200925323 - 九、發明說明； 【發明所屬之技術領域】 本發明是關於熱輻射性及耐損傷性等特性佳的專色氧 化紀炫射皮膜的形成方法及彩色式樣性佳的黑色氧化纪炫 射皮膜被覆材料。 〜 【先前技術】 q 溶射法係藉由電漿喷射或燃燒焰熔融金屬或陶究、金 屬陶瓷等粉末，經飛行吹附於被熔射體（基材）表面，以於 該基材表面形成皮膜的技術’此係為在大多數產業領域中 所廣泛採用表面處理技術之一。適用前述熔射法所得之熔 射皮膜，已知會因構成此皮膜粒子間結合力強弱、未結合 粒子罝及未熔融粒子（以下稱為「未熔融粒子」量等，在皮 膜機械強度或耐勒性上產生極大的差異。 為此，習知熔射技術開發目標例如是藉由使用電漿中 © 巧’夏的熱源，在被熔射體表面發生強的衝擊能量，以提高 粒子間結合力並同時減小氣孔率，甚至提升皮膜與基 的接著力。 ,另方面金屬溶射皮膜係於大氣中形成，全部炫射 粒子係與空氣接觸，粒子表面生成氧化膜，鑑於此粒子間 合力降低，也使此粒子與基材的密著性惡化。習知解決 此問題的方法，例如是日本專利特開平6_1 96421號公報中 所提出之在低壓惰性氣體氣氛氣中進行熔射的方法（― 稱為減壓電漿熔射法)。具體而纟，在排出空氣的真空容 2〇53-9829-PF;Ahddub 5 200925323 -中，以50百帕（hPa)至200百帕導入氬氣，以於此氣氛氣 中進行電漿熔射的方法。 關於此點’氧化物系陶瓷的熔射皮膜，由於是氧化炫 射材料粉末本身，，:故在大氣中熔射也不會再被氧化，另一 方面還有在減壓下氬氣氣氛氣中熔射也不會在熔射粒子上 發生化學變化的特性。自此，氧化物系陶瓷減壓電漿炼射 法之現狀是在大氣電漿熔射上比較少研究開發的案例。 Q 還有，習知熔射皮膜的研究，由於在此皮膜所具有之 硬度、耐磨耗性、耐熱性、耐蝕性或密著性等的提升，故 以金屬（合金）、陶瓷、金屬陶瓷等熔射材料種類及化學成 为的選疋’並於熔射法選擇與熔射條件決定等上置於重點 位置。因此，對習知熔射皮膜而言，幾乎沒有的研究工學 上利用皮膜色彩，以提升熔射皮膜製品彩色式樣之商品價 值。 口口貝 然而，觀察陶瓷熔射皮膜外觀色發現，作為熔射材料 © 的氧化鉻（Cr2〇3)粉末係為接近黑色的墨綠色，以之電漿熔 射時會成為黑色的皮膜。另—方面，氧化紹（Ah()3)粉末為 白色，以之電漿熔射所得皮膜也是白色。但氧化鈦（Ti〇2) 粉末雖為白色系，以之電漿熔射所得則是黑色系皮臈。前 述中，熔射皮膜色彩變化的原因應該是熔射熱源中例如^ 構成氧化鈦的氧—部份消失而成為（TinU的氧化物所 致。（曰本專利特開平9-069554號公報） 以上說明中，氧化物系陶瓷熔射皮膜除去—部份氧化 物後，熔射用粉末材料本身的色彩原本普通是僅再現作為 2053-9829-PF;Ahddub 6 200925323 - 皮膜色彩。例如氧化釔（Υ2〇〇通常與氧化鋁（人丨⑷^相3 為粉末材料狀態時是白色系，以此粉末材料熔射所得4射 皮膜也為白色系。氧化釔例如是於電漿熱源中熔射，構成 氧化釔粒子的釔及氧結合狀態.可..能不會變。 馬金屬元 素的紹或釔與氧的化學親和力同.時也是極強 _ J 仕尚溫電 漿環境中氧也不會诮失，故可以在成為熔射皮膜後，持續 維持粉末材料時氧化鋁、氧化釔的物理化學特性。 Φ 上述氧化釔熔射皮膜不僅耐熱性或耐高溫氧化性、耐 蝕性優異，而且藉由使用鹵化物之低溫電漿時已知可以 在電漿蝕刻氣氛氣中發揮優異的抵抗性（耐電漿侵蝕 性）（曰本專利特開平10-004083號公報、曰本專利特=平 1 0-1 631 80號公報、日本專利特開平1〇_547744號公報、 曰本專利特開2001-164354號公報、日本專利特開 2003-321 760 號公報）。 前述文獻所揭露之氧化釔熔射皮膜係為全部白色系。 ©€有，前述文獻中由於白色系氧化祕射皮膜特性不會變 化，故並非變化此皮膜色彩，以利用於工學的及彩色式樣 的商品價值提升者。 作為改質基材表面的技術，除被覆形成上述熔射皮膜 外，也有利用電子束照射或雷射光束照射的技術。例如是 在關於電子束照射的日本專利特開昭6卜1〇4〇62號公報 中，具有在金屬皮膜上照射電子束熔融此皮膜以消除氣孔 的技術。還有，日本專利特開平9_316624號公報中，揭示 對奴化物金屬陶瓷皮膜或金屬皮膜照射電子束，以提升皮 2053-9829-PF;Ahddub 7 200925323 膜性能的技術。還有，在曰本專利特開平1〇_2〇2782號公 報中，揭不對氧化鍅（2r〇2)系陶瓷熔射皮膜照射雷射光束 的技術。：甚至，在at本專利特開20〇4_1〇〇〇39號公報中， 揭不在形成稀土類氧化物熔射皮膜的情形下，將碳、鈦、 鉬添加至熔妒材料中，使皮膜變化至灰色〜黑色的技術。200925323 - IX. Description of the Invention: Technical Field of the Invention The present invention relates to a method for forming a spot color oxidized glare film having excellent properties such as heat radiation and damage resistance, and a black oxidized ray ray with good color pattern. The film is covered with a material. ~ [Prior Art] q The spray method is a method of spraying a metal or ceramics, cermet or the like by means of a plasma jet or a flame, and blowing it on the surface of the substrate (substrate) by flying to form a surface of the substrate. The technology of the film is one of the widely used surface treatment technologies in most industrial fields. The molten film obtained by the above-described spraying method is known to have a strong mechanical strength between the particles, unbonded particles and unmelted particles (hereinafter referred to as "unmelted particles", etc., in the mechanical strength of the film or Nile There is a great difference in sexuality. For this reason, the development goal of conventional melting technology is, for example, by using a heat source in the plasma, which generates a strong impact energy on the surface of the fused body to improve the interparticle bonding force. At the same time, the porosity is reduced, and the adhesion between the film and the substrate is increased. On the other hand, the metal-solubilized film is formed in the atmosphere, and all the scatter particles are in contact with the air, and an oxide film is formed on the surface of the particles. The adhesion between the particles and the substrate is also deteriorated. A method for solving this problem is known, for example, in the method of spraying in a low-pressure inert gas atmosphere as proposed in Japanese Laid-Open Patent Publication No. Hei 6-1 96421 ( It is a vacuum plasma spray method. Specifically, in the vacuum capacity of the exhaust air 2〇53-9829-PF; Ahddub 5 200925323 -, argon gas is introduced at 50 hectopascals (hPa) to 200 hectopascals. A method of performing plasma spraying in this atmosphere. Regarding this point, the molten film of the oxide-based ceramic is not oxidized by melting in the atmosphere because it is the powder of the oxidized luminescent material itself. On the other hand, there is also a property that the molten material in the argon atmosphere does not undergo chemical change on the molten particles under reduced pressure. Since then, the current state of the oxide ceramic decompression plasma smelting method is in the atmosphere. There are relatively few research and development cases on the plasma spray. Q Also, the research on the conventional spray film is due to the improvement of the hardness, wear resistance, heat resistance, corrosion resistance or adhesion of the film. Therefore, the type of the molten material such as metal (alloy), ceramics, and cermet, and the choice of chemistry are selected in the focus of the choice of the spray method and the determination of the spray conditions. Therefore, the conventional spray film is applied. In fact, there is almost no research work to use the color of the film to enhance the commercial value of the color pattern of the spray film product. However, observing the appearance of the ceramic spray film, it is found that the chromium oxide (Cr2) as the molten material© 〇3) The end is dark green, which will become a black film when it is sprayed. On the other hand, the oxide (Ah()3) powder is white, and the film obtained by plasma spraying is also white. Although the titanium oxide (Ti〇2) powder is white, the plasma is obtained by spraying the plasma. In the above, the color change of the molten film should be caused by, for example, oxygen in the molten heat source. - Partially disappeared and caused by the oxide of TinU. (In the above description, the oxide-based ceramic spray film is removed - part of the oxide, and the powder material for the spray is used. The color itself is usually reproduced only as 2053-9829-PF; Ahddub 6 200925323 - film color. For example, yttrium oxide (Υ2〇〇 usually with white alumina (human 丨(4)^ phase 3 is white when the powder material state is The four-shot film obtained by this powder material is also white. The cerium oxide is, for example, sprayed in a plasma heat source to form a cerium oxide-containing cerium and an oxygen-bonding state. The chemical affinity of the metal element of the horse is the same as that of oxygen. It is also extremely strong. _J Shi Shangwen plasma environment will not lose oxygen, so it can be used to maintain the powder material after the molten film is maintained. And physicochemical properties of cerium oxide. Φ The above-mentioned yttria-sprayed film is excellent not only in heat resistance, high-temperature oxidation resistance, and corrosion resistance, but also exhibits excellent resistance in plasma etching atmosphere by using low-temperature plasma of halide (resistance to plasma corrosion) (Japanese Patent Laid-Open Publication No. Hei 10-004083, Japanese Patent Application No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. 2001-164354 Japanese Patent Laid-Open Publication No. 2003-321 760). The cerium oxide spray film disclosed in the above documents is all white. ©€有有,, in the aforementioned literature, since the characteristics of the white oxidized secret film do not change, the color of the film is not changed, and it is used for the improvement of the product value of engineering and color patterns. As a technique for modifying the surface of the substrate, in addition to coating the above-mentioned molten film, there is also a technique of irradiating with an electron beam or a laser beam. For example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 62-62, which has an electron beam irradiation, the electron beam is irradiated on the metal film to melt the film to eliminate pores. Further, Japanese Laid-Open Patent Publication No. Hei 9-316624 discloses a technique of irradiating an electron beam to an ionic metal cermet film or a metal film to enhance the film properties of the skin 2053-9829-PF; Ahddub 7 200925323. Further, in the publication of Japanese Patent Laid-Open Publication No. Hei No. Hei. No. 1278, the technique of irradiating a laser beam of a cerium oxide (2r〇2) ceramic spray film is disclosed. In addition, in the publication of Japanese Patent Laid-Open No. 20〇4_1〇〇〇39, it is disclosed that carbon, titanium, and molybdenum are not added to the molten material in the case of forming a rare earth oxide molten film, and the film is changed. To gray ~ black technology.
❹ 然而，前述所揭示之技術中，由於是以添加異種成分 至炼射粉末材料為必要條件，如此射使添加作業增大、 因皮膜成分純度降低而招致物理化學性質降低。 總之，前述先前技術係為以熔射皮膜中氣孔消滅、密 著性提升或在㈣於㈣融後冷卻製程的皮膜上發生縱向 切割等為目的之技術’而沒有針對不添加其他種成分 變化溶射皮膜外觀色彩的方法提出。 即可 相對於目前的現狀，發 赞明耆冒於日本專利特開 2006-118053號公专g中招；+斗4·人a· A報肀揭不對白色的氧化釔熔射皮膜，藉 由照射雷射光束或雷子步w i 9 飞冤子束以使之成功變化成黑&，而成功 藉由溶射皮膜$辛仆裎斗也卜Λ 色化如升熱輻射性及彩色式樣的商品價 值。 【發明内容】 [發明所欲解決的課題] 本發明目的是提供一種使 更用由白色氧化釔粉末所構成 之熔射材料，不依賴雷射光 ..^ , 電子束，藉由熔射直接形 成虱化釔黑色熔射皮膜的方 ,,^ ^ ^ 藉由此方法可以解決習知 技術所擁有之下述問題。 2053-9829-PF;Ahddub 8 200925323 (1)白知技術中，著色稀土類氧化物熔射皮膜時，由於 需於炼射粉末中添加碳、鈦、㈣著色成分，故不僅會使 生產製程增加，還會增加成本上揚、因其他種成分混入而 致之皮膜純度降低、耐蝕性及耐熱性等物理化學性質劣化。 (2)習知技術尹，氧化釔熔射皮膜黑色化處理，由於是 在形成白色乳化纪炫射皮膜後，對前述皮膜表面照射雷射 光束或電子束而得’故必須要針對此之專用設備，而招致 生產性降低及生產成本上昇。 [用以解決課題的手段] 為了解決習知技術所擁有之上述問題，本發明係採用 下述解決方法。 本發明提出一種黑色氧化釔熔射皮膜的形成方法，係 以惰性氣體與氫氣的混合氣體作為電漿.喷射產生用操作 氣體，並以之電衆熔射白色氧化纪粉末，以形成氧化在乙$ 色熔射皮膜。 還有’本發明中較佳是給予下述解決方法。 ⑴供炼射材料飛行线射氣氛氣藉由惰性氣體維持 於50百帕至600百帕的減壓環境中。 (2) 前述氧化釔黑色熔射皮膜係藉由前述電漿.喷射中 所含之原子狀氫所擁有之還元作用，由氧化摩)粉末的 ^分氧消失狀態下之Y2l所示黑色粒子堆積而成。 (3) 熔射氣氛，係將非氣仆 虱化拴軋體流動於電漿熔射搶 周圍，使空氣無法侵入朝被覆* 復表面射出電漿.喷射的環境。 ⑷由前述白色氧化釔粉末所構成的熔射材料粒徑為5 2053-9829-PF;Ahddub 200925323 . 微米至8〇微米。 (5) 用以發生電漿.喷射的前述操作氣體中，係為惰 .氣體與氳氣.的容積比在湖〜3/1.制 (6) 前述氧化釔黑色炫射皮膜係直接或經底漆 基材表面。 ；： ， (7) 前述基材係選自含不銹鋼的各種鋼、鋁及其合金、 欽及其合金、鎢及其合金、鉬及其合金、燒結碳、石英、 ❻玻璃、塑膠類、氧化物及非氧化物系陶瓷燒結體所組成族 群中一種以上的金屬系或非金屬系基材。 (8) 前述底漆係選自鎳及其合金、鉻及其合金、鎢及其 合金、錮及其合金、鈦及其合金、紹及其合金所組成族群 中一種以上的金屬及其合金。 還有，本發明提出一種黑色氧化紀熔射皮膜被覆材 料’係為使藉由上述方法所形成之γ2〇3 χ組成的氧化釔黑色 熔射皮膜膜厚形成為50微米到2000微米厚。 Φ 本發明中較佳是給予下述解決方法。 (1) 刖述氧化釔黑色熔射皮膜和基材之間設有膜厚為 5 0微米到5 0 0微米的底漆。 … (2) 前述基材係選自含不銹鋼的各種鋼、鋁及其合金、 鈦及其合金、鎢及其合金、鉬及其合金、燒結碳、石英、 玻璃、塑膠類、氧化物及非氧化物系陶瓷燒結體所組成族 群中一種以上的金屬系或非金屬系基材。 (3) 前述底漆係選自鎳及其合金、鉻及其合金、鎢及其 合金、鉬及其合金、鈦及其合金、鋁及其合金所組成族群 2053-9829-PF;Ahddub 10 200925323 中一種以上的金屬及其合金。 1(4二:氣氛氣係流動於電㈣射搶周圍的非氧化性 :體:使被覆表面處於防止朝電漿.喷射之空氣侵入的環 ⑸由前述白色氧化紀粉末所構成的溶射材徑 微米至.80微米。 W ^ 5 ⑹用以發生電漿·喷射的前述操作氣體中，係為惰性 氣體與氨氣的容積比在10/1〜3/1範圍内的氣體。 依據本發明可期待有以下所示之效果。 ⑴本發明在作㈣射熱源之m射產生用惰性氣 體中，藉由添加還元性強的氨氣，即可在不使用碳或敛 广色成分，即可使用市售溶射用白色氧化纪溶射粉 末，直接形成黑色氧化妃熔射皮膜。因此可以僅使用包含 減壓電漿熔射裝置的既存熔射相關裝置。 *⑺依據本發明’由於可以省略雷射光束或電子束照射 等用以二次黑色化的處理’故不需要高能量照射設備等。 因此’加上作業性提高、不需新㈣等經濟效果會增大。 ⑶在藉由減壓下無氧電漿熔射法之黑色氧化 =成方法（日本專利特開2006-1 1 8053號公報）中，會出現 從灰色至黑色漢淡摻雜的黑色，而有品質不穩定之情況。 依據本發明則可以得到怪常穩定黑色氧化纪皮膜，而可以 獲得品質提升及生產性提升。 U)適用本發明方法之黑色氧化釔熔射皮膜，因具有與 白色虱化釔熔射皮膜同等耐蝕性及耐電漿·侵蝕性，故可 2053-9829-PF;Ahddub 11 200925323 以使用於同一用途。 ⑸依據本發明由㈣射皮膜本身是黑色，故形成有此 黑色炼射皮則材料，可將此作為傳熱面或受熱面？除了 可以有熱吸收能力及遠紅外線幸畐射能力的提升外，亦可以 提升_特性及受熱效率。尤其是在編入半導體加工裝 置與提升電锻姓刻加工速度之同時’可以發揮品質均一化 的效果。 ❹ ❹ 。-有依據本發明所形成黑色氧化釔熔射皮膜的產 品’為了厚度方向全體維持黑色光澤，例如是可以進行表 面切削機械加工以使皮料黑，而提升商品品質。 ⑺本發明黑色氧化釔熔射皮膜被覆材料使用於 體加工裝置時，由於 ^ mb _ / 作用所導致之反應生成物 附者不_’故不f額外洗淨裝置，讀升操作效率。 ^使用於半導體製造，加q置的熔射 鋁陶瓷係以白色系代矣，、《士 T 乳化 射皮膜r“、 31有習知技術所形成之氧化釔熔 、疋白色。為此保守檢查時會難以 區別，在受到損傷砵典士 反联材資的 .，費事的工作是要準備很多對策。此 點以黑色氧化釔熔射 .了朿此 易，亦可提升保守檢查精確度及生產性。 別變谷 T依據本發明材料可以得_色式 面的半導體加工裝置等工業產品。 K 貝值 【實施方式】 對使用由白色惫儿A / 化釔⑽)粉末所構成之熔射材料形 2053-9829-PP；Ahddub 12 200925323 . 成黑色氧化紀、熔射皮膜的方法進行說明。 本發明中，為了使用市售由白色氧化紀（Υ2〇3)粉末所構 成之溶射材料以形成黑铺化柄射皮膜，在炫射槍 f人作為.熱源之操作氣體者.，不僅是氬或氦等惰性氣體， 更一併於操作氣體.中添加氫氣等還元性氣體，從溶射搶向 基材之熔射粒子飛行路徑必需降低成膜（熔射）氣氛氣童 位能。 乳 ❹ 以下，根據溶射生成黑色氧化纪皮膜的理由進㈣ 明。一般而言，電渡溶射法操作氣體是使用氨或氛等惰性 氣體。此在負擔直流電壓而得之溶射搶中之弧中，藉# 性氣體流動’產生高溫《•噴射，以作為熱源。此 喷射熱源之環境中，因是由從氯或氛等電離的電+、離子、 子及分子結合體所構成’故環境中只要無來自外部之空 氣混入’會是還元性或非氧化性。 但是’此狀態下之熔射槍中的電裂熱源，供給白色氧 ® 化釔（Y2〇3)粉末進行熔射所得熔射皮膜係為白色，外觀顏色 沒有產生變化。理由是，通常電漿熔射法中電漿.噴射還 元力弱，由於、熔射粒子飛行所處之炼射氣氛氣係為大氣，、 故藉熱源熔融後噴射飛行之氧化釔（H)粉末粒子與空氣 接觸，而僅為白色結構。 但，減壓電漿熔射法中，炼射氣氛氣亦即自溶射搶喷 出之熔滴朝被覆面飛行並將熔射環境中氧分壓大幅降低。、 實質上無氧氬氣在50百帕至200百帕的減壓下成膜，在弱 氧化性下有時會變化成灰色，但不會變化至黑色。 2053-9829-PF;Ahddub 13 200925323 為此，本發明中， 氣置於減壓容11 1内之溶射槍2内的操.作 .的氯氣、加習知的氬或氦外，還導入混合還元性強 ❹ Ο 内t騎射搶2及被處縣材3係被配置 1内:、：即，射氣氛氣係維持於㈣等惰性氣體中。 體錢用=發明中供給至溶射槍2的電衆產生用操作氣 用此r作:、°作為還元性氣體之氫氣而成的混合氣體。使 用此刼作氣體時，產 災 原子狀生電漿過程中，因有顯示強還元性之 项于狀氫存在，故可间牛肢撞 色氧化記（叫粉末）5還 射搶2中的熔射材料（白 料乘著電漿.喷射6被霜70。而且已被還原的溶射材 釔忮 、 覆至基材表面。其中所形成之氧化 射皮膑7因堆積熔射中被 ^b^(Y2°3^ 色氧1=發明者發現黑色氧化紀㈣ (γ〇 ^ 粒子消失—部份氧原子而成之氧化紀 (Υζ〇3-χ)組成粒子所構 以「ΥΠ志_ 取的皮膜。在此’發明者白色氧化釔 Υ2〇3」表不，依據本發明適用所得之 成則為黑色氧化纪，也稱為「氧 Υ2〇3-χ」組 使用前述含有氣氣之電：：」物化紹(Ah〇3) 色，故氧化記（y2〇3)s色化u射熱源成膜時，也是呈現白 …色化現象係為本發明特有現象。 依編明者研究’使用炫射槍2中惰性氣體中添加 有風氣之混合操作氣體4作A雪將勒 處理表“其㈣、 為電名熱源時’從熔射槍朝被 面（基材表面）之溶射粒子飛行路經為大氣中時（氧 2〇53-9829-PF;Ahddub 14 200925323 化氣氛氣），炫融粒子與空氣接觸再 此，本發明巾，熔㈣气”』 巴及灰色。因 要。亦即 &射…(粒子飛行路徑)的控制也报重 ’不使用減壓容器i，進行大氣電聚 =大氣下）之情形下，前述電漿.噴射6需安裝 境遮斷裝置，或物.喷射職僅流過氣、氣Γ ❹ 行之^氣體或反應性低的氣體，必須避免炼融狀態下飛 :二：：：與空氣直接接觸。基於此點，使用可在減壓 二行：：乳風乳下f膜的減壓電漿熔射裝置，較佳是熔射 灯14粒子與空氣（正確說是氧）間的接觸不發生。 還有，氬或氦等電漿產生氣體中添加氫氣量較 積比如下的混合比率。亦即， 氬氣/氫氣= 10/1至3/1 氫氣混合比為則’較佳是5/卜比5/1 "黑色化會不完全，彩色品質不固定。另-方面，氯氣比 W還多進行混合時，|色化效果會飽和。 作為電疑產生氣體，也可以使用氬與氦的混合氣體， 只要維持前述氫氣對氬氣單獨量的比率即可達成發明目 的。上述比率較佳是5/1至3/1左右。 第2圖⑷至⑷，係繪示依據本發明技術所形成之黑 色氧化妃熔射皮膜與依據習知技術所得γ2〇3皮膜外觀的圖 形。從此圖可明顯得知，制適合本發明之氬/氫混合氣體 作為電漿·喷射產生用操作氣體，甚至炼射環境也控制於 非氧化性氣氛氣中，並於氧分廢較少之氣氛氣下進行溶 射，以讓黑色氧化釔熔射皮膜的形成變可能。 2053-9829-PF;Ahddub 15 200925323 —(a)使用氬/氫容積比=4/1作為電裝·喷射產生氣體， 於氬氣200百帕氣氛氣.中溶.射自色.γ2〇3(蒙瑟爾記號：⑽、 黑色或暗灰色）..b _ (b)僅使用氬作為電漿·.喷射產生氣體，於氬氣2〇〇百 帕氣氛氣中炼射白色γ2〇3(Ν5、亮灰色）。 (C)使用（a)的條件氣體，於大氣中炼射槍氣氛氣中氮 氣體流動之同時熔射κοκ·、中度灰色）。 e (d)使用（b)的條件氣體，於大氣中熔射白色y2〇3(N9、 白色）。 …接者，關於本發明作為用以形成黑t氧化㈣射皮g 材料的Y2〇3粉末，對此粉末粒度與純度進行說明。 ❹ Υ-粉末粒度較佳是5微米至8〇微米的粒徑範圍，更 佳是5微米至50微米的結構。理由是粒徑比別微求還大 的粉末包括多個未完全溶融於溶射熱源中的未溶融粒子。 未炫融粒子内部由於未受到包含氫氣之電蒙熱源影響，故 可以認定其維持著白色狀態，而成為降低皮膜品質的主要 原口另方面’5微米以下的粒子，至内部為止是完全 熔融黑色化’由於自粉末供給機至熔射槍的運送供给速产 不穩定、在電製熱源中溶融昇畢狀態、無法成㈣以構: 皮膜的強度因故溶射皮膜的剖面組織可能會不均等、 不齊全，而有可能使皮膜強度劣化。 本發明所使用的氧化紀粉末純度較佳是不純物（例如 鐵、鎮、鉻、紹、錄、石夕等)較少者。最近發明者調查市隹 品，全部成分在98重量百分率以上，即使使用此市售口 ： 2053-9829-PF;Ahddub 16 200925323 成黑色氧化釔熔射皮臈較佳，然本發明不以此為限。 接著，對用以形成黑色氧化釔熔射皮膜的基材進行說 明。本發明中形成.上述氧化釔黑色熔射皮膜的對象，亦即 基材，開始是鋁及其合金、不銹鋼、鈦及其合金、陶I燒 結體（例如氧化物、氮化物、硼化物、矽化物及前述化合物 的混合物），也可.以使用石英、玻璃、塑膠等所構成的材料。 還有，在此種材料上也可以纟用施加有m著膜或錢 膜，也可以在此材料表面直接或介由底漆或中間層而成膜。 接著，對黑色氧化釔熔射皮膜被覆材料的皮膜結構進 行說明。 本發明材料中除了可以在基材表面直接被覆上述氧化 記黑色溶射皮膜外，還可以在形成此騎皮膜之前，先在 該基材表面形成底漆，之後形成前述黑色氧化釔熔射皮膜 作為表面塗層，以提升皮膜的密著性^此時，底漆材料可 以使用選自錄及其合金、鉻及其合金、鶴及其合金、翻及❹ However, in the above-described technique, since the addition of the dissimilar component to the refining powder material is necessary, the addition operation is increased, and the physicochemical property is lowered due to a decrease in the purity of the film component. In summary, the foregoing prior art is a technique for the purpose of eliminating the pores in the molten film, improving the adhesion, or performing longitudinal cutting on the film of the (IV) cooling process after the (four) melting process, and does not change the spray without adding other components. The method of color appearance of the film is proposed. It can be compared with the current status quo, and it is praised that it is smashed in the Japanese Patent Special Open 2006-118053, and it is recruited by the Japanese Patent Special Opener 2006-118053. Irradiate the laser beam or the thunder step wi 9 to fly the scorpion beam to make it successfully change into black & and succeed in smelting the film by the smear film, and also to color the product such as the heat radiation and color pattern. value. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a molten material which is made of white cerium oxide powder and which is formed directly by sputtering without depending on laser light. The method of the black fused film of bismuth telluride, which can solve the following problems of the prior art by this method. 2053-9829-PF; Ahddub 8 200925323 (1) In the Baizhi technology, when the rare earth oxide film is colored, it is necessary to add carbon, titanium, and (4) coloring components to the powder, so that the production process is not only increased. It will also increase the cost and increase the physical and chemical properties such as the decrease in film purity, corrosion resistance and heat resistance due to the incorporation of other components. (2) The conventional technique Yin, yttrium oxide spray film blackening treatment, because after the formation of the white emulsified glare film, the surface of the film is irradiated with a laser beam or electron beam, so it must be dedicated to this Equipment, resulting in reduced productivity and increased production costs. [Means for Solving the Problems] In order to solve the above problems of the prior art, the present invention adopts the following solutions. The invention provides a method for forming a black cerium oxide molten film, which is a mixed gas of an inert gas and a hydrogen gas as a plasma. The operating gas for jetting is generated, and the white oxide powder is sprayed by the electricity to form an oxidation in B. $ color spray film. Further, in the present invention, it is preferred to give the following solution. (1) The atmosphere for the flight of the refining material is maintained in a decompression environment of 50 to 600 hectopascals by inert gas. (2) The yttrium oxide black molten film is formed by the regenerative action of the atomic hydrogen contained in the plasma, and the black particles are deposited by Y2l in the state of disappearance of oxygen in the oxidized powder. Made. (3) The spray atmosphere is to flow the non-gas smelting and rolling body around the plasma spray to prevent the air from invading the environment where the plasma is sprayed toward the coated surface. (4) The particle size of the molten material composed of the aforementioned white cerium oxide powder is 5 2053-9829-PF; Ahddub 200925323. micron to 8 〇 micron. (5) Among the above-mentioned operating gases used for plasma generation, the volume ratio of inert gas to helium gas is in the lake ~3/1. (6) The above-mentioned cerium oxide black glare film system is directly or via Primer substrate surface. ;: , (7) The above substrate is selected from various steels containing stainless steel, aluminum and its alloys, and its alloys, tungsten and its alloys, molybdenum and its alloys, sintered carbon, quartz, bismuth glass, plastics, oxidation One or more metal-based or non-metallic base materials in the group of the material and the non-oxide-based ceramic sintered body. (8) The primer is selected from the group consisting of nickel and its alloys, chromium and its alloys, tungsten and its alloys, niobium and its alloys, titanium and its alloys, and metals and alloys thereof. Further, the present invention proposes a black oxidized-period film coating material which is formed to have a thickness of 50 μm to 2000 μm thick in a yttria black molten film film composed of γ 2 〇 3 χ formed by the above method. Φ In the present invention, it is preferred to give the following solution. (1) A primer having a film thickness of 50 μm to 500 μm is provided between the black oxidized film and the substrate. (2) The foregoing substrate is selected from various steels containing stainless steel, aluminum and alloys thereof, titanium and alloys thereof, tungsten and its alloys, molybdenum and its alloys, sintered carbon, quartz, glass, plastics, oxides and non- One or more metal-based or non-metal-based substrates in the group of the oxide-based ceramic sintered body. (3) The aforementioned primer is selected from the group consisting of nickel and its alloys, chromium and its alloys, tungsten and its alloys, molybdenum and its alloys, titanium and its alloys, aluminum and its alloys, 2053-9829-PF; Ahddub 10 200925323 More than one metal and its alloys. 1 (4 2: atmosphere gas flow in electricity (4) shot around the non-oxidation: body: the coated surface is in the ring to prevent the intrusion of air into the plasma. (5) The diameter of the molten material composed of the aforementioned white oxidized powder Micron to .80 μm. W ^ 5 (6) Among the aforementioned operating gases for generating plasma and jet, a gas having a volume ratio of inert gas to ammonia gas in the range of 10/1 to 3/1. The effect shown below is expected. (1) In the present invention, by adding a regenerative ammonia gas to the inert gas for generating m (4), it is possible to use without using carbon or a wide-color component. Commercially available white oxidized spray powder for spray formation, directly forming a black yttrium oxide sprayed film. Therefore, it is possible to use only the existing spray-related device including the reduced-pressure plasma spray device. *(7) According to the present invention 'Because the laser beam can be omitted Or electron beam irradiation and other treatments for secondary blackening. Therefore, high-energy irradiation equipment is not required. Therefore, the economic efficiency of the workability improvement and the need for new (four) will increase. (3) Under no pressure reduction Oxygen plasma spray method black In the method of forming a method (Japanese Patent Laid-Open Publication No. 2006-1 1 8053), black which is lightly doped from gray to black is present, and there is a case where the quality is unstable. According to the present invention, a strangely stable black color can be obtained. Oxidation film can be used to improve quality and productivity. U) The black yttrium oxide spray film which is suitable for the method of the present invention has the same corrosion resistance and plasma corrosion resistance as the white bismuth telluride spray film. 2053-9829-PF; Ahddub 11 200925323 for use in the same purpose. (5) According to the present invention, the (4) film itself is black, so that the material of the black film is formed, which can be used as a heat transfer surface or a heat receiving surface. In addition to the ability to absorb heat and the ability to transmit far-infrared rays, it also improves _ characteristics and heat efficiency. In particular, it is possible to achieve uniformity of quality while being programmed into a semiconductor processing device and improving the processing speed of the electric forging. ❹ ❹. - The product of the black yttrium oxide sprayed film formed according to the present invention maintains a black gloss for the entire thickness direction. For example, it is possible to perform surface cutting machining to blacken the leather to improve the quality of the product. (7) When the black cerium oxide spray coating material of the present invention is used in a body processing apparatus, the reaction product due to ^ mb _ / action is not attached to the apparatus, and the operation efficiency is read. ^Used in semiconductor manufacturing, the sprayed aluminum ceramics with the addition of q are replaced by a white system, the "T-emulsion emulsion film r", 31 has a conventional technique to form a cerium oxide melting, whitening. For this conservative inspection It will be difficult to distinguish when it is damaged. The troublesome work is to prepare a lot of countermeasures. This point is sprayed with black yttrium oxide. This is easy, and it can also improve the accuracy and production of conservative inspection. According to the material of the present invention, an industrial product such as a semiconductor processing device of a color surface can be obtained. K Bayer value [Embodiment] A spray material composed of a powder of white enamel A / bismuth (10) powder is used. Shape 2053-9829-PP; Ahddub 12 200925323. A method of forming a black oxidized film and a molten film. In the present invention, in order to use a commercially available molten material composed of white oxidized (Υ2〇3) powder to form black The squeezing handle is used to spray the film, and the ray gun is used as the operating gas of the heat source. It is not only an inert gas such as argon or helium, but also a regenerative gas such as hydrogen gas in the operating gas. Sprayed particles The path of the film must reduce the gas-forming potential of the film-forming (spraying) atmosphere. The nipple is as follows. The reason for the formation of the black oxidized film according to the spray is (4). In general, the operating gas of the electric spray method is inert using ammonia or atmosphere. Gas. In the arc of the solvent that is responsible for the DC voltage, the 'gas flow' generates high temperature. • Sprays as a heat source. In the environment of this jet heat source, it is ionized by chlorine or atmosphere. The electric +, ion, sub- and molecular combination constitutes 'in the environment, as long as there is no air from the outside', it will be reductive or non-oxidizing. But in this state, the electric heat source in the spray gun is supplied to white. The spray film obtained by spraying oxygen powder (Y2〇3) powder is white, and the appearance color does not change. The reason is that in the plasma spray method, the plasma is also weak in the spray, due to the molten particles. The atmosphere of the refining atmosphere in which the flight is located is the atmosphere, so the cerium oxide (H) powder particles which are sprayed by the heat source and are in contact with the air are only in contact with the air, but only the white structure. However, in the vacuum plasma spraying method, the refining process Shoot The atmosphere gas, that is, the droplets ejected from the spray, flies toward the coated surface and greatly reduces the oxygen partial pressure in the spray environment. The substantially oxygen-free argon gas is formed under a reduced pressure of 50 hectopascals to 200 hectopascals. In the weak oxidizing property, it sometimes changes to gray, but does not change to black. 2053-9829-PF; Ahddub 13 200925323 For this reason, in the present invention, the gas is placed in the squirt gun 2 in the decompression chamber 11 1 In the case of the chlorine gas, the conventional argon or the sputum, the introduction of the mixture is also strong. Ο t 骑 骑 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 In the inert gas such as (4), the body gas is used as the mixed gas for the generation of the operating gas supplied to the spray gun 2 in the invention, and is used as the hydrogen of the regenerative gas. When using this gas as a gas, in the process of atomic atomic plasma production, there is a strong reductive element in the presence of hydrogen, so it is possible to record the color of the bovine limbs (called powder). The molten material (white material is taken by the plasma. The spray 6 is frosted 70. And the molten material that has been reduced is coated on the surface of the substrate. The formed oxidized shot 膑 7 is formed by the deposition of the melt. ^(Y2°3^ Oxygen 1 = Inventor found that black oxidized (4) (γ 〇 ^ particles disappeared - part of the oxygen atom formed by the oxidized (Υζ〇3-χ) composed of particles composed of "ΥΠ志_ The film of the 'inventor's white yttrium oxide 2 〇 3' is not black, and the composition obtained according to the present invention is black oxidized, also referred to as "oxygen Υ 2 〇 χ χ χ 组 使用 使用 使用 使用 使用 使用 使用 使用:: "Ah〇3" color, so the oxidation (y2〇3) s coloring u-ray heat source film formation, is also white... colorization phenomenon is a unique phenomenon of the invention. Use the mixed operating gas 4 added with the air in the inert gas of the stun gun 2 as the A shovel treatment table "when (4), when it is the electric name heat source" When the spray gun is flying toward the surface of the surface (substrate surface), it is in the atmosphere (oxygen 2〇53-9829-PF; Ahddub 14 200925323 atmosphere), and the particles are in contact with air. , (4) gas, "bar" and gray. Because of the need, that is, the control of the "particle flight path" is also reported to be 'not using the decompression container i, performing atmospheric electricity polymerization = atmospheric atmosphere." Plasma. Jet 6 requires the installation of a shut-off device, or the material. The gas is only flowing through gas, gas, gas, or low-reactivity gas. It must be avoided in the smelting state: two::: with air Direct contact. Based on this, a pressure-reducing plasma spray device capable of depressurizing two lines: a milk film under the emulsion, preferably a contact between the particles of the spray lamp 14 and air (correctly speaking, oxygen) is used. Also, there is a mixing ratio of the amount of hydrogen added to the gas generated by the plasma such as argon or helium, that is, argon/hydrogen = 10/1 to 3/1, and the hydrogen mixing ratio is preferably 5/bbi 5/1 " blackening will not be complete, color quality is not fixed. On the other hand, chlorine is more mixed than W When the colorization effect is saturated, it is also possible to use a mixed gas of argon and helium as the gas generated by the electric suspect, and the purpose of the invention can be achieved by maintaining the ratio of the hydrogen gas to the argon gas alone. The above ratio is preferably 5/1. Fig. 2 (4) to (4) show the appearance of the black yttrium oxide sprayed film formed according to the technique of the present invention and the appearance of the γ2〇3 film obtained according to the prior art. It is apparent from this figure that The argon/hydrogen mixed gas suitable for the present invention is used as an operating gas for plasma/spray generation, and even the refining environment is controlled in a non-oxidizing atmosphere, and is sprayed under an atmosphere of less oxygen waste to allow The formation of a black cerium oxide spray film becomes possible. 2053-9829-PF; Ahddub 15 200925323—(a) Use argon/hydrogen volume ratio = 4/1 as the electricity and injection to generate gas, and dissolve in argon gas at 200 hectopascal atmosphere. The color is emitted from the color. γ2〇3 (Monsell mark: (10), black or dark gray)..b _ (b) Use only argon as the plasma. · Produce a gas, and smash white γ2〇3 in an argon atmosphere of 2 〇〇 MPa. Ν5, bright gray). (C) The conditional gas of (a) is used to pulverize κοκ·, moderate gray at the same time as the nitrogen gas flows in the atmosphere of the refining gun in the atmosphere. e (d) Using the conditional gas of (b), white y2〇3 (N9, white) is sprayed in the atmosphere. Next, the present invention is described as a Y2〇3 powder for forming a black t-oxidized (tetra)-epi-g material, and the powder particle size and purity are explained. The ❹-powder particle size is preferably in the range of 5 μm to 8 μm, more preferably 5 μm to 50 μm. The reason is that the powder having a larger particle diameter than the other micro-pitch includes a plurality of un-melted particles which are not completely dissolved in the molten heat source. Since the inside of the non-glazed particles is not affected by the electric heat source containing hydrogen, it can be considered to maintain the white state, and it is the main raw material for reducing the quality of the film. The particles below 5 microns are completely melted and blackened to the inside. 'Because the delivery from the powder feeder to the spray gun is unstable, it is not stable in the electric heat source, and it cannot be formed. (IV) The structure of the film may be uneven. It is complete, and it is possible to deteriorate the film strength. The purity of the oxidized powder used in the present invention is preferably less than that of impurities (e.g., iron, town, chromium, Shao, Lu, Shi Xi, etc.). Recently, the inventors investigated the market products, all of which are above 98% by weight, even if the commercially available port is used: 2053-9829-PF; Ahddub 16 200925323 is a black yttrium oxide sprayed skin, but the present invention does not limit. Next, a substrate for forming a black cerium oxide sprayed film will be described. The object of forming the above-mentioned yttria black molten film, that is, the substrate, is initially composed of aluminum and its alloys, stainless steel, titanium and alloys thereof, and sintered ceramics (for example, oxides, nitrides, borides, bismuth). The material and the mixture of the above compounds may be made of quartz, glass, plastic or the like. Further, it is also possible to apply a film or a film of m on the material, or to form a film directly or via a primer or an intermediate layer on the surface of the material. Next, the film structure of the black cerium oxide spray coating material will be described. In the material of the present invention, in addition to directly coating the above-mentioned oxidized black-solubilized film on the surface of the substrate, a primer may be formed on the surface of the substrate before forming the film, and then the black yttrium oxide film is formed as a surface. Coating to enhance the adhesion of the film. At this time, the primer material can be selected from the group and its alloys, chromium and its alloys, cranes and their alloys, and
其合金、鈦及其合金、紹及其合金、鎂合金所組成族群中 種以上的金屬、合金。此外，較佳是將底漆施工至厚度 5〇微米至5 00微米左右。 在此情形下，底漆熔射皮膜比5〇微米還薄時，底漆的 作用效果較弱。另一方面’底漆熔射皮膜厚度超過5〇〇微 米時，被覆效果飽和，且可能引起依據成膜作業製作費用 的提馬。 還有，底漆較佳是使用電弧熔射法、火焰熔射法、高 速火焰熔射法、大氣電漿熔射法、減壓電漿熔射法、爆炸 2053-9829-PF；Ahddub 17 200925323 嫁射法等。 另一方面，成為表面塗層的本 膜，不认a产甘u 士 犬乃黑色虱化釔熔射皮 膜不姻疋在基材表面直接成膜，反 4# a , v 疋在則迹底漆上炼射 積層成膜，本發明黑色氧化 ,^ 5 9ηηπ ^ ^ 冷耵反膘較佳是施工至50微 =7 微米還薄的皮膜，性及耐《· 3 t面比2_微米還厚的皮膜，因效果已 飽和而不經濟。 W双衣匕 前述底漆係形成作為黑色氧化紀炫射皮膜 中間層，較袪县、g嫂/ 4 、” 材間的 ]層較佳疋選擇任務―邊是發揮與基材間的密著強 二:另-邊也與作為表面塗層之黑色氧化紀維持良好的密 者卜材質較佳是使用金屬材質的物f，選自錦及U金、 金、鶴及其合金、翻及其合金、鈦及其合金、銘 其.金、鎖合金所組成族群中一種以上的金屬、合金。 此外’較，是將底漆施工至厚度50微米至50。微米左右： 在此％合下，底漆熔射皮膜比50微米還薄時，底漆的 作=效果較弱。另一方面’底漆熔射皮膜厚度超過_微 只了被覆效果飽和，且可能引起依據成膜作業製作費用 的提高。 (實施例1 ) 在此實施例中，於内藏電熱線之石英玻璃製保護管表 面上形成依據習知技術的Y2〇3白色熔射皮膜、習知技術(日 本專利特開2006-1 1 8053號公報）所示之利用電子束照射 白色Υζ〇3熔射皮膜形成黑色化皮膜、以及本發明氧化釔黑 色熔射皮膜（50微米厚）後，於電熱線中通入電流，調查從 2053-9829-PF；Ahddub 18 200925323 ^ 各皮膜放出之波長。 、’口果顯不'，γ2〇3白’色熔射皮膜為〇. 2微米i "数米左 右，氧化妃黑,色炫射皮膜中、分別藉由電子束照射處理及 紅外線放射，ί且加熱器的效率有所差異。 還有，為替換石英玻璃製加熱器，在齒㈣(高亮度燈) 表面施工則述2種氧化纪黑色炫射皮膜⑸微米厚），相對 〇於沒有皮膜狀態的燈波長為0·2至U微米範圍内，施加 ，專、色溶射皮膜者則為〇· 3微米至1〇微米，處於可以利用的 遠紅外線區域，可明顯地提升加熱器的效率。還有依據習 知技術而得之γ2〇3白色溶射皮膜，與溶射皮膜未施工狀態 下相同，或在其以下的波長範圍内。 " 從以上結果可知，適用本發明方法所形成之黑色氧化 釔熔射皮膜，作為半導體加工裝置用材料’不僅耐電繁 =性提升，也可以作W進㈣加卫速度的熱源相 當有用。 (實施例2) 在此實施例中，對3_10鋼（50毫米χ5〇毫米χ5 測4片表面進订轟擊粗面化處理後，藉由將氯氣控制在氣 風氣壓力為5°百帕至200百帕的減壓電毅熔射法，形成 150微米厚的γ2〇3。此時，在形成μ膜之前，對測試片上 有無藉由大氣電裝炫射法施工得到1〇〇 的底漆，調查其效果。 金 還有，減麼電聚炫射之際，形成本發明黑色皮膜時， 2053-9829-PF;Ahddub 19 200925323 4 使用氬/氳容積比為5/1的混合氣體作為操作氣體。還有在 比較飼之情形下則使用氬/氦比為5/1的混合氣體。. 形成有熔射皮膜的測試片’在調查熔射氧化釔（Y2〇3); 所形成.之.表面塗層外觀色後，進行下述熱衝擊測試’以:調 查該熔射皮膜的耐剝離性。 表1係為上述結果的簡要内容。由此結果可知本發明 以氬/氳容積比為5 /1的混合氣體作為電漿熱源操作氣體 的條件下，所成膜之測試片（No. 1至4)係呈黑色。而在不 含氳之氬/氦比為5/1的混合氣體條件下，所得之測試片 (N 〇. 5至8 )僅顯示灰色而非黑色。 前述測試片先加熱至攝氏5 0 0度並維持於電爐中1 5分 鐘左右後，將之投入攝氏2 5度的水中並重覆5次操作，在 全供測試皮膜亦即基材上，直接形成氧化釔（Υ2〇3)熔射皮 膜，以及施工有鎳-鋁合金的底漆等2種情況跟Υ2〇3熔射皮 膜外觀色無關。在本實施例條件下確認可以發揮全部優異 m 的耐熱衝擊性，且可以使因黑色化而來之耐剝離性降低。 (表 ) No. 熔射法 電漿 氣體 熔射 氣氛氣 皮膜結構 皮膜 外觀色 熱循環測試結果 備註 底漆 表面塗層 攝氏500度Χ15分鐘》 攝氏25度水中投下 1 減壓電漿 炫射法 (100百帕） 氬/氫 氬 無 Y2〇3 黑 未剝離 適合例 2 Ni-5A1 Υ2〇3 黑 未剝離 3 氬/氫 無 Υ2〇3 黑 未剝離 適合例 4 ΝΪ-5Α1 Υ2〇3 黑 未剝離 5 氬/氦 氬 無 Υ2〇3 灰色 未剝離 6 Ni-5A1 Υ2〇3 灰色 未剝離 7 氬/氦 無 Υ2〇3 灰色 未剝離 8 ΝΪ-5Α1 γ2〇3 灰色 未剝離 備註： (1) 電漿氣體中氬/氫比=5八，氬/氦比則是5八。 (2) 皮膜厚度：底漆為100微米，表層塗膜為150奈米。 (3) 熱循環數量：（攝氏500度xl5分鐘θ攝氏25度水中投下)x反覆10次。 2053-9829-PF;Ahddub 20 200925323 (實施例3) 在此實施例中，一切藉由大氣電漿熔射法形成皮膜於 實施例2所示熔射測試片.，藉由以與實施例2湘同條件者 的熱衝擊測試’調查皮膜的耐剝離性，還有，在大氣電槳 熔射法中，使用氬/氫容積比4/1的同時，熔射搶周緣，特 別是溶射搶出口附近流經大量氬氣，以防止朝電裝.噴射 的空氣侵入。 ❹ 表2係顯示此結果。不論是依據大氣熔射法形成黑色 氧化釔熔射皮臈，還是藉由實施例2的減壓電漿熔射法， 均可與藉由習知技術而得之白色Υ2〇3熔射皮膜相同，並保 持優異的财剝離性。 (表2) No. 熔射 電漿 氮噴射 皮 皮膜 外觀色 熱循環測試結果 氣氛氣 氣體 之有無 底漆 表面塗層 攝氏500度χΐ 5分鐘㊁ 揭^氏烈麽·?1ί Φ柏·*ττ 備註 1 2 有 無 Y2〇3 黑 未剥離 適合例 Q 氬/氫 ΝΪ-5Α1 Υ2〇3 黑 未剝離 4 無 無 Υδ〇3 白 未剝離 5 大氣 ΝΪ-5Α1 __Υ2〇3_ 卜白 未剝離 比較例 6 有 Y2lfe 黑 未剝離 7 氬/氦 ΝΪ-5Α1 Υ2〇3 黑 未剝離 通合例 8 無 無 Y2〇3 白 未剝離 比較例 備註 ΝΪ-5Α1 Υ2〇3 白 未剝離 + 氦比則是额測試片Να 5至8) 環皮水中投下)χ反覆1G次。 ❹ 搶出口附近有氮氣屏蔽，赌氣之氬/氫比=4/1麟合氣體’轉搶周邊’特別 (5)Να 5、6的皮膜係加入作為·2射綮，侵入。 * — 搶出口附近有氮氣屏蔽，氫比=4/1的混合氣趙，軸搶周邊’特別是 朝電漿·喷射的空氣侵入。 (實施例4 ) 在此貫加例中，使用50毫米χ50毫米x5毫米厚的鋁基 材’其表面上藉由大氣電㈣射法，並使用組成相異之電 2053-9829-PF;Ahddub 21Metals and alloys of the alloys, titanium and alloys thereof, and their alloys and magnesium alloys. Further, it is preferred to apply the primer to a thickness of from about 5 μm to about 500 μm. In this case, when the primer spray film is thinner than 5 μm, the primer has a weak effect. On the other hand, when the thickness of the primer spray film exceeds 5 μm, the coating effect is saturated, and it may cause the horse to be produced according to the film forming operation. Also, the primer is preferably an arc spray method, a flame spray method, a high speed flame spray method, an atmospheric plasma spray method, a reduced pressure plasma spray method, an explosion 2053-9829-PF; Ahddub 17 200925323 Marriage law and so on. On the other hand, the film that becomes the surface coating does not recognize that the a-growth dog is a black film of bismuth, and the film is formed directly on the surface of the substrate, and the anti-4# a , v 疋 is at the bottom. The film is formed by filming on the paint, and the black oxidation of the present invention is preferably 5 5 ηηπ ^ ^ cold 耵 是 是 施工 施工 施工 施工 施工 施工 施工 施工 施工 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 A thick film is not economical because the effect is saturated. W double 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕 匕Strong two: the other side is also well-maintained with the black oxidized period as the surface coating. The material is preferably made of metal material f, selected from Jin and U gold, gold, crane and its alloy, and Alloys, titanium and alloys thereof, more than one metal or alloy in the group consisting of gold and lock alloys. In addition, the primer is applied to a thickness of 50 μm to 50 μm: at this %, When the primer spray film is thinner than 50 micrometers, the primer has a weak effect. On the other hand, the thickness of the primer spray film is more than _micro, and the coating effect is saturated, and may cause the production cost according to the film forming operation. (Example 1) In this embodiment, a Y2〇3 white spray film according to a conventional technique is formed on the surface of a quartz glass protection tube having a built-in heating wire, and a conventional technique (Japanese Patent Laid-Open No. 2006- Illumination of white Υζ〇3 by electron beam as shown in 1 1 8053) After the molten film was formed into a blackened film and the yttria black molten film (50 μm thick) of the present invention, a current was passed through the heating wire, and the wavelength emitted from each of the films of 2053-9829-PF and Ahddub 18 200925323 was investigated. , 'mouth fruit is not ', γ2 〇 3 white 'color spray film is 〇. 2 micron i " a few meters or so, oxidized 妃 black, color stun film, by electron beam irradiation treatment and infrared radiation, respectively ί and the efficiency of the heater is different. Also, in order to replace the quartz glass heater, the surface of the tooth (four) (high-brightness lamp) is described as two kinds of oxidized black glare film (5) micron thick), relatively no In the film state, the wavelength of the lamp is in the range of 0·2 to U micrometer, and the application of the special and color-dissolving film is 〇·3 μm to 1 μm, which is in the far infrared region that can be utilized, which can obviously improve the efficiency of the heater. There is also a γ2〇3 white spray film obtained according to the prior art, which is the same as or in the wavelength range below which the sprayed film is not applied. " From the above results, it is known that the black formed by the method of the present invention is applied. oxygen The 钇 钇 皮 , 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇 钇Χ5〇mmχ5 Measure 4 surface after the surface of the bombardment roughening treatment, by controlling the chlorine gas to a decompression electrolysis method with a gas pressure of 5°HPa to 200HPa, forming a 150 μm thick γ2 〇 3. At this time, before the formation of the μ film, whether or not a primer of 1 〇〇 is obtained by the atmospheric electricity glazing method on the test piece, and the effect is investigated. The gold is also reduced, and the electricity is reduced. When the black film of the present invention is formed, 2053-9829-PF; Ahddub 19 200925323 4 uses a mixed gas having an argon/helium volume ratio of 5/1 as an operating gas. Also, in the case of comparative feeding, a mixed gas having an argon/rhenium ratio of 5/1 is used. The test piece having the molten film formed is inspected for the molten yttrium oxide (Y2〇3); after the appearance of the surface coating is formed, the following thermal shock test is performed to: investigate the resistance of the molten film Peelability. Table 1 is a summary of the above results. From the results, it was found that the test piece (No. 1 to 4) formed in the film was black under the condition that the mixed gas having an argon/helium volume ratio of 5 / 1 was used as the plasma heat source operating gas. The test pieces (N 〇. 5 to 8) showed only gray instead of black in a mixed gas atmosphere containing no argon/rhenium ratio of 5/1. The test piece is first heated to 500 degrees Celsius and maintained in an electric furnace for about 15 minutes, then put into water of 25 degrees Celsius and repeated 5 times, directly formed on the whole test film, that is, the substrate. The oxidized yttrium oxide (Υ2〇3) spray film and the nickel-aluminum alloy primer are not related to the appearance of the Υ2〇3 spray film. Under the conditions of the examples, it was confirmed that the thermal shock resistance of all the excellent m can be exhibited, and the peeling resistance due to blackening can be lowered. (Table) No. Spraying plasma gas spray atmosphere Gas film structure Film appearance Color heat cycle test result Remarks Primer surface coating Celsius 500 degrees Χ 15 minutes" Celsius 25 degrees water drop 1 Vacuum plasma blaze method ( 100 hectopascals argon/hydrogen argon no Y2〇3 black unpeeled suitable example 2 Ni-5A1 Υ2〇3 black unpeeled 3 argon/hydrogen free Υ2〇3 black unpeeled suitable example 4 ΝΪ-5Α1 Υ2〇3 black unstripped 5 Argon/argon argon free 〇2〇3 Gray unpeeled 6 Ni-5A1 Υ2〇3 Gray unpeeled 7 Argon/氦无Υ2〇3 Gray unpeeled 8 ΝΪ-5Α1 γ2〇3 Gray unpeeled Remarks: (1) Plasma The argon/hydrogen ratio in the gas is 5-8, and the argon/helium ratio is 5-8. (2) Film thickness: The primer is 100 μm and the surface coating is 150 nm. (3) Number of thermal cycles: (500 degrees x 15 minutes Celsius, 25 degrees Celsius, 25 degrees water drop) x repeated 10 times. 2053-9829-PF; Ahddub 20 200925323 (Embodiment 3) In this embodiment, all of the film is formed by the atmospheric plasma spray method in the spray test piece shown in Embodiment 2. By using Example 2 The thermal shock test of the same conditions of the same person's investigation of the peeling resistance of the film, and in the atmospheric electric paddle spraying method, while using the argon/hydrogen volume ratio of 4/1, the molten film grabs the periphery, especially the spray grabs the exit. A large amount of argon gas flows through the vicinity to prevent intrusion of air injected toward the electric installation. ❹ Table 2 shows this result. Whether the black yttrium oxide sprayed skin is formed according to the atmospheric spray method or the reduced pressure plasma spray method of the second embodiment can be the same as the white Υ2〇3 sprayed film obtained by the conventional technique. And maintain excellent financial stripping. (Table 2) No. Spray plasma Nitrogen sprayed skin film appearance color heat cycle test result Atmosphere gas gas with or without primer surface coating Celsius 500 degrees χΐ 5 minutes two Unveiled 氏 烈 、 、 、 、 、 、 、 、 、 、 、 、 、 、 1 2 With or without Y2〇3 Black unpeeled Suitable example Q Argon/hydroquinone-5Α1 Υ2〇3 Black unpeeled 4 No Υδ〇3 White unpeeled 5 Atmosphere ΝΪ-5Α1 __Υ2〇3_ 卜白未脱比 Comparative Example 6 With Y2lfe Black unpeeled 7 Argon/氦ΝΪ-5Α1 Υ2〇3 Black unpeeled common case 8 No Y2〇3 White unpeeled Comparative example Remarks ΝΪ-5Α1 Υ2〇3 White unpeeled + 氦 ratio is the test piece Να 5 To 8) Drop in the skin water) χ Repeat 1G times.氮气 There is a nitrogen shield near the exit, and the argon/hydrogen ratio of the smashing gas = 4/1 lining gas 'returns to the surrounding area' special (5) 皮α 5, 6 is added to the film system as a 2 ray and invades. * — There is a nitrogen shield near the exit, and the hydrogen ratio=4/1 is mixed with the gas. The shaft grabs the surrounding area, especially the air invaded by the plasma. (Embodiment 4) In this embodiment, an aluminum substrate of 50 mm χ 50 mm x 5 mm thick is used, and the surface thereof is irradiated by atmospheric electricity (four), and the composition of the electricity is different, 2053-9829-PF; Ahddub twenty one
200925323 漿·喷射產生用操作氣體作為炫射熱源，以形成⑸微米 厚的Y2〇3mm與氧化时射皮膜。此時，將作為底漆 之錄—銘合金膜（剛微米）的有無，加人測試條件中。之f 露出職片中央部表面積！ 〇毫米χ】〇毫米的範圍，並罩幕 其他部分，在下述條件巾奢 千τ貫鉍2〇小時電漿侵钱測試.。還 有作為其他表面處理法’係、以紹基材被陽極氧化（防腐仙） 為比較試樣。 〈電渡餘刻條件〉 蝕刻氣體：四敗化碳（CFO、氬、氧（容積比在1〇:1〇〇 1 ) 電漿輸出：1 300瓦。 測試結果如表3所示。此結果可明顯發現依據比較例 現行技術所得之陽極氧化皮膜（N〇1〇)、氧化鋁熔射皮膜 (Ν〇· 7、8)及碳化硼熔射皮膜（Ν〇·9)，無論哪一個係隨著電 漿.侵蝕量而變大，且此種在電漿環境中缺乏耐久性。 相對於此，本發明黑色氧化釔熔射皮膜（N〇. i至4)， 跟底漆之有無沒關，且可以發揮優異的耐電漿侵蝕性。還 有，在同一條件下，以熔射皮膜（N〇. 5至8)跟被測試之白 色氧化釔（Y2〇3)進行比較，而且也確認本發明之熔射皮臈可 以發揮全不遜色的耐久性。 2〇53-9829-PF;Ahddub 22 200925323 (表3)200925323 The slurry/spray generation operating gas is used as a blaze heat source to form a (5) micron thick Y2 〇 3 mm and an oxidized time film. At this time, it will be used as a primer for the presence or absence of the alloy film (just micron), which is added to the test conditions. The f reveals the surface area of the film! 〇 χ χ 〇 〇 〇 〇 , , 〇 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他There are also other surface treatment methods, and the base material is anodized (antiseptic) as a comparative sample. <Electrical Residual Condition> Etching gas: Four carbonized carbon (CFO, argon, oxygen (volume ratio: 1〇:1〇〇1) Plasma output: 1 300 watts. The test results are shown in Table 3. An anodized film (N〇1〇), an alumina spray film (Ν〇·7, 8), and a boron carbide spray film (Ν〇·9) obtained according to the prior art of the comparative example can be clearly found, whichever system is With the amount of plasma erosion, it becomes large, and this lacks durability in the plasma environment. In contrast, the black cerium oxide spray film of the present invention (N〇.i to 4), with or without primer It is excellent in resistance to plasma erosion. Also, under the same conditions, the molten film (N〇. 5 to 8) is compared with the white yttrium oxide (Y2〇3) to be tested, and it is also confirmed. The sprayed skin of the present invention can exert durability which is not inferior. 2〇53-9829-PF; Ahddub 22 200925323 (Table 3)
No. 成膜方法 成膜材料或 成膜成分 皮膜結構 皮膜 外觀色 侵蝕損失深度 (被米） ，備註 底漆 表面塗層 1. 疼射法 氧化釔（γ2〇3) ΝΪ-5Α1 Y2〇3 黑 6.0 適合例 2 無 Υ2〇3 黑 5:9 3 Ni-20Cr Υ2〇3 黑 6.1 4 Mo Υ2〇3 里 5.8 5 Ni-5A1 Υ2〇3 白 7.0 比較例 6 無 Υ2〇3 白 6.5 7 氧化鋁 Ni-5A1 氧化鋁 白 8.5 8 無 氧化鋁 白 8.2 9 碳化硼 無 碳化硼 灰色 29.0 10 陽極氧化 三氧化二鋁 無 三氧化二鋁 灰色 41.0 備註： φ (1)熔射係使用大氣電漿熔射法，電漿產生用氣體組成係如下所示。 氬/氫= 3/1(氬氣屏蔽)No. 1至4 氬/氦=4/1(無氬氣屏蔽)No. 5至9 (2)陽極氧化係以JIS H8601規定之AA25號為基準成膜。 [產業上利用可能性] 本發明技術，不僅將氧化釔黑色化，也可利用於其他 陶瓷例如是二氧化鈦及二氧化鈦-三氧化二鋁等黑色化技 術，故可以應用至半導體、液晶、其他、高分子工業或機 〇 械工業等領域所使用之材料而形成。 【圖式簡單說明】 第1圖係繪示電漿熔射槍的概略線路圖。 第2圖係繪示氧化釔熔射皮膜外觀色電子顯微鏡照 片。 【主要元件符號說明】 1〜減壓容器（熔射環境）； 2053-9829-PF;Ahddub 23 200925323 2〜熔射槍； 3〜被處理基材；.No. Film formation method Film-forming material or film-forming component Film structure film Appearance color erosion loss depth (by rice), Remarks Primer surface coating 1. Pain shot yttrium oxide (γ2〇3) ΝΪ-5Α1 Y2〇3 black 6.0 Suitable example 2 No Υ2〇3 Black 5:9 3 Ni-20Cr Υ2〇3 Black 6.1 4 Mo Υ2〇3 5.8 5 Ni-5A1 Υ2〇3 White 7.0 Comparative Example 6 无Υ2〇3 White 6.5 7 Alumina Ni -5A1 Alumina White 8.5 8 No Alumina White 8.2 9 Boron Carbide No Boron Carbide Gray 29.0 10 Anodized Al2O3 No Alumina Gray 41.0 Remarks: φ (1) Spraying System Using Atmospheric Plasma Spraying Method The composition of the gas for plasma generation is as follows. Argon/hydrogen = 3/1 (argon shielding) No. 1 to 4 Argon/氦=4/1 (no argon shielding) No. 5 to 9 (2) Anodizing is based on AA25 specified in JIS H8601 Film formation. [Industrial Applicability] The present invention can be applied not only to blackening of cerium oxide but also to other ceramics such as titanium dioxide and titanium dioxide-alumina, so that it can be applied to semiconductors, liquid crystals, others, and the like. Formed from materials used in the molecular industry or the machine industry. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic circuit diagram showing a plasma spray gun. Fig. 2 is a photomicrograph showing the appearance of a yttrium oxide spray film. [Main component symbol description] 1~Relief container (spraying environment); 2053-9829-PF; Ahddub 23 200925323 2~spray gun; 3~ treated substrate;
4〜操作氣體； J 5〜炫射材料·、;一 6〜電漿·喷射； 7〜氧化紀溶射'皮膜。4 ~ operating gas; J 5 ~ sleek material ·,; a 6 ~ plasma · spray; 7 ~ Oxide spray 'film.
2053-9829-PF;Ahddub2053-9829-PF; Ahddub