1321592 九、發明說明： 【發明所屬之技術領域】 - 本發明係關於一種低密度、高強度、高韌性之合金材料 . 及其製法。該材料除了具有極佳的延伸性、強度與吸震性 外’特別適合用於高爾夫球桿頭之製造上，其可使在高爾夫 球桿頭的設計上達到優異的設計變化空間、高強度、高延伸 性，並且更能降低高爾夫球桿頭在電鍍過程中所產生的孔蝕 (pitting )孔洞及缺陷的發生，因此大幅降低產品的不良率 0及成本。 【先前技術】 所謂合金材料係藉由兩種或兩種以上的金屬（或金屬跟 ' 非金屬或元素）熔合而成的具有金屬特性的物質。因此該融 - 合而成的金屬合金材料，其本身的性質因其所添加物的不同 會隨之發生變化，例如，熔點降低、強度升高、延展性降低、 導熱度降低、耐蝕性變化或密度變化等等。所以隨著各種機 械與器具等不同的應用與設計需求，選擇適當的合金材料並 ® 控制其含量、製造程序、加工程序等，以配製成適用的合金 材料。 例如，鐵-鋁-錳合金材料是以鐵鋁錳三元素合金爲基材 而發展出的合金系列。其經過國內外學者專家廣泛的硏究， ' 顯示不同的合金設計能使鐵-鋁-錳合金材料分別具有高強 ' 度、高韌性、耐低溫、耐高溫、耐耗磨等特性。 而本發明者於1989年利用新的合金設計理念成功開發 之熱乳合金鋼板（hot-rolled alloy steel plate)，其可經過 1321592 適當的合金設計，使得鐵-錳-合金材料在熱軋的狀態下，不 須再經過任何後續熱處理，則其機械性質便可以達到或更優 • 於目前須經過沃斯田鐵化、淬火與回火的商業用或軍事用之 . 淬火-回火合金材料（美國專利第4968357號、中華民國專 利第42454號、日本專利第1971688號、韓國專利第53613 號、法國專利第8902580號、英國專利第2227495號、加拿 大專利第1 3 3 3 5 5 6號、德國專利第3 9 03 774號）。而且該鐵 -鋁-錳-碳合金經固溶化、淬火及時效處理後，依合金成份不 1 同，其機械性質之抗拉強度介於80〜200ksi之間，降伏強 度介於70〜160ksi之間，而延伸率則介於50〜25%之間。而 將鋁、錳、碳等元素含量作適合之調整後，並添加少量的鈦、 鈮或釩等元素（Ti+Nb + VS0.5重量百分比），經過巧妙的 設計與連續熱滾軋後，則鐵·鋁-錳熱軋合金材料在熱軋的狀 態下（不須再經過任何後續熱處理），便可具有120〜200ksi 之間的抗拉強度和介於80〜160ksi之間的降伏強度，同時 其延伸與衝擊韌性値在60〜30%與1 80〜40ft-Ib之間，其性 質可以達到甚至更優於AIS13 〇4、306不銹鋼和經沃斯田鐵 化、淬火及回火的9%鎳剛合金材料。 高強度高韌性合金材料，與目前商業化用合金材料來比 較時，其意義上是指能同時具有高強度與高韌性之組合性 質。舉例而言，目前商業化用合金材料具有高靭性者（如延 伸率30%以上）首推鐵-鉻-鎳系沃斯田鐵型不銹鋼。例如304 不銹鋼，其延伸率約爲3 0%至4 0% ’但其抗拉強度和降伏強 度分別爲70至90 ksi和25至45 ksi，韌性値在室溫時約 1321592 爲154ft-lb，在-196°C時約爲70ft-ib。此合金材料能具有 如此優異的延伸率，主要乃導因於擁有完全沃斯田鐵面心立 方（face-centered cubic, FCC)結構。 目前商業化用合金材料有高強度者甚多，但大多乃利用 經過沃斯田鐵化—淬火〜回火等熱處理步驟，使其具有回火 麻田散鐵顯微結構。以廣被使用的4340合金材料爲例，在 經過沃斯田鐵化、淬火、回火後，其抗拉強度、降伏強度、 延伸率和衝擊値分別約爲：1 8 〇 k s i，1 6 8 k s i，1 7 %和3 5 f t -1 b (回火溫度5 4 0 °C，時間一小時），或1 4 8 k s i，1 2 5 k s i，2 0 % 和74 ft-lb (回火溫度6 5 0 °C，時間一小時）。所以所謂「高 強度高韌性鐵鋁錳合金材料」其意乃指「同時具有像沃斯田 鐵型不銹鋼的延伸 率和具有合金鋼淬火回火後的強度」。高強度高韌性鐵 鋁錳合金材料主要成分爲鐵鋁錳碳，錳元素的添加主要是穩 定沃斯田鐵相，而使此合金材料在室溫或低溫均爲面心立方 結構’以改善Fe-Al或Fe-Al-C合金材料的脆性，而使此 合金材料具有良好的韌性和加工性。此合金材料主要的強化 方法爲析出強化，即將合金於1 050至1 1 00。(：間做固溶化熱 處理後急速淬火，並於4 5 0 °C至7 5 0。(：間做時效熱處理。當 合金在淬火狀態時爲單一沃斯田鐵相；時效熱處理後有細微 (Fe，Mn)3AlCx (κ-相）碳化物均勻整合在基材內析出， (Fe，Mn)3AlCx具有規律面心立方（ordered FCC) L'l2結構， 此析出反應乃爲鐵鋁錳碳合金最主要的強化機構。依據硏究 成果發現，鐵鋁錳碳合金經固溶化、淬火及時效處理後，依 1321592 合金成分不同’其機械性質：抗拉強度介於80至2 OOksi之 間，降伏強度介於70至160 ksi之間，而延伸率介於70至 2 0 %之間。 鐵-鋁-錳合金材料經過國內外專家學者的廣泛硏究後 發現，經由鉻及鉬合金元素的添加，能增加合金的抗鞞能 力，下列文獻對於這些性質均有詳細的描述，且在此倂入本 發明的參考內容中： 1 . 1989 年三月J·EIectronchem.Soc·期刊，第136期，No·3, 由 Jeng-Gong Duh 等人所發表之國外期刊論文 「D i f f u s i ο η - R e 1 a t e d Kinetics in the Oxidation-Induced1321592 IX. Description of the invention: [Technical field to which the invention pertains] - The present invention relates to an alloy material of low density, high strength and high toughness and a method for producing the same. In addition to its excellent extensibility, strength and shock absorption, the material is especially suitable for the manufacture of golf club heads, which can achieve excellent design change space, high strength and high in the design of golf club heads. It is more extensible and can reduce the occurrence of pitting holes and defects generated during the electroplating process of the golf club head, thereby greatly reducing the defect rate and cost of the product. [Prior Art] The alloy material is a material having metal characteristics obtained by fusing two or more kinds of metals (or metals with 'nonmetals or elements). Therefore, the metal alloy material which is melted and combined may have its own properties which vary depending on the additives to be added, for example, a decrease in melting point, an increase in strength, a decrease in ductility, a decrease in thermal conductivity, a change in corrosion resistance, or Density changes and more. Therefore, with the different application and design requirements of various machinery and appliances, select the appropriate alloy material and ® to control its content, manufacturing procedures, processing procedures, etc., to prepare suitable alloy materials. For example, an iron-aluminum-manganese alloy material is an alloy series developed from an iron-aluminum-manganese three-element alloy. It has been extensively studied by scholars at home and abroad, 'showing different alloy designs can make iron-aluminum-manganese alloy materials have high strength, high toughness, low temperature resistance, high temperature resistance and wear resistance. The inventor succeeded in developing a hot-rolled alloy steel plate in 1989 using a new alloy design concept, which can be subjected to a suitable alloy design of 1321592, so that the iron-manganese-alloy material is in a hot rolled state. Under no further heat treatment, the mechanical properties can be achieved or better. It is currently used for commercial or military use in the fertilization, quenching and tempering of Vostian. Quenching-tempering alloy materials ( U.S. Patent No. 4,968,357, Republic of China Patent No. 42454, Japanese Patent No. 1971688, Korean Patent No. 53613, French Patent No. 8902580, British Patent No. 2227495, Canadian Patent No. 1 3 3 3 5 5 6 , Germany Patent No. 3 9 03 774). Moreover, after the iron-aluminum-manganese-carbon alloy is solution-solved, quenched and treated in a timely manner, the tensile strength of the mechanical properties is between 80 and 200 ksi, and the tensile strength is between 70 and 160 ksi. Between, and the elongation is between 50~25%. After adjusting the content of aluminum, manganese, carbon and other elements as appropriate, and adding a small amount of elements such as titanium, tantalum or vanadium (Ti+Nb + VS0.5% by weight), after ingenious design and continuous hot rolling, The iron-aluminum-manganese hot rolled alloy material has a tensile strength between 120 and 200 ksi and a strength between 80 and 160 ksi in the hot rolled state (without any subsequent heat treatment). At the same time, its extension and impact toughness 之间 between 60~30% and 180~40ft-Ib, its properties can reach even better than AIS13 〇4, 306 stainless steel and fermented, quenched and tempered by Worthfield 9 % nickel alloy material. High-strength and high-toughness alloy materials, when compared with current commercial alloy materials, mean a combination of high strength and high toughness. For example, currently commercial alloy materials with high toughness (such as elongation of 30% or more) are the first to push iron-chromium-nickel-type Worth-type iron-type stainless steel. For example, 304 stainless steel has an elongation of about 30% to 40% 'but its tensile strength and lodging strength are 70 to 90 ksi and 25 to 45 ksi, respectively, and the toughness is about 154 ft-lb at 1321592 at room temperature. It is about 70 ft-ib at -196 °C. This alloy material has such an excellent elongation, which is mainly due to the fact that it has a completely face-centered cubic (FCC) structure. At present, there are many high-strength alloy materials for commercial use, but most of them use heat treatment steps such as ironation-quenching-tempering in Vostian to make the microstructure of tempered granules. Taking the widely used 4340 alloy material as an example, after fertilization, quenching and tempering in Worthing, the tensile strength, the lodging strength, the elongation and the impact enthalpy are respectively about: 18 〇ksi, 1 6 8 Ksi, 1 7 % and 3 5 ft -1 b (tempering temperature 5 4 0 °C, time one hour), or 1 4 8 ksi, 1 2 5 ksi, 20% and 74 ft-lb (tempering temperature) 6 5 0 °C, time one hour). Therefore, the so-called "high-strength, high-toughness iron-aluminum-manganese alloy material" means "the elongation of the steel-type stainless steel like Vostian and the strength of the alloy steel after quenching and tempering". The main component of the high-strength and high-toughness iron-aluminum-manganese alloy material is iron-aluminum-manganese carbon. The addition of manganese element mainly stabilizes the iron phase of the Vostian, and the alloy material is a face-centered cubic structure at room temperature or low temperature to improve Fe. - The brittleness of the Al or Fe-Al-C alloy material gives the alloy material good toughness and processability. The main strengthening method for this alloy material is precipitation strengthening, which is about 1 050 to 1 00. (: After quenching heat treatment, it is quenched rapidly, and it is aged at 450 ° C to 7 5 0. (: aging heat treatment. When the alloy is quenched, it is a single Worth iron phase; after aging heat treatment, there is fine ( Fe, Mn)3AlCx (κ-phase) carbides are uniformly integrated in the substrate, and (Fe,Mn)3AlCx has a regular ordered FCC L'l2 structure. The precipitation reaction is iron-aluminum-manganese carbon alloy. The most important strengthening mechanism. According to the results of the research, it is found that the iron-aluminum-manganese carbon alloy is solution-dissolved, quenched and treated in a timely manner, according to the composition of the alloy 1321592. Its mechanical properties: tensile strength between 80 and 2,000 ksi, lodging The strength is between 70 and 160 ksi, and the elongation is between 70 and 20%. The iron-aluminum-manganese alloy material has been extensively studied by experts and scholars at home and abroad, and found through the addition of chromium and molybdenum alloy elements. It can increase the anti-cracking ability of the alloy. The following documents have a detailed description of these properties, and are incorporated herein by reference: 1. March 1989 J. EIectronchem. Soc·Journal, No. 136, No.3, published by Jeng-Gong Duh et al. Papers outer "D i f f u s i ο η - R e 1 a t e d Kinetics in the Oxidation-Induced
Phase Transformation of Fe- 9 A1 -3 Cr-3 1 Μn A11 oy s」。 2. 1 9 89 年 JOURNAL OF MATERIALS S CIEN C E 期刊，第 2 3 期，由 Jeng-Gong Duh 等人所發表之國外期刊論文 Γ M i c r 〇 s t r u c t u r a 1 development in the oxidation-induced phase transformation of F e - A1 - C r-Μ n - C alloys j 。Phase Transformation of Fe- 9 A1 -3 Cr-3 1 Μn A11 oy s". 2. 1989, Journal of MATERIALS S CIEN CE, Issue 2, Foreign Journals published by Jeng-Gong Duh et al. Γ M icr 〇 structura 1 development in the oxidation-induced phase transformation of F e - A1 - C r-Μ n - C alloys j .
3. 1 993 年 JOURNAL OF M A TE RIA L S S CIE N C E 期刊，第 2 8 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 1000-1 100 °C」。 4. 1995 年 CORROSION 期干IJ，第 51 期，由 S. C. Chang 等人所 發表之國外期刊論文「Environment-Assisted Cracking of3. 1 993 JOURNAL OF MA TE RIA LSS CIE NCE Journal, Issue 28, Foreign Journal Papers by JG Duh et al. "Nitriding behavior in Fe-Al-Mn-Cr-C alloys at 1000-1 100 °C". 4. 1995 CORROSION period IJ, issue 51, foreign journal article "Environment-Assisted Cracking of" published by S. C. Chang et al.
Fe-32%Mn-9%Al Alloys in 3.5% Sodium Chloride Solution」 。 5. 1 990 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 1321592 ·* Kinetics of Fe-Al-Mn-Cr-C alloys at 1000 〇C」。 6. 1 990 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「HighFe-32% Mn-9% Al Alloys in 3.5% Sodium Chloride Solution". 5. 1 990 JOURNAL OF MATERIALS SCIENCE Journal, Issue 25, foreign journal article "Nitriding 1321592 · * Kinetics of Fe-Al-Mn-Cr-C alloys at 1000 〇C" published by J. G. Duh et al. 6. 1 990 JOURNAL OF MATERIALS SCIENCE Journal, Issue 25*, a foreign journal article published by J. G. Duh et al.
temperature oxidation of F e - 3 1 Μη - 9 A1-x C r-0 · 8 7 C alloys(x = 0, 3 and 6)」。 7. 民國89年（ 1 990)國立交通大學劉增豐教授（本專利申請 之發明人之一）所指導之碩士論文「鐵-8.8鋁- 30.0錳-6.0 絡-1.0 碳合金相變化」（Phase Transformations in an • Fe-8.8Al-30.0Mn-6.0Cr-l .0C Alloy)。 是故，鐵-鋁-錳合金材料的優質機械性質與低密度特 性，在各個商業應用的領域中，均可適用，特別是在於高爾 夫球桿頭製造產業領域。 ' 高爾夫球爲了要打得更遠，其桿頭的合金材料必須十分 的優異，且須具備以下特性：（〇低密度：在同樣號數桿 頭必須在規定的重量之下，低密度的材質可加大桿頭體積， 增加擊球的甜蜜區’以提局正確位置的擊球率，並且可增加 配重的設計空間，設計低重心桿頭，將桿頭重心往下，增加 擊球時的穩定性及扭力，打得更穩更遠。（2)高延伸性與 適當強度的組合：要打得更穩、震動力越小、控球方向要準， . 則桿頭合金材料的延伸性、靭性要更優異，如此在這樣的條 件下打擊時球與桿頭間黏球的時間才會越長，而且高延伸性 材質球頭可依照打球者的身高，調整最適合打球者身高的桿 身與打擊面間的角度，延伸性越高，可調整桿身角度範圍就 越大。（3)高阻尼比：吸震能力高，打擊者不會有手麻及 1321592 震動的不舒服感覺，打感佳控球穩。（4)高彈性係數（楊氏係 數）：彈性#數高，擊球距離遠。（5)材質本身或經表面處理 * 後具有高抗蝕能力··可長期在含水份及化學除草劑的草地上 . 使用不易生鏽，維持桿頭功能及美觀。 因此要達到上述的擊球條件，許多商業化合金材料不斷 的被嘗試應用在高爾夫球桿頭上。而依據所欲擊球的目的之 不同’又可將高爾夫球桿分爲木桿桿頭與鐵桿桿頭》—般而 言’木桿桿頭呈中空球形，桿身長度較長，主要使用於開球 或長距離打擊。傳統的木桿桿頭係由木頭製成，主要原料爲 柿木，但由於其抗腐蝕性、韌性與強度不佳，已被金屬合金 材料所製成之桿頭所取代。目前商業上用來製作木桿桿頭常 見的材質例如，純鈦、Ti-6A1-4V合金、β -鈦、17-4PH不銹 鋼與高強度的431、455麻田散鐵型不銹鋼。另外，鐵桿主 要用以將球擊至目標處，其特徵爲球飛行距離比木桿稍短， 但可將球擊得較高，且控球性較佳。而目前商業上用來製作 鐵桿桿頭常見的材質，主要爲不銹鋼系列合金材料，例如， 17-4ΡΗ不銹鋼、8620鋼、304不銹鋼、18Ni(200)麻時效鋼 或鈦合金。 而在上述這些材料中有些是擁有很好的延伸性但強度 卻嚴重不足’例如，8620鋼與304不銹鋼的強度及延伸性約 爲6 0 ksi和3 0%。另有些是擁有很好的強度但延伸性卻很 差，例如’ 43 1、45 5麻田散鐵型不銹鋼、丨8Ni(200)麻時效 鋼’其強度大約爲150〜2〇〇ksi但延伸性約只有10 %以下。 至於鈦合金材料’其密度介於4.5〜4.8 g/cm3之間，強度及 -10- 1321592 -* 延伸率約爲1 4 0〜1 8 0 k s i及7〜1 4 %之間，而鈦合金的開 發與量產使得高爾夫球桿頭之設計產生極大的變化空間，惟 - 鈦合金價格實在太高，而且延伸性不高。 . 因此，目前工業量產之高爾夫球桿頭所需的條件特性 爲：（1 ) 7.8 g/cm3以下的低密度。（2 )延伸率10%以上。 (3)抗拉強度lOOksi以上》(4)材質本身或經表面處理 後能通過24至48小時5%濃度的鹽霧試驗。 以上均爲基本之需求，當然強度與延伸率的組合越高以 ® 及密度越低越好，藉以增加桿頭體積、擴大擊球甜蜜區、增 加擊球的距離與操控性。然而綜觀相關參考文獻所述相關的 合金材料應用在高爾夫球桿頭之專利文獻，包括鐵鋁錳碳合 ' 金材料，除了台灣專利公告編號第178 648號所揭示的合金 ' 材料成分中不含有鉻元素，以及台灣專利公告編號第5 06 84 5 號所揭示的合金材料成分中可不含有鉻元素但含有鈦元素 外（但在其成分中因爲分別含有高含量的碳及鈦元素，很容 _ 易在晶界上析出粗大的碳化物，造成合金的韌性降低，而使 得以此類合金材料製成的高爾夫球桿頭在進行打擊面砲擊 測試時，很容易就產生裂痕或破裂），其餘專利文獻中所揭 示的高爾夫球桿頭合金材料成份中，其爲了提高抗蝕性均添 加了重量百分比5至9的鉻元素，但其抗蝕性仍不及於 17-4PH不銹鋼與高強度的431、455麻田散鐵型不銹鋼等常 ' 用於高爾夫球桿頭上的各式不銹鋼合金材料。爲了使鐵鋁錳 碳合金材質高爾夫球桿頭能達到上述抗蝕能力，即通過鹽霧 測試，仍必須在原材質上施以電鍍表面處理》 1321592 由於在鐵鋁錳碳合金材料中添加鉻元素時，會使得合金 表面自發性的產生三氧化二鉻（Cr2〇3 )氧化層，雖然鉻元 素的加入使得合金的抗蝕性增加，但卻因爲無法利用普通的 酸處理及活性化處理來去除附著性強的三氧化二鉻氧化 層，因爲此氧化層不導電，如同一絕緣層，造成電鍍層與高 爾夫球桿頭本身基材的附著性降低，使得電鍍層很容易在擊 球時剝落或者根本無法附著在基材上。但若是以利用電鍍不 銹鋼時的酸處理及活性化處理來去除含有鉻的鐵鋁錳碳合 金表面上的不連續三氧化二鉻氧化層時，其於酸處理時的高 氯離子濃度則會造成鐵鋁錳碳合金高爾夫球桿頭表面上嚴 重的孔触孔洞，而造成在電鍍過程中產生極高的不良率與壞 品。 因此，若能開發出低密度、高延伸性或高韌性、價格合 理、具有一定硬度且可避免在電鑛過程中產生孔蝕孔洞之合 金材料’則其低密度與適當的強度將使高爾夫球桿頭之設計 空間增加’高延伸性或高韌性則可使控球性能增加，如此一 來便可使高爾夫球桿頭之打擊效果發揮到極致，且亦可大幅 降低量產製造之成本。 【發明內容】 有鑑於此，本發明者乃利用合金設計與製程處理之槪 念’針對上述其他有關鐵鋁錳碳合金高爾夫球桿頭所存在之 缺點’硏發出本發明之低密度高強度高韌性合金材料及其製 法’該合金材料能同時兼具有6.6〜6.9 g/cm3的密度、25〜 70%的延伸性與韌性以及！ 〇〇〜190ksi的抗拉強度，並將其 -12- 1321592 應用在高爾夫球桿頭上’而且可以降低目前電鍍鐵鋁錳碳合 金材料之高爾夫球桿頭過程中所產生的孔蝕孔洞，大幅增加 產品的良率。 而以各種添加元素之設計原理與其對於材料性質的影 響，詳述如下， 1. 錳··錳元素爲沃斯田鐵相的強化元素，由於沃斯田鐵相 爲面心立方結構，具有較多的滑移系統，因此能有較佳 的延伸性.，所以錳的添加能增加沃斯田鐵相的比例，同 時也提高合金的延伸性，欲使合金具有極佳延展性，錳 元素添加量至少須在15重量百分比或以上，但錳元素添 加量超過33重量百分比以上時，由於β-Μη的析出，反 而造成合金延展性的下降。故本發明中錳元素的添加應 限制在大於等於1 5小於等於3 3重量百分比之間。 2. 鋁：鋁元素不但是肥粒鐵的強化元素，同時也是 (Fe,Mn)3AlCx超結晶格子碳化物的主要形成元素之一， 所以（Fe，Mn)3AlCx碳化物的析出狀況及量的多寡與銘元 素的添加量間有極密切的關係。當鋁元素添加量在6重 量百分比以下時，（Fe，Mn)3AlCx碳化物在沃斯田鐵基地 內的析出量太少，合金將達不到令人滿意的強度。但是 當鋁元素添加量超過10重量百分比以上時，不但會有肥 粒鐵相的形成，而且會促使無序的（disordered)肥粒鐵相 (bcc)轉變爲一種極脆的D03有序（ordered)相。另外，由 於碳在肥粒鐵相的飽和濃度相當低，很容易導致粗大的 (Fe，Mn)3AlCx碳化物在沃斯田鐵相與肥粒鐵相間的晶界 -13- 1321592 上析出，此現象不但未能提高合金的強度’反而使合金 的延展性急遽的降低，形成脆性的沿晶破裂。因此’本 發明中鋁元素的添加量宜限制在大於等於6小於等於1 〇 重量百分比之間》 3. 碳：碳元素不但是沃斯田鐵鐵的強化元素，同時也是形 成（Fe，Mn)3AlCx超結晶格子碳化物的基本元素。同樣的’ 當碳元素的添加量在 0.6重量百分比以下時， (Fe，Mn)3AlCx碳化物在沃斯田鐵基地內的析出量太少， 合金將無法達到令人滿意的強度。但是當碳元素的含量 超過1 .2重量百分比以上時，則在沃斯田鐵晶粒邊界上析 出的碳化物含量急速的增加且顆粒變大，合金容易成爲 沿晶破裂模式，反而使合金的延展性急遽的降低》因此， 本發明中碳元素的添加量宜限制在大於等於〇. 6小於等 於1.2重量百分比之間。 4. 矽：矽元素的微量添加在0.1重量百分比或以上時可以促 使（Fe，Mn)3AlCx碳化物於冷卻的過程中經由史賓若多相 分解反應（spinodal decomposition)在沃斯田鐵相中微細 且均勻地析出，可提高合金的強度並且對延展性影響不 大，另外，矽元素的添加也增加合金在液態時的流動性， 提高合金的鑄造性。然而，矽元素在鐵錳鋁合金系統中 不但是肥粒鐵相的強化元素，更是一種很強的D03有序 (ordered)相的形成元素，當矽元素的含量超過1.〇重量百 分比以上時，會促使脆性的D03有序相的形成，一旦合 金中有D03有序相的析出，合金的延展性將會嚴重的被 -14- 1321592 破壞。因此，本發明中矽元素的添加量宜限制在大於等 於0 · 1小於等於1 · 0重量百分比之間。 5 .鉬··鉬元素雖然是一種很強的碳化物形成元素，但是對 (Fe, Mn)3 A1CX碳化物的形成並沒有明顯的效果，但是根 據發明人的實驗發現，鉬的添加可以造成合金的固溶強 化，因此，可以增加合金的強度，而且對延展性影響不 大。但是，當鉬元素的含量超過1.5重量百分比以上時， MzC ’ MuC6及M6C等碳化鉬的析出，導致其附近的沃斯 田鐵相因爲缺乏足夠的碳元素而變得相當不穩定，很容 易轉變爲肥粒鐵相，反而對合金的延展性有不利的影 響。因此，本發明中鉬元素的添加量宜限制在小於等於 1 . 5重量百分比。 因此爲達成前述之目的，本發明係針對各種添加元素設 計比例與成分範圍反覆硏究，終於發明一種低密度高強度高 韌性合金材料，其合金材料包含15〜33重量百分比之錳、6 〜10重量百分比之鋁、0.6〜1.2重量百分比之碳、〇.1〜1.〇 重量百分比之矽，其中亦可添加至多1.5重量百分比的鉬， 其餘比例以鐵爲基材所組合而成。 本發明之合金材料，其包含包含15〜33重量百分比之 錳、6〜10重量百分比之鋁、0.6〜1.2重量百分比之碳、〇.1 〜1.0重量百分比之砂，其中亦可添加至多1.5重量百分比 的鉬，其餘比例以鐵爲基材，其經一熔煉程序形成一鑄件 後，其可選擇在950至1200 °C溫度之間進行0.5〜1〇小時的 固溶熱處理，接著在5 00至7 00°C溫度之間進行至多24小時 -15- 1321592 的時效熱處理，或者也可選擇不經任何熱處理。 本發明之合金材料，其包含包含15〜33重量百分比之 錳、6〜10重量百分比之鋁、〇.6〜1.2重量百分比之碳、〇」 〜1.0重量百分比之矽，其中亦可添加至多1.5重量百分比 的鉬’其餘比例以鐵爲基材，其經一熔煉程序形成一合金材 料，該合金材料在800至1200°C溫度之間進行锻造、軋延等 塑性加工’而該合金材料在經過塑性加工後可選擇在950至 1200 °C溫度之間進行0.5〜10小時的固溶熱處理，接著在500 至700 °C溫度之間進行至多24小時的時效熱處理，或者也可 選擇不經任何熱處理。 【實施方式】 爲使該所屬技術領域中具有通常知識者能更進一步瞭 解本發明之組成成分及其機械特性，茲配合具體實施例、圖 式與表格詳加說明，當更容易瞭解本發明之目的、技術內 容、特點及其所達成之功效。 本發明係關於一種低密度高強度高韌性合金材料，並可 應用於高爾夫球桿頭之製造，其主要之元素組成成分包含15 〜33重量百分比之錳、6〜10重量百分比之鋁、0.6〜1.2重 量百分比之碳、0.1〜1.0重量百分比之矽，其中亦可添加至 多1 .5重量百分比的鉬，其餘比例以鐵爲基材所組合而成之 合金材料。 以下即配合實施例詳細說明，如第1圖所示，合金編號 1〜7爲本發明之成份範疇，編號8〜13爲習知技術所製成之 合金材料組成成分的範圍，在此將之列爲比較實施例，並且 -16- 1321592 倂入本發明之參考資料。 合金編號1 : 27.8重量百分比之錳、8.8重量百分比之 - 鋁、0.95重量百分比之碳、0.28重量百分比之矽及其餘比例 . 以鐵爲基材之本發明較佳實施例，其以高周波感應爐熔煉 後’澆鑄在已預熱過的高爾夫桿頭脫蠟殻模內，待其殻模鑄 件冷卻後，即可進行震殼、切割流道澆口、噴砂、硏磨、焊 接、桿身鑽铣孔 '電鍍、表面處理及美工等程序步驟。不須 任何锻造及軋延等熱作和冷作塑性加工，也不須經過任何熱 1 處理的情況下，高爾夫桿頭鑄件即具有6.70g/cm3的低密 度' 38.6%的延伸率及122.5ksi的抗拉強度等極佳性質，而 且桿頭經過電鍍後，可大幅降低孔蝕孔洞的產生。 合金編號2: 30.3重量百分比之錳，8.8重量百分比之 鋁’ 1.15重量百分比之之碳，0.16重量百分比之矽、1.05 重量百分比之鉬及其餘比例以鐵爲基材之本發明另一較佳 實施例，其以高周波感應爐熔煉後，澆鑄在已預熱過的高爾 夫桿頭脫蠟殼模內，待其殼模鑄件冷卻後，即可進行震殼、 1 切割流道澆口、噴砂、硏磨、焊接、桿身鑽铣孔、電鍍、表 面處理及美工等程序步驟。由於另外添加了 1.05重量百分 比之鉬，所以能在不須任何鍛造及軋延等熱作和冷作塑性加 工以及任何熱處理的情況下，高爾夫桿頭鑄件強度可再增加 8〜lOksi，即具有6.79g/cm3的低密度、35.1%的延伸率及 130.7ksi的抗拉強度等極佳性質，而且桿頭經過電鍍後，可 大幅降低孔蝕孔洞的產生。 合金編號3: 17.5重量百分比之錳、6.2重量百分比之 -17- 1321592 ' 鋁、1.08重量百分比之碳、0·15重量百分比之矽及其餘比例 以鐵爲基材之本發明另一較佳實施例，其以高周波感應爐熔 • 煉後，澆鑄在已預熱過的高爾夫桿頭脫蠟殼模內，桿頭鑄件 • 在經過1 1 001真空固溶熱處理4小時後，不須任何鍛造及軋 延等熱作和冷作塑性加工，高爾夫桿頭即具有6.73g/cm3的 低密度、45.4%的延伸率及116.8ksi的抗拉強度等極佳性 質，而且桿頭經過電鍍後，可大幅降低孔蝕孔洞的產生。 合金編號4: 24.9重量百分比之錳、7.3重量百分比之 ® 鋁、1.05重量百分比之碳、0.17重量百分比之矽及其餘比例 以鐵爲基材之本發明另一較佳實施例，其以高周波感應爐熔 煉後，澆鑄在已預熱過的高爾夫桿頭脫蠟殼模內，桿頭鑄件 ' 在經過1 1 〇〇°C真空固溶熱處理2小時後，不須任何锻造及軋 - 延等熱作和冷作塑性加工，高爾夫桿頭即具有6.73g/cm3的 低密度、64.5%的延伸率及120.lksi的抗拉強度等極佳性 質，而且桿頭經過電鍍後，可大幅降低孔蝕孔洞的產生。 合金編號5: 29.1重量百分比之錳、8.5重量百分比之 ® 鋁、0.62重量百分比之碳、0.26重量百分比之矽及其餘比例 以鐵爲基材之本發明另一較佳實施例，其以高周波感應爐熔 煉後，澆鑄在已預熱過的高爾夫桿頭脫蠟殻模內，桿頭鑄件 在經過105CTC真空固溶熱處理2小時及600°C時效熱處理2 ' 小時後，不須任何锻造及軋延等熱作和冷作塑性加工，高爾 _ 夫桿頭即具有 6.70§/(：1]13的低密度、36.9%的延伸率及 I48.7ksi的抗拉強度等極佳性質，而且桿頭經過電鍍後，可 大幅降低孔蝕孔洞的產生。 -18- 1321592 合金編號6: 32.1重量百分比之錳、9.0重量百分比之 鋁、0.7 8重量百分比之碳、〇 . 3 1重量百分比之矽及其餘比例 以鐵爲基材之本發明另一較佳實施例，其鑄錠經由锻造及軋 延等熱作和冷作塑性加工，成爲高爾夫桿頭鍛件或打擊面板 材’經過1 050 °C真空固溶熱處理2小時及600 °C時效熱處理 2小時後，闻爾夫桿頭即具有6.67g/cm3的低密度、36.1 %的 延伸率及189.5 ksi的抗拉強度等極佳性質的高爾夫桿頭，而 且桿頭經過電鍍後，可大幅降低孔蝕孔洞的產生。 合金編號7: 31.6重量百分比之鑑、8.7重量百分比之 鋁、1.10重量百分比之碳、0.5 6重量百分比之矽及其餘比例 以鐵爲基材之本發明另一較佳實施例，其鑄錠經由鍛造及軋 延等熱作和冷作塑性加工，成爲高爾夫桿頭鍛件或打擊面板 材’經過1 0 5 0 °c真空固溶熱處理2小時及5 0 0 °c時效熱處理 6小時後，高爾夫桿頭即具有6.65g/cm3的低密度、30.8 %的 延伸率及178.2ksi的抗拉強度等極佳性質的高爾夫桿頭，而 且桿頭經過電鑛後，可大幅降低孔餓孔洞的產生。 合金編號8: 22〜36重量百分比之猛，6〜8重量百分比 之銘，1.5〜2.0重量百分比之碳，1·〇〜1.5重量百分比之銀， 及其餘爲鐵之鐵猛銘合金，必需利用1030〜1〇50。〇，1〜2 小時之固溶化熱處理，再經4 5 0〜5 5 0 °C，1〜2小時時效熱 處理後，才能具有其設定的機械性質（台灣專利公告編號第 178 648號，鐵錳鋁合金精細鑄件之製造方法）。 合金編號9: 26〜28重量百分比之鍤，6.5〜8重量百分 比之錦，5.0〜6.0重量百分比之銘’ 〇.9〜1.1重量百分比之 -19- 1321592 • 碳，0.2〜1.5重量百分比之矽，1.0〜1.2重量百分比之鉬， 0.9〜1.1重量百分比之銅，0.02〜0.04重量百分比之鈮，及 . 其餘主要爲鐵之合金，其合金鑄品需在大氣爐、氣氛控制 . 爐、真空爐環境中施以均質化熱處理（台灣專利公告編號第 185568號，精密鑄造耐銹合金之製造方法）。 合金編號10: 25〜31重量百分比之鍾，6.3〜7.8重量 百分比之鋁，5.5〜9.0重量百分比之鉻，0.65〜0.85重量百 分比之碳，及其餘比例以鐵爲基材所組合而成，並將合金材 _ 料在8 00〜1 05 0°C溫度之間熱鍛加工。其中該合金材料亦可 添加0.8〜1.5重量百分比之矽及2.0〜5.0重量百分比之 隹太。另該合金材料亦可添加〇.5〜1.0重量百分比之鉬。在 ，800〜1050 °C溫度熱锻加工後，，並經過980〜1080 °C溫度1 • 〜24小時熱處理而成（台灣專利公告編號第460591號，低 密度高延展性鐵基之高爾夫球鐵桿頭合金材料）。 合金編號11 :28.0〜31.5重量百分比之錳，7.8〜10.0 重量百分比之鋁，0.9〜1.10重量百分比之碳，0.35〜2.5重 ® 量百分比之鈦及其餘比例以鐵爲基材所組合而成，並將合金 材料在900〜1 l〇〇°C溫度之間熱鍛加工。其中該合金材料亦 可添加5.0〜7.0重量百分比之鉻或〇.8〜1.5重量百分比之 矽。而在經過950〜1270 °C溫度1〜24小時熱處理而成（台 • 灣專利公告編號第506845號，低密度鐵基之高爾夫球桿頭 材料）。 合金編號12: 25〜31重量百分比之錳，5〜7重量百分 比之鉻，7〜10重量百分比之鋁，0.9〜1.1重量百分比之碳， -20 - 1321592 : 及其餘比例以鐵爲基材所組合而成。其中該合金材料亦可添 加0.8〜1.5重量百分比之矽、2〜5重量百分比之鉻或可進 •—步添加0.5〜1.0重量百分比之鉬。在經塑性加工（冷作及 • 熱作）後，以950〜1270 °C溫度1〜24小時熱處理，且在800 〜1050 °c溫度熱鍛加工，另於980〜1080 °c溫度1〜4小時熱 處理及500〜650°C溫度4〜8小時。C熱處理，再利用冷作輥 軋加工改變晶粒結構及時效處理而成之高爾夫球桿頭（台灣 專利公告編號第584568號，低密度鐵基之高爾夫球桿頭合 _ 金材料）。 合金編號13: 23.0〜30.0重量百分比之錳，6.3〜10.0 重量百分比之鋁’ 0_8〜1.05重量百分比之碳，5.0〜9.0重 • 量百分比之鉻’ 〇.2〜10.0鈷，其餘比例以鐵爲基材所組合 - 而成，其中該合金材料亦可添加0.6〜1.0重量百分比之砂及 0.2〜0.4重量百分比之氮’並在1000〜1050 eC溫度熱鍛加 工，再經由，1000〜1050 °C溫度下熱锻處理，再經由1〇3〇 〜1080 °C溫度15〜60分鐘熱處理及450〜850 °C溫度4〜24 ® 小時熱處理而成之高爾夫球頭鐵桿頭（台灣專利公告編號第 1235677號’低密度高延展性鐵基之高爾夫球鐵桿頭合金材 料）。 因此’本發明所提供之低密度高強度高韌性合金材料可 • 應用於锻造型、鑄造型或兩種的混合型高爾夫球桿頭之硏 - 製’其所硏製完成之桿頭之機械性質爲密度6.6〜6.9 g/cm3、抗拉強度可達100〜1 90ksi、延伸率爲25%〜70% » 而且因該合金材料中未添加習知技術中所使用之鉻元素，故 -21- 1321592 其桿頭經過電鍍後’其孔蝕孔洞發生的現象有相當明顯且大 幅的降低。 此外，利用本發明之合金材料所製成之高爾夫球桿頭， 較習知技術所製成合金材料之機械性質更爲優異，如第2圖 所示，並具有以下的特性： 1.低密度的特性，使得高爾夫球桿頭在設計上比習知的 17-4PH不銹鋼桿頭多出15%〜23%的設計空間，可使桿 頭朝向大型化的設計，增大球桿甜蜜區，有效提高擊球 的成功機率，並且可降低重心，增加穩定的揮擊與擊球 點，並增加扭轉慣性、提高擊球距離等效果。 2 .阻尼比高（制振能高），依據本發明之測試結果顯示， 本發明合金之阻尼比與習知之 Ti-6A1-4V鈦合金與 1 7-4P Η不銹鋼相比，本發明之合金材料吸振能力遠高於 習知之合金材料1 . 5〜3倍，可使桿頭的控球性更佳，並 且降低打擊者的手部震動，打感更舒適。 3·楊氏係數高（反彈位能大），依據本發明之測試結果顯 示’本發明之合金材料之楊氏係數高均較Ti-6A1-4V鈦 合金與〗7-4PH不銹鋼高，因此可提昇擊球的距離。 4·降低製造成本，依據本發明之實際生產線上量產，由於 本發明之合金材料未添加鉻元素，大幅降低在桿頭電鍍 過程中極易產生的孔洞孔蝕，因此可顯著地提升產品良 率，降低生產成本。 綜上所述’本發明之低密度高強度高韌性合金材料，以 特定的金屬元素組成，發明出—種電鍍表面處理良率高且能 -22- 1321592 同時兼具低密度、高強度、高韌性及高制振等多功能鐵錳鋁 合金材料’而應用在高爾夫球桿頭上更可以將揮桿的擊球力 . 道與控球能力發揮至極致，實爲製作高爾夫球桿頭之最佳合 . 金材料，應符合發明專利要件。 惟以上所述者’僅爲本發明之較佳實施例，當無法據此 限定本發明之實施範圍，而所屬技術領域中具有通常知識者 依據本發明申請專利範圍及發明說明書內容所作之修飾與 變化’皆應屬於本發明專利涵蓋之範圍。 > 【圖式簡單說明】 第1圖 本發明與習知技術所製成之合金材料組成成分 比較圖 ' 第2圖 本發明與習知技術所製成之合金材料機械性質 - 比較圖 【主要元件符號說明】 Μ 〇 y»v\Temperature oxidation of F e - 3 1 Μη - 9 A1-x C r-0 · 8 7 C alloys(x = 0, 3 and 6)". 7. In the Republic of China in 1989 (1 990) Professor Liu Zengfeng of the National Chiao Tung University (one of the inventors of this patent application), the master thesis "Iron-8.8 Aluminum - 30.0 Manganese-6.0 Complex-1.0 Carbon Alloy Phase Change" (Phase Transformations) In an • Fe-8.8Al-30.0Mn-6.0Cr-l .0C Alloy). Therefore, the high-quality mechanical properties and low-density properties of iron-aluminum-manganese alloy materials are applicable in various commercial applications, especially in the golf club manufacturing industry. In order to play farther, the alloy material of the club head must be excellent and must have the following characteristics: (low density: the same number of club heads must be under the specified weight, low density material) Can increase the size of the club head, increase the sweet area of the hitting ball to pick up the hitting rate of the correct position, and increase the design space of the counterweight, design the low center of gravity head, lower the center of gravity of the club head, increase the hitting The stability and torsion are played more stably and farther. (2) The combination of high elongation and appropriate strength: to make it more stable, the vibration force is smaller, the direction of the ball is accurate, and the extension of the head alloy material Sex and toughness should be better, so the time between the ball and the head will be longer when the ball is struck under such conditions, and the high-extension material ball head can adjust the height of the player according to the height of the player. The angle between the shaft and the striking surface is higher, and the range of the angle of the adjustable shaft is larger. (3) High damping ratio: high shock absorption capability, the striker will not have the uncomfortable feeling of the hand and the 1321592 vibration. It feels good to control the ball. (4) Elastic coefficient (Young's coefficient): high elasticity #, high hitting distance. (5) High corrosion resistance after the material itself or after surface treatment * · Long-term on the grass with water and chemical herbicide. It is not easy to rust and maintain the function of the club head and the appearance. Therefore, in order to achieve the above-mentioned batting conditions, many commercial alloy materials are continuously tried on the golf club head, and depending on the purpose of the desired shot, The golf club is divided into a wood club head and an iron club head. In general, the wood club head has a hollow spherical shape and a long shaft length, which is mainly used for kicking or long distance striking. The traditional wooden club head Made of wood, the main raw material is persimmon wood, but due to its corrosion resistance, toughness and strength, it has been replaced by a metal alloy material. It is currently used commercially to make wood rod heads. Materials such as pure titanium, Ti-6A1-4V alloy, β-titanium, 17-4PH stainless steel and high-strength 431, 455 Ma Tian loose-iron stainless steel. In addition, the iron is mainly used to hit the ball to the target, which is characterized by Ball flying distance than wood Slightly shorter, but the ball can be hit higher, and the ball control is better. Currently, the material commonly used in the production of iron heads is mainly stainless steel alloy materials, for example, 17-4 inch stainless steel, 8620 steel, 304 stainless steel, 18Ni (200) aging steel or titanium alloy. Some of these materials have good elongation but the strength is seriously insufficient. For example, the strength and elongation of 8620 steel and 304 stainless steel are about 60. Ksi and 30%. Others have good strength but poor elongation, such as '43 1, 45 5 Ma Tian loose iron stainless steel, 丨 8Ni (200) hemp aging steel's strength is about 150~2 〇〇ksi but the elongation is only about 10%. As for the titanium alloy material, its density is between 4.5~4.8 g/cm3, the strength and the elongation of -10- 1321592 -* is about 1 4 0~1 8 0 ksi And between 7 and 1 4%, and the development and mass production of titanium alloys make the design of golf club heads have great room for change, but the price of titanium alloy is too high and the elongation is not high. Therefore, the current conditional characteristics required for industrially produced golf club heads are: (1) Low density below 7.8 g/cm3. (2) The elongation rate is 10% or more. (3) Tensile strength lOOksi or more (4) The material itself or after surface treatment can pass the salt spray test of 5% concentration for 24 to 48 hours. All of the above are basic requirements. Of course, the higher the combination of strength and elongation, the lower the ® and the lower the density, so as to increase the head volume, expand the sweet spot of the shot, increase the distance and control of the shot. However, the related patent materials described in the relevant references are applied to the patent document of golf club heads, including iron-aluminum-manganese-carbon composite materials, which are not contained in the alloy material disclosed in Taiwan Patent Publication No. 178 648. The chromium element and the alloy material composition disclosed in Taiwan Patent Publication No. 5 06 84 5 may not contain chromium but contain titanium (but in its composition, because it contains high content of carbon and titanium, respectively) It is easy to precipitate coarse carbides on the grain boundary, which causes the toughness of the alloy to be reduced, so that the golf club head made of such alloy material can easily crack or crack when it is tested on the face. Among the components of the golf club head alloy material disclosed in the literature, in order to improve the corrosion resistance, a chromium element of 5 to 9 weight percent is added, but the corrosion resistance is still less than that of 17-4PH stainless steel and high strength 431. 455 Ma Tian loose iron type stainless steel, etc. 'A variety of stainless steel alloy materials used on golf club heads. In order to achieve the above-mentioned corrosion resistance of the iron-aluminum-manganese-carbon alloy golf club head, that is, through the salt spray test, it is still necessary to apply the plating surface treatment on the original material. 1321592 Due to the addition of chromium in the iron-aluminum-manganese carbon alloy material It will cause the surface of the alloy to spontaneously produce a chromium oxide (Cr2〇3) oxide layer. Although the addition of chromium element increases the corrosion resistance of the alloy, it cannot be removed by ordinary acid treatment and activation treatment. a strong chromic oxide layer, because the oxide layer is not conductive, such as the same insulating layer, causing the adhesion of the plating layer to the substrate of the golf club head itself to be reduced, so that the plating layer is easily peeled off at the time of hitting the ball or Cannot attach to the substrate. However, if the acid treatment and activation treatment using electroplated stainless steel is used to remove the discontinuous chromium oxide oxide layer on the surface of the chromium-containing iron-aluminum-manganese carbon alloy, the high chloride ion concentration in the acid treatment may cause Severe holes on the surface of the iron-aluminum-manganese carbon alloy golf club head touch holes, resulting in extremely high defect rate and bad products during the electroplating process. Therefore, if we can develop alloy materials with low density, high elongation or high toughness, reasonable price, certain hardness and avoiding pitting holes in the process of electric ore, then its low density and appropriate strength will make the golf ball The increase in the design space of the club head 'high extensibility or high toughness can increase the ball control performance, so that the impact of the golf club head can be maximized, and the cost of mass production can be greatly reduced. SUMMARY OF THE INVENTION In view of the above, the present inventors have utilized the concept of alloy design and process processing to address the shortcomings of the above-mentioned other iron-aluminum-manganese carbon alloy golf club heads. Tough alloy material and its preparation method 'The alloy material can simultaneously have a density of 6.6~6.9 g/cm3, 25~70% extensibility and toughness as well!抗 ~190ksi tensile strength, and its -12- 1321592 applied to the golf club head' and can reduce the hole-cavity holes generated in the current process of electroplating iron-manganese-carbon alloy material golf club head, greatly increased Product yield. The design principle of various added elements and its influence on the material properties are as follows: 1. The manganese·manganese element is the strengthening element of the Worthfield iron phase, because the Worthfield iron phase is a face-centered cubic structure. The multi-slip system can therefore have better extensibility. Therefore, the addition of manganese can increase the proportion of the iron phase of the Vostian, and also improve the elongation of the alloy. The alloy has excellent ductility and the addition of manganese. The amount must be at least 15% by weight or more, but when the amount of the manganese element added exceeds 33% by weight or more, the precipitation of β-Μη is caused to cause a decrease in the ductility of the alloy. Therefore, the addition of the manganese element in the present invention should be limited to between 1 and 5 and less than or equal to 3% by weight. 2. Aluminium: Aluminum is not only a strengthening element of ferrite and iron, but also one of the main forming elements of (Fe,Mn)3AlCx supercrystalline lattice carbide, so the precipitation state and amount of (Fe,Mn)3AlCx carbide There is a very close relationship between the amount of addition and the amount of addition of the element. When the amount of aluminum added is less than 6% by weight, the precipitation of (Fe,Mn)3AlCx carbide in the Worthite iron base is too small, and the alloy will not reach satisfactory strength. However, when the amount of aluminum added exceeds 10% by weight, not only the formation of ferrite iron phase but also the disordered ferrite iron phase (bcc) is transformed into a very brittle D03 order (ordered )phase. In addition, due to the relatively low saturation concentration of carbon in the ferrite phase, it is easy to cause coarse (Fe,Mn)3AlCx carbides to precipitate on the grain boundary-13-1321592 between the iron phase and the ferrite phase. Not only does the phenomenon fail to increase the strength of the alloy, but the ductility of the alloy is drastically reduced, resulting in brittle intergranular cracking. Therefore, the amount of aluminum added in the present invention should be limited to between 6 and less than or equal to 1% by weight. 3. Carbon: Carbon is not only a strengthening element of Vostian iron but also a (Fe, Mn). The basic element of 3AlCx supercrystalline lattice carbide. Similarly, when the amount of carbon added is less than 0.6% by weight, the amount of (Fe,Mn)3AlCx carbide precipitated in the Worthite iron base is too small, and the alloy will not reach a satisfactory strength. However, when the content of carbon exceeds 1.2% by weight, the carbide content precipitated on the iron grain boundary of the Worthfield increases rapidly and the particles become large, and the alloy tends to become an intergranular fracture mode, which in turn makes the alloy ductile. Therefore, the amount of carbon added in the present invention is preferably limited to between 2.6 or less and 1.2% by weight. 4. 矽: A trace amount of cerium element added at 0.1% by weight or more can promote (Fe,Mn)3AlCx carbide during the cooling process via the Spinodal decomposition in the iron phase of Vostian Fine and uniform precipitation increases the strength of the alloy and has little effect on the ductility. In addition, the addition of niobium increases the fluidity of the alloy in the liquid state and improves the castability of the alloy. However, the lanthanum element is not only a strengthening element of the ferrite grain iron phase in the iron-manganese-aluminum alloy system, but also a strong D03 ordered phase forming element. When the lanthanum element content exceeds 1. 〇 weight percentage or more At the same time, the formation of the brittle D03 ordered phase is promoted. Once the D03 ordered phase is precipitated in the alloy, the ductility of the alloy will be severely destroyed by -14-21321. Therefore, the amount of the lanthanum element added in the present invention is preferably limited to be greater than or equal to 0. 1 and less than or equal to 1.0% by weight. 5. Molybdenum··Molybdenum element is a strong carbide forming element, but has no obvious effect on the formation of (Fe, Mn)3 A1CX carbide. However, according to the experiments of the inventors, the addition of molybdenum can cause The solid solution strengthening of the alloy, therefore, can increase the strength of the alloy and has little effect on the ductility. However, when the content of molybdenum element exceeds 1.5% by weight or more, the precipitation of molybdenum carbide such as MzC 'MuC6 and M6C causes the nearby Wolster iron phase to become quite unstable due to lack of sufficient carbon, and is easily converted. For the ferrite phase, it has an adverse effect on the ductility of the alloy. Therefore, the amount of the molybdenum element added in the present invention is preferably limited to 1.5% by weight or less. Therefore, in order to achieve the foregoing objects, the present invention is directed to a variety of additive element design ratios and composition ranges, and finally invented a low-density high-strength and high-toughness alloy material, the alloy material comprising 15 to 33 weight percent of manganese, 6 to 10 A weight percentage of aluminum, 0.6 to 1.2 weight percent of carbon, 〇.1 to 1. 〇 by weight of 矽, wherein up to 1.5% by weight of molybdenum may be added, and the remaining proportions are combined with iron as a substrate. The alloy material of the present invention comprises 15 to 33 weight percent of manganese, 6 to 10 weight percent of aluminum, 0.6 to 1.2 weight percent of carbon, 0.1 to 1.0 weight percent of sand, and may also add up to 1.5 weights. Percentage of molybdenum, the remaining proportion of iron as a substrate, after a casting process to form a casting, it can choose between 950 to 1200 °C temperature for 0.5 ~ 1 〇 hour solution heat treatment, followed by 500 to 00 An aging heat treatment of up to 24 hours -15 - 1321592 is carried out between temperatures of 00 ° C, or alternatively, without any heat treatment. The alloy material of the present invention comprises 15 to 33% by weight of manganese, 6 to 10% by weight of aluminum, 〇.6 to 1.2% by weight of carbon, 〇" to 1.0% by weight of ruthenium, which may also be added up to 1.5. The remaining percentage of molybdenum by weight is based on iron, which is formed into an alloy material by a melting process. The alloy material is subjected to plastic working such as forging, rolling, etc. between 800 and 1200 ° C. After plastic working, it is possible to carry out a solution heat treatment at a temperature of 950 to 1200 ° C for 0.5 to 10 hours, followed by an aging heat treatment of at most 24 hours between 500 and 700 ° C, or alternatively, without any heat treatment. . [Embodiment] In order to further understand the constituents of the present invention and the mechanical characteristics thereof, those skilled in the art will be described in detail with reference to the specific embodiments, drawings and tables. Purpose, technical content, characteristics and the effects achieved. The invention relates to a low-density high-strength and high-toughness alloy material, and can be applied to the manufacture of a golf club head. The main elemental composition comprises 15 to 33 weight percent manganese, 6 to 10 weight percent aluminum, 0.6~ 1.2% by weight of carbon, 0.1 to 1.0% by weight of bismuth, wherein up to 1.5% by weight of molybdenum may be added, and the remaining proportion is an alloy material obtained by combining iron as a substrate. The following is a detailed description of the embodiment. As shown in FIG. 1, alloy numbers 1 to 7 are the component ranges of the present invention, and numbers 8 to 13 are ranges of the alloy material components prepared by the prior art, and are Reference is made to the comparative examples, and the reference to the present invention is incorporated by reference. Alloy No. 1: 27.8 weight percent manganese, 8.8 weight percent - aluminum, 0.95 weight percent carbon, 0.28 weight percent rhodium and the remaining ratio. Iron based substrate preferred embodiment of the invention, with high frequency induction furnace After smelting, 'casting in the pre-heated golf club head dewaxing shell mold, after the shell mold casting is cooled, it can be used for seismic shell, cutting runner gate, sand blasting, honing, welding, shaft drilling and milling Hole 'plating, surface treatment and art procedures. Without any hot work such as forging and rolling, and cold plastic working, without any heat 1 treatment, the golf club head casting has a low density of 3.70g/cm3 '38.6% elongation and 122.5ksi Excellent tensile strength and other properties, and the rod head after plating can greatly reduce the occurrence of pitting holes. Alloy No. 2: 30.3 weight percent manganese, 8.8 weight percent aluminum '1.115 weight percent carbon, 0.16 weight percent rhodium, 1.05 weight percent molybdenum and the remainder ratio iron based substrate another preferred embodiment of the invention For example, after being smelted in a high-frequency induction furnace, it is cast in a pre-heated golf club head dewaxing shell mold, and after the shell mold casting is cooled, the seismic shell, the 1 cutting runner gate, the sandblasting, the crucible can be performed. Grinding, welding, shaft drilling and milling, plating, surface treatment and art procedures. Since 1.05 wt% of molybdenum is additionally added, the strength of the golf club head casting can be further increased by 8 to 10 ksi without any forging and rolling and other hot working and cold working plastic processing and any heat treatment, that is, having 6.79 The low density of g/cm3, the elongation of 35.1% and the tensile strength of 130.7ksi, etc., and the rod head after electroplating can greatly reduce the occurrence of pitting holes. Alloy No. 3: 17.5 weight percent manganese, 6.2 weight percent -17-1321592 'aluminum, 1.08 weight percent carbon, 0.15 weight percent bismuth and the remainder ratio of iron based substrate another preferred embodiment of the invention For example, after melting and refining in a high-frequency induction furnace, it is cast in a preheated golf club head dewaxing shell mold. The head castings • After 4 hours of vacuum heat treatment in 1 1 001, no forging and no need Rolling and other hot work and cold work plastic processing, golf club head has a low density of 6.73g / cm3, 45.4% elongation and 116.8ksi tensile strength and other excellent properties, and the head can be greatly Reduce the occurrence of pitting holes. Alloy No. 4: 24.9 weight percent manganese, 7.3 weight percent aluminum, 1.05 weight percent carbon, 0.17 weight percent ruthenium and the remainder ratio of iron based substrate to another preferred embodiment of the invention, which is characterized by high frequency induction After the furnace is smelted, it is cast in the pre-heated golf club head dewaxing shell mold. The rod head casting ' does not require any forging and rolling-delay after 2 hours of vacuum solid solution heat treatment at 1 〇〇 °C. For cold working and cold working, the golf club head has excellent properties such as low density of 6.73g/cm3, elongation of 64.5% and tensile strength of 120.lksi, and the head can be greatly reduced after electroplating. The creation of holes. Alloy No. 5: 29.1 weight percent manganese, 8.5 weight percent aluminum, 0.62 weight percent carbon, 0.26 weight percent ruthenium and the remainder ratio of iron based substrate to another preferred embodiment of the invention, which is characterized by high frequency induction After the furnace is smelted, it is cast in the preheated golf club head dewaxing shell mold. The head castings are subjected to vacuum heat treatment at 105 CTC for 2 hours and 600 °C aging heat treatment for 2 ' hours without any forging and rolling. For hot work and cold work plastic processing, the Golfer head has excellent properties such as low density of 6.70§/(:1]13, elongation of 36.9% and tensile strength of I48.7ksi, and the head After electroplating, the pitting hole can be greatly reduced. -18- 1321592 Alloy No. 6: 32.1% by weight of manganese, 9.0% by weight of aluminum, 0.78% by weight of carbon, 〇. 3 1% by weight and the rest According to another preferred embodiment of the present invention in which iron is used as a base material, the ingot is subjected to hot work and cold work plastic processing such as forging and rolling, and becomes a golf club head forging or striking sheet material 'vacuum solidification at 1 050 ° C Heat treatment 2 small After 2 hours of heat treatment at 600 °C, the Werff head has a golf club head with a low density of 6.67g/cm3, an elongation of 36.1% and a tensile strength of 189.5 ksi. After electroplating, the pitting hole can be greatly reduced. Alloy No. 7: 31.6 wt%, 8.7 wt% aluminum, 1.10 wt% carbon, 0.56 wt% bismuth and the rest ratio iron-based According to another preferred embodiment of the invention, the ingot is subjected to hot working and cold working plastic processing such as forging and rolling, and becomes a golf club head forging or a face sheet. After vacuum treatment at 10.5°c for 2 hours and 5 After 6 hours of aging treatment at 0 0 °c, the golf club head has a golf club head with a low density of 6.65 g/cm3, an elongation of 30.8% and a tensile strength of 178.2 ksi, and the head passes through the electric mine. After that, the production of holes and holes can be greatly reduced. Alloy No. 8: 22~36% by weight, 6~8 weight percent, 1.5~2.0% by weight of carbon, 1·〇~1.5% by weight of silver, and The rest is iron iron Ming alloy, must use 1030 ~ 1 〇 50. 〇, 1 ~ 2 hours of solution heat treatment, and then 455 ~ 5 50 ° C, 1 ~ 2 hours aging heat treatment, in order to have its set mechanical properties ( Taiwan Patent Publication No. 178 648, Method for manufacturing fine manganese-aluminum alloy castings. Alloy No. 9: 26~28 weight percent bismuth, 6.5~8 weight percent brocade, 5.0~6.0 weight percent of the title ' 〇. 9 to 1.1% by weight -19- 1321592 • Carbon, 0.2 to 1.5% by weight of bismuth, 1.0 to 1.2% by weight of molybdenum, 0.9 to 1.1% by weight of copper, 0.02 to 0.04% by weight of bismuth, and. In the alloy of iron, the alloy casting needs to be homogenized in the atmosphere furnace, atmosphere control, furnace and vacuum furnace environment (Taiwan Patent Publication No. 185568, manufacturing method of precision casting rust-resistant alloy). Alloy No. 10: 25 to 31 weight percent of the bell, 6.3 to 7.8 weight percent of aluminum, 5.5 to 9.0 weight percent of chromium, 0.65 to 0.85 weight percent of carbon, and the balance of iron based on the substrate, and The alloy material is hot forged between 8 00 and 1 0 0 °C. The alloy material may also be added in an amount of 0.8 to 1.5% by weight and 2.0 to 5.0% by weight. In addition, the alloy material may also be added with 0.5 to 1.0% by weight of molybdenum. After hot forging at 800~1050 °C, and heat treated at 980~1080 °C for 1 to 24 hours (Taiwan Patent Publication No. 460591, low density and high ductility iron-based golf irons Head alloy material). Alloy No. 11: 28.0~31.5% by weight of manganese, 7.8~10.0% by weight of aluminum, 0.9~1.10% by weight of carbon, 0.35~2.5 parts by weight of titanium and the other proportions are combined with iron as a substrate. The alloy material is hot forged between 900 and 1 l ° °C. The alloy material may also be added with 5.0 to 7.0 weight percent of chromium or 〇.8 to 1.5 weight percent of ruthenium. It is heat-treated at a temperature of 950 to 1270 °C for 1 to 24 hours (Taiwan Bay Patent Publication No. 506845, low-density iron-based golf club head material). Alloy No. 12: 25 to 31 weight percent manganese, 5 to 7 weight percent chromium, 7 to 10 weight percent aluminum, 0.9 to 1.1 weight percent carbon, -20 - 1321592: and the remainder ratio is based on iron Combined. The alloy material may also be added with 0.8 to 1.5 weight percent of ruthenium, 2 to 5 weight percent of chromium or 0.5 to 1.0 weight percent of molybdenum. After plastic working (cold work and hot work), heat treatment at 950~1270 °C for 1~24 hours, hot forging at 800~1050 °C, and temperature 〜1~4 at 980~1080 °C Hour heat treatment and temperature of 500~650 °C for 4~8 hours. C heat treatment, and then use the cold rolling process to change the grain structure and timely treatment of the golf club head (Taiwan Patent Publication No. 584568, low-density iron-based golf club head _ gold material). Alloy No. 13: 23.0~30.0% by weight of manganese, 6.3~10.0% by weight of aluminum '0_8~1.05% by weight of carbon, 5.0~9.0 by weight ・Quantitative percentage of chromium' 〇.2~10.0 cobalt, the remaining proportion is iron The substrate is combined and formed, wherein the alloy material may also be added with 0.6~1.0% by weight of sand and 0.2~0.4% by weight of nitrogen' and hot forged at a temperature of 1000~1050 eC, and then passed through 1000~1050 °C. Hot forging treatment at temperature, heat treatment at 1〇3〇~1080 °C for 15~60 minutes and heat treatment at 450~850 °C for 4~24 ® hours (Taiwan Patent Bulletin No. 1235677 No. 'Low density and high ductility iron-based golf iron head alloy material). Therefore, the low-density, high-strength, high-toughness alloy material provided by the present invention can be applied to the forging, casting or two types of hybrid golf club heads - the mechanical properties of the finished head It has a density of 6.6~6.9 g/cm3, a tensile strength of 100~1 90ksi, an elongation of 25%~70% » and because the alloy material does not contain the chromium element used in the prior art, so 21- 1321592 After the rod is plated, the phenomenon of pitting holes is quite obvious and greatly reduced. Further, the golf club head made by using the alloy material of the present invention is more excellent in mechanical properties than the alloy material prepared by the prior art, as shown in Fig. 2, and has the following characteristics: 1. Low density The characteristics of the golf club head are 15%~23% more design space than the conventional 17-4PH stainless steel head, which can make the club head face large-sized design and increase the sweet area of the club. Improve the chance of success in hitting the ball, and reduce the center of gravity, increase the stable swing and hitting point, and increase the effect of torsional inertia and increase the hitting distance. 2. The damping ratio is high (the damping energy is high), and the test result according to the present invention shows that the damping ratio of the alloy of the present invention is compared with the conventional Ti-6A1-4V titanium alloy and the 1 7-4P Η stainless steel. The material's vibration absorption capacity is much higher than that of the conventional alloy material of 1.5 to 3 times, which makes the head of the club better, and reduces the shock of the hitter's hand, making the feeling more comfortable. 3. The Young's coefficient is high (the rebound potential is large), and the test result according to the present invention shows that the Young's modulus of the alloy material of the present invention is higher than that of the Ti-6A1-4V titanium alloy and the 7-4PH stainless steel, so Increase the distance of the shot. 4. Reducing the manufacturing cost, mass production according to the actual production line of the present invention, since the alloy material of the present invention does not add chromium element, the hole pitting which is easily generated in the head plating process is greatly reduced, so that the product can be remarkably improved. Rate, reduce production costs. In summary, the low-density, high-strength, high-toughness alloy material of the present invention is composed of a specific metal element, and has been invented with a high surface treatment yield and can be -22- 1321592 while having low density, high strength, and high Multi-functional iron-manganese-aluminum alloy materials such as toughness and high vibration resistance, and applied to the golf club head, the ball's hitting force, the ball and the ball-handling ability can be maximized, which is the best for making golf club heads. The gold material shall meet the requirements of the invention patent. However, the above description is only a preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, and those skilled in the art have the modifications and the contents of the patent application scope and the description of the invention according to the present invention. The changes 'should fall within the scope of the invention patent. > BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a comparison of the composition of alloy materials prepared by the present invention and the prior art. FIG. 2 is a mechanical property of an alloy material prepared by the present invention and a conventional technique - comparison chart [mainly Component symbol description] Μ 〇y»v\
-23 --twenty three -