499341 A7 B7_ 五、發明說明（） 發明範圍 本創作係關於一種製備鈦基非晶質合金的方法，其係 利用一高能量球磨機將鈦、銅、鎳、矽、硼純元素混合粉 進行機械合金化處理，藉此合成化學式為T i a C u b N i e S i 4 B 2 且具寬廣過冷液態區的鈦基非晶質合金粉末。 發明背景 非晶質合金為一固體但其原子結構排列類似液態物質 固液態物質的原子結構非常散亂且不具長程規律性，這樣 的結果，使得非晶質合晶具有許多異於結晶態合金的誘人 性質，諸如高抗蝕性，高機械強度、硬度，優異的光、電、 磁特性，以及抗而ί磨性等等。 經濟部智慧財產局員工消費合作社印製 -------------裳—— (請先閱讀背面之注意事項HI寫本頁) -線· 欽基合金是一種重要的工程材料’擁有南比強度和局抗 腐蝕等優良特性，因此廣為應用在航太與化學工業中，然 為了尋求更卓越的機械性質、延性和抗腐蝕性，乃陸續進 行許多鈦基合金非晶質化之研究，綜合這些研究結果可知 製作鈦基非晶質合金的方法大致以液態急冷法 （Liquid Quenching )為主；此法是利用諸如自由流熔液旋喷、單輪 熔液旋喷、熔液汲取、金屬抽引、平面流動鑄造、高壓氣 體霧化、離心霧化、超音波氣體霧化、喷覆沉積、高壓水 霧化、旋轉水霧化等製程，將溫度超過 1 2 0 0 °C以上之鈦 合金熔液以高達 1 〇 6 °C / s e c 以上的冷卻速率形成鈦基非晶 質合金，故製備的非晶質合金大多是以箔片（Ribbon)或 粉末（P 〇 w d e r ) 狀出現；事實上，鈦基非晶質合金之合 2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 499341 A7 B7_499341 A7 B7_ V. Description of the invention () The scope of the invention This invention relates to a method for preparing a titanium-based amorphous alloy, which uses a high-energy ball mill to mix titanium, copper, nickel, silicon and boron pure element powders for mechanical alloying. By chemical treatment, a titanium-based amorphous alloy powder with a chemical formula of Tia Cub Nie S i 4 B 2 and a wide supercooled liquid region is synthesized. BACKGROUND OF THE INVENTION Amorphous alloys are solid, but their atomic structure is similar to that of liquid substances. The atomic structure of solid and liquid substances is very scattered and does not have long-range regularity. As a result, amorphous crystals have many properties different from those of crystalline alloys. Attractive properties, such as high corrosion resistance, high mechanical strength, hardness, excellent optical, electrical, and magnetic properties, and resistance to abrasion. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ------------- Shang—— (Please read the note on the back HI first to write this page)-Wire · Qinji alloy is an important project The material 'has excellent properties such as South specific strength and local corrosion resistance, so it is widely used in the aerospace and chemical industries. However, in order to seek more excellent mechanical properties, ductility and corrosion resistance, many titanium-based alloys have been successively made amorphous. Research on qualitative research. Based on the results of these studies, it can be known that the method for making titanium-based amorphous alloys is mainly liquid quenching (Liquid Quenching); this method uses such methods as free-flow melt spinning, single-round melt spinning, Processes such as melt extraction, metal extraction, plane flow casting, high-pressure gas atomization, centrifugal atomization, ultrasonic gas atomization, spray deposition, high-pressure water atomization, and rotating water atomization, which will exceed 1 2 0 0 Titanium alloy melts above ° C form titanium-based amorphous alloys at a cooling rate of up to 106 ° C / sec or higher. Therefore, most of the prepared amorphous alloys are foils or powders (Powder). ) Appears; in fact The combination of titanium-based amorphous alloys 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499341 A7 B7_
五、發明說明（I 成研究在 1970年便已開始，而於1970〜1980年間研究 資料顯示可形成非晶質合金相的組成有：Ti-Be-Zr、 Ti-Ni、Ti-Ni-Si、Ti-Be、Ti-M-Si、Ti-M-Si-B(M = IV 〜 V金屬）等合金系統，但只在 T i - B e與 T i - B e - Z r非晶質 合金相有玻璃轉換溫度出現，而從1 9 8 0年以後的1 4年 間就無任何新型 Ti基非晶質合金被成功製備，其主要 原在於鈦金屬化性很強，易與空氣中的氧、氮起反應， 故很難控制其實驗參數所造成。 從製程觀點而言，以液態急冷法製備的鈦基非晶質合金 具有下列缺失： (1 )當合成之箔片或粉末的尺寸愈大時，其所需之冷卻 速率越高，故製備也越困難； (2 )鈦基合金成分的改變會使熔點溫度發生變化進而強 烈影響形成非晶態所需的冷卻速率，故製備將受限於材 料組成， (3 )需使用到高週波感應加熱、真空、喷嘴、冷¥卩等精 密設備，故製造成本很高。 再就材質觀點而言，液態急冷法製備之鈦基非晶質合金 因其玻璃轉換溫度（T g )幾乎與結晶化溫度（T X )相同，既 以玻璃轉換溫度和結晶化溫度之溫度差值界定的過冷政 態區A T ( A T = T X - T g )範圍，在液態急冷法製備的鈦基 非晶質合金是很小甚至是不存在的，因此當此類薄片或 粉末狀的欽基非晶質合金在△ T的溫度區間以熱壓、熱 均壓、擠製等方法成型為塊狀非晶質合金時，因成型溫 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事項H寫本頁) · --線· 經濟部智慧財產局員工消費合作社印製 499341 A7 B7_ 五、發明說明（+) 度太接近結晶化溫度，故會使非晶質合金於塊狀減型過 程中變成結晶態，進而喪失非晶質相所擁有的諸般優異 材質特性而大大的降低其應用價值。 發明要旨 有鑑於習用液態急冷法製備的鈦基非晶質合金無可 避免的會有前述製程及材質上之缺失，本案創作人乃積 其從事非晶質合金多年之合成經驗，因此乃積極進行研 究如何以嶄新的方法來製備具寬廣過冷液態區之鈦基非 晶質合金，以解決相關業界極欲克服之問題，經不斷的 嚐試與試驗後，終發現本創作之製造含寬廣過冷液態區 之飲基非晶質合金的方法。 本發明乃使用合金化原理完全迥異於習用液態急冷 法的機械合金方式來合成具寬廣過冷液態區的鈦基非晶 質合金粉末，機械合金法之執行是藉一高能量球磨機進 行，既依設定組成TiaCubNieSi4B2秤取Ti、Cu、Ni、Si、 B等純元素混合粉末，把此等粉末與適當磨球數量於一 手套箱中裝填入球磨罐中，而後將此球磨罐置入高能量 球磨機中進行機械合金化之高能量球磨處理一段時間後， 既可獲得△ T = 25〜94°C的 TiaCubNicSi4B2非晶質合金粉 末。 本發明所提出的合成方法和習用技術所使用的急冷 凝固法相比較，因係屬固態反應製程，此不似急冷凝固 法有冷卻速率之限制，故可以在不同合金系的廣闊範圍 形成非晶質合金粉末，又機械合金化的高能量球磨處理 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） :-------------裝—— (請先閱讀背面之注意事項HI寫本頁) 訂： --線· 經濟部智慧財產局員工消費合作社印製 499341 A7 B7_ 四 五、發明說明（） 方法在設備上只需一高能量球磨機便可進行成丰很低， 且可大量生產粉末，因此也極適合工業化的量產需求。 本發明合成之鈦基非晶質合金粉末，因具有△ T = 2 5〜1 2 4 °C ( △ T = T X - T g )的寬廣過冷液態區，故若在玻 璃轉換溫度（T g )和結晶化溫度（T X )之溫度區間進行塊材 成形製成時，將有以下兩項優點：（a)因成型溫度高於 玻璃轉換溫度，故材料本身此時黏性很小，類似超型性 狀，故可在很小的成型壓力下即形成高緻密狀的塊材； (b)因成型溫度低於結晶化溫度，故材料本身仍是非晶 質態，所以本創作製備之鈦基非晶質合金粉末非常適合 作為以熱壓、熱均壓或擠製等成型法製造塊材鈦基非晶 質合金的原料。 為使貴審查委員對本創作之方式及其特徵能有更 深一層的認識與暸解，茲附以圖示詳細說明如后： 圖示部份 第一圖：為本發明實施例的粉末製備流程示意圖。 第二圖：為本發明實施例一合成之鈦基非晶質合金粉末 的X -射線繞射圖。 第三圖：為本發明實施例一合成之鈦基非晶質合金粉末 的熱差掃描分析圖。 第四圖··為本發明實施例二合成之鈦基非晶質合金粉末 的X -射線繞射圖。 第五圖：為本發明實施例二合成之鈦基非晶質合金粉末 的熱差掃描分析圖。 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事項HI寫本頁) · -線· 499341 經濟部智慧財產局員工消費合作社印製 A7 B7_五、發明說明（i) 第六圖：為本發明合成之Ti74Ni1()Cu1()Si4B2非晶質合金 粉末的X -射線繞射圖。 第七圖：為本發明合成之Ti74Ni1()Cu1()Si4B2非晶質合金 粉末的熱差掃描分析圖。 請參閱第一圖為本發明一較佳實施例的粉末合成流 程示意圖，如圖中所示，本實施具寬廣過冷液態區之鈦 基非晶質合金粉末之製備方法，主要係依序包含備料步 驟 1 . 封罐步驟 2 . 機械合金步驟 3 以下茲就各製程 作進一步的詳述如下： (1) 備料步驟：先依設定之 TiaCubNieSi4B2組成秤取適 量的 Ti、Cu、Ni、Si、B 等純元素混合粉末，同時也 按設計的粉末/磨球比選取所需的磨球顆粒和重量，而 後把混合粉末與磨球一併置入球磨罐中。 (2) 封罐步驟：將步驟（1 )之球磨罐在一含抗氧化的保護 性氣氛之環境中，進行球磨罐的封閉作業以確保混合 粉末於後續的機械合金化高能量球磨處理時不會氧 化。 (3) 機械合金步驟：將步驟（2)之球磨罐移入一高能量 球磨機中進行機械合金化之高能量球磨處理一段時間 後，既可獲得的具寬廣過冷液態區之 TiaCubNieSi4B2非 晶質合金粉末。實施例一：Ti“Ni30Si4B2 將4 g的含鈦純元素混合粉末，其中包括2.4 7 g的鈦、 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項^^寫本頁) --裝 · -線· 經濟部智慧財產局員工消費合作社印製 499341 A7 B7_ 五、發明說明（^) 1 . 4 2 g 的鎳、0.0 9 g 的石夕、0.0 2 g 的硼，在依粉本/磨球 比為1 / 5選取 1 0顆直徑3 / 1 6英吋總重2 0 g的磨球，而 後把 4 g之混合粉末與 2 0 g的磨球一併置入球磨罐中， 將此球磨罐移入一手套箱中並對手套箱充填氬氣，當置 於手套箱中的氧氣指示計顯示氧含量為零時，隨既封閉 球磨罐並將其移至一震動式高能量球磨機進行五小時的 機械合金化處理後便可合成組成為 Ti64Ni^Si4B2的鈦 基球磨粉末。 本實施例所合成的 T i 6 4 N i 3 〇 S i 4 B 2鈦基球磨粉末的 結晶構造，由圖二之X光射線饒射圖案僅含一寬廣繞射 岭可知其確為一非晶質相，而由圖三之熱差掃描圖案發 現此T i 6 4 N i 3。S i 4 B 2非晶質合金粉末的玻璃轉換溫度（T g ) 和結晶化溫度（Tx)分別位於 4 0 5 °C和 4 9 9 °C ， 既 Ti64Ni30Si4B2非晶質合金粉末之過冷液態區A T( △ T = Tx-Tg)為 94 °C 。 實施例二：Ti54Cu3〇Ni10Si4B2 在本實施例中，我們以 3 0 a t % C u 取代 1 0 a t % T i 與 2 0 a t % N i，既 4 g 的含鈦鎳銅矽硼純元素混合粉末，其 中包括 1 . 9 8 g的鈦、1 · 4 6 g的銅、0.4 5 g的鎳、0 · 0 9 g的 矽，0.02g 的硼，其餘實施步驟與實施例一相同，由圖 四之 X 光射線饒射圖案僅含一寬廣繞射峰可知五小時 的機械合金化處理後亦可合成組成為 T i 5 4 C u 3 Q N i , Q S i 4 B 2 的鈦基非晶質合金粉末，再由圖五之熱差掃描圖案發現 此 Ti54Ni1()Cu3()Si4B2非晶質合金粉末的玻璃轉換溫度 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事項HI寫本頁) .. -線· 經濟部智慧財產局員工消費合作社印製 499341 A7 B7_ 五、發明說明（t) (T g )和結晶化溫度（T X )分別位於 3 7 0 °C和 4 9 4 °C ，此代 表五小時的機械合金化處理可成功製備具寬廣過冷液態 區△ T達 1 2 4 〇C之 T i 5 4 C u 3 0 N i I。S i 4 B 2非晶質合金粉末。 另由圖六與圖七亦可清楚查知具寬廣過冷液態區△ T達 6 1 °C之T i 7 4 C u丨。N i丨q S i 4 B 2非晶質合金粉末經五小時的機 械合金化處理後可被成功製備。 經由以上的實施例可知，本發明所提出的具寬廣過 冷液態區之鈦基非晶質合金粉末的製備方法和習用技術 所使用的急冷凝固法相比較，因係以固態反應製程的機 械合金法進行，此不似急冷凝固法有冷卻速率之限制， 故可以在廣闊的合金組成範圍形成非晶質合金粉末，又 機械合金化的高能量球磨處理方法在設備上只需一高能 量球磨機便可進行成本很低且實用性高，因此也極適合 工業化的量產需求，另本發明合成之鈦基非晶質合金粉 末，因具有△ T = 2 5〜1 2 4 °C的寬廣過冷液態區，故非常 適合作為以熱壓、熱均壓或擠製等成型法製造塊材鈦基 非晶質合金的原料。 綜上所述，本創作在鈦基非晶質合金粉末的製備 方法和此等粉末具廣過冷液態區的性質均屬首先創作 者，且具產業上利用價值，誠屬充份符合發明專利申 請之要件，又本創作於申請前並未有已見於任何刊物 及公開使用之情事，故乃爰依專利法之規定具文提出 申請，懇請貴審查委員惠予審查，並賜准專利，實感 德便。 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —— — — — — — — — — — — II I I (請先閱讀背面之注意事項寫本頁) --線·V. Description of the invention (The research on I-Cheng began in 1970, and the research data from 1970 to 1980 showed that the composition that can form the amorphous alloy phase is: Ti-Be-Zr, Ti-Ni, Ti-Ni-Si , Ti-Be, Ti-M-Si, Ti-M-Si-B (M = IV ~ V metal) and other alloy systems, but only in T i-B e and T i-B e-Z r amorphous The alloy phase has a glass transition temperature, and no new Ti-based amorphous alloy has been successfully prepared in 14 years from 1800. The main reason is that titanium is highly metallizable and easily interacts with air. Oxygen and nitrogen react, so it is difficult to control its experimental parameters. From a process point of view, the titanium-based amorphous alloy prepared by the liquid quench method has the following defects: (1) when the size of the foil or powder is synthesized The larger the cooling rate required, the more difficult it is to prepare; (2) changes in the composition of the titanium-based alloy will change the melting point temperature and then strongly affect the cooling rate required to form an amorphous state, so the preparation will be Limited by material composition, (3) precision equipment such as high frequency induction heating, vacuum, nozzle, cold air, etc. are required, so The cost is very high. In terms of materials, the titanium-based amorphous alloy prepared by the liquid quenching method has almost the same glass transition temperature (T g) as the glass transition temperature (TX). The temperature range of the subcooled state AT (AT = TX-T g) defined by the temperature difference. The titanium-based amorphous alloy prepared by the liquid quench method is very small or even non-existent. When a chitin-based amorphous alloy is formed into a bulk amorphous alloy in a temperature range of △ T by hot pressing, hot equalization, extrusion, etc., the forming temperature is 3 due to the forming temperature. This paper size applies to Chinese National Standards (CNS) A4 specification (210 X 297 mm) -------------- install --- (Please read the precautions on the back first to write this page) · --- line · Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 499341 A7 B7_ 5. Description of the invention (+) Degrees are too close to the crystallization temperature, which will cause the amorphous alloy to become crystalline in the process of bulk reduction, and then lose all the properties of the amorphous phase. Excellent material characteristics and greatly reduce its application value. The titanium-based amorphous alloy prepared by the liquid quenching method will inevitably have the aforementioned process and material defects. The author of this case has accumulated many years of experience in the synthesis of amorphous alloys, so he is actively researching how to use brand new Method to prepare a titanium-based amorphous alloy with a wide supercooled liquid region to solve the problems that the related industry is desperate to overcome. After continuous trials and experiments, it was found that the creation of a beverage base with a wide supercooled liquid region Amorphous alloy method. The present invention uses a mechanical alloying method that is completely different from the conventional liquid quenching method to synthesize titanium-based amorphous alloy powder with a wide supercooled liquid region. The implementation of the mechanical alloying method is borrowed from The high energy ball mill is carried out. According to the set composition TiaCubNieSi4B2, the pure powders of Ti, Cu, Ni, Si, B and other pure elements are weighed. The powders and the appropriate number of grinding balls are filled into a ball mill tank in a glove box, and then This ball mill tank is placed in a high-energy ball mill for mechanical alloying and high-energy ball milling. After a period of time, TiaCubNicSi4B2 with △ T = 25 ~ 94 ° C can be obtained. Amorphous alloy powder. Compared with the rapid condensation method used in the conventional technology, the synthesis method proposed by the present invention is a solid state reaction process. Unlike the rapid condensation method, which has a cooling rate limitation, it can form amorphous in a wide range of different alloy systems. Alloy powder, mechanically alloyed high-energy ball milling 4 Paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm): ------------- installation—— ( Please read the note on the back HI first write this page) Order:-Line Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499341 A7 B7_ IV. Description of the invention () The method only needs a high-energy ball mill on the device. The Chengfeng is very low, and it can produce powder in large quantities, so it is also very suitable for industrial mass production needs. The titanium-based amorphous alloy powder synthesized by the present invention has a wide supercooled liquid region of △ T = 2 5 ~ 1 2 4 ° C (△ T = TX-T g), so if the glass transition temperature (T g ) And the crystallization temperature (TX) temperature range for block forming, there will be the following two advantages: (a) because the molding temperature is higher than the glass transition temperature, the material itself is very viscous at this time, similar to ultra Shape properties, so it can form a high-density block under a small molding pressure; (b) because the molding temperature is lower than the crystallization temperature, the material itself is still amorphous, so the titanium-based The crystalline alloy powder is very suitable as a raw material for manufacturing bulk titanium-based amorphous alloys by forming methods such as hot pressing, hot equalizing, or extrusion. In order to allow your reviewers to have a deeper understanding and understanding of the method and characteristics of this creation, detailed illustrations are attached as follows: The illustrated part The first figure: a schematic diagram of the powder preparation process according to the embodiment of the present invention. Fig. 2 is an X-ray diffraction pattern of the titanium-based amorphous alloy powder synthesized in Example 1 of the present invention. FIG. 3 is a thermal scanning analysis chart of the titanium-based amorphous alloy powder synthesized in Example 1 of the present invention. Fig. 4 is an X-ray diffraction pattern of the titanium-based amorphous alloy powder synthesized in Example 2 of the present invention. Fig. 5 is a thermal differential scanning analysis chart of the titanium-based amorphous alloy powder synthesized in Example 2 of the present invention. 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------- Loading --- (Please read the precautions on the back first to write this page ) ·-Line · 499341 Printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (i) Picture 6: X74 of Ti74Ni1 () Cu1 () Si4B2 amorphous alloy powder synthesized according to the present invention- Ray diffraction pattern. The seventh figure is a thermal differential scanning analysis diagram of the Ti74Ni1 () Cu1 () Si4B2 amorphous alloy powder synthesized by the present invention. Please refer to the first diagram for a schematic diagram of the powder synthesis process according to a preferred embodiment of the present invention. As shown in the figure, the method for preparing a titanium-based amorphous alloy powder with a wide supercooled liquid region in this embodiment mainly includes sequentially Material preparation step 1. Sealing step 2. Mechanical alloy step 3 The following is a detailed description of each process as follows: (1) Material preparation step: First, take the appropriate amount of Ti, Cu, Ni, Si, B according to the set composition of TiaCubNieSi4B2. Mix the powder with iso-pure elements, select the required ball particles and weight according to the designed powder / mill ball ratio, and then place the mixed powder and the ball into the ball mill tank. (2) Sealing step: The ball mill tank in step (1) is sealed in a protective atmosphere containing oxidation resistance, and the ball mill tank is closed to ensure that the mixed powder is not used in the subsequent mechanical alloying high-energy ball milling process. Will oxidize. (3) Mechanical alloy step: After moving the ball milling tank of step (2) into a high energy ball mill for mechanical alloying and high energy ball milling for a period of time, a TiaCubNieSi4B2 amorphous alloy with a wide supercooled liquid region can be obtained. powder. Example 1: Ti "Ni30Si4B2 4 g of titanium-containing pure element mixed powder, including 2.47 g of titanium, 6 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read first Note on the back ^^ write this page) --installation · -line · printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499341 A7 B7_ V. Description of the invention (^) 1.4 2 g of nickel, 0.0 9 g of stone In the evening, 0.0 2 g of boron, select 10 grinding balls with a diameter of 3/16 inches and a total weight of 20 g at a powder / mill ball ratio of 1/5, and then mix 4 g of powder with 20 The grinding ball of g is put into the ball grinding tank together, the ball grinding tank is moved into a glove box and the glove box is filled with argon. When the oxygen indicator in the glove box shows that the oxygen content is zero, the ball grinding tank is closed. After moving it to a vibration-type high-energy ball mill for five hours of mechanical alloying treatment, a titanium-based ball mill powder having a composition of Ti64Ni ^ Si4B2 can be synthesized. T i 6 4 N i 3 〇S i synthesized in this embodiment The crystal structure of 4 B 2 titanium-based ball-milled powder. The X-ray ray pattern shown in Figure 2 contains only a wide diffraction ridge. Knowing that it is an amorphous phase, the T i 6 4 N i 3 was found from the thermal scanning pattern in Figure 3. The glass transition temperature (T g) and crystallization of the Si 4 B 2 amorphous alloy powder The temperature (Tx) is located at 450 ° C and 499 ° C, respectively. The supercooled liquid region AT (△ T = Tx-Tg) of the Ti64Ni30Si4B2 amorphous alloy powder is 94 ° C. Example 2: Ti54Cu3. Ni10Si4B2 In this example, we replaced 30 at% Cu with 10 at% T i and 20 at% Ni, 4 g of titanium-containing nickel-copper-silicon-boron pure element mixed powder, including 1.9 8 g of titanium, 1.46 g of copper, 0.4 5 g of nickel, 0.09 g of silicon, and 0.02 g of boron. The rest of the implementation steps are the same as those of the first embodiment, and are radiated by X-rays in Figure 4 The pattern contains only a broad diffraction peak. It can be seen that after five hours of mechanical alloying treatment, titanium-based amorphous alloy powders with the composition of T i 5 4 C u 3 QN i and QS i 4 B 2 can be synthesized. The thermal difference scanning pattern found that the glass transition temperature of this Ti54Ni1 () Cu3 () Si4B2 amorphous alloy powder 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- ------------ Equipment --- (Please read the note on the back HI first to write this page) .. -Line · Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 499341 A7 B7_ V. Invention Note (t) (T g) and crystallization temperature (TX) are located at 370 ° C and 494 ° C, respectively. This means that five hours of mechanical alloying can successfully prepare a wide supercooled liquid region △ T up to T i 5 4 C u 3 0 N i I of 1 2 4 OC. S i 4 B 2 amorphous alloy powder. In addition, from Figure 6 and Figure 7, it is also clear that T i 7 4 C u 丨 with a wide supercooled liquid region △ T reaches 6 1 ° C. Ni i q S i 4 B 2 amorphous alloy powder can be successfully prepared after five hours of mechanical alloying. From the above examples, it can be seen that the method for preparing the titanium-based amorphous alloy powder with a wide supercooled liquid region proposed in the present invention is compared with the rapid condensation solidification method used in conventional technology, because it is a mechanical alloy method using a solid-state reaction process. This is not like the rapid condensation solidification method which has the limitation of the cooling rate, so it can form amorphous alloy powder in a wide range of alloy composition, and the mechanically alloyed high-energy ball milling method requires only a high-energy ball mill on the equipment. The running cost is very low and the practicability is high, so it is also very suitable for industrial mass production needs. In addition, the titanium-based amorphous alloy powder synthesized by the present invention has a wide supercooled liquid of △ T = 2 5 ~ 1 2 4 ° C. Therefore, it is very suitable as a raw material for manufacturing bulk titanium-based amorphous alloys by forming methods such as hot pressing, hot equalizing, or extrusion. To sum up, this method is the first creator in the preparation method of titanium-based amorphous alloy powder and the properties of these powders with a wide supercooled liquid region, and it has industrial use value. It is in full compliance with the invention patent. The requirements of the application, and the creation has not been seen in any publications and public use before the application. Therefore, the application was submitted in accordance with the provisions of the Patent Law, and I ask your reviewing committee to review it and grant the patent. Deben. 8 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) —— — — — — — — — — — — II I I (Please read the precautions on the back first to write this page)-Line ·