201219592 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種非晶合金殼體及其製造方法。 【先前技術·】 [0002] 非晶合金具有類似玻璃之結構特徵’於業界被稱之為金 屬玻璃’具有強度高、韌性強、耐腐钱及易於成型複雜 結構等特性。由非晶合金製得之殼體類產品’其表面可 獲得特殊之金屬質感，藉由鏡面拋光後產品具有金屬光 A 澤，藉由拉絲處理後可強烈地襯托出產品高貴之金屬質 〇 感。然，由於拉絲衡殼想較易刮傷，從而大大束缚了非 晶合金材質於殼體類外觀件上之·應用。. 【發明内容】 ，’ [0003] 有鑑於此，有必要提供一種不易刮傷之非晶合金殼體及 其製造方法。 [0004] —種非晶合金殼體，其包括非晶合金基殼及藉由真空鍍 膜於該非晶合金基殼表面形成之耐磨性保護層。 ❹ [0005] —種非晶合金殼體製造方法，包括以下步驟： [0006] 提供由非晶合金材質製成之基殼； [0007] 對該非晶合金基殼進行表面拉絲或拋光預處理；及 [0008] 對該非晶合金基殼進行真空鍍膜處理，於該非晶合金基 殼表面形成一财磨性保護層。 [0009] 由於上述非晶合金殼體於其非晶合金基殼表面形成一耐 磨性保護層’故該非晶合金基殼不易刮傷。 099137708 表單編號A0101 第3頁/共12頁 0992065740-0 201219592 【實施方式】 [0010] 下面將結合附圖及具體實施方式對本發明#晶合金殼體 及其製造方法作進一步之詳細說明。 [0011] 請參見圖1，本發明實施方式之非晶合金殼體10包括由非 晶合金材質製成之非晶合金基殼12以及藉由真空鍍膜方 法形成於非晶合金基殼12表面之耐磨性保護層14。可理 解’非晶合金基殼12可為行動電話、MP3、DVD、筆記本 電腦、機箱等各種電子產品之外殼，非晶合金基殼12於 鍍膜前可經拋光或拉絲等工藝處理以獲得不同之外觀效 田 果。 [0012] 優選地’本發明非晶合金基轉:12為锆（Zr)基非晶合金 。可理解，非晶合金基殼12逢可為鐵(F:e)基、鈷（Co)基 、鎳（Ni)基或其他非晶合金。 [0013] 優選地，耐磨性保護層14為氮化鈦（TiN)層，其厚度為 1. 〇〜2. 0//m。可理解，耐磨牲保護層14還可為氮碳化鈦 (TiCN)層’氮化鋁鈦（—Α1Ν)層，氮化鉻（CrN)層 ’類金剛石（DLC)層或氮化鉻鋁鈦（TiAlCrN)層等其 他耐磨性保護層。 [0014] 優選地，耐磨性保護層14藉由離子鍍之方法沉積形成。 可理解’耐磨性保護層14亦可藉由蒸發鍍膜、濺射鍍膜 等其他真空鍍膜方法形成。 [0015] 一種可製備非晶合金殼體10之製造方法，包括以下步驟 (1 )提供一種鍅（Zr )基母合金，採用該锆（Zr )基母 099137708 表單編號 AGiGl ^ 4 I/* 12 S 0992065740-0 [0016] 201219592 [0017] ❹ [0018] [0019] [0020] ❹ [0021] 合金製成非晶合金基殼； 本實施方式中，該鍅（Zr)基母合金形成方法如下：採 用真空電弧熔煉爐製造得到鎳（Ni)鈥（Nb)合金，再採 用真空感應爐熔煉該鎳（Ni)鈥（Nb)合金並向其添加锆 (Zr)、銅（Cu)、鋁（A1 )等元素，並使鍅（Zr)含 量大於其他元素之含量，得到鍅（Zr)基母合金。該非 晶合金基殼採用壓鑄方法成型，具體步驟如下：將錯（ Zr)基母合金融熔後倒入模具之通孔内，採用一推桿將 該融熔合金推入模腔内；合模，並同時施加一定壓力， 使熔融合金充滿模腔；快速冷卻，以形成鍅（Zr)基非 晶合金基殼。 (2) 對該非晶合金基殼進行表面拉絲或拋光等預處理； (3) 採用無水乙醇對锆（Zr)基非晶合金基殼進行超聲 波清洗，以除去非晶合金基殼表面之髒汙； (4) 以鈦（Ti)為靶材，採用離子鍍之方法於經清洗後 之锆（Zr)基非晶合金基殼表面鍍制一層氮化鈦（TiN) 薄膜。該離子鍍方法於真空度S4xl(T3Pa之真空腔内進 行，腔體内溫度為200〜300°C，轉架轉速為0. 5〜3. 0轉 /分鐘，通入之Ar氣體流量為400〜600sccm (標準狀態 毫升/分鐘），N2氣體流量為200〜300sccm，Ti靶材功 率為10〜14Kw，偏壓為80〜90v，占空比為20-70%，濺射 時間為3〜4小時。由此於锆（Zr)基非晶合金基殼表面獲 得厚度大約1. 0〜2. Ο/zm之氮化鈦（TiN)薄膜。 由上述非晶合金製造方法所制得之锆（Zr)基非晶合金 099137708 表單編號A0101 第5頁/共12頁 0992065740-0 201219592 殼體，包括鍅（Zr)基非晶合金基殼及形成於該锆（Zr )基非晶合金基殼表面之氮化鈦（T i N )薄膜，該氮化鈦 (TiN)薄膜中鈦原子個數百分比為50〜60%，氮原子個 數百分比為40〜50%。該氮化鈦（TiN)薄膜由直徑大約 為5 0〜1 0 0 nm之晶粒組成。 [0022] 以下為採用上述銼（Zr)基非晶合金殼體製造方法之二 優選實施方式： [0023] 實施方式1 [0024] 採用無水乙醇對锆（Zr)基非晶合金基殼進行超聲波清 洗大約3 0分鐘。 [0025] 將清洗好之鍅（Zr)基非晶合金基殼放入中頻磁控濺射 鍍膜機之真空腔中。 [0026] 開啟真空泵對真空腔抽真空並設定真空度為3xlO_3Pa， 開啟轉架並設定轉速為0.5轉/分鐘，開啟真空腔烘烤並 設定腔内溫度為200°C。 [0027] 待真空腔之真空度抽至上述設定值後，通入工作氣體氬 氣及反應氣體氮氣，氬氣流量為400sccm，氮氣流量為 200sccm ;開啟鈦靶並調節鈦靶功率為14kw，偏壓80v， 占空比為20%，濺射3小時，由此於銼（Zr)基非晶合金 基殼表面獲得一氮化鈦（TiN)薄膜。 [0028] 實施方式2 [0029] 採用無水乙醇對锆（Zr)基非晶合金基殼進行超聲波清 洗大約30分鐘。 099137708 表單編號A0101 第6頁/共12頁 0992065740-0 201219592 [0030] [0031] [0032] Ο [0033] [0034] ❹ [0035] [0036] 將清洗好之鍅（Zr)基非晶合金殼體放入中頻磁控濺射 鍍膜機之真空腔中。 開啟真空泵對真空腔抽真空並設定真空度為3x1 (T3Pa ’ 開啟轉架並設定轉速為3.0轉/分鐘，開啟真空腔烘烤並 設定腔内溫度為300X：。 待真空腔之真空度抽至上述設定值後，通入工作氣體氬 氣及反應氣體氮氣，氬氣流量為600sccm，氮氣流量為 300sccm ;開啟鈦靶並調節鈦靶功率為l〇kw，偏壓90v， 占空比為70%，濺射4小時，由此於癡（Zr)基非晶合金 表面獲得一層氮化鈦（TiN)薄膜。 .¾¾¾ 1¾ 丨丨-::肩的 由實施方式1與實施方式2製得之錘（2Γ)基非晶合金殼 體之氮化鈦（TiN)薄膜結構比較類似，且具有類似之抗 刮傷性能、耐磨性能及硬度。 將本發明實施方式1所製得之锆（ Zr)基非晶合金殼體與 未經本發明製造方法處理之锆（Zr)基非晶合金基殼於 财磨性、附著力及硬度方面“進行對·比。 时磨性 採用橡膠刮頭，加壓ikg，以25mm/min之速度分別於锆 (Zr)基非晶合金殼體和錯（zr)基非晶合金基殼表面 進行10次、20次、100次之來回摩擦測試◊測試結果為： 鉛（Zr)基非晶合金基殼隨著摩擦次數增多，磨損愈來 愈嚴重，而銼（Zr)基非晶合金殼體經1〇〇次之來回摩擦 仍無明顯變化。 099137708 表單編號A0101 0992065740-0 201219592 [0037] 附著力 [0038] 對錯（Zr)基非晶合金殼體進行附著力測試，利用規定 之3M600膠帶黏貼於百格中，快速拉起3M膠帶，結果顯示 .切口之邊緣完全光滑’格子邊緣沒有任何剝落，以IS 0 等級標準判定為5B。 [0039] 硬度 [0040] 對錯（Zr)基非晶合金殼體和錯（Zr)基非晶合金基殼 分別取三點進行維式硬度測試，測得結果為：锆（Zr) 基非晶合金殼體之平均硬度為623. 21V，錯（Zr)基非 晶合金基殼之平均硬度為484. 3HV。 [0041] 從以上可看出’經上述非晶合金殼體製造方法製得之錄 (Zr)基非晶合金殼體，由於鍅（Zr)基非晶合金基殼 表面形成一層耐磨性保護層，該耐磨性保護層耐磨性好 、附著力強、強度高，從而該非晶合金基殼不易刮傷。 [0042] 综上所述，本發明確已符合發明專利之要件，爰依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，本發明之範圍並不以上述實施方式為限，舉凡熟悉 本案技藝之人士援依本發明之精神所作之等效修飾或變 化，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 剛圖1係本發明實施方式之非晶合金殼體。 【主要元件符號說明】 [0044] 非晶合金殼體：1 〇 099137708 表單編號A0101 苐8頁/共12頁 0992065740-0 12 201219592 [0045] 非晶合金基殼 14 [0046] 耐磨性保護層201219592 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to an amorphous alloy casing and a method of manufacturing the same. [Prior Art] [0002] Amorphous alloys have a glass-like structural feature, which is known in the industry as a metal glass, which has characteristics of high strength, toughness, corrosion resistance, and easy formation of complicated structures. The shell-like product made of amorphous alloy can obtain a special metallic texture on the surface. After mirror polishing, the product has a metallic light A, which can strongly set off the noble metal sensation of the product by wire drawing. . However, since the wire-drawing case is more likely to be scratched, the application of the amorphous alloy material to the shell-like appearance member is greatly restrained. SUMMARY OF THE INVENTION [0003] In view of the above, it is necessary to provide an amorphous alloy casing which is not easily scratched and a method of manufacturing the same. An amorphous alloy casing comprising an amorphous alloy base shell and an abrasion resistant protective layer formed on the surface of the amorphous alloy base shell by a vacuum plating film. [0005] A method for manufacturing an amorphous alloy casing, comprising the steps of: [0006] providing a base shell made of an amorphous alloy material; [0007] subjecting the amorphous alloy base shell to surface drawing or polishing pretreatment; [0008] The amorphous alloy base shell is subjected to vacuum coating treatment to form a protective layer on the surface of the amorphous alloy base shell. [0009] Since the amorphous alloy case forms a wear-resistant protective layer on the surface of the amorphous alloy base case, the amorphous alloy base case is not easily scratched. 099137708 Form No. A0101 Page 3 of 12 0992065740-0 201219592 [Embodiment] [0010] The present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. Referring to FIG. 1, an amorphous alloy casing 10 according to an embodiment of the present invention includes an amorphous alloy base 12 made of an amorphous alloy material and formed on the surface of the amorphous alloy base 12 by a vacuum coating method. Wear resistant protective layer 14. It can be understood that the amorphous alloy base 12 can be a casing of various electronic products such as a mobile phone, an MP3, a DVD, a notebook computer, a chassis, etc. The amorphous alloy base case 12 can be processed by polishing or drawing before the coating to obtain different ones. Appearance effect fruit. [0012] Preferably, the amorphous alloy base of the present invention is: 12 is a zirconium (Zr)-based amorphous alloy. It will be understood that the amorphous alloy base 12 may be an iron (F:e) group, a cobalt (Co) group, a nickel (Ni) group or other amorphous alloy. /〜2. 0 / / m。 [0013] Preferably, the wear-resistant protective layer 14 is a layer of titanium nitride (TiN), the thickness of which is 1. 〇 ~ 2. 0 / / m. It can be understood that the wear protection layer 14 can also be a titanium carbonitride (TiCN) layer 'aluminum nitride titanium (—Α1Ν) layer, a chromium nitride (CrN) layer, a diamond-like carbon (DLC) layer or a chromium nitride aluminum titanium. Other wear resistant protective layers such as (TiAlCrN) layers. [0014] Preferably, the abrasion resistant protective layer 14 is deposited by ion plating. It is understood that the abrasion resistant protective layer 14 can also be formed by other vacuum coating methods such as evaporation coating and sputter coating. [0015] A manufacturing method for preparing an amorphous alloy casing 10, comprising the following step (1): providing a bismuth (Zr)-based master alloy using the zirconium (Zr)-based parent 099137708 Form No. AGiGl ^ 4 I/* 12 S 0992065740-0 [0016] [0020] [0020] [0021] The alloy is made into an amorphous alloy base; in this embodiment, the method of forming the bismuth (Zr) base alloy is as follows A nickel (Ni) niobium (Nb) alloy is produced by a vacuum arc melting furnace, and the nickel (Ni) niobium (Nb) alloy is melted by a vacuum induction furnace and zirconium (Zr), copper (Cu), and aluminum are added thereto. A1) and other elements, and the content of cerium (Zr) is greater than the content of other elements, to obtain a cerium (Zr) based master alloy. The amorphous alloy base shell is formed by a die-casting method, and the specific steps are as follows: the wrong (Zr) base matrix is financially melted and poured into the through hole of the mold, and the molten alloy is pushed into the cavity by a push rod; At the same time, a certain pressure is applied to fill the cavity with the molten alloy; rapid cooling is performed to form a bismuth (Zr)-based amorphous alloy base. (2) pre-treating the amorphous alloy base shell by surface drawing or polishing; (3) ultrasonically cleaning the zirconium (Zr)-based amorphous alloy base shell with anhydrous ethanol to remove the surface of the amorphous alloy base shell (4) Titanium (Ti) is used as a target, and a titanium nitride (TiN) film is deposited on the surface of the cleaned zirconium (Zr)-based amorphous alloy base by ion plating. The argon plating method is carried out in a vacuum chamber of S4xl (T3Pa, the temperature in the chamber is 200 to 300 ° C, the rotation speed of the turret is 0. 5 to 3. 0 rpm, the flow rate of the Ar gas is 400. ~600sccm (standard state ML/min), N2 gas flow rate is 200~300sccm, Ti target power is 10~14Kw, bias voltage is 80~90v, duty ratio is 20-70%, sputtering time is 3~4 The titanium nitride (TiN) film having a thickness of about 1. 0~2. Ο/zm is obtained on the surface of the zirconium (Zr)-based amorphous alloy base shell. Zirconium (made by the above amorphous alloy manufacturing method) Zr)-based amorphous alloy 099137708 Form No. A0101 Page 5 of 12 0992065740-0 201219592 The casing comprises a yttrium-based (Zr)-based amorphous alloy base shell and is formed on the surface of the zirconium (Zr)-based amorphous alloy base shell The titanium nitride (TiN) film, the titanium atom (TiN) film has a percentage of titanium atoms of 50 to 60%, and the number of nitrogen atoms is 40 to 50%. The titanium nitride (TiN) film It consists of crystal grains having a diameter of about 50 to 100 nm. [0022] The following is a second preferred embodiment of the method for manufacturing a bismuth (Zr)-based amorphous alloy casing: [0] 023] Embodiment 1 [0024] The zirconium (Zr)-based amorphous alloy base shell is ultrasonically cleaned with absolute ethanol for about 30 minutes. [0025] The cleaned bismuth (Zr)-based amorphous alloy base shell is placed in the middle. [0026] Open the vacuum pump to vacuum the vacuum chamber and set the vacuum to 3xlO_3Pa, open the turret and set the speed to 0.5 rev / min, open the vacuum chamber to bake and set the cavity The temperature is 200 ° C. [0027] After the vacuum degree of the vacuum chamber is drawn to the above set value, the working gas argon gas and the reaction gas nitrogen gas are introduced, the flow rate of the argon gas is 400 sccm, the flow rate of the nitrogen gas is 200 sccm, the titanium target is turned on and the titanium is adjusted. The target power was 14 kw, the bias voltage was 80 v, the duty ratio was 20%, and sputtering was performed for 3 hours, thereby obtaining a titanium nitride (TiN) film on the surface of the ytterbium (Zr)-based amorphous alloy base shell. [0028] [0029] The zirconium (Zr)-based amorphous alloy base shell is ultrasonically cleaned with anhydrous ethanol for about 30 minutes. 099137708 Form No. A0101 Page 6 of 12 0992065740-0 201219592 [0030] [0032] Ο [0034] [0036] [0036] The cleaned 鍅 (Zr) base will be cleaned [0036] The crystal alloy shell is placed in the vacuum chamber of the medium frequency magnetron sputtering coating machine. Open the vacuum pump to vacuum the vacuum chamber and set the vacuum to 3x1 (T3Pa ' turn the turret and set the speed to 3.0 rev / min, open the vacuum chamber Bake and set the chamber temperature to 300X:. After the vacuum of the vacuum chamber is pumped to the above set value, the working gas argon gas and the reaction gas nitrogen gas are introduced, the flow rate of the argon gas is 600 sccm, the flow rate of the nitrogen gas is 300 sccm, the titanium target is turned on and the power of the titanium target is adjusted to be l〇kw, and the bias voltage is applied. 90v, a duty ratio of 70%, and sputtering for 4 hours, thereby obtaining a titanium nitride (TiN) film on the surface of the Zr-based amorphous alloy. .3⁄43⁄43⁄4 13⁄4 丨丨-:: The titanium nitride (TiN) film structure of the hammer (2Γ)-based amorphous alloy case produced by Embodiment 1 and Embodiment 2 is similar, and has similar scratch resistance. Performance, wear resistance and hardness. The zirconium (Zr)-based amorphous alloy shell obtained in the first embodiment of the present invention and the zirconium (Zr)-based amorphous alloy base shell not treated by the method of the present invention are "performed in terms of grindability, adhesion and hardness" For the time-grinding, a rubber scraper is used, and the pressure is ikg, and the surface of the zirconium (Zr)-based amorphous alloy shell and the (zr)-based amorphous alloy base shell are respectively 10 times at a speed of 25 mm/min. The test results of 20 times and 100 times of back and forth friction test are as follows: Lead (Zr)-based amorphous alloy base shells wear more and more with the increase of friction times, and the 锉(Zr)-based amorphous alloy shell passes through 1〇 There is no significant change in the back and forth friction. 099137708 Form No. A0101 0992065740-0 201219592 [0037] Adhesion [0038] Adhesion test of the right (Zr)-based amorphous alloy casing, using the specified 3M600 tape to adhere to In the grid, the 3M tape was quickly pulled up, and the result showed that the edge of the slit was completely smooth. The edge of the lattice did not peel off, and it was judged as 5B by the IS 0 grade standard. [0039] Hardness [0040] Right and wrong (Zr)-based amorphous alloy shell Body and fault (Zr)-based amorphous alloy base shells take three points The average hardness of the shell of the Zr-based amorphous alloy shell is 623. 21 V, and the average hardness of the base shell of the (Zr)-based amorphous alloy is 484. 3 HV. [0041] It can be seen from the above that the Zr-based amorphous alloy shell obtained by the above-mentioned amorphous alloy shell manufacturing method has a wear-resistant protective layer formed on the surface of the (Zr)-based amorphous alloy base shell. The abrasive protective layer has good wear resistance, strong adhesion and high strength, so that the amorphous alloy base shell is not easily scratched. [0042] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only the preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiments, and equivalent modifications or variations made by those skilled in the art in light of the spirit of the present invention are It is intended to be included in the following patent application. [Simplified illustration of the drawings] Fig. 1 is an amorphous alloy case according to an embodiment of the present invention. [Main element symbol description] [0044] Amorphous alloy case: 1 〇099137708 Form number A0101 苐8 pages/ Total 12 pages 099206 5740-0 12 201219592 [0045] Amorphous alloy base shell 14 [0046] wear resistant protective layer
〇 099137708 表單編號A0101 第9頁/共12頁 0992065740-0〇 099137708 Form No. A0101 Page 9 of 12 0992065740-0