200811297 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種低密度合金技術， 任何鍛造及軋延等熱作和冷作塑性加工之條2疋關於在不需要 性'強度、吸震性及高抗錄之-種低密轉=具有極佳的延展 其製法。 職山度巧爾夫球桿頭合金材料及 【先前技術】 • 為了能讓使用者在打高爾夫球揮桿時打感更好、打得更 穩(黏球時間長、控球性佳、震動力小）而且更遠，許多商業化 材質已被廣泛地應用在球頭材質上，例如862〇軟鐵、3〇4、沃 斯田鐵型不鏽鋼、17-4PH析出硬化型不鏽鋼、高強度的 AISI431、AISI455麻田散鐵型不鏽鋼、18Ni(2⑽)麻時效鋼、 鈦_6鋁_4釩合金和SP-700鈦合金等。但是，在這些材料中有 些是擁有很好的延伸性但強度卻嚴重不足（如8620軟鐵，304 沃斯田鐵型不鏽鋼的強度及延伸性約為6〇ksi和30%)，有些是 擁有很好的強度但延性卻很差（如AISI431，AISI455麻田散鐵 # 型不鏽鋼，18Ni(200)麻時效鋼強度為150〜200ksi但延伸性約 只有10%或以下）。 近年來，許多國内外專家學者已發展出一系列以鐵錳鋁 碳為基底之低密度高強度及高延展性合金，下列論文對這些性 質均有詳細地說明及描述。 l.G. L· Kayak 所發表，1969 年，第 2 冊，Metal Science and Heat Treatment ，第 95 頁，標題為”Fe_Mn-Al Precipitation-Hardening Austenitic Alloys^ 0 200811297 2. M.F. Alekseenko 等人所發表，1972 年，第 14 冊，Metal Science and Heat Treatment，第 187 頁，標題為丨’Phase Composition Structure and Properties of Low-Density Steel 9G28Yu9MVB"。 3. G. S. Krivonogov 等人所發表，1975 年，第 4 冊，Phys· Met. & Metallog·，第 86 頁，標題為"phase Transformation Kinetics in Steel 9G28Yu9MVBn 〇200811297 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a low-density alloy technology, any hot work for cold forging and cold working, and the like, regarding the undesired 'strength, shock absorption And high anti-recording - a kind of low-density rotation = has an excellent extension of its production method. Occupy Mountain Qiaoer Club Head Alloy Material and [Prior Art] • In order to make the user feel better and play more stable when playing golf (long sticking time, good ball control, vibration) Smaller and farther, many commercial materials have been widely used in ball head materials, such as 862 〇 soft iron, 3 〇 4, Worthfield iron stainless steel, 17-4PH precipitation hardened stainless steel, high strength AISI431, AISI455 Ma Tian loose iron type stainless steel, 18Ni (2 (10)) hemp aged steel, titanium _6 aluminum _4 vanadium alloy and SP-700 titanium alloy. However, some of these materials have good extensibility but are not sufficiently strong (such as 8620 soft iron, 304 Worthfield iron stainless steel has a strength and elongation of about 6〇ksi and 30%), and some have Very good strength but poor ductility (such as AISI 431, AISI 455 Ma Tian loose iron # type stainless steel, 18Ni (200) aging steel strength is 150~200ksi but the elongation is only about 10% or less). In recent years, many domestic and foreign experts and scholars have developed a series of low-density, high-strength and high-ductility alloys based on iron-manganese-aluminum carbon. These properties are described and described in detail in the following papers. lG L. Kayak, 1969, Volume 2, Metal Science and Heat Treatment, p. 95, entitled "Fe_Mn-Al Precipitation-Hardening Austenitic Alloys^ 0 200811297 2. MF Alekseenko et al., 1972, Volume 14, Metal Science and Heat Treatment, p. 187, entitled “Phase Composition Structure and Properties of Low-Density Steel 9G28Yu9MVB" 3. GS Krivonogov et al., 1975, Volume 4, Phys·Met & Metallog·, p. 86, titled "phase Transformation Kinetics in Steel 9G28Yu9MVBn 〇
4丄·Ι. Lysak等人所發表，1975年，第59冊， Metallogizika，第 29 頁，標題為"Stnictural and Phase Change in Steel 9G28Yu9MVB During Aging” 〇 5. J· Charles 等人所發表，1981 年 5 月，Metal Progress， 第 71 頁，標題gnNew Cryogenic Materials: Fe-Mn-Al Alloys"。 6. C_ J.Altstetter 等人所發表，1986 年，第 82 冊，Materials Science and Engineering，第 13 頁，標題為’’Processing and Properties of Fe-Mn-Al Alloys11 ° 7. K. H. Ham 等人所發表，1986 年，第 20 冊，Scripta Metal. ’ 第 33 頁’標題為’’The Evidence of Modulated Structure in Fe-Mn-Al-G Austenitic Alloys”。 8·Ρ· J· James 所發表，1969 年 1 月，J· Iron & Steel Inst·，第 54 頁，標題為”Precipitation of the Carbide (Fe， Mn)3AlC in an Fe-Al Alloy"。 綜觀上述論文研究中，以重量百分比鐵-(28〜35)錳 -(4.9〜11)鋁-(0.5〜2·0)碳為基底之合金，在經過鍛造、軋延等塑 性加工後，將合金在950°C至1200°C範圍内施以固溶熱處理後 急速淬火，然後接著將淬火後的合金在450°C至750°C範圍内 做時效熱處理，即可獲得以沃斯田鐵為基地之組織，密度介於 6 200811297 6·6至6.8g/cm3之間，抗拉強度介於lOOksi至180ksi之間， - 降伏強度介於90ksi至160ksi之間以及延伸率介於25%至65% • 之間的高強度高韌性鐵錳鋁碳合金。 除此之外，也有許多專家學者為了提高上述鐵錳鋁碳合 金之抗蝕性，另外添加了 2.98wt.%〜6wt.%的鉻以及 〇.9wt·%〜1.03wt.%的鉬等合金元素來增加合金的抗餘能力，其 腐蝕性質亦曾在下列的論文中被詳細的研究及探討過。 1.1989 年三月 J.Electronchem.Soc.期刊，第 136 期 _ 由 Jeng_Gong Duh 等人所發表之國外期刊論文 「Diffusion-Related Kinetics in the Oxidation-Induced Phase Transformation of Fe-9A1 ·3〇Γ_31Μη Alloys」。 2.1989 年 JOURNAL OF MATERIALS SCIENCE 期刊，第 23期，由Jeng-Gong Duh等人所發表之國外期刊論文 「Microstmctural development in the oxidation-induced phase transformation of Fe-Al-Cr_Mn-C alloys」。 3.1993 年 JOURNAL OF MATERIALS SCIENCE 期刊，第 28期，由J. G. Duh等人所發表之國外期刊論文「Nitriding • behavior in Fe-Al_Mn-Cr-C alloys at 1000-1100〇C」。 4.1995 年 CORROSION 期刊，第 51 期，由 S. C. Chang 等人 所發表之國外期刊論文「Environment-Assisted Cracking of Fe，32%Mn-9%Al Alloys in 3.5% Sodium Chloride Solution」。 5.1990 年 JOURNAL OF MATERIALS SCIENCE 期刊，第 25期，由J. G. Duh等人所發表之國外期刊論文「Nitriding Kinetics of Fe-Al-Mn-Cr-C alloys at 1000°C」。 6.1990 年 JOURNAL OF MATERIALS SCIENCE 期刊，第 25期，由J. G. Duh等人所發表之國外期刊論文「High 7 200811297 temperature oxidation of Fe-3 lMn-9Al-xCr-0.87C alloys(x=0? ^ and 6)」。 綜合上述有關鐵錳鋁碳合金應用在高爾夫球桿頭材質上 之中華民國專利，如第一圖所示，為其成份、熱處理及鍛造條 件比較表，由於專利第178648號合金成分中不含鉻元素，因 此合金抗蝕性不理想。專利第185568號合金之抗蝕性雖優於 專利第178648號之合金，但其於表面研磨拋光後無法通過高 爾夫球桿頭的5%氯化鈉濃度48小時的鹽霧試驗為其不足之 處。4丄·Ι. Lysak et al., 1975, Vol. 59, Metallogizika, p. 29, entitled "Stnictural and Phase Change in Steel 9G28Yu9MVB During Aging” 〇5. J. Charles et al., 1981 May, Metal Progress, p. 71, title gnNew Cryogenic Materials: Fe-Mn-Al Alloys" 6. C_J. Altstetter et al., 1986, Vol. 82, Materials Science and Engineering, page 13 , entitled ''Processing and Properties of Fe-Mn-Al Alloys11 ° 7. KH Ham et al., 1986, Vol. 20, Scripta Metal. 'Page 33' titled ''The Evidence of Modulated Structure in Fe-Mn-Al-G Austenitic Alloys". 8·Ρ·J· James, January 1969, J. Iron & Steel Inst., p. 54 entitled “Precipitation of the Carbide (Fe, Mn) 3AlC in an Fe-Al Alloy". In the above research, the alloy is based on iron-(28~35) manganese-(4.9~11) aluminum-(0.5~2·0) carbon, and after alloying by forging, rolling, etc. After quenching in a solution heat treatment in the range of 950 ° C to 1200 ° C, and then aging the alloy after quenching in the range of 450 ° C to 750 ° C, the Worstian iron is obtained. Tissue with a density between 6 200811297 6·6 and 6.8 g/cm3, tensile strength between 100 ksi and 180 ksi, - a drop strength between 90 ksi and 160 ksi and an elongation between 25% and 65% • High-strength and high-toughness iron-manganese-aluminum-carbon alloy between them. In addition, many experts and scholars have added 2.98wt.%~6wt.% of chromium to improve the corrosion resistance of the above-mentioned iron-manganese-aluminum alloy. 9.9wt·%~1.03wt.% of alloying elements such as molybdenum to increase the residual capacity of the alloy, and its corrosive properties have also been The paper was studied and discussed in detail. 1. March 1989 J. Electronchem. Soc. Journal, No. 136 _ Foreign journal article "Diffusion-Related Kinetics in the Oxidation-Induced Phase" published by Jeng_Gong Duh et al. Transformation of Fe-9A1 ·3〇Γ_31Μη Alloys". 2. 1989 JOURNAL OF MATERIALS SCIENCE, No. 23, "Microstmctural development in the oxidation-induced phase transformation of Fe-Al-Cr_Mn-C alloys" published by Jeng-Gong Duh et al. 3. 1993 JOURNAL OF MATERIALS SCIENCE, No. 28, foreign journal article "Nitriding • behavior in Fe-Al_Mn-Cr-C alloys at 1000-1100〇C" published by J. G. Duh et al. 4. 1995 CORROSION Journal, Issue 51, a foreign journal article entitled "Environment-Assisted Cracking of Fe, 32% Mn-9% Al Alloys in 3.5% Sodium Chloride Solution" by S. C. Chang et al. 5. 1990 JOURNAL OF MATERIALS SCIENCE Journal, No. 25, foreign journal article "Nitriding Kinetics of Fe-Al-Mn-Cr-C alloys at 1000 ° C" published by J. G. Duh et al. 6.1990 Journal of MATERIALS SCIENCE, No. 25, a foreign journal published by JG Duh et al. "High 7 200811297 temperature oxidation of Fe-3 lMn-9Al-xCr-0.87C alloys (x=0? ^ and 6)". The above-mentioned iron-manganese-aluminum-carbon alloy is applied to the golf club head material in the Republic of China patent, as shown in the first figure, as a comparison table of its composition, heat treatment and forging conditions, because the alloy composition of patent No. 178648 does not contain chromium. Element, therefore the corrosion resistance of the alloy is not ideal. Although the corrosion resistance of the alloy No. 185568 is superior to the alloy of the patent No. 178648, it cannot be passed through the salt spray test of the golf club head with a 5% sodium chloride concentration of 48 hours after the surface is polished and polished. .
除此之外，雖然上述專利第46〇591、5〇6845、584568及 1235677號中說明了其發明合金可通過高爾夫球桿頭的5%氯 化鈉濃度48小時的鹽霧試驗，但值得注意的是，其合金皆必 ，先進行鍛造、軋延等熱作和冷作塑性加工，將原來較差的鑄造狀 態之樹枝狀轉經由鍛造或軋延加卫改變成較佳之細微且均勻的多晶 結構，並獲得較，的表面性質，減才能通過高爾夫球桿獅鹽霧試 驗。但是，-個高爾夫球桿頭的锻造包含了多道粗鍛及精锻程序，同 時必須配合多組昂貴的鍛造模具，大幅地提高製造成本，而且重要的 是由於鍛造加工的形狀限制，造成高爾夫球桿頭形狀外觀大大的受 限’無法像精輯造般能夠有多樣㈣調功能性及㈣ 計。然而，若利用上述已公開專利合金成分以精密禱造法製 ^ 球桿頭時即無法通過鹽霧試驗。 间 【發明内容】 為了解決上述問題，本發明提出一種低密度之合 可大幅降低目前生產鐵㈣碳合金材料之高爾的 本，並且增加“夫球桿頭外㈣ 高爾夫球桿頭的材料。 應'用在製作 8 200811297 本發明目的之-’储出__種低密度之合 法，在不須任何锻造軋延衫作和冷作塑性加卫條^及^ 有極佳的延伸性、強度、吸輕及高抗純。 下，P/、 ，發明目的之-，储[種低錢之合金 法，在不須任何鍛造軋延等熱作和冷作塑性加工之條 〃 可通過鹽霧試驗，大幅降低生產成本，此外，低密度合金之設 計，致使高爾夫球桿頭較以往有更多的配重空間，^二增加= 爾夫球桿頭外型設計的多樣性。 θIn addition, although the salt spray test of the inventive alloy which can pass the 5% sodium chloride concentration of the golf club head for 48 hours is described in the above-mentioned patents Nos. 46,591, 5,684, 584, 584,568 and 1,235,677, it is worth noting that The alloys must be firstly subjected to hot work and cold work plastic processing such as forging, rolling, etc., and the dendritic transformation of the original poor casting state is changed into a fine and uniform polycrystalline by forging or rolling. Structure, and obtain a better surface properties, minus the ability to pass the golf club lion salt spray test. However, the forging of a golf club head involves multiple rough forging and precision forging procedures. At the same time, it must cooperate with multiple sets of expensive forging dies to greatly increase the manufacturing cost, and it is important to cause golf due to the shape limitation of the forging process. The shape of the club head is greatly limited in appearance. It cannot be as diverse as (fine) and functional (4). However, if the club head is manufactured by the precision prayer method using the above-mentioned patented alloy composition, the salt spray test cannot be passed. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention proposes that a low density combination can greatly reduce the current Gower of the iron (tetra) carbon alloy material and increase the material of the "four" golf club head. Should be used in the production of 8 200811297 the purpose of the invention - 'storage _ _ low-density legal, without any forging and rolling shirts and cold work plastic strips ^ and ^ have excellent extensibility, strength , light absorption and high anti-purity. Next, P /,, the purpose of the invention - storage [alloying low-alloy alloy method, without any need for forging rolling and other hot work and cold work plastic processing can pass the salt spray test, Significantly reduce production costs, in addition, the design of low-density alloys, resulting in more golf club head weight space, ^ two increase = the diversity of the design of the head of the golf club head.
本發明的目的之一，係提出一種低密度之合金材料及其製 法，此合金具有6.6g/cm3〜6.9g/cm3之間的低密度，在不須任 何鍛造軋延等熱作和冷作塑性加工之條件下，即具有 30%〜77%之間的極佳延伸性、iooks^MOksi之間的極佳抗拉 強度、高吸震性及高抗蝕性。 為了達到上述目的，本發明一實施例之低密度之合金材 料，包括重量百分比（wt·%)大於等於15小於等於22.5的錳、 大於等於7.2wt.%小於等於9.0wt_%的銘、大於等於5.1wt·%小 於等於7.8wt.%的鉻、大於等於0.6wt.%小於等於1.2wt·%的碳 及其餘比例為鐵所組合而成。 為了達到上述目的，本發明之又一實施例之低密度合金材 料之製造方法，其係對組成重量百分比（wt.%)大於等於15wt·% 小於等於22.5wt.%的錳、大於等於7.2wt·%小於等於9.0wt.o/〇 的鋁、大於等於5.lwt.%小於等於7.8wt.%的鉻、大於等於 0.6wt.%小於等於1.2wt·%的碳及其餘比例為鐵之材料經一溶 煉程序形成一合金材料。 200811297 【實施方式】 本發明合金成份係以鐵、錳、鋁、鉻及碳元素為基礎之合金，其 中猛為沃斯田鐵的強化元素，合金中沃斯田鐵相的比例將隨著合金中 錳含ΐ的增加而增加，由於沃斯田鐵相為面心立方結構，具有較多的 滑移系統，因此能有較佳的延伸性，所以錳元素的添加將有助於合金 延伸性的提升。然而，從發明人的研究發現，雖然合金中錳含量的增 加能提升合金的延展性，但是合金的抗蝕能力卻隨著合金中錳含量的 增加而降低，這是因為短元素在大氣環境中很容易氧化成不具有保護 性且與基_著性差的氧硫。進—步利絲面分析電子能譜儀 (XPS/ESCA)分析合金表面的鈍化層氧化物組成，從分析結果得知，鈍 化層的氧化敝駐縣具有綠縣縣材絲的、处〇3氧 似勿’以及不耐餘的和少量的Fe〇(Fe3〇4) F_ 氧化物。當合金恤含魏高時，將在合金表面形成一層含有較高比 例氧化链的不賴氧化鉻和氧化_倾層。所以大氣巾的氧原子將 會，氧化猛處不斷地氧化腐触並且擴散至基材内造成孔购itting)，而 不疋在表面上全面性的均勻腐钱，這理論與在含有高猛含量的鐵馳 鉻碳合金鹽霧實驗中所發現的孔蝕現象是一致的。 _ /因此’為了改善合金的祕情況，增加合金的抗賊力並且在不 須任何、軋延等齡和冷作塑性加卫之條件下，通過高爾夫球頭 的5%氯化鈉濃度48 +時的鹽霧實驗，發明人將合金中的猛含量降低 並觀察其合金表面氧化物組成的變化，第二、三、四圖分別是各含32、 28 ^ 19.5wt.〇/〇M W2 > 28.19.5)^8.2 |S.5.1 ^0.9 * 百分比計)的表面氧化物含量對合金縱深之圖表(depth ρ滿）。從這些 ’可娜見，隨著龄量的降低，合絲Φ氧碰敝成比例也隨 f降低，而且當猛含量降低至设細·％時，氧化猛的組成比例會有明 摘降低彳目反的，氧化纟g及氧化絡比例則有明顯的增加。進一步比 較其抗雜力，如紅_示，如重量百分比計騰28脸2銘_5」 (0·9石反和鐵-19.5猛-8·2銘·5.1鉻-〇·9碳兩種各含28及19细％猛含 10 200811297 里勺5金於5 /〇氣化納〉谷液中的動態電位極化曲線⑦ polarization cmves)圖，比較第五圖可發現，當合金的錳含量降至 • 19·5被％時，鈍化電流密度(IP)棚的下降，鈍化電位範圍及孔餘 電位(Epp)也明顯的增加許多，其抗蝕性優於含28wt %猛之鐵_32錳_8 2 銘-5.1鉻-0.9碳合金甚多。而且，鐵49 5躺2於5]鉻_〇 9碳合金在 不須鍛造、軋延等任何熱作和冷作塑性加工之條件下，即能通過高爾 夫球頭的5%氯化鈉濃度你小時的鹽霧實驗。然而，如先前所述，合 金中沃斯田鐵相的比例將隨著合金中猛含量的增加而增加，進而提升 合金的延展性，相對地當猛含量降低至15wt %以下時，合金的延伸性 # 將會不足。·，綜合考量合金的抗謝生及韌性等因素下，猛含量的 添加應控制在15〜22·5 wt·%之間。 鋁元素為肥粒鐵的強化元素，所以增加合金中的鋁含量會增加肥 粒鐵相的比例，相對地也會降低沃斯田鐵相的比例而降低合金的延展 性，而且，過量的鋁含量會促使一種脆性的D〇3有序規律相(〇rdercd phase)在肥粒鐵内形成進而造成合金延性嚴重的破壞。但是，鋁元素同 時也是造成鐵猛銘碳合金強化的主要碳化物的形成元素 之一，當合金鋁含量不足時，(FejVinhAjCx碳化物將無法在沃斯田鐵相 中細小且均勻整合(coherent)的析出造成合金強度的降低。除此之外， • 根據發明人的研究，齡量的不足也會抑制A12G3氧化物在合金表面的 形成，降低合金的抗餘能力。因此，配合本發明合金中15〜22 5被％猛 的添加量，以及綜合考量合金延性、強度及抗蝕能力，鋁含量的添加 -- 應控制在7.2〜9.0 wt·%之間。 • * ' * - * ^ *«. - * . … 鉻元素的添加能夠在合金表面上形成一種具有保護性的Cq〇3氧 化層，增強合金的抗钕能力。然而，鉻不但是肥粒鐵相的強化元素， 亦是碳化物的強化元素。鉻含量不足會降低合金的抗蝕性，但過多的 鉻含量及碳含量則會促使一種具有六方最密堆積結構 dose-packed structure，hq>)之碳化鉻的形成，不但造成合金的延 性降低，而且會形成鉻的空乏區，使合金容易產生孔蝕或沿晶腐蝕。 200811297 因此’配合本1¾明合金中15〜22.5 wt.%|孟的添加量，絡元素的添加應限 制在5·1〜7.8wt.%之間，碳元素的添加也應限制在〇μ 2wt%之間。另 外，矽與鉬元素少量的添加也能適度地增加合金的抗蝕能力。 依據本發明之一實施例提供一種低密度合金材料，其成分 包括15〜22.5wt.%的猛、7.2〜9,〇wt·%的銘、5·1〜7.8wt.%的鉻、 0.6〜1.2\^1:.%的峡及其餘比例為鐵，其中可添加〇〜1 %的銦 來增加合金的抗孔蝕能力。於又一實施例中，亦可加入最多 0.7wt·%的矽，矽於合金材料内能夠改善鐵錳鋁碳合金鑄造 性，南合金在液體狀態時的流動性。依據本發明所得之合金 在鑄造的狀態下具有6.6〜6.9g/em3的低密度、3〇〜77%之間的 極佳延展性、100〜140ksi之間的抗拉強度、高吸震性及高抗蝕 性之特性且不需塑性加工即可通過鹽霧試驗，可大幅降低生產 成本。 利用本發明所揭示之合金成份主要組成為以重量百分比 大於等於15小於等於22·5的錳，大於等於7.2小於等於9 〇 的銘，大於等於5.1小於等於7.8的鉻，大於等於〇 6小於等 於1 ·2的碳，及其餘比例為鐵之材料，其合金中亦可添加最多 1.5 wt·%的鉬且/或最多ο；/ wt %的矽，經一熔煉程序，例如大 氣溶煉、真空熔煉或還原氣氛熔煉，其後澆注於模内，不用再 經任何锻造及軋延等熱作或冷作的塑性加工，球頭鑄件可直接 經喷砂、研磨、焊接、桿身鑽铣孔、表面處理及美工等程序步 驟後’製作成鑄造型高爾夫球桿頭。於一實施例中，更包含在 950°C〜I200°c之間進行0.5〜10小時及於500°C〜7〇〇。〇之間進 行0〜10小時之一熱處理程序，例如固溶熱處理後，施以時效 熱處理’用以再提高合金材料之延展性及強度。由於本發明合 金在鑄造狀態下（As-Cast)即具有極佳的韌性，因此，也相當適 合進行後續的冷作及熱作等塑性加工，製作成鍛造型或禱造加 鍛造的複合型高爾夫球桿頭。 12 200811297 於一杈佳實施例中，例如由22.1wt.〇/〇的錳、8 〇lwt %的 鋁、6.21wt·%的鉻、〇.99wt·%的碳及其餘為鐵所組成的合金， • 以高週波感應爐熔煉後，澆鑄在已預熱過的高爾夫球桿頭脫蠟 殼模内，待其殼模鑄件冷卻後，即可進行震殼、切割流道澆口、 喷砂、研磨、焊接、桿身鑽铣孔、表面處理及美工等程序步驟。 不須任何鍛造及軋延等熱作和冷作等塑性加工，即能通過高爾 夫球桿頭的5%氯化鈉濃度48小時的鹽霧試驗，並具有 6.74g/cm3的低密度、38.6%的延伸率及U2.iksi的抗拉強度等 極隹性質的尚爾夫球桿頭，可大幅降低製造成本。 • 再於一較佳實施例中，例如由16.3wt.%錳、8.56wt.%鋁、 5.16wt·%鉻、UOwt·%碳及其餘為鐵的本發明合金，以高周波感應爐熔 煉後，澆鑄在已預熱過的高爾夫球頭脫蠟殼模内，鑄件在經過 真空固溶熱處理1小時後，不須任何鍛造及軋延等熱作和冷作塑性加 工，即能通過高爾域頭的5%氣化鋼濃度4M、時的鹽霧實驗，並具 有efg/cm3的低密度、76.9%的延伸率及m7ksi的抗拉強度等極佳性 質的高爾夫球頭，大幅降低製造成本。 再於一較佳實施例中，例如由19.2wt %錳、7 78wt %鋁、 6.73wt·%鉻、i.〇3wt·%碳、〇.21wt.%矽及其餘為鐵的本發明合金，以高 财感應爐麟後，麟在已賴過的高爾夫麵㈣殼模内，禱件 在經過1050 C真空固溶熱處理1小時後，不須任何锻造及軋延等熱作 作塑性加工’即能通過高爾夫球頭的5%氣化鈉濃度48小時的鹽 .…霧實驗，並具有6.78g/cm3的低密度、66·9%的延伸率及115 3ksi的抗拉 強度等極佳性質的高爾夫球頭，大幅降低製造成本。 u &藉由上述說明，利用本發明之一實施例之低密度合金材料 製造方法形成一種具有6.6g/cm3〜6.9g/cm3之間的低密度之高 爾夫球桿碩合金材料，在不須任何鍛造及軋延等熱作和冷作塑 11加工之條件下，即具有30%〜77%之間的極佳延伸性、 13 200811297 looks卜14Gksi之_邮錄強度、高吸震性及冑抗餘性（通 過5%氯化鈉濃度48小時歸試驗），而且經由適當的合金設 計，可改善合金在液· _的流祕，提高_成型性及塑 性加工性，而且可大幅降低目前生產鐵錳鋁碳合金材質之高爾 夫球桿頭的成本及時間，並能增加高爾夫球桿頭外型的設計空 間，適合應用在製作高爾夫球桿頭的材料。 綜合上述，利用本發明所揭示之合金成份及技術製作高爾 夫球桿頭，除了具有低密度、高強度、高韌性、高制震能及高 =蝕性等優異特性外，不需經由塑性加工即可通過5%氯化鈉 /辰度48小時的鹽霧試驗，更者，由於流動性的增加，可順利 地將微小字體、打擊面線溝及球頭薄區等澆鑄成型，不須再以 機械雕刻成型，大幅降低目前生產製造鐵錳鋁碳材質高爾夫球 桿頭的成本及不良率。 以上所述之實施例僅係為說明本發明之技術思想及特 點，其目的在使熟習此項技藝之人士能夠瞭解本發明之内容並 據以實施，當不能以之限定本發明之專利範圍，即大凡依本發 明所揭示之精神所作之均等變化或修飾，仍應涵蓋在本發明之 專利範圍内。 【圖式簡單說明】 第一圖所示為習知專利公開技術關於鐵錳鋁碳合金應用在高爾夫球桿 頭材質上之成分、熱處理及鍛造條件比較表。 第二圖係為與本發明比較用之一種以重量百分比計之鐵_32錳·8 2鋁 鉻4.9碳合金表面元素含ϊ與合金縱深(depth profile)之關係示意 圖。 第三圖係為與本發明比較用之一種以重量百分比計之鐵-28錳-8.2鋁 ϋ鉻碳合金表面元素含ϊ與合金縱深(depth profile)之關係示意 200811297 圖。 第四圖係為依據本發明之一實施例以重量百分比計之鐵49.5錳-8.2鋁 巧·1路_0·9碳合金表面元素含量與合金縱深(depth profile)之關係示意 圖。 第五圖係為依據本發明以重量百分比計之鐵_28錳·8.2鋁-5.1鉻-0.9碳 和鐵-19.5錳-8.2鋁-5.1鉻-0.9碳兩種各含不同錳含量的合金於5%氯化 夜中的動悲電位極化曲線(p〇tentiodynamic polarization curves)比較 示意圖。 【主要元件符號說明】One of the objects of the present invention is to provide a low-density alloy material having a low density of between 6.6 g/cm 3 and 6.9 g/cm 3 and a hot work and cold work without any forging and rolling. Under the conditions of plastic processing, it has excellent elongation between 30% and 77%, excellent tensile strength between iooks^MOksi, high shock absorption and high corrosion resistance. In order to achieve the above object, the low-density alloy material according to an embodiment of the present invention includes manganese having a weight percentage (wt·%) of 15 or more and 22.5 or less, and 7.2 wt.% or more of 9.0 wt% or less, greater than or equal to 5.1 wt·% is less than or equal to 7.8 wt.% of chromium, 0.6 wt.% or more of carbon equal to or less than 1.2 wt.%, and the balance is iron. In order to achieve the above object, a method for producing a low-density alloy material according to still another embodiment of the present invention is a composition weight percentage (wt.%) of 15 wt.% or more and 22.5 wt.% or less of manganese, and 7.2 wt% or more. ·% by weight of 9.0wt.o/〇 of aluminum, 5.lwt.% or less of 7.8wt.% of chromium, 0.6wt.% or more of 1.2wt% or less of carbon and the rest of the proportion of iron material An alloy material is formed by a melting process. 200811297 [Embodiment] The alloy composition of the present invention is an alloy based on iron, manganese, aluminum, chromium and carbon, and the ferrite element of the Worthite iron in the alloy, the proportion of the iron phase in the alloy will follow the alloy The addition of lanthanum to lanthanum increases, because the iron phase of Worth is a face-centered cubic structure with many slip systems, so it can have better extensibility, so the addition of manganese will contribute to the elongation of the alloy. Improvement. However, from the inventors' research, it is found that although the increase of manganese content in the alloy can improve the ductility of the alloy, the corrosion resistance of the alloy decreases with the increase of the manganese content in the alloy, because the short elements are in the atmosphere. It is easily oxidized to oxygen sulphur which is not protective and has poor basic properties. The inductive silk surface analysis electron spectrometer (XPS/ESCA) was used to analyze the oxide composition of the passivation layer on the surface of the alloy. From the analysis results, it was found that the oxidation layer of the passivation layer was in the county of Luxian County. Oxygen does not appear as well as a small amount of Fe(Fe3〇4) F_ oxide. When the alloy shirt contains Wei Gao, a layer of chromium oxide and oxidized _ pour layer containing a higher proportion of oxidized chains will be formed on the surface of the alloy. Therefore, the oxygen atoms of the air towel will oxidize and violently oxidize and rot, and diffuse into the substrate to cause the hole to buy, without smashing the surface of the overall uniform rot, the theory and the high content The pitting phenomenon found in the salt spray test of the iron-chromium carbon alloy is consistent. _ / Therefore 'In order to improve the secret condition of the alloy, increase the anti-thief strength of the alloy and pass the 5% sodium chloride concentration of the golf club head 48 + without any need for age, rolling age and cold plasticity In the salt spray experiment, the inventors reduced the violent content in the alloy and observed the change in the oxide composition of the alloy surface. The second, third, and fourth graphs each contained 32, 28 ^ 19.5 wt. 〇 / 〇 M W2 > ; 28.19.5) ^ 8.2 | S.5.1 ^ 0.9 * Percentage of the surface oxide content versus the depth of the alloy (depth ρ full). From these 'Kona see, as the age decreases, the proportion of Φ oxygen bumps decreases with f, and when the turbid content decreases to the fine %, the composition ratio of oxidized fierce will be reduced. Conversely, there is a significant increase in the ratio of yttrium oxide g to oxidized complex. Further compare its anti-aliasing force, such as red _ show, such as the weight percentage of Teng 28 face 2 Ming _5" (0·9 stone anti-iron and iron -19.5 Meng-8·2 Ming · 5.1 chrome - 〇 · 9 carbon two Each of the 28 and 19% fines contains 10 200811297 and 5 gold in the 5 /〇 gasification nano> valley liquid dynamic polarization polarization curve 7 polarization cmves) map, compare the fifth figure can be found when the manganese content of the alloy When it is reduced to 19.5%, the passivation current density (IP) shed decreases, the passivation potential range and the hole residual potential (Epp) also increase significantly, and its corrosion resistance is better than that containing 28wt% of the iron. Manganese _8 2 Ming-5.1 Chromium-0.9 carbon alloy is very much. Moreover, the iron 49 5 lies 2 in the 5] chromium _ 〇 9 carbon alloy without any forging, rolling and other hot work and cold plastic processing conditions, that is, you can pass the golf ball head 5% sodium chloride concentration An hourly salt spray experiment. However, as previously stated, the proportion of the iron phase in the alloy will increase as the ram content in the alloy increases, thereby increasing the ductility of the alloy, and relatively extending the alloy when the ram content is reduced to less than 15 wt%. Sex # will be insufficient. · Considering the factors such as anti-xistence and toughness of the alloy, the addition of the content should be controlled between 15~22·5 wt·%. The aluminum element is a strengthening element of the ferrite iron, so increasing the aluminum content in the alloy increases the proportion of the iron phase of the fertiliser, and relatively reduces the proportion of the iron phase of the Vostian and reduces the ductility of the alloy. Moreover, the excess aluminum The content causes a brittle D〇3 ordered regular phase (〇rdercd phase) to form in the ferrite iron and cause severe ductility of the alloy. However, aluminum is also one of the major carbide forming elements for the strengthening of the iron alloy. When the aluminum content of the alloy is insufficient, (FejVinhAjCx carbide will not be fine and uniformly integrated in the Worthfield iron phase). The precipitation causes a decrease in the strength of the alloy. In addition, according to the study by the inventors, the lack of age also inhibits the formation of the A12G3 oxide on the surface of the alloy and reduces the residual resistance of the alloy. 15~22 5 is added by %, and comprehensive consideration of alloy ductility, strength and corrosion resistance, the addition of aluminum content should be controlled between 7.2~9.0 wt·%. • * ' * - * ^ *« - - . . . The addition of chromium can form a protective Cq〇3 oxide layer on the surface of the alloy to enhance the alloy's resistance to cockroaches. However, chromium is not only a strengthening element of the ferrite phase, but also a carbide. Intensive element. Insufficient chromium content will reduce the corrosion resistance of the alloy, but excessive chromium content and carbon content will promote a chromium carbide with a hexagonal packed-packed structure, hq> To not only cause decreases ductility of the alloy, and chromium depletion region will form the alloy prone to pitting or intergranular corrosion. 200811297 Therefore, 'the addition amount of 15~22.5 wt.%|Meng in the alloy of this 13⁄4 Ming alloy, the addition of the complex element should be limited to between 5.1 and 7.8 wt.%, and the addition of carbon should also be limited to 〇μ 2wt. %between. In addition, the addition of a small amount of bismuth and molybdenum can also moderately increase the corrosion resistance of the alloy. According to an embodiment of the present invention, a low-density alloy material is provided, the composition comprising 15~22.5wt.% of fierce, 7.2~9, 〇wt·% of the Ming, 5. 1~7.8wt.% of chromium, 0.6~ 1.2\^1: The proportion of the gorge and the rest is iron, which can add 〇~1% of indium to increase the pitting resistance of the alloy. In still another embodiment, a maximum of 0.7 wt% of niobium may be added, which improves the castability of the iron-manganese-aluminum carbon alloy and the fluidity of the south alloy in a liquid state. The alloy obtained according to the present invention has a low density of 6.6 to 6.9 g/em3, an excellent ductility of between 3 Å and 77%, a tensile strength of between 100 and 140 ksi, high shock absorption and high in a cast state. The characteristics of corrosion resistance and the need of plastic processing can pass the salt spray test, which can greatly reduce the production cost. The alloy composition disclosed by the present invention mainly comprises manganese having a weight percentage of 15 or more and 22 or less, and ≥ 7.2 or less, and cerium of not less than or equal to 7.8, and greater than or equal to 5.7, less than or equal to 7.8, and greater than or equal to 〇6 and less than or equal to 〇6. 1 · 2 of carbon, and the rest of the proportion of iron material, the alloy may also add up to 1.5 wt·% of molybdenum and / or up to ο; / wt % of 矽, through a melting process, such as atmospheric melting, vacuum Smelting or reducing atmosphere smelting, and then pouring into the mold, without any hot work such as forging and rolling, or plastic processing for cold work, ball-head castings can be directly sandblasted, ground, welded, drilled and drilled, After the process steps such as surface treatment and art work, it is made into a cast golf club head. In one embodiment, it is further included between 950 ° C and 1 200 ° C for 0.5 to 10 hours and at 500 ° C to 7 °. A heat treatment process between 0 and 10 hours is carried out between the crucibles, for example, after solution heat treatment, an aging heat treatment is applied to further increase the ductility and strength of the alloy material. Since the alloy of the invention has excellent toughness in the as-cast state (As-Cast), it is also suitable for subsequent plastic processing such as cold work and hot work, and is made into a forged shape or a forged composite golf. Club head. 12 200811297 In a preferred embodiment, for example, an alloy composed of 22.1 wt. 〇/〇 of manganese, 8 〇 1 wt% of aluminum, 6.21 wt·% of chromium, 〇.99 wt·% of carbon, and the balance of iron • After being melted in a high-frequency induction furnace, it is cast in a pre-heated golf club head dewaxing shell mold. After the shell mold casting is cooled, the shell can be shaken, the runner gate is cut, and sandblasted. Grinding, welding, shaft drilling and milling, surface treatment and art procedures. It does not require any plastic processing such as forging and rolling, such as hot work and cold work, which can pass the salt spray test of 5% sodium chloride concentration of golf club head for 48 hours, and has a low density of 6.74g/cm3, 38.6%. The elongation of the armor and the tensile strength of the U2.iksi and other extreme properties of the Schalf club head can significantly reduce manufacturing costs. • In a further preferred embodiment, the alloy of the invention, for example, 16.3 wt.% manganese, 8.56 wt.% aluminum, 5.16 wt.% chromium, UOwt.% carbon and the balance iron, is smelted in a high frequency induction furnace. Casting in the pre-heated golf ball dewaxing shell mold, the casting is subjected to vacuum solution heat treatment for 1 hour, without any hot work such as forging and rolling, and cold plastic processing, that is, it can pass through the high-altitude head. The 5% carbon steel has a concentration of 4M, a salt spray test, and has a golf ball head with excellent properties such as low density of efg/cm3, elongation of 76.9%, and tensile strength of m7ksi, which greatly reduces the manufacturing cost. In still another preferred embodiment, the alloy of the present invention is, for example, 19.2 wt% manganese, 778 wt% aluminum, 6.73 wt.% chromium, i.3 wt.% carbon, 〇.21 wt.% bismuth and the balance iron. After the high-intensity induction furnace, Lin is in the golf shell (4) shell mold that he has already relied on. After 1 hour of vacuum solution heat treatment at 1050 C, the prayer piece does not require any hot work such as forging and rolling. It can pass the salt of 5% sodium carbonate concentration of the golf ball for 48 hours. It has excellent properties such as low density of 6.78g/cm3, elongation of 66.9% and tensile strength of 115 3ksi. The golf head greatly reduces manufacturing costs. u & By the above description, a low-density alloy material manufacturing method according to an embodiment of the present invention is used to form a golf club having a low density of between 6.6 g/cm 3 and 6.9 g/cm 3 , without Under the conditions of hot work such as forging and rolling and cold working, it has excellent extensibility between 30% and 77%, 13 200811297 looks, 14Gksi, postal intensity, high shock absorption and anti-shock resistance. Residue (tested by 5% sodium chloride concentration for 48 hours), and through the appropriate alloy design, can improve the flow of the alloy in the liquid, improve the moldability and plastic workability, and can greatly reduce the current production of iron The cost and time of the golf club head made of manganese aluminum alloy can increase the design space of the golf club head and is suitable for the material used in the production of golf club heads. In summary, the golf club head made by using the alloy composition and technology disclosed by the invention has the advantages of low density, high strength, high toughness, high seismic energy and high corrosion resistance, and does not need to be plasticized. It can pass the salt spray test of 5% sodium chloride/minus 48 hours. Moreover, due to the increase of fluidity, it can smoothly cast tiny fonts, blown surface grooves and thin ball-shaped areas, etc. Mechanical engraving and molding, greatly reducing the cost and non-performing rate of the current production of iron manganese aluminum carbon golf club head. The embodiments described above are merely illustrative of the technical spirit and the features of the present invention, and the objects of the present invention can be understood by those skilled in the art, and the scope of the present invention cannot be limited thereto. That is, the equivalent variations or modifications made by the spirit of the present invention should still be included in the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows a comparison table of the composition, heat treatment and forging conditions of the iron manganese aluminum alloy applied to the golf club head material. The second figure is a schematic diagram showing the relationship between the surface element of lanthanum _32 manganese·8 2 aluminum chrome 4.9 carbon alloy and the depth profile of the alloy in comparison with the present invention. The third figure is a graph showing the relationship between the surface element of lanthanum -28-manganese-8.2 aluminum lanthanum-chromium carbon alloy and the depth profile of the alloy in comparison with the present invention. The fourth figure is a schematic diagram showing the relationship between the surface element content of iron 49.5 manganese-8.2 aluminum and one-way_0·9 carbon alloy and the depth profile of the alloy according to an embodiment of the present invention. The fifth figure is an alloy of different manganese content in the weight percentage of iron _28 manganese·8.2 aluminum-5.1 chromium-0.9 carbon and iron-19.5 manganese-8.2 aluminum-5.1 chromium-0.9 carbon according to the invention. A schematic diagram comparing the p〇tentiodynamic polarization curves of 5% chlorinated nights. [Main component symbol description]
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