TWI247818B - The improvement of high temperature oxidation resistance of alpha2-Ti3Al intermetallic by using physical vapor Al-deposition process - Google Patents

Abstract

A method for forming the protective and continuous TiAl3 layer on alpha2-Ti3Al alloy can improve its high temperature oxidation resistance. Based on the invention, the high temperature oxidation resistance of alpha2-Ti3Al intermetallics can be improved by physical vapor Al-deposition and subsequent interdiffusion treatment. The process relates to the applications of titanium aluminides materials, and, more particularly, to the use of such materials against high temperature, oxidative environments, such as turbine blades, exhausted valves and aircraft components used in energy/aircraft industries.

Description

1247818 五、發明說明α) 【發明所屬之技術領域】 一種使α 2-鈦鋁介金屬表面產生連續T i A 1保護膜的方 法，特別適用於改善α 2-鈦鋁介金屬高溫氧化抵抗。根據此 發明，α 2-鈦鋁介金屬可藉著物理氣相沉積法如濺鍍法、蒸 鍍法等，在表面鍍上一層適當厚度之鋁薄膜，再利用高真 空熱處理，使此鋁薄膜變成T i A 1連續介金屬膜，以改善其 高溫耐氧化性。此製程可應用於以α 2-鈦鋁介金屬為材料且 需要在高溫環境使用的元件，如渦輪引擎的葉片、汽車引 擎排氣閥及能源、航太工業用零件等。 【產業上利用之範疇】 由於α 2-鈦鋁介金屬即使在高溫下也有很高的比強度 (強度/密度），因此特別適用於移動且需要高溫強度的 構造，如飛行器中的高溫零件、渦輪引擎葉片、汽車引擎 的氣閥等。但其在高溫（6 5 0°C以上）氧化抵抗性質不佳 一直是α 2_鈦鋁介金屬實際應用上的瓶頸。本發明主要是藉 著物理蒸鍍鋁薄膜於α 2 -鈦鋁介金屬表面的方法，加上隨 後高真空加熱處理之配合，使表面產生氧化鋁惰性膜來增 加其高溫氧化抵抗，而使α 2-鈦鋁介金屬更能適用於高溫的 使用環境。 【先前技術】 以往之技術除了利用合金之設計（如添加合金元素 等）來改善α 2-鈦鋁介金屬的高溫耐氧化性外，也可以利用1247818 V. INSTRUCTION DESCRIPTION α) [Technical Field of the Invention] A method for producing a continuous Ti 2 A protective film on an α 2 -titanium aluminum intermetallic surface is particularly suitable for improving high temperature oxidation resistance of α 2 -titanium aluminum intermetallic. According to the invention, the α2-titanium aluminum intermetallic metal can be coated with a thin film of an appropriate thickness on the surface by physical vapor deposition such as sputtering, evaporation, or the like, and then subjected to high vacuum heat treatment to make the aluminum thin film. It becomes a continuous dielectric film of T i A 1 to improve its high temperature oxidation resistance. This process can be applied to components that use α2-titanium aluminum intercalation materials and need to be used in high temperature environments, such as turbine engine blades, automotive engine exhaust valves and energy, and aerospace industrial parts. [Scope of industrial use] Since α 2-titanium aluminum intermetallics have high specific strength (strength/density) even at high temperatures, they are particularly suitable for structures that require high-temperature strength, such as high-temperature parts in aircraft. Turbine engine blades, gas valves for automobile engines, etc. However, its poor oxidation resistance at high temperatures (above 65 °C) has been the bottleneck in the practical application of α 2_ titanium aluminum intercalation metal. The invention mainly comprises the method of physically vapor-depositing an aluminum film on the surface of the α 2 -titanium aluminum intercalation metal, and the subsequent high vacuum heat treatment to make the surface produce an alumina inert film to increase the high temperature oxidation resistance, and α 2-Titanium aluminum intermetallics are more suitable for use in high temperature environments. [Prior Art] In addition to the use of alloy design (such as the addition of alloying elements) to improve the high temperature oxidation resistance of α2-titanium aluminum intermetallics, the prior art can also be utilized.

1247818 一------- 五、發明說明（2) ^面改質，如障礙層的塗佈、離子植入法、磷酸溶液中之 /又塗或陽極處理等，來改善α 鈦鋁介金屬的高溫耐氧化 性。 美國專利號碼5，4 1 3，8 7 1 (專利日期：1 9 9 5年5月）利 用電襞喷塗熱障礙層，包括金屬障礙層及陶瓷障礙層噴塗 於Τ -鈦鋁介金屬及α 2-鈦鋁介金屬之航空器喷射引擎零件 上’可使喷射引擎零件的耐氧化溫度由6 5 0°C提升至 7 6 0 C。美國專利號碼5，6 9 5，8 2 7 (專利日期：1 9 9 7年1 2 月）以將鋁、氧、氬、硼、氮和磷等離子，利用離子植入 法植入於T -鈦鋁介金屬及α 2-鈦鋁介金屬表面内，可改善 铭介金屬的高溫氧化抵抗。美國專利號碼5，6 4 5，M3 (專 利日期：1 9 9 7年12月）利用塗上85〇/减酸後，經過約150。〇 乾燥、5 0 0°C以上的鍛燒後，可有效的提高r -鈦鋁介金屬 8 0 0°C的耐氧化性。美國專利號碼5, 83 7,387 (專利日期： 1 9 9 8年1 1月）利用低壓電漿喷塗法（Low Pressure Plasma Spray, LPPS)在r -鈦鋁介金屬及α 2-鈦鋁介金屬 面喷塗上一層兩相（TiAl+TiCrAl)鍍層，可改善鈦I呂介 金屬在高溫的抗氧化性。中華國發明專利號碼1 4 5 9 1 2 (專利日期：2 0 0 1年1 0月2 1日），在0〜4 0狀粦酸溶液中， 利用陽極處理可改善r -鈦鋁介金屬在高溫的抗氧化性。 【内容】 利用電漿喷塗障礙層法、離子植入法或其他表面改質 的方法，如液態鋁化披覆（A 1 um i n u m C 1 a d d i ng)、鋁化 ___________ I . I f i: ·，. f 、 » · -. 11 * ' *· '：·' · ：t » » > I» tr： . ' l '· ·. r ; ί ! · ' ' . ,.' 第7頁 鈦 在 表 iii ίΐΚ fiir iii lii 1247818 五 、發明說明 (3) 包 覆 法 ( Pack Cement; at ion A 1um i η i z ing) 和 電 鍍火 4务 化 沈 積 法 ( E] .ec t ro- -Spark Deposit: ion) 等 雖然 可 以 改善 a 2_鈦 在呂 介 金 屬 的南 溫 抗氧 化 性 質，但 其設 備 投資 大 操作 較 複 雜 且 成 本 高， 且 鍍層 本 身 内應力 所造 成 的微 孔 洞 ，再 加 上 與 基 材 的 附著 性 不佳 j 使 這些方 法對 a 2—鈦 !呂 介 金屬 高 溫而于 氧 化 性 的 提升 受 到一 定 的 限制。 同時 因 其覆 蓋 性 差， 所 以 對 於 形 狀 較複 雜 的工 件 無法均 勻的 植 入或 覆 蓋 ；而 利 用 構 酸 被 覆 鍛燒 法 雖其 被 覆 性佳， 和設 備 投資 低 等 優點 但 其 操 作 時 間長 ， 不符 合 經 濟效益 ，且 其 處理 後 的 工件 表 面 質 感 較 差 〇 本專利發明是利用物理氣相沉積 (PVD) 之 濺 锻法 Λ 蒸 鍍 法 等 5 將適 當 厚度 的 鋁 鍍層沉 積於 a 2_鈦' ί呂 介 金屬. 之 表 面 再 加 上隨 後 而真 空 加 熱處理 之配 合 ，使 a 欽在呂> 介 金屬 表 面 產 生 一層 T i A 1 拥 1 ? 在 •南溫白勺 使用 環 -境下 .會 ‘在 表面 形 ，成 一 層 緻 密 且具 有 保護 性 的 氧化鋁 惰性 膜 來改 善 高 溫而才 氧 化 ? 且 因 為表 裏 相互 擴 散 會增加 鋁鑛, 層 與基 材 的 附著 性 〇 其 -i-rL 5又 備 投 資小 操作 簡 便 、操作 時間 短 ，況 且 濺 鍍法 或 蒗 鍍 法 等 可 以精 確 的控 制 鍍 膜厚度 ，鍍 膜 具有 良 好 之性 質 和 均 勻 性 表面 平 整無 缺 陷 且能完 整的 被 覆於 工 件 ，同 時 處 理 後 的 工 件表 面 具有 極 佳 的質感 〇 [ 發 明 詳 細說 明 ] 茲 以 下列 實 例詳 細 說 明本發 明之 具 體工 藝 〇 本創 作 選 擇 a 2— Ti 3A1鈦 鋁 介金 屬 合 金。此 發明 可 適用 於 此 等的 序 化結 ______ 國画 ______ .1:.. 1 ： . · 1 ^ · ; . ,ι-ι,ι· I f 〆 矣 i , i v I . I 1 : : : . · » | 1 1 » < ； ' f' ' - , I ; ‘ . ‘ . . . . 1 i r·. V!…I ； > x't·^. ·«>· * · p '» I ' '‘‘ ·)·'·： 1 ,;..· '；·. It ' 1 · - :..',丫' I i * ： ' i ,.·? [*i * ;· ; · , « 1 t '* * I ; ·- T i _' J - _ I ： I · - r ; i :， r! : (. ； t ;· ； -. , 1 :1画過__瞬 - I · i * :' i ,.·? f*i * 1 ;，-r - , < 1 1 1., t , __ ^ 第8頁 1247818 五、發明說明（4) 構之α厂T 1 SA 1介金屬材料以及富α相之鈦鋁介金屬，例如成 分（原子比）介於TiSQAl2與Ti6QAl4濶之各鈦鋁介金屬。 藉由真空電孤溶練爐（Vacuuin Arc Remelter，VAR)重溶 純鈦（99· 97wt% )和純鋁（99· 98wt% )成所需要成分的 鑄錠，經過長時間和高溫（1〇〇(rc X l〇〇hrs)的真空均質 化熱處理’爐冷至室溫後，利用X光繞射圖形確認其結晶 結構。如第一圖所示，為α 2_ T丨3A丨經過上述處理後之X光繞 射圖形’ α厂T i A 1為序化的六面體d 〇 !結構。其他常用的配 置合金方法也可配置出所需成分的鈦鋁介金屬合金，如真 空感應熔煉（Vacuum Induction Melty，VIM)和粉末冶 金法等。鑄旋切割成所需形狀的試片後（丨〇 χ丨〇 χ 1 mm和 10x5x1 mm)，用砂紙研磨至12〇〇號，再以氧化鋁粉拋光 至0 · 3 // m。經切割後，以丙酮及酒精溶液在超音波震盪下 去脂、洗淨、乾燥後，實施濺鍍處理。本創作的靶材亦是 由真空電弧熔練爐將純鋁（9 9. 98wt% )重熔成2吋 (inch)的圓形靶，表面再經過砂紙研磨至6〇〇號所製 成。鋁鍍層在本創作的實施例中是以射頻磁控濺鍍 (Radio Frequency， RF， Magnetron Sputter D e p o s i t i οn)製得，而用鋁粒在高真空中實施蒸鍍 (E v a ρ 〇 r a t i ο η)方法亦可得到相同之鋁鍍層。本創作是 先將錢鍵真空室抽至 6xl0-7 tor r以下的壓力，再將超高 純度的氬氣導入系統中，以1 0 0W的能量行鍍層之工作。將 基材至於祀材正下方約8公分處’且面朝上。為了使紹錢 膜能完整的被覆於基材上，在試片的表面沉積鍍膜後，需 ______ 圖 _____ 1247818 五、發明說明（5) ;j片翻面，在忒片的另一表面再進行相同的濺鍍處理， 勻，膝！ί膜便能完整的覆蓋於試片表面上；且為求鍍層均 要參數二，程中基材以定速做旋轉運動。其他濺鍍製程重 埶i理葡表所示。在不同的鋁鍍層厚度及高真空擴散 、一 1桎專變數下，探討經這些處理後之a 2-Ti3Al介金屬 之咼溫耐氧化性的改善情形。 、’ 功率T二為：心立方（FCC)結構，第二圖所示為在濺鍍 薄膜Dim 距8公分及濺鍍壓力5m t〇rrF所得到之純鋁 能、射圖形。由圖中可以看出有5個復強的純鋁結晶 %射峰’因此本貫施例中之薄膜應該為純鋁之結晶薄 在濺，功率10〇w、槍距8公分及濺鍍壓力5m torr條件 I 及由薄膜厚度量測儀（α — step)測量薄膜厚度，可 士出純鋁薄膜之濺鍍速率約為3· 5 A/sec，由此沉積速率° 就可=精確的控制所需鋁薄膜之厚度。將不同厚度的純鋁 錢層’儿積在α 2— τ“αι介金屬之表面上，再將其置於高真空擔 中 在6 〇 〇 C的溫度下擴散熱處理2 4小時，高真空擴散熱卢、 理製程參數如第二表所示。 义 在欽叙介金屬合金中，含鋁量不同，所生成之氧化物 f構也不同。含鋁量愈高，則抗氧化性亦愈佳，因為鋁含 星愈南愈容易在表面生成一層連續且緻密的氧化鋁層，所 以T i A 1介金屬的耐氧化性要比α 2—τ丨a丨介金屬好报多。此本 貫施例中’ α 2- T i A 1介金屬基材和其表面的純鋁鍍層，會細 由6 0 0°C的高真空擴散熱處理而相互擴散形成τ丨A丨相，如二 第三圖所示。第三圖為在a「T i A 1介金屬表面濺鍍沉積不 同1247818 一------- V. Description of invention (2) ^ Surface modification, such as coating of barrier layer, ion implantation, / coating or anodizing in phosphoric acid solution, etc. to improve α titanium aluminum High temperature oxidation resistance of the intermetallic. U.S. Patent No. 5,4 1 3,8 7 1 (Patent Date: May 19, 1995) sprayed a thermal barrier layer using an electric raft, including a metal barrier layer and a ceramic barrier layer sprayed on a bismuth-titanium aluminum intercalation metal and The α2-titanium-aluminum metal-based aircraft injection engine part 'can increase the oxidation resistance temperature of the injection engine parts from 650 °C to 760 °C. U.S. Patent No. 5,6 9 5,8 2 7 (patent date: January 1979) to implant aluminum, oxygen, argon, boron, nitrogen and phosphorus ions into the T by ion implantation. The surface of titanium-aluminum-based metal and α2-titanium-aluminum intermetallic metal can improve the high temperature oxidation resistance of Mingshi metal. U.S. Patent No. 5,6 4 5, M3 (patent date: December 1979) was applied after applying 85 〇/acid reduction and passing about 150.干燥 Drying, after calcination at 500 °C or higher, can effectively improve the oxidation resistance of r-titanium aluminum intermetallics at 80 °C. U.S. Patent No. 5, 83 7,387 (Patent Date: January 1 1989) utilizes Low Pressure Plasma Spray (LPPS) in r-titanium aluminum intermetallic and alpha 2-titanium aluminum The metal surface is sprayed with a two-phase (TiAl+TiCrAl) coating to improve the oxidation resistance of the titanium I-ruthenium metal at high temperatures. China's invention patent number 1 4 5 9 1 2 (patent date: January 2, 2001), in the 0~4 0 bismuth acid solution, the anode treatment can improve the r-titanium aluminum intermetallic Oxidation resistance at high temperatures. [Content] Using plasma spray barrier method, ion implantation method or other surface modification methods, such as liquid aluminizing coating (A 1 um inum C 1 addi ng), aluminizing ___________ I. I fi: ·, f, » · -. 11 * ' *· ':·' · :t » » > I» tr: . ' l '· ·. r ; ί ! · ' ' . ,.' Page 7 Titanium in Table iii ίΐΚ fiir iii lii 1247818 V. Inventive Note (3) Coating Method (Packing; Ation A 1um i η iz ing) and Electroplating Fire (E] .ec t ro- -Spark Deposit: ion), etc., although it can improve the anti-oxidation properties of a 2_titanium in Lushang metal, but its equipment investment is more complicated and costly, and the micropores caused by the internal stress of the coating itself, plus Poor adhesion to the substrate. These methods are limited to the high temperature of a 2 - Titanium! At the same time, due to its poor coverage, it is impossible to uniformly implant or cover the workpiece with complex shape. However, the acid-coated coating calcination method has good coating performance and low equipment investment, but its operation time is long and it is not economical. Benefits, and the surface texture of the processed workpiece is poor. The patented invention uses physical vapor deposition (PVD), sputtering, vapor deposition, etc. 5 deposition of an appropriate thickness of aluminum plating on a 2_titanium The surface of the metal. Combined with the subsequent vacuum heat treatment, a layer of T i A 1 is produced on the surface of the metal layer of the austenium. In the use of the ring, the surface is used. Shape, a dense and protective alumina inert film to improve high temperature before oxidation; and because the surface diffusion will increase the aluminum ore, the adhesion of the layer to the substrate, and its -i-rL 5 Simple, short operating time, and sputtering The coating method can precisely control the thickness of the coating. The coating has good properties and uniformity. The surface is flat and flawless and can be completely covered on the workpiece. At the same time, the surface of the workpiece after processing has excellent texture 〇 [Detailed description of the invention] The column example illustrates in detail the specific process of the present invention. The creation of a 2 - Ti 3A1 titanium aluminum intermetallic alloy is selected. This invention can be applied to the ordering of such a ______ Chinese painting ______ .1:.. 1 : . · 1 ^ · ; . , ι-ι,ι· I f 〆矣i , iv I . I 1 : : : . · » | 1 1 » <; ' f' ' - , I ; ' . ' . . . . 1 ir·. V!...I ; > x't·^. ·«>· * · p '» I ' ''' ·)·'·: 1 ,;..· ';·. It ' 1 · - :..',丫' I i * : ' i ,.·? [*i * ;· ; · , « 1 t '* * I ; · - T i _' J - _ I : I · - r ; i :, r! : (. ; t ;· ; -. , 1 : 1 __瞬- I · i * :' i ,.·? f*i * 1 ;,-r - , < 1 1 1., t , __ ^ Page 8 1247818 V. Description of invention (4) The α 1 plant T 1 SA 1 intermetallic material and the α phase rich titanium aluminum intermetallic metal, for example, the composition (atomic ratio) of TiSQAl2 and Ti6QAl4 濶 each titanium aluminum intermetallic. By vacuum electric soaking furnace (Vacuuin Arc Remelter, VAR) re-dissolved pure titanium (99. 97wt%) and pure aluminum (99. 98wt%) into the ingot of the desired composition, after a long time and high temperature (1 〇〇 (rc X l〇〇hrs) vacuum Homogenization heat treatment 'after cooling to room temperature, the crystal structure was confirmed by X-ray diffraction pattern As shown in the first figure, the X-ray diffraction pattern 'α factory T i A 1 after the above treatment is α 2_ T 丨 3A 为 is a sequenced hexahedral d 〇 ! structure. Other commonly used alloy methods are also Titanium-aluminum intermetallic alloys with the desired composition, such as Vacuum Induction Melty (VIM) and powder metallurgy, etc. After casting and cutting into test pieces of the desired shape (丨〇χ丨〇χ 1 mm And 10x5x1 mm), grind to 12 〇〇 with sandpaper, and then polish to 0 · 3 // m with alumina powder. After cutting, use acetone and alcohol solution to oscillate in the ultrasonic wave, wash, dry, Sputtering treatment was carried out. The target of this creation was also a re-melting of pure aluminum (9 9. 98wt%) into a circular target of 2 inches (inch) by vacuum arc melting furnace, and the surface was ground to 6〇〇 by sandpaper. The aluminum coating is made in the embodiment of the present invention by radio frequency magnetron sputtering (Radio Frequency, RF, Magnetron Sputter D epositi οn), and the aluminum particle is vapor-deposited in a high vacuum (E va The ρ 〇rati ο η) method also gives the same aluminum coating. This creation is to first pump the vacuum chamber of the money to a pressure below 6xl0-7 tor r, and then introduce ultra-high purity argon into the system to work with the energy of 1000W. Place the substrate approximately 8 cm below the coffin and face up. In order to make the film can be completely covered on the substrate, after depositing the coating on the surface of the test piece, ______ Fig. _____ 1247818 V. Invention description (5); j piece turning over the other surface of the cymbal Then carry out the same sputtering process, even, knee! The film can be completely covered on the surface of the test piece; and for the plating layer, the parameter 2 is required, and the substrate is rotated at a constant speed. Other sputtering processes are shown in the table. The improvement of the temperature and oxidation resistance of the a 2-Ti3Al intermetallics after these treatments was investigated under different aluminum plating thicknesses, high vacuum diffusion, and specific strains. , power T is: heart cube (FCC) structure, the second figure shows the pure aluminum energy and radiation pattern obtained by sputtering the film Dim distance of 8 cm and the sputtering pressure 5m t〇rrF. It can be seen from the figure that there are 5 complexes of pure aluminum crystal % peaks. Therefore, the film in the present example should be pure aluminum crystal thin and splashed, power 10 〇 w, gun distance 8 cm and sputtering pressure. 5m torr condition I and film thickness measured by film thickness measuring instrument (α - step), the sputtering rate of pure aluminum film is about 3.5 A / sec, so the deposition rate ° can be = precise control The thickness of the desired aluminum film. Different thicknesses of pure aluminum money layer are accumulated on the surface of α 2 - τ "αι dielectric metal, and then placed in a high vacuum load at a temperature of 6 〇〇 C for diffusion heat treatment for 24 hours, high vacuum diffusion The parameters of the heating process and the process parameters are shown in the second table. In the metal alloy of the Qinxuan, the aluminum content is different, and the oxide structure of the oxide is different. The higher the aluminum content, the better the oxidation resistance. Because the aluminum-containing star is more likely to form a continuous and dense layer of aluminum oxide on the surface, the oxidation resistance of the T i A 1 metal is much better than that of the α 2 -τ丨a丨 metal. In the example, the 'α 2- T i A 1 dielectric metal substrate and the pure aluminum coating on the surface thereof are finely dispersed by a high vacuum diffusion heat treatment at 600 ° C to form a τ 丨 A 丨 phase, such as two third. The figure shows the difference in the sputtering of a "T i A 1 metal surface"

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:' V'V:.. V ：' Vi；iv： 1247818 五、發明說明（6) 厚度的鋁鍍層，經過6 0 (TC高真空擴散熱處理2 4小時後的X 光繞射圖形。圖中清楚的顯示，T i A 1相的繞射峰強度會隨 著銘鑛層厚度的增加而增加，相反的，基材α 2- T i 3A 1的繞射 峰強度則隨著鋁鍍層厚度的增加而降低；當厚度達到5# m 時，則全部皆成為T i A 1的繞射岭，而完全看不到基材的繞 射峰。此表示當铭鑛層厚度到3// m以上時，其與α 2_T i 3A 1基 材界面經過高真空擴散熱處理後會完全形成T i A 1相，此 T i A 1相在a 2-T i 3A 1介金屬高溫氧化的過程中，扮演著極重要 的角色。 氧化試驗是在8 0 0°C的空氣中加熱試片，於一定間隔 時間取出試片空冷至室溫，於電子天平秤取重量後，再放 回8 0 0°C的空氣中氧化，由試片單位面積的重量增加量來 評估其高溫的耐氧化性。a 2-T i 3A 1介金屬經過純鋁鍍層的濺 鍍沈積及高真空擴散熱處理之後，在高溫8 0 (TC的空氣中 循環氧化8 0小時，量取其單位面積的重量增加量與高溫氧 化時間的關係，如第四圖所示。顯然的，經過純紹鍍層的 被覆及高真空擴散熱處理之後，是可以有效的減緩a 2-T i 3A 1 介金屬的高溫氧化速率。而且紹鑛層的厚度愈厚，其處理 後的α 2- T i 3A 1鈦鋁介金屬高溫耐氧化性質愈好。8 0 0°C高溫 氧化曲線於2小時以後，其氧化速率即順從拋物線氧化之 公式：:' V'V:.. V :' Vi;iv: 1247818 V. INSTRUCTIONS (6) Thickness of the aluminum coating, X-ray diffraction pattern after 60 hours of TC high vacuum diffusion heat treatment for 24 hours. It is clearly shown that the diffraction peak intensity of the TiI1 phase increases with the thickness of the ore layer. Conversely, the diffraction peak intensity of the substrate α2-T i 3A 1 varies with the thickness of the aluminum coating. Increase and decrease; when the thickness reaches 5# m, all of them become the diffraction ridge of T i A 1 , and the diffraction peak of the substrate is not seen at all. This means that when the thickness of the ore layer is above 3/m When it is subjected to high vacuum diffusion heat treatment at the interface of α 2_T i 3A 1 substrate, the T i A 1 phase is completely formed. This T i A 1 phase plays a role in the high temperature oxidation of a 2-T i 3A 1 intermetallic metal. The most important role is the oxidation test, which is to heat the test piece in air at 800 ° C. The test piece is taken out at room temperature and cooled to room temperature. After weighing the electronic balance, it is returned to 800 ° C. Oxidation in the air, the high temperature oxidation resistance is evaluated by the weight increase per unit area of the test piece. a 2-T i 3A 1 intermetallic metal is sputter deposited by pure aluminum plating After high vacuum diffusion heat treatment, the temperature is cyclically oxidized for 80 hours in a high temperature of 80 (TC), and the relationship between the weight increase per unit area and the high temperature oxidation time is measured, as shown in the fourth figure. Obviously, after pure After coating and high vacuum diffusion heat treatment, the high temperature oxidation rate of a 2-T i 3A 1 metal can be effectively slowed down. The thicker the layer is, the treated α 2 - T i 3A 1 titanium The high temperature oxidation resistance of aluminum intermetallics is better. After 2 hours, the oxidation rate of the high temperature oxidation curve is the parabolic oxidation formula:

-K + (1) 式中W為單位面積重量增加值，t為氧化時間，K為二次方 氧化速率常數（Parabolic oxide rate constant)。 圓灘画圈!_酬______ 第11頁 1247818 五、發明說明（7) 〔P· Kofstad， High Temperature Corrosion， Elsevier-K + (1) where W is the weight gain per unit area, t is the oxidation time, and K is the Parabolic oxide rate constant. Round the beach circle!_付______ Page 11 1247818 V. Invention description (7) [P· Kofstad, High Temperature Corrosion, Elsevier

Applied Science Pub· Ltd·， New York， 1988， p.163〕 利用公式（1 )，由第四圖的各個曲線可算出厚度不同的鋁 錢層’經過6 0 0°C高真空擴散處理2 4小時後的2_τ i 3A 1介金 ^ ^次方氧化速率常數Kp，如第三表所示。由第三表可 /降其Κ眞隨著銘鏡層厚度的增加而明顯減少。在鋁鍍層 ;;二7到& m時，其耐氧化性可從未經藏鑛處理的Κ與 幅产约工/ cm4hr減到為〇. 00115mg2 / cm4hr，減少的 ㈤度約為兩千分之一， — · 化性皙is w le · 又不α 2— T i 1鈦铭介金屬的高溫耐氧 貝化、貝者提升。而當知力由 4.278E-4 mg2 / cm4hF，、\鏡度達到 M m時，其 K偉為 千分之一，即 ，、值為未經濺鍍處理的時K瘅的五 化效果相當顯著’。由本J:5數以上的w，顯示其耐氧 屬的耐氧化性有明顯的改^ 9可知，要使α 2-T i SA 1鈦鋁介金 上；但在當鋁鍍層厚度到;，鋁鍍層厚度要達到爪以 著薄膜厚度的增加而上升V m時’由於薄膜的内應力會隨 散熱處理後，有些試片的获$以在經過601TC高真空的擴 部分的些微剝落情況，使二^會因為熱應力的關係而有小 後的試片表面不平整，2母材裸露於大氣，這造成處理 於表面要求需具有質感且會影響其耐氧化的效果。對 選擇3//爪以上5以下 i屬光澤的產品應用例，則可 範圍的厚度做6 0 Ot的高直&处鍍層沉積於試片表面上，在此 剝離的情形發生，且處理、二擴散處理，試片表面不會有 感。由第三表可知厚声 < 的試片表面能具有相當佳的質 乂子度~ ™的I呂鑛層試片其κ瘅約為未經 _____ , '' .> ： , ；· . · . . . ·· I Μ ► f t I · '>i f - ; · < ' i . :, ill 1247818 五、發明說明（8) _ 處理的兩千分之一，在8 〇 (TC的高温下，緩過長、 士 後，其表面能仍然保有高真空擴散熱處理後的^達<80小時 而未經處理的a 2-Ti 3A1介金屬素材則約在5小日〆來色j睪； 表面產生一層易剝落且不連續的白色氧化 =内’就會在 光澤。 並失去金屬 利用熱重分析儀（Thermogravitic 可於高溫的空氣中做靜態的連續氧化實驗。ysis’、TGA) Τι Mi介金屬表面濺鍍沉積不同厚度的鋁鍍禺五圖為在α r 60 0°c高真空擴散熱處理2 4小時後，以熱重八< ’，再經過 空氣中持溫7G小時的氧化曲線分析圖。$ /析儀於8峨 單位面積的重量增加量隨著鋁鍍層的厚度描，圖可知，其 鍍層厚度為3/z m時，αi 3A 1介金屬的氡化、I而降低，鋁 度的減緩。而當厚度達到m時，其氧化b，率已有相當程 下降。第五圖之8 0 (TC靜態恆溫連續氧化實、:；更是明顯的 80(TC動態循環氧化實驗具有相同的實驗社=和第四圖之 相似的範圍内，更驗證了當鋁鍍層厚度，K瘅也士都在 a「Ti 鈦鋁介金屬具有極佳的高溫耐氧乂 = m以上日守， 第六圖為在a「TiAl介金屬表面濺鍍^ = n 銘鍵層’再經過60(TC的高真空擴散熱處理J不同厚 '的 ί ί Ϊ 物W 於_氧化後會在表面形成 大里的T1〇載化物，其繞射峰強度隨著純鋁 加而降低；當厚度達到以上時， 1_|_||_隨_ :: · : . .'V ' 人： ，:： ：，'.1 .二:’ Ά:.、：：." 第13頁 1247818 五、發明說明（9) 繞射♦，而顯現的是A 1 2〇和T i A 1的繞射峰，A 1 2〇相的繞射 峰則隨著铭鐘層厚度的增加而明顯的變多，且繞射岭強度 也會增強。此X光繞射圖形表示a 2-T i 3A 1介金屬素材經過 8 0 0°C空氣氧化8 0小時後，其表面主要形成不緻密、不連 續、易剝離且不具保護性的T i 0舍色氧化層；在铭鍍層3 // 以上之a 2-Ti 3A 1鈦鋁介金屬經過高溫氧化後，則主要生成 緻密、連續且具抗氧化性的A 1 20保護層。在A 1 20層的保護 下，α 2- T i 3A 1基材便能在高溫的環境下避免持續的氧化， 所以氧化抵抗能力便能大幅的提升。值得注意的是，T i A 1 繞射峰的出現，說明了在高溫循環氧化過程當中，T i A 1層 會和α 2- T i 3A 1基材發生固態擴散反應而逐漸由T i A 1相轉變 形成T i A 1相。 * _疆_國醒圖___ 第14頁 1247818Applied Science Pub· Ltd., New York, 1988, p.163] Using the formula (1), the aluminum layer of different thickness can be calculated from the curves of the fourth figure'. After high vacuum diffusion treatment at 60 °C 2 4 After 2 hours, the 2_τ i 3A 1 intervening ^ ^ power oxidation rate constant Kp, as shown in the third table. From the third table, it can be significantly reduced as the thickness of the mirror layer increases. In the case of aluminum coatings;; 2 to & m, the oxidation resistance can be reduced from the untreated ore-treated crucible to the mass production / cm4hr to 〇. 00115mg2 / cm4hr, the reduced (five) degrees are about two thousand One of the points, — · 皙 w is w le · and not α 2 — T i 1 Titanium metal high temperature oxygen-resistant shelling, sheller upgrade. When the intellectual power is 4.278E-4 mg2 / cm4hF, and the mirror degree reaches M m, the K dimension is one thousandth, that is, the value of K is less significant when the value is not sputtered. '. From the present J: 5 or more w, it is shown that the oxidation resistance of the oxygen-resistant genus has a significant change. It can be known that the α2-T i SA 1 titanium aluminum is intercalated; however, when the thickness of the aluminum plating layer is reached; The thickness of the aluminum coating is such that the claws rise by Vm with an increase in the thickness of the film. 'Because the internal stress of the film is treated with heat dissipation, some of the test pieces are obtained by the micro-peeling of the expanded portion of the 601TC high vacuum. Because of the thermal stress, the surface of the test piece is small, and the base material is exposed to the atmosphere. This causes the surface to be treated with a texture and affects its oxidation resistance. For the application example of selecting 3//claw or more and 5 or less i-gloss, the range of thickness can be made to a high straightness of 60 Ot, and the plating layer is deposited on the surface of the test piece, where the peeling occurs, and the treatment, Two diffusion treatment, the surface of the test piece does not feel. It can be seen from the third table that the surface of the test piece with a thick sound <RTIgt;>> is not _____, ''.> : , ; · · · · · · I Μ ► ft I · '>if - ; · < ' i . : ill 1247818 V. Invention description (8) _ Two thousandths of processing, at 8 〇 (TC At the high temperature, after the long time, the surface energy still retains the high vacuum diffusion heat treatment after the heat treatment of 80 hours and the untreated a 2-Ti 3A1 metal material is about 5 days later. j睪; The surface produces a layer of easily flaking and discontinuous white oxidation = the inner 'will be shiny. And lose the metal using a thermogravimetric analyzer (Thermogravitic can perform static continuous oxidation experiments in high temperature air. ysis', TGA) Τι Mi-Metal surface sputter deposition of different thicknesses of aluminum-plated ruthenium is shown in the high-vacuum diffusion heat treatment of α r 60 0 °c for 24 hours, with a heat weight of eight < ', and then held in the air for 7G hours Oxidation curve analysis chart. The weight increase per unit area of the 8 / analyzer is shown by the thickness of the aluminum coating. The thickness of the coating is known. When it is 3/zm, the αi 3A 1 metal is deuterated, I decreases, and the aluminum degree is slowed down. When the thickness reaches m, its oxidation b rate has decreased considerably. The fifth figure is 8 0 (TC Static constant temperature continuous oxidation,:; more obvious 80 (TC dynamic cycle oxidation experiment has the same experimental agency = and the similar range of the fourth figure, more verified that when the thickness of the aluminum coating, K 瘅 都 are in a "Ti-titanium-aluminum-based metal has excellent high-temperature and high-temperature resistance 乂 = m or more, and the sixth picture shows a high-vacuum diffusion heat treatment of TC on a "TiAl intermetallic surface sputtering ^ = n key layer" J different thickness ' ί ί W W will form a large T1 〇 on the surface after oxidation, the diffraction peak intensity decreases with the addition of pure aluminum; when the thickness reaches above, 1_|_||_ With _::: . . 'V ' person: ,:: :,'.1 . 2: ' Ά:.,::." Page 13 1247818 V. Invention description (9) Diffraction ♦, and The diffraction peaks of A 1 2〇 and T i A 1 appear, and the diffraction peaks of the A 1 2〇 phase become more and more obvious as the thickness of the bell layer increases, and the intensity of the diffraction ridge increases. This X-ray diffraction pattern The shape shows that a 2-T i 3A 1 intermetallic material is oxidized by air at 80 ° C for 80 hours, and its surface mainly forms a T i 0 colored oxide layer which is not dense, discontinuous, easily peelable and non-protective; After a high temperature oxidation of the a 2-Ti 3A 1 titanium aluminum intermetallic layer of the inscription layer 3 // above, a dense, continuous and oxidation-resistant A 1 20 protective layer is mainly formed. Under the protection of A 1 20 layer, the α 2 - T i 3A 1 substrate can avoid continuous oxidation in a high temperature environment, so the oxidation resistance can be greatly improved. It is worth noting that the appearance of the diffraction peak of T i A 1 indicates that during the high temperature cyclic oxidation process, the Ti i 1 layer will undergo solid-state diffusion reaction with the α 2 - T i 3A 1 substrate and gradually become T i A The 1 phase transition forms the T i A 1 phase. * _ _ _ country awake ___ page 14 1247818

【圖式簡單說明】 以下，就本發明中濺鍍法之圖表作簡單之說明 ，一表所示係實施例中濺鍍製程的重要參數。 ，二表所示係實施例高溫擴散熱處理參數。 ^ 第二表所示係由第四圖的氧化曲線，依公式一所計 异不同鋁鍍層厚度經過6 0 (TC擴散熱處理2 4小時後，其α 2- 欽铭介金屬（或簡稱a r T i SA 1)氧化速率常數κ瘅的變化情 形。 第一圖為α 2- T i 3Α 1介金屬經均質化熱處理後的X光繞射 圖形。 第二圖為a 2-Ti 3A1介金屬表面經濺鍍3// m之鋁鍍層的X光 繞射圖形。 第三圖為在a 2-Ti3Al介金屬表面濺鍍沉積不同厚度的鋁 鍍層，再經過60(TC高真空（3 xl 0 -7 torr以下）擴散熱處 理2 4小時後的X光繞射圖形。 第四圖為在α 2- T i 3A 1介金屬表面濺鍍沉積不同厚度的鋁 鍍層後’再經過6 0 0°C高真空擴散熱處理2 4小時後，在高 溫8 0 0°C的空氣中循環氧化8 0小時之後，其單位面積的重 量增加與高溫氧化時間之關係圖。 第五圖為在α 2_Ti3Al介金屬表面濺鍍沉積不同厚度的鋁 鍍層後，再經過6 0 0°C高真空擴散熱處理2 4小時後，以熱 重分析儀（Thermogravitic Analysis，TGA)於 80 0°C 空氣中持溫7 0小時後的分析結果。 晒圓__|_1 _______ · I ! · I ； · ·'·. i. > * ' j ί I ' i ? t i W* 1 · ,V *' ' I ΐ! i ,11; hi - Γ H'M f'Vf'.h 第15頁 1247818 圖式簡單說明 第六圖為在a 2_Ti3Al介金屬表面錢鑛 鍍層，再經過6 0 0°C高真空擴散熱處理2 44 8 0 0°C的空氣中氧化8 0小時後的X光繞射圖 沉積不同厚度的鋁 、時後’在南溫 形0 1247818 表式 第一表本實施例濺渡製程之重要參數BRIEF DESCRIPTION OF THE DRAWINGS In the following, a graph of a sputtering method in the present invention will be briefly described. A table shows important parameters of a sputtering process in the embodiment. The second table shows the high temperature diffusion heat treatment parameters of the examples. ^ The second table shows the oxidation curve of the fourth figure. According to the formula 1, the thickness of the aluminum coating varies after 60 (the diffusion heat treatment for 24 hours, the α 2 - Chinson metal (or ar T for short) i SA 1) Change in oxidation rate constant κ瘅. The first figure shows the X-ray diffraction pattern of α 2 - T i 3Α 1 intermetallic metal after homogenization heat treatment. The second picture shows a 2-Ti 3A1 intermetallic surface. The X-ray diffraction pattern of the 3//m aluminum coating is sputtered. The third figure shows the deposition of different thicknesses of aluminum on the surface of a 2-Ti3Al intermetallic metal, followed by 60 (TC high vacuum (3 xl 0 - 7 torr or less) X-ray diffraction pattern after diffusion heat treatment for 2 hours. The fourth picture shows the high-temperature of 600 °C after sputtering of different thicknesses of aluminum plating on the α2-T i 3A 1 metal surface. After 4 hours of vacuum diffusion heat treatment, the relationship between the weight increase per unit area and the high temperature oxidation time after cyclic oxidation for 80 hours in air at a high temperature of 800 ° C. The fifth figure shows the splash on the α 2_Ti3Al intermetallic surface. After depositing aluminum plating with different thicknesses, it is subjected to high vacuum diffusion heat treatment at 600 ° C for 24 hours, followed by thermogravimetric The analysis results of the Thermogravitic Analysis (TGA) after holding the temperature at 80 ° C for 70 hours in the air. Sun __|_1 _______ · I ! · I ; · · '·. i. > * ' j ί I ' i ? ti W* 1 · , V *' ' I ΐ! i ,11; hi - Γ H'M f'Vf'.h Page 15 1247818 Simple illustration of the figure The sixth picture shows the a 2_Ti3Al The metal surface is coated with gold ore, and then subjected to high-vacuum diffusion heat treatment at 60 °C for 2,480 °C, and the X-ray diffraction pattern after 80 hours of oxidation in the air is deposited with different thicknesses of aluminum. Shape 0 1247818 Table 1 The important parameters of the splash process of this embodiment

製程參數項目 參數 | 濺鍍系統基本真空壓力 (System base pressure) 6 X 10·7 torr 以下 濺鍍系統工作壓力 (Working pressure) 5 X 10'3torr 潑鍍高週波能量(RF power) 100W 靶材 純鋁(99.98°/。） 靶材與基材相對位置與距離 基材位於材正下方相距80mm 純鋁鍍層厚度 0·5μηι 〜5μηι 基材溫度 常溫(不加熱)至約l〇〇°C 第二表本實施例高真空擴散熱處理參數 基本真空度 擴散熱處理溫度 升溫速率 擴散時間 (Torr) (°C) (°C/min) (hr) <3 X 10-7 600 15 6〜72 1247818 第三表 鋁鍍層厚度 (μπι) 0(α2·Τί3Α1) 3.0 4.0 50 i Κρ (mg2/cm4hr) 2.2937 0.00115 8Ε-4 1 4.278Ε-4Process Parameter Item Parameters | Sputter System System Base Pressure 6 X 10·7 torr Sputtering System Working Pressure 5 X 10'3torr Sputtering High Frequency Energy (RF power) 100W Target Pure Aluminum (99.98°/.) The relative position of the target and the substrate is 80mm away from the substrate. The thickness of the pure aluminum coating is 0·5μηι 〜5μηι. The substrate temperature is normal (not heated) to about l〇〇°C. Table Example High Vacuum Diffusion Heat Treatment Parameters Basic Vacuum Diffusion Heat Treatment Temperature Heating Rate Diffusion Time (Torr) (°C) (°C/min) (hr) <3 X 10-7 600 15 6~72 1247818 Third Table aluminum plating thickness (μπι) 0(α2·Τί3Α1) 3.0 4.0 50 i Κρ (mg2/cm4hr) 2.2937 0.00115 8Ε-4 1 4.278Ε-4

Claims (1)

1247818 六、申請專利範圍 1 · 一種以物理氣相沉積法改善α 2_鈦鋁介金屬高溫耐氧化 性的方法至少包含下列步驟： (1 )提供2-鈦铭介金屬；及 (2 )將上述α 2_鈦铭介金屬施以物理氣相沉積法之表面處 理，以沉積適當厚度的鋁薄膜於介金屬表面上；及 (3)對上述α 2-鈦鋁介金屬施行真空熱處理，使得其表面形 成一連續之T i A 1介金屬層，以改善其高溫抗氧化。 2. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2-鈦紹介金屬高溫耐氧化性的方法，其中上述之α 、 鈦紹介金屬為α相的鈦銘介金屬或富α相之鈦紹介金 屬’其成分（原子比）介於TisGAl〗到Ti^oAl 範 圍。 3. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2-鈦铭介金屬高溫耐氧化性的方法，其中物理氣相沉 積法包括濺鍍法、蒸鍍法及其他物理氣相沉積法之其中 一種。 4. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善2_欽铭介金屬向溫对氧化性的方法’其中铭鍛層的在呂 可為純鋁，或為鋁合金（其含鋁量至少在9 5 %以上）之 -種 ° 第17頁 1247818 六、申請專利範圍 5. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2-鈦鋁介金屬高溫耐氧化性的方法，其中、鋁鍍層厚度 範圍為0 . 1 // m到2 0 // m。 6. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2-鈦鋁介金屬高溫耐氧化性的方法，其中鋁鍍層厚度 最佳厚度範圍為3// m到5// m)。 7. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2_鈦鋁介金屬高溫耐氧化性的方法，其中真空熱處理 之溫度範圍在2 0 0°C〜6 5 0°C之間，處理時間範圍為0. 1 小時以上。 8. 如申請專利範圍第1項所述之一種以物理氣相沉積法改 善α 2-鈦鋁介金屬高溫耐氧化性的方法，最佳真空熱處理 溫度為6 0 0°C ;最佳真空熱處理時間為2 4小時。1247818 VI. Patent Application Range 1 · A method for improving the high temperature oxidation resistance of α 2_titanium aluminum intermetallic by physical vapor deposition comprises at least the following steps: (1) providing 2-titanium metal; and (2) The above α 2_Titanium metal is subjected to a surface treatment by physical vapor deposition to deposit an aluminum film of a suitable thickness on the surface of the metal; and (3) a vacuum heat treatment is performed on the α 2 -titanium aluminum alloy A continuous T i A 1 dielectric layer is formed on the surface to improve its high temperature oxidation resistance. 2. A method for improving the high temperature oxidation resistance of α2-titanium metal by physical vapor deposition according to the first aspect of the patent application, wherein the α, titanium, and the metal are α phase titanium alloys or The titanium-rich metal of the α-rich phase has a composition (atomic ratio) ranging from TisGAl to Ti^oAl. 3. A method for improving the high temperature oxidation resistance of α2-Titanium metal by physical vapor deposition as described in claim 1, wherein the physical vapor deposition method includes sputtering, evaporation, and the like. One of physical vapor deposition methods. 4. A method for improving the oxidation to the temperature of 2_Chenmingjie metal by physical vapor deposition as described in Item 1 of the patent application' wherein the ingot layer is pure aluminum or aluminum alloy (The aluminum content is at least 95% or more) - Page 17 1247818 VI. Patent application scope 5. As described in claim 1, the physical vapor deposition method improves α 2-titanium aluminum. A method for high-temperature oxidation resistance of a metal, wherein the thickness of the aluminum coating ranges from 0.1 to 2 0 // m. 6. A method for improving the high temperature oxidation resistance of α2-titanium aluminum intermetallics by physical vapor deposition as described in claim 1, wherein the optimum thickness of the aluminum plating layer ranges from 3/m to 5/ / m). 7. A method for improving high temperature oxidation resistance of α 2_titanium aluminum intermetallics by physical vapor deposition as described in claim 1 wherein the vacuum heat treatment temperature ranges from 200 ° C to 6 5 0 Between °C, the processing time range is more than 0.1 hours. 8. A method for improving the high temperature oxidation resistance of α2-titanium aluminum intermetallics by physical vapor deposition as described in claim 1, the optimum vacuum heat treatment temperature is 600 ° C; optimal vacuum heat treatment The time is 24 hours.