was immersed in a room temperature water bath or 80 ° C or 180 ° C oil. In the bath. The surface of the alloy sample was then visually inspected for cracks. Table 4 shows that the B4 and B5 alloys of the present invention are least sensitive to quenching-crack formation. Table 4 Water oil 80oC oil 180oC A2 +++ ++ + B1 +++ + + B2 ++ + + B3 +++ + + B4 + 0 0 B5 + 0 0 C) Through the drilling test (illustrated the cutting speed , feed and wafer length), the processability of the B4 to C2 alloys of the present invention was found to be similar to other alloys containing no P or B. Compared with other A1 to C2 alloys, the B5 alloy was found to have the best processability. The foregoing results show that the hard second phase particles 1 do not represent the alloy 12 201042060
粒間空穴的較佳集結位置，但會防礙在沒有空穴集結的 情況下產生晶界滑移（這是銅合金在中間溫度（3 00。C -700 C )跪化的主要原因）。此外’在本發明之含Zr、含 B及含P合金（B3、B4、B5、Cl、C2)中，Pb夾雜物 2明顯容易落在臨接固體的含B或含P第二相沉澱物1 的位置’且具有較為不規則、複雜的形狀。這可能會在 中間溫度於熔融的鉛夾雜物2與及硬質第二相1之間造 成低能量的界面’以至Pb「弄溼」了第二相顆粒1。這 會增加使熔融的Pb夾雜物2變得不穩定所需的應力， 延遲含B及含P合金斷裂，讓它們的強度更高，延展性 更好’且可月b改善其於十間溫度的拉伸性質。易言之， 在Cu基合金中加入的元素（如p、B或Zr)會使硬質 第二相1形成’它會與炼融的Pb接觸，且代表界面能 里（interfacial energy )低，如此在施加應力的情況下可 使顆粒穩定不變形。與A2及其餘的B系合金相較，B4 及B5具有較高的拉伸性質（表2)，這一點也可用晶粒 大小的差異（其中B及P係作為晶粒細化劑）及第二相 1延展性較低所導致的承載差異來解釋。 本發明之B4、B5、C1及C2合金在很大的程度上 顯然解決了加鉛改善CuNi9Sn6合金之可加工性所引起 的中間溫度脆化問題。含鉛的B3至C2合金仍然保有他 們容易加工的迷人特質。 在本發明之一具體實施態樣中，由本發明之Cu基 成之可加工性金屬產物係藉由—包含連續或 笛造製程的方法得出。在該方法中，—般係將一 塊擠壓成其直徑包含在如25麵與1酿之 ^杯一Ϊ將該合金冷卻，如以壓縮過的空氣流或水噴霧 I、#庚二他可士達到適當冷卻速度的方法，前述適當冷 形成又為高到足以限制易碎白勺（fragilizing)第二相 元成Θ時快到足以預防破裂，將於下文中進行討論。 13 201042060 之後使第一金屬塊的材料接受一或多種冷成型操 作’如親壓（rolling )、拉線（wire-drawing )、拉伸成型 (stretch-forming)、鍵打（hammering)、或任何其他冷 變形（cold deformation)製程。在冷成型步驟之後，使 第二金屬塊退火，一般是在直通式爐（through-type furnace)或可移蓋式爐（rem〇vabie c〇ver furnace)進行， 退火溫度必須是在該合金為單相 〇 (one-phased)的範圍 内在本气明之Cu合金具有前述組合物之一的情況下， 退火溫度係包含在69(rc與88(rc之間。使用退火步驟 或熱均質化處理步驟來誘發延展性、並藉由使之均質化 來細化（refine )結構、同時改善該合金的冷成型性質。 f本具體貫施態樣的另一個版本中，係在冷成型製 程之前5第二金屬塊接受退火或熱均質化處理步驟。 曰，火步驟中，第二金屬塊會發生至少部分再結 曰曰.’〗、1第二金屬塊内的新的無應變晶粒（strain_free =集結及生長’而取代那些因内部應力而變形的 步驟後，再次將第二金屬塊冷卻，其冷卻 破『以限制易碎的第二相形成，同時快到 直右或多個連續的冷成型製程步驟，依序得出 退火及;;卻屬塊，其中各冷成型步驟係在 金屬:退火及冷卻步驟之後，可將最終 而得===成直=狀， 終的離相分解熱=== 械性質。後者的熱處理可以在最終加工之前； 定的處速理卻步驟必須要在- 们速度要杈到足以預防因冷卻期間 14 201042060 溫差而產生之内部拘束力所導致的合金破裂情形，但又 要快到足以限制兩相結構的形成。如果速度太慢，就可 能會有大量的第二相出現。這個第二相非常脆弱，而且 會大大降低合金的形變性（deformability)。要避免太大 量的第二相形成，所需的關鍵冷卻速度係取決於該合金 的化學，而鎳及錫的量越高，這個速度就越大。 . 此外，在冷卻期間，合金内部產生了過渡性内部拘 . 束力（transitory internal constraint)。它們與金屬塊或產 物表面與中心之間的溫差有關。若這些拘束力超過合金 的阻力’合金就會破裂，再也無法使用。產物直徑越大， 〇 因冷卻而產生的内部拘束力就越高。因此，要避免破裂 的關鍵冷卻速度係取決於產物直徑。在本發明之方法 中’壓出及/或退火步驟之後的冷卻係於包含在50°C/min 與50000°C/min之間的冷卻速度進行。 銅-鎳-錫合金的固化時間長，故在鑄造期間引起明 顯的偏析（segregation )。在連續或半連續的鑄造製程 中’可攪拌熔融合金而得出表面狀態及其内部性性質 (如偏析及收縮）之規律性更強的禱造金屬。此外，當 熔融合金被熔融及進行鑄造時，會產生樹突結構 (dendrite structure )，無法得出精細晶粒的合金。 可以電磁方式攪拌該銅合金，以攪動該熔融物。這 樣的磁力可使該金屬塊產生足量的攪拌，而使偏析中心 (segregation center)的數目減少，得出具有平均粒徑 貫質上低於5 mm之精細等軸晶（equiaxed crystal)的 Cu基合金。 或者’可使用超音波裝置對該金屬塊中的熔融Cu 合金進行機械式攪動，而在熔融材料中製造孔穴 (cavitation )及聲流（acoustic streaming )。也可使用其 他類型的機械式攪拌，如強制氣體混合（forced gas mixing )及物理混合（如振盪(osciilating)或搖動（也仏丨叩) 15 201042060 2融合金），或使用機械裝置（如轉子、螺旋毕 =間：喷流)。或者’可將電磁攪拌與機械攪拌3 使用，或將超音波攪拌與機械攪拌組合使用。 斤發明之另一具體實施態樣中，該Cu基合金之 A直^高達32G mm，係使用噴覆成型製程 來衣作，刖述製程係如被稱為「〇 Z22573i專利所述的方法。在此，係使用i寸在；500 C) 之原子化顆粒，而可得出平均粒徑低於 未合金。可使用喷覆成型法得出一幾近均勻的 偏析程度降到最低。亦可用喷覆成型製程來 i作其他類型的金屬塊，如具有四角形剖面之鍵狀、碟 狀狀。熔融金屬或金屬合金顆粒的喷覆係在理想的 大，環境下進行，較佳為在惰性氣體環境下進行，^氮 或氬。 .或者，該金屬產物亦可藉由靜態小坯鑄造法（static billet casting meth〇d)或任一其他適當的方法得出。 該Cu基合金產物之特性為：在退火處理及冷卻步 驟後^室溫測量所得之抗拉強度包含在5⑻ N/mm2之間（700_1500 MPa);在退火處理及冷卻步驟 後測量所得之維氏硬度（HV10)包含在250與400之間； 以及以標準ASTM C36000黃銅而言，其可加工性指數〇 大於70%。此外，可輕易地對該Cu基合金產物進行加 工因為在車削時產生的碎片容易去除，有利於需要進 行特別是車削、或易削（free-cutting )、沖壓、彎曲、鑽 孔等步驟的加工操作。 本發明之Cu基合金產物有利於得出一具有下列形 狀的產物：棒狀、線狀（環狀或其他任一輪廓外形(pr〇file shape))、條狀（如軋帶(rolled strip)) '板狀、錠狀、片 狀等。該Cu基合金產物亦有利於製作一具有如高於7〇〇 N/mm2之高彈性極限（elastic limit)之加工物件（如導 16 201042060 電物件）的整體或部分，其中該加工物件係如 機電物件、電話組件、彈簧等，或應用於如二風 (micromechanics )、鐘錶學（horology )、磨刀予 (tribology )、航空學（aer〇nautic )等的微 厚潤學 或應用於任何其他各種範疇中的物件。 '蛾物件， 本發明之方法係使之得以製作一種含有古、 重量百分比之Pb及在0.01%與〇.5%之間之p 2達數個 可加工性Cu-Ni-Sn基產物，其於製作過程中 戍B的 且具有優異的機械及拉伸性質。 會破裂， Ο 〇 【圖式簡單說明】 閱言買後附申請專利範圍及本文中以實施 及以後附圖式來描述的内容將會更加理解表達 中. 其 第一圖表示本發明含B之Cu-Ni-Sn-Pb合4 切片（metallographic section)。 的金相 第二圖表示本發明之含P之Cu-Ni-Sruj^ a 相切片。 合金的金 【主要元件符號說明】 1 第二相顆粒 2 Pb夾雜物 17The preferred agglomeration position of intergranular holes, but will prevent grain boundary slip in the absence of hole aggregation (this is the main reason for the copper alloy to degenerate at an intermediate temperature (300 ° C -700 C)) . In addition, in the Zr-containing, B-containing and P-containing alloys (B3, B4, B5, Cl, C2) of the present invention, Pb inclusions 2 are likely to fall on the solid-containing B-containing or P-containing second phase precipitates. The position of 1 'has a relatively irregular, complex shape. This may cause a low-energy interface between the molten lead inclusion 2 and the hard second phase 1 at an intermediate temperature so that Pb "wet" the second phase particles 1. This increases the stress required to destabilize the molten Pb inclusions 2, delays the fracture of the B-containing and P-containing alloys, gives them higher strength and better ductility, and can improve their temperature at ten temperatures. Tensile properties. In other words, an element added to a Cu-based alloy (such as p, B, or Zr) causes the hard second phase 1 to form 'it will come into contact with the fused Pb and represent low interfacial energy, so The particles can be stabilized without deformation under stress. Compared with A2 and the remaining B-based alloys, B4 and B5 have higher tensile properties (Table 2), which can also be used for grain size differences (where B and P are used as grain refiners) and The difference in load bearing caused by the lower ductility of the two phases is explained. The B4, B5, C1 and C2 alloys of the present invention largely solve the problem of intermediate temperature embrittlement caused by the addition of lead to improve the processability of the CuNi9Sn6 alloy. Lead-containing B3 to C2 alloys still retain their fascinating qualities that are easy to process. In one embodiment of the invention, the processable metal product formed from the Cu of the present invention is obtained by a process comprising a continuous or flute process. In this method, a piece is extruded into a diameter such as 25 sides and a cup of the cup to cool the alloy, such as a compressed air stream or water spray I, #庚二他可In order to achieve a suitable cooling rate, the aforementioned suitable cold formation is again high enough to limit the fragiling of the second phase element into a crucible sufficiently fast to prevent cracking, as discussed below. 13 201042060 The material of the first metal block is then subjected to one or more cold forming operations such as rolling, wire-drawing, stretch-forming, hammering, or any Other cold deformation (cold deformation) process. After the cold forming step, the second metal block is annealed, generally in a through-type furnace or a rem〇vabie c〇ver furnace, and the annealing temperature must be in the alloy. In the case of one-phased, in the case where the present Cu alloy has one of the foregoing compositions, the annealing temperature is included between 69 (rc and 88 (rc. Using an annealing step or a thermal homogenization treatment step) To induce ductility and to refine the structure by homogenizing, while improving the cold forming properties of the alloy. f Another version of this specific aspect is before the cold forming process 5 The two metal blocks are subjected to an annealing or thermal homogenization treatment step. In the fire step, the second metal block is at least partially re-crusted. ', 1 new unstrained grains in the second metal block (strain_free = After assembling and growing, and replacing those steps that are deformed by internal stress, the second metal block is cooled again, and the cooling is broken to limit the formation of the fragile second phase, and it is as fast as right or multiple continuous cold forming. Process step Annealing is obtained in sequence; however, it is a block in which each cold forming step is after the metal: annealing and cooling steps, and finally the final === straight = shape, the final phase decomposing heat === The latter heat treatment can be performed before the final processing; the speed of the step must be at a speed sufficient to prevent the alloy fracture caused by the internal restraint caused by the temperature difference during the cooling period 14 201042060, but It is fast enough to limit the formation of a two-phase structure. If the speed is too slow, there may be a large number of second phases. This second phase is very fragile and will greatly reduce the deformability of the alloy. To avoid too much The formation of the second phase, the critical cooling rate required depends on the chemistry of the alloy, and the higher the amount of nickel and tin, the greater the speed. In addition, during the cooling, the interior of the alloy creates a transitional internal restraint. Transitory internal constraint. They are related to the temperature difference between the surface of the metal block or the product and the center. If these binding forces exceed the resistance of the alloy, the alloy will break, and again Unusable. The larger the diameter of the product, the higher the internal restraint due to cooling. Therefore, the critical cooling rate to avoid cracking depends on the diameter of the product. In the method of the invention, the 'extrusion and/or annealing step The subsequent cooling is carried out at a cooling rate comprised between 50 ° C / min and 50000 ° C / min. The copper-nickel-tin alloy has a long curing time, so it causes significant segregation during casting. Or a semi-continuous casting process in which the molten alloy can be stirred to give a more regular praying metal for the surface state and its internal properties (such as segregation and shrinkage). Further, when the molten alloy is melted and cast, a dendrite structure is generated, and an alloy of fine crystal grains cannot be obtained. The copper alloy can be stirred electromagnetically to agitate the melt. Such a magnetic force causes the metal block to generate a sufficient amount of agitation, and the number of segregation centers is reduced, resulting in Cu having a fine equiaxed crystal having an average particle diameter of less than 5 mm. Base alloy. Alternatively, the molten Cu alloy in the metal block may be mechanically agitated using an ultrasonic device to create cavitation and acoustic streaming in the molten material. Other types of mechanical agitation can also be used, such as forced gas mixing and physical mixing (such as osciilating or shaking (2010)), or using mechanical devices (such as rotors). , spiral completion = between: jet flow). Alternatively, electromagnetic stirring and mechanical agitation 3 can be used, or ultrasonic agitation can be used in combination with mechanical agitation. In another embodiment of the invention, the Cu-based alloy has a diameter of up to 32 Gmm and is applied by a spray forming process. The process is as described in the "Z22573i patent". Here, the atomized particles of i inch at 500 C) are used, and the average particle size is lower than that of the unalloyed. The nearly uniform degree of segregation can be minimized by spray coating. The spray forming process is used for other types of metal blocks, such as a key shape or a dish shape having a quadrangular cross section. The spray coating of molten metal or metal alloy particles is carried out under an ideal large environment, preferably in an inert gas. The environment is carried out, nitrogen or argon. Alternatively, the metal product can also be obtained by static billet casting meth〇d or any other suitable method. The properties of the Cu-based alloy product are : After the annealing treatment and cooling step, the tensile strength measured at room temperature is included between 5 (8) N / mm 2 (700 1500 MPa); the Vickers hardness (HV10) measured after the annealing treatment and cooling step is included in 250 Between 400; and with standard A For STM C36000 brass, the workability index 〇 is greater than 70%. In addition, the Cu-based alloy product can be easily processed because the chips generated during turning are easily removed, which is beneficial for special turning, or Processing operations for steps such as free-cutting, stamping, bending, drilling, etc. The Cu-based alloy product of the present invention facilitates the production of a product having the following shape: rod-shaped, linear (annular or any other Pr〇file shape), strip shape (such as rolled strip) 'plate shape, ingot shape, sheet shape, etc. The Cu-based alloy product is also advantageous for producing one having a value higher than 7〇〇N /mm2 of the elastic limit of the workpiece (such as guide 16 201042060 electrical object) in whole or in part, wherein the processed object is such as electromechanical parts, telephone components, springs, etc., or applied to such as two wind (micromechanics) , horology, tribology, aer〇nautic, etc., or applied to any other category of objects. 'Moth objects, the method of the present invention enables Make a kind There are ancient, weight percent Pb and p 2 between 0.01% and 〇.5% of several processable Cu-Ni-Sn based products, which are 戍B in the production process and have excellent mechanical and pull The nature of the invention will be broken. Ο 〇 [Simple description of the drawings] The contents of the patent application and the descriptions of the embodiments and the following descriptions will be more fully understood. The first figure shows the invention. A Cu-Ni-Sn-Pb-containing metallographic section containing B. Metallographic Figure 2 shows the Cu-containing Cu-Ni-Sruj^ a phase slice of the present invention. Alloy gold [Main component symbol description] 1 Second phase particles 2 Pb inclusions 17