555609、. j» A7 __B7五、發明說明（+)發明範圍 經濟部智慧时產局3工消费合作社印鉍 於 關 係 明 發利 本係 其 用 化 +昔 氧4 或理 物處 匕 匕 /1 /1 高 物 能 或 製磨 種球 一 量 熔 高 極 將耐 機點 括 屬包 金 璃 玻 金 火 純屬 法 方 的 末 粉 料 材 合素 複元 素 元 冷 過 廣 寬 具 成 合 此 法 方 備 製景 末背 粉明 料發 金 金 的 區 態 末 粉屬 碳 金 及 合 末械 粉機 合行 混進 材 合 複 基 璃 玻 構 結 列 LTP 子 原 其 料 材 的 構 結 晶 結 tr 具 為 金 合 璃 玻 屬 金 金優相 合及璃 璃度玻 玻硬屬 屬 、金 金度， 得強現 使械表 此機的 ， 高 面 性、 方 律性質 規蝕性 程腐磁 長抗在 具 高 。 不如性 且 ·， 特 亂 質 磁 散特、 為的電 體異 、 液優光 似著的 類有異 软合 為璃 作玻 有屬 具 金 金 ·’ 合力 的 需 所 料 材 磁 阻 電 的 高 有 具 金 (請先閱讀背面之注意事項再填寫本頁) 磁 導 異 及 磁 ， 頑性 矯特 的磁 低軟 及的 率異 由界 ， 晶 上無 質 及 LL LUUI 學 差 化無 在 、 •,ft 象 質 現均 損 的 鐵構 料結 材列 、> hr 鐵子 器 原 壓金 變合 低 璃 降玻 幅 屬 大金 可於 的構 良 結 優 子 有 原 具的 故金 滑 合 平璃 勻玻 均屬 的金 常 於 非由 膜 ， 態 面 鈍方 的 質 成性 形械 面機 表在 性性 特li 等耐 固移 的滑 料排 材差 態 生 晶發 結 因 有會 沒 不 且而 排時 差 力 何 應 任剪 在 受 存 ’ 不移 ， 滑 性供 律可 規統 程 系 短移 具 滑 僅 定 璃 、 玻限 屬 除 金彈 於 、 用 度 適強 不拉 並抗 ^的 理佳 移極 滑 有 排擁 差 其 此 以 因所 象 制 現機 形形 變變 生 的 產 金 而 合 度 高 和值 性比 勒論 斷理 破近 9 2 度 屬 金 管 儘 接， ， 性 間特 之的 2 異 3 優 5 此 2 如 在有 約 具 值 金 比 合 度璃 強玻 約 κί\ 率 速 卻 冷 高 的 需 所 時 觜 2 製 金 合 璃 玻 屬 金 統 傳 而 然 本紙張 <度適用中國國家標準（CNS)A 1规格（LMO X 297公f ) 555609 t 、 1 A7 B7 五、發明說明（/) (請先閱讀背面之注意事項再填寫本頁) 1 0 6 K / s e c )及在拉伸或壓縮測試中的表現卻如同脆性材料 般沒有顯著的塑性變形量，缺乏延展性乃因此成為金屬玻 璃合金在應用上的一大隱憂。延展性之缺乏主要歸因於塊 狀金屬玻璃合金的變形機制乃藉由高度局部化剪變帶的產 生使合金發生塑性變形，高度局部化的剪變變形使金屬玻 璃合金的塑性變形只集中在少數的剪變帶，即低應變就可 使剪變帶往未變形區域快速的拓展，故金屬玻璃的抗拉強 度約等於其降服強度而缺乏展性；以複合材料的觀點，脆 性材料如陶瓷材料可添加強化相在陶瓷基地中，當受剪應 力而發生變形時強化相會抑制單一裂紋的成長，使其生成 微裂缝來增加陶兗的破裂面積和吸收破裂能而提升陶瓷材 料的破壞韌性。基於這個理念若在金屬玻璃合金中添加陶 瓷或極高熔點耐火金屬顆粒強化相形成金屬玻璃複合材的 話，將可藉強化相的存在來抑制單一剪變帶擴展並使其轉 而生成多重剪變帶的話，此將可提升金屬玻璃合金的降伏 強度、破壞韌性並可提高塑性變形量。 經濟部智慧財產局3工消伢合作社印奴 傳統製作金屬玻璃的方法大致以液態急冷法為主；此法 是利用諸如自由流熔液旋喷、單輪熔液旋噴 '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、噴覆沉積、高壓水霧化、旋轉水霧化專製 程，將溫度超過 1 2 0 0 °C以上之合金熔液以高達 1 〇 6 °C / s e c 以上的冷卻速率形成金屬玻璃合金，然以此種方法製造金 屬玻璃複合材料時，因其起始原料含欲製備之金屬玻璃成 份及陶瓷或極高熔點金屬元素顆粒’從製程觀點而言具有 3 本紙張尺度適用中0國家標準（CNS)A丨規格（21〇χ 297公f ) 555609 經濟部智祛財產局3工消货合作社印奴 A7 ___B7_ 五、發明說明（ 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) 在玻璃基地相與陶瓷或極高熔點耐火金屬顆粒相間之 介面極易引發部份結晶化反應，進而無法形成玻璃相結 構； (3) 存在於原料間的熔點或密度之高低差異性會使陶瓷或 極高熔點耐火金屬顆粒無法均勻分散於合金熔液T，此 導致合成之金屬玻璃複合材料組織不一致； (4) 需使用到高週波感應加熱、真空、喷嘴、冷卻等精密設 備，故製造成本很高。 發明要旨 有鑑於習用液態急冷法製備的金屬玻璃複合材料無可 避免的會有前述製程上之缺失，本案創作人乃積其從事金 屬玻璃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金屬玻璃複合材 料，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金屬玻璃 複合材料粉末的方法。 本發明乃使用合金化原理完全迥異於習罔液態急冷法 的機械合金方式來合成具寬廣過冷液態區的金屬玻璃複合 材料粉末，機械合金法之執行是藉一高能量球磨機進行，既 依欲製備之金屬玻璃複合材料組成秤取適量的純元素混合 粉末及陶瓷或極高熔點耐火金屬粉末，把此等粉末與適當 4 本紙張尺度適用中國國家標準（CNS)Al規格（210 X 297公梦） ------------^^裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 555609 A7 . _ B7_ 五、發明說明（ 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，既可獲得具寬廣過冷液態區的金屬玻璃複合材 料粉末。 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 前述冷卻速率或金屬玻璃相基地會與強化相介面間發生異 質成核風險等之限制，故可以在不同合金系中形成強化相 含量高但卻可均勻散佈於金屬玻璃相基地的金屬玻璃複合 材料粉末，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。 本發明合成之金屬玻璃複合材料粉末，因具有 Zl r=8 3〜1 1 9°C ( J Γ=Γχ-7>)的寬廣過冷液態區，故若在玻璃 轉換溫度（rg)和結晶化溫度（7^)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 (請先閱讀背面之注意事項再填寫本頁) 裝"-------訂--------- 力 度 壓 溫 型化 成 晶 的 結 小於 艮 氏- .//1 7Ί 度作 溫 創 型 本 成以 因所 b , ;(能？ 材 質 塊 晶 勺 -ιϋ- 狀是 密 仍 緻身 高 本 成材 形基 即故 均 熱 。 、 料 壓 原 熱 的 以料 為材 作合 合複 適璃 常玻 非屬 未金 粉材 料塊 材造 合 製 複法 璃型 玻成 屬 等 金 製 之擠 備或 製壓 深 更 有 能 徵 特 其 及 式 方 之 作 創 本 對 員 委 查 貴 我 --ο 使認 為 的 層 解 暸 與 后 如 明 說 細 詳 示 圖 以 附 茲 5 本紙張&嗖適用中阀阀家標準（CNS)A丨規格（210 X 297公餐） 經濟部智慧时產局轉' u消赀合作社卬公 555609555609,. J »A7 __B7 V. Description of the invention (+) The scope of the invention The Ministry of Economy, Wisdom, Time and Industry Bureau, 3 Industrial Consumer Cooperatives, India and Bismuth, which are related to Mingfali, are used in the past + Oxygen 4 or physical processing dagger / 1 / 1 high-energy or grinding seed balls with a high melting point. The machine-resistant point is covered with gold, glass, glass, fire, and pure powder. The material is a complex element that has been cold-cooled and wide-formed. This method is prepared by this method. The background powder of the background powder and the gold material is gold and the powder is carbon gold and the powder powder machine is mixed into the composite material and the glass and glass structure of the LTP is the structure of the material. The structure is gold. Heli glass belongs to the combination of gold and gold, and vitreous glass and hard metal, and gold degree. It is better to use the machine to display this machine. The high surface, regular nature, corrosion resistance, and long corrosion resistance are very high. . Not as good and ..., special magnetic dispersion, special electric body, and liquid like light, different types, soft and soft, glass, glass, gold, gold, and other materials. Gao Youjin (please read the precautions on the back before filling in this page) Permeability and magnetic properties, low magnetic softness and rate ratio of coercivity, no crystal quality and LL LUUI difference 、,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,-hskage'ageageages's '' 's's' colors 'color' color = 'color' color color 'color =' color = 'our' a ratio` across the ratio & As A &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& into into has has has has has been has has been made, in which in which in the image, for which in the iron material structure, the iron material structure will be evenly damaged, > hr, the original iron pressure transformers, low glass transitions, and lower glass drop widths are available for Daikin may also be good. " The metal that belongs to flat glass and uniform glass is often composed of non-membrane, blunt-shaped, qualitative mechanical surfaces, mechanical surfaces, and other special solid-resistant sliding materials, which have poor crystal growth. Will not fail, but the time difference is what should be cut in the stored 'unchanged, slippery supply law can be regulated by a short-moving slide only fixed glass, glass limit is in addition to gold bombs, moderately strong does not pull The good anti-skid polarizer has poor tolerance, which is why Deformation and deformation of the current production of gold and high degree of integration and the value of Biele's theorem is close to 92 degrees. It is a golden pipe connection, and the special characteristics are 2 different 3 excellent 5 this 2 if there is a value ratio Hedu Liqiang is about κί \ Time-consuming but cold, time-consuming 觜 2 gold-making Heli is made of gold and this paper is suitable for China National Standard (CNS) A 1 (LMO X 297 male f) ) 555609 t 、 1 A7 B7 V. Description of the invention (/) (Please read the notes on the back before filling in this page) 1 0 6 K / sec) and the performance in tensile or compression test is not as brittle material Significant plastic deformation and lack of ductility have become a major concern in the application of metallic glass alloys. The lack of ductility is mainly due to the deformation mechanism of the bulk metallic glass alloy. The plastic deformation of the alloy is caused by the generation of highly localized shear bands. The highly localized shear deformation causes the plastic deformation of metallic glass alloys to focus only on A small number of shear bands, that is, low strain, can rapidly expand the shear band to the undeformed area, so the tensile strength of metallic glass is approximately equal to its yield strength and lacks ductility; from the perspective of composite materials, brittle materials such as ceramics Material can be added with a strengthening phase. In the ceramic base, when the shear stress deforms, the strengthening phase will inhibit the growth of a single crack, causing it to generate micro-cracks to increase the fracture area of the ceramic urn and absorb the fracture energy to improve the fracture toughness of the ceramic material. . Based on this concept, if a ceramic or extremely high melting point refractory metal particle reinforced phase is added to a metallic glass alloy to form a metallic glass composite, the presence of the reinforced phase can inhibit the expansion of a single shear band and cause it to generate multiple shear If it is used, this will increase the drop strength of the metallic glass alloy, damage the toughness, and increase the amount of plastic deformation. The traditional method of making metallic glass by the Indo-Slaves of the Intellectual Property Department of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economics is mainly the liquid quenching method; this method uses such methods as free-flow melt spinning, single-round melt spinning Extraction, plane flow casting, high-pressure gas atomization, centrifugal atomization, ultrasonic gas atomization, spray deposition, high-pressure water atomization, and rotating water atomization. Special processes for alloys whose temperature exceeds 1 200 ° C The molten metal forms a metallic glass alloy at a cooling rate of more than 106 ° C / sec. However, when manufacturing a metallic glass composite material by this method, the starting material contains the metallic glass component and ceramic or extremely high melting point to be prepared. From the process point of view, the metal element particles have 3 paper standards applicable to 0 National Standards (CNS) A 丨 specifications (21〇χ 297 公 f) 555609 Intellectual Property Bureau of the Ministry of Economic Affairs 3 Industrial Consumer Goods Cooperatives Indus A7 ___B7_ 5 2. Description of the invention (the following defects: (1) when the size of the synthesized foil or powder is larger, the higher the cooling rate required, the more difficult it is to prepare; (2) the glass base phase and the ceramic or extremely high melt The interface between the refractory metal particles is likely to cause a partial crystallization reaction, so that it cannot form a glass phase structure; (3) The difference in melting point or density between the raw materials can make ceramics or extremely high melting point refractory metal particles not uniformly dispersed. In the alloy melt T, this results in an inconsistent microstructure of the synthesized metallic glass composite material; (4) High-frequency induction heating, vacuum, nozzles, cooling and other precision equipment are required, so the manufacturing cost is high. The purpose of the invention is to consider the rapid cooling of liquid The metal-glass composite materials prepared by the method will inevitably have the aforementioned process defects. The creator of this case has accumulated many years of experience in the synthesis of metal-glass alloys, so he is actively researching how to use a new method to prepare a wide range of supercooling. The metal-glass composite material in the liquid region solves the problems that the related industry is desperate to overcome. After continuous trials and experiments, the method of manufacturing the metal-glass composite powder with a wide supercooled liquid region has finally been found. This invention is The principle of alloying is completely different from the mechanical alloy method of liquid quenching. To synthesize metal-glass composite powder with a wide supercooled liquid region, the implementation of the mechanical alloy method is performed by a high-energy ball mill. According to the composition of the metal-glass composite material to be prepared, a suitable amount of pure element mixed powder and ceramic or electrode are weighed. Refractory metal powder with high melting point, suitable for these papers and 4 paper sizes. Applicable to China National Standard (CNS) Al specification (210 X 297 public dream) ------------ ^^ pack --- ----- Order --------- (Please read the notes on the back before filling in this page) 555609 A7. _ B7_ V. Description of the invention (The number of grinding balls is filled into a glove box in a glove box In a tank, and then placing the ball mill tank in a high-energy ball mill for mechanical alloying and high-energy ball milling for a period of time, a metal-glass composite powder having a wide supercooled liquid region can be obtained. 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, the aforementioned cooling rate or heterogeneous nucleation between the metal glass phase base and the strengthening phase interface occurs. Due to the limitation of risks, etc., it is possible to form metal-glass composite powders with a high content of strengthening phases in different alloy systems, but which can be evenly dispersed in the metal-glass phase base. Mechanically alloyed high-energy ball milling treatment methods only require one on the equipment. The high-energy ball mill can be carried out at a low cost and can produce powder in large quantities, so it is also very suitable for industrial mass production needs. The metallic glass composite material powder synthesized by the present invention has a wide supercooled liquid region of Zl r = 8 3 ~ 1 19 ° C (J Γ = Γχ-7 >). Therefore, if the glass transition temperature (rg) and crystal When the block is formed at a temperature range of (7 ^), the following two advantages will be obtained: (a) Because the molding temperature is higher than the glass transition temperature, the material itself is very viscous at this time, similar to a super type Traits' can be found in (Please read the precautions on the back before filling out this page) .//1 7Ίdegrees are used for warm wounds, so b,; (can? Material block crystal spoon -ιϋ- shape is dense and still make the height of the material shape base, so it is uniform. The material is made of composite materials, and the glass is not a non-gold powder material. The block material is made of composite glass, glass, glass, and other gold materials. This pair of members of the committee inspected you-ο I explained the layers and explained the details in detail later with 5 papers & 嗖 Applicable to China Valves Standard (CNS) A 丨 Specifications (210 X 297 meals) Transferred by the Ministry of Economic Affairs and Smart Production Bureau
I Λ7 B7 五、發明說明（i ) 圖示告卩份 第一圖：為本發明合成之金屬玻璃複合材料粉末的X -射 線繞射圖。 第二圖：為本發明合成之金屬玻璃複合材料粉末的熱差掃 描分析圖。 第三圖：為本發明合成之金屬玻璃複合材料粉末的顯微組 織圖。 本實施具寬廣過冷液態區之金屬玻璃複合材料粉末之 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：先依設定之金屬玻璃複合材料組成秤取適量 的適量的純元素混合粉末及陶瓷或極高熔點耐火金屬 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金屬玻璃複合材料粉末。 發明詳細說明 金屬玻璃複合材料合金基材組成設定為 N i 5 7 Z r 2 〇 T i 2 3 S i 3，另添加體積百分比為1 〇 %的各種強化相顆 粒（W、S i C、W C、A 1 2 0 3 )，先依此設定組成在精密天平 6 本紙張反度適用中國國家標準（CNS)Al规格（210x297公堃） -------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 555609 經濟部智竑財產局：肖工消货合作社印於 Λ7 B7 五、發明說明（1 上量取總重為4 g的混合粉末，元素粉末是由S t r e m化學公 司購得，下列為粉末之純度及粒度：N i ( 3 N，< 1 Ο 0 m e s h )、 Zr ( 3N，<3 2 5 mesh )、Ti ( 2N，<3 2 5 mesh )、Si ( 2N， < 3 2 5 mesh ) > W ( 3N8，< 1 OOmesh ) SiC (〈lOOmesh)、WC (3N，〈lOOmesh)、Al2〇3(3N，<100mesh)，將所科取之 粉末與1 0顆直徑5 / 1 6英吋（重量約2克）高鉻鋼球一同 裝入高7 5 m m、直徑5 5 m m的工具鋼球磨罐中，磨球與混合 粉末重量比為 5 ·. 1，為避免球磨時粉末產生氧化反應，所 以球磨過程需在惰性保護氣氛下進行；將含有混合粉末與 鋼球之球磨罐置入手套箱中，以反覆充填氬氣與抽氣的動 作使氬氣置換手套箱中氣體，以氧氣偵測計測量手套箱内 氧含量，直到手套箱中氧含量為零時停止，將球磨罐封罐 並移出手套箱，放入球磨機中開始進行機械合金化處理， 球磨進行五小時後便可合成基材組成為N i 5 7 Z r 2 〇 T i 2 3 S i 3的 金屬玻璃複合材料粉末。 本實施例所合成Ni57Zr2〇Ti23Si3金屬玻璃相複合材料 粉末的結晶構造，由圖一之X光射線饒射圖案均含一寬廣 繞射峰可知基材確為一玻璃相，除此之外，W及W C強化 相的繞射峰依然明顯的存在並堆於在寬廣繞射峰上’另 X - r a y繞射圖樣中無法觀察到S i C與A 12 Ο 3強化相繞射峰， 此乃因球磨處理使結晶繞射峰強度本就不高的強化相降 低太多並在相較於玻璃相高繞射峰強度掩蓋下而無法顯 現出來，然從後續圖三的金相顯微組織可知 S i C與 A 12 0 3 強化相顆粒並未消失可知，基材雖經球磨處理已形成玻璃 7 本紙張又度適用中國國家標準（CNSMl蜆格（210 X 297公發） (請先閱讀背面之注意事項再填寫本頁) 夏--------訂---------線座 經濟部智慧財產局Μ工消t合作社印製 555609 A7 ___B7__ 五、發明說明（t) 相但強化相並沒有因球磨處理而固溶於玻璃相的基地中 既其結晶結構亦未因球磨處理而發生變化。圖二為本實施 例所合成N i 5 7 Z r 2 〇 T i 2 3 s i 3金屬玻璃相複合材料粉末的熱差 掃描圖案。由圖中之D S C曲線可發現N i 5 7 Z r 2 〇 T i 2 3 S i 3金屬 玻璃相複合材料粉末均在低溫時會先出現一個代表玻璃 轉換行為的吸熱峰，此為玻璃轉化溫度〔〕，並隨之在 較高溫處則會出現一個結晶化反應產生的放熱峰，此為結 晶溫度〔7\〕，由玻璃轉化溫度〔。〕與結晶溫度〔〕 界定的過冷液態區」Γ(ζ! r=rx-：Tg)則歸納在表一，合成之 金屬玻璃複合材料粉末都具有△ T = 83〜119°C (Z1 Γ=Γχ-Γ§) 的寬廣過冷液態區。圖三為經過5小時球磨處理後的各金 屬玻璃複合材料於掃瞄電子顯微鏡下的橫截面圖。圖中顯 示經5小時球磨處理後，白色細小的強化相顆粒都均勻的 散佈在金屬玻璃相基地中，經由以上各複合材料粉末所展 現出的熱行為、玻璃相結構及金相組織，證實機械合金法 可成功的製備強化相為碳化物或氧化物或極高熔點金屬 元素的金屬玻璃複合材料粉末。 表一 N i 5 7 Z r 2 〇 T i 2 〇 S i 3金屬玻璃複合材料粉末之7>、Γ.Υ、/1 Γ 金屬玻璃複合材料組成 Tg Tx Zl T Ni 57 Zr2〇Ti 2 3 s i 3 + 1 〇 ν〇 1 % W 769 870 10 1 N i 5 7 Z r 2 ο T i 2 3 S i 3 + 1 〇 Vo 1 % W C 769 880 111 Ni 5 7Zr2〇Ti 2 3 S i 3 + 1 〇 Vo 1 %S i C 793 876 83 Ni57Zr20Ti23Si3 + 1 OV〇1%A12〇3 7 7 3 873 1 00 經由以上的實施例可知，本發明所提出的具寬廣過冷 8 本紙張尺度適用中阀0家標^(CNS)Al现格（21〇χ‘」97公t ) -----------0^--------訂---------^0. (請先閱讀背面之注意事項再填寫本頁) « 1 555609 ' 丨 Λ7 . _B7_ 五、發明說明（~) (請先閱讀背面之注意事項再填寫本頁) 液態區之的金屬玻璃複合材料粉末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 不同合金系中形成強化相含量高但卻可均勻散佈於金屬玻 璃相基地的金屬玻璃複合材料粉末，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 本發明合成之金屬玻璃基複合材料粉末，因具有 d Γ=83〜119 °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金屬玻璃複合材料的 原料。 綜上所述，本創作在金屬玻璃複合材料粉末的製備方 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。 經濟部智U財產局員工消费合作社印％ 9 本紙張&度適用中國國家標準（CNS)Al規恪（21〇χ 297公坌）I Λ7 B7 V. Description of the invention (i) Graphical report first picture: X-ray diffraction diagram of the metallic glass composite powder synthesized by the present invention. The second figure is a thermal scanning analysis chart of the metallic glass composite powder synthesized by the present invention. The third figure is a microstructure diagram of the metallic glass composite powder synthesized by the present invention. The method for preparing a metal-glass composite material powder with a wide supercooled liquid region in the present embodiment mainly includes a preparation step 1, a can sealing step 2, and a mechanical alloy step 3 in order. The following detailed description of each process is as follows: (1 ) Material preparation step: First, take the appropriate amount of pure element mixed powder and ceramic or extremely high melting point refractory metal powder according to the set composition of the metal-glass composite material, and also select the required ball particles according to the designed powder / mill-ball ratio And the weight, and then put the mixed powder into the ball mill pot together with the mill ball. (2) Can sealing step: The ball mill can of step (1) is sealed in a protective atmosphere containing an anti-oxidation atmosphere, and the ball mill can is closed to ensure that the mixed powder is not used in the subsequent mechanical alloying high-energy ball milling treatment. Will oxidize. (3) Mechanical alloy step: After the ball mill tank of step (2) is moved into a high energy ball mill for mechanical alloyed high energy ball milling for a period of time, a metallic glass composite powder having a wide supercooled liquid region can be obtained . Detailed description of the invention The composition of the metallic glass composite material alloy base material is set to Ni 5 7 Z r 2 〇T i 2 3 S i 3, and various strengthening phase particles (W, S i C, WC are added in a volume percentage of 10%. , A 1 2 0 3), according to this setting, the composition of the precision balance 6 paper is adapted to the Chinese National Standard (CNS) Al specification (210x297 cm) --------------- ---- Order --------- line (please read the notes on the back before filling this page) 555609 Intellectual Property Bureau of the Ministry of Economic Affairs: Xiao Gong Consumer Cooperative Co., Ltd. Printed on Λ7 B7 V. Description of Invention ( 1 Weigh the mixed powder with a total weight of 4 g. The elemental powder was purchased from Strem Chemical Company. The following is the purity and particle size of the powder: N i (3 N, < 1 0 0 mesh), Zr (3N, < 3 2 5 mesh), Ti (2N, < 3 2 5 mesh), Si (2N, < 3 2 5 mesh) > W (3N8, < 1 OOmesh) SiC (<lOOmesh), WC ( 3N, <100mesh), Al203 (3N, <100mesh), put the obtained powder together with 10 high-chromium steel balls with a diameter of 5/16 inches (weight about 2 grams) high 7 5 mm, 5 5 mm diameter tool steel ball grinding tank, grinding ball and mixed The powder weight ratio is 5. · 1. In order to avoid oxidation reaction of the powder during ball milling, the ball milling process needs to be performed under an inert protective atmosphere; a ball mill tank containing mixed powder and steel balls is placed in a glove box to repeatedly fill with argon With the action of pumping, argon is used to replace the gas in the glove box, and the oxygen content in the glove box is measured with an oxygen detector until it stops when the oxygen content in the glove box is zero. The ball mill can is sealed and removed from the glove box and put into the ball mill. The mechanical alloying treatment was started in the middle of the process, and the metal glass composite material powder with a substrate composition of N i 5 7 Z r 2 〇 T i 2 3 S i 3 was synthesized after ball milling for five hours. Ni57Zr2〇Ti23Si3 synthesized in this embodiment The crystal structure of the metallic glass phase composite powder, from the X-ray ray diffraction pattern in Figure 1, contains a broad diffraction peak. It can be seen that the substrate is indeed a glass phase. In addition, the diffraction peaks of the W and WC strengthened phases It still clearly exists and piles on the broad diffraction peaks. In addition, the diffraction peaks of S i C and A 12 Ο 3 enhanced phases cannot be observed in the X-ray diffraction pattern. This is because the intensity of the crystal diffraction peaks is caused by the ball milling process. Not high The strengthening phase is reduced too much and cannot be seen under the masking of the higher diffraction peak intensity compared to the glass phase. However, from the metallurgical microstructure of Figure 3, it can be seen that S i C and A 12 0 3 strengthening phase particles have not disappeared. Although the base material has been formed into glass by ball milling 7 This paper is also applicable to the Chinese national standard (CNSMl 蚬 Grid (210 X 297)) (Please read the precautions on the back before filling this page) Xia ------- -Order --------- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative Co., Ltd. 555609 A7 ___B7__ 5. Description of the invention (t) phase but the strengthening phase is not solid-soluble in the glass phase due to ball milling The crystal structure of the base was not changed by ball milling. Fig. 2 is a thermal differential scanning pattern of the Ni 5 7 Z r 2 0 T i 2 3 s i 3 metal-glass phase composite material powder synthesized in this embodiment. From the DSC curve in the figure, it can be found that Ni 5 7 Z r 2 〇T i 2 3 S i 3 metallic glass phase composite powder will first appear an endothermic peak representing the glass transition behavior at low temperature. This is the glass transition temperature [], And an exothermic peak due to the crystallization reaction will appear at a higher temperature, which is the crystallization temperature [7 \], and the glass transition temperature [. The subcooled liquid region defined by the 〔〕 and the crystallization temperature 〔Γ (ζ! R = rx-: Tg) is summarized in Table 1. The synthesized metallic glass composite powders have △ T = 83 ~ 119 ° C (Z1 Γ = Γχ-Γ§). Figure 3 is a cross-sectional view of each metal glass composite material after scanning for 5 hours under a scanning electron microscope. The figure shows that after 5 hours of ball milling treatment, the white fine reinforcing phase particles are evenly dispersed in the metallic glass phase base. The thermal behavior, glass phase structure and metallographic structure of the composite powders shown above confirm the mechanical The alloy method can successfully prepare metallic glass composite powders whose strengthening phase is carbides or oxides or extremely high melting point metal elements. Table 1 N i 5 7 Z r 2 〇T i 2 〇S i 3 Metal glass composite powder 7 >, Γ.Υ, / 1 Γ Metal glass composite material composition Tg Tx Zl T Ni 57 Zr2 Ti 2 3 si 3 + 1 〇ν〇1% W 769 870 10 1 N i 5 7 Z r 2 ο T i 2 3 S i 3 + 1 〇Vo 1% WC 769 880 111 Ni 5 7Zr2〇Ti 2 3 S i 3 + 1 〇Vo 1% S i C 793 876 83 Ni57Zr20Ti23Si3 + 1 OV〇1% A12〇3 7 7 3 873 1 00 According to the above examples, it can be seen that the present invention has a wide range of supercooling. 8 This paper scale is applicable to the valve 0 Housemark ^ (CNS) Al appears (21〇χ '' '97g t) ----------- 0 ^ -------- Order --------- ^ 0. (Please read the precautions on the back before filling out this page) «1 555609 '丨 Λ7. _B7_ V. Description of the invention (~) (Please read the precautions on the back before filling out this page) Metal glass in the liquid area Compared with the rapid condensation solidification method used in conventional technology, the method for preparing composite powders is performed by the mechanical alloy method of the solid state reaction process. This is not like the rapid condensation solidification method, which has a cooling rate limitation, so it can form a strengthening phase in different alloy systems. High in content but spread evenly The metal-glass composite material powder of the metal-glass phase base and the mechanically alloyed high-energy ball milling method require only a high-energy ball mill on the equipment to perform low cost and high practicality, so it is also very suitable for industrial mass production needs. In addition, the metal-glass-based composite material powder synthesized by the present invention has a wide supercooled liquid region of d Γ = 83 ~ 119 ° C, so it is very suitable as a method for manufacturing blocks by hot pressing, hot equalizing or extrusion. Raw materials for metallic glass composites. To sum up, the creation method of the metallic glass composite material powder and the properties of these powders with a wide supercooled liquid region are the first creators and have industrial utility value. They are in full compliance with the invention patent application. Requirement 'Also, before the application was created, it has not been seen in any publications and public use. 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. . Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9% of this paper & degree is subject to Chinese National Standards (CNS) Al Regulations (21〇χ 297)