1304843 七、指定代表圖： (一）、本案指定代表圖為：第（5)圖 (一）、本案指定代表圖之符號簡單說明: 1〇電鑄鎳箔 11規則性六角柱形鎳奈米線 八、本案若有化學式時，1304843 VII. Designated representative map: (1) The representative representative figure of this case is: (5) Figure (1), the symbol of the designated representative figure of this case is briefly explained: 1〇Electroforming nickel foil 11 regular hexagonal cylindrical nickel nanometer Line VIII. If there is a chemical formula in this case,
無 請揭示最能顯示發明特徵的化學式： 九、發明説明： 【發明所屬之技術領域】 本發明有關電鑄方法製造具有非均勾磁場強度的金屬件，特別 π用陽極處理(anodizing)獲取之規則性六角蜂窩多孔性的鋁戋鋁人 氧化膜作為磁性金屬之電鑄模版(template)，使電鑄的金屬件之—: 選擇的部分面上有磁性金屬奈米線(nanowire)的結構，電鑄金屬件因 在選擇性的面積上有較高的磁場強度，形成具有非均勻磁場 屬電鍀件。 又 【先前技術】 .磁性材料在近代電子與生化工業的應用日漸重要，應用於高密声 磁性數據儲存(high density magnetic data storage device)的硬碟，戋高广 磁性的薄膜磁頭(thin-film magnetic head)等即為例子。 另外’奈米科技的發展已創造了新一代的技術與應用，廣為人知的$ 1304843 米級之規則性六角蜂窩多孔性銘氧化膜(an〇dic p〇r〇us 加)於新的 奈米時代中也引發了新的探討與應用。本發明述說的鋁或其合金之氧 化膜的蜂寫狀孔取六肖形駐’但是因孔洞形成的條件不盡在理想 的平衡態，所以常為六角形的變形而狀如五角或四角形，但是在業界 與科學文章中乃以六肖形稱之，所以具蜂窩多孔性的鋁或其合金之氧 化膜在本發明中皆以”規則性六角蜂窩多孔性鋁氧化膜’，稱之。傳統工 業中以鋁為陽極而於酸性電解質中電解出的規則性六角蜂窩多孔性氧 化膜具有硬、耐磨與耐腐蝕的特性，而使得此鋁陽極處理廣用於工業 界已多年。除了氧化電解的條件外，此氧化膜的孔洞大小決定於電解 質組成，不同酸性電解質配合不同氧化電解條件可獲取各種大小的孔 洞，此孔洞的孔徑寬可從5至25G奈来，而長度也可大至數百微米， 亦即可獲取不同深寬比(aspect rati〇)的奈米級孔洞，此深寬比值也可利 用後續的擴孔處理加以改變。除了鋁金屬外，鋁合金也能獲取相同的 陽極處理之結果而適用於本發明，就如2〇〇〇年的J〇umal 〇f Applied Physics雜誌第87(9)冊第4?21頁就指出鎂金屬如同鋁金屬，所以鋁鎂 合金的陽極處理就如同鋁金屬。除了鋁鎂合金外，RA. L〇wenheim先 生於美國紐約市McGmw-Hill書局在ι978年出版的EleetIOplating書 中也指出陽極處理的鋁合金也包括鋁鎂矽合金、鋁辞鎂合金、鋁錳合 金、鋁猛鉻合金與鋁鎂矽銅鉻合金。上述之奈米級孔洞的氧化膜之阻 障層(barrierlayer)薄而具導電性，所以可由此氧化膜孔洞的深底處鍍取 金屬的奈米顆粒或奈米線，例如在1997年的Electrochimica Acta雜誌 1304843 【發明内容】 於金屬材朗縣性表社產轉㈣磁麵度較複雜 ’較可行的 • 料是採用電鍍或其他_被覆方式於金屬材料的選擇性表面私皮覆 • +同磁場強度的磁性物質，使金屬件的表面具有非均勻磁場強度的特 )·生仨疋此方法有其盲點，尤其當金屬材料的形狀特殊時，例如於管 狀金屬内要獲取特殊部分面積有較高的磁場強度時，此方法根本無法 • 製得。為解決這些問題乃提出此新穎發明，利用於工業界已使用多年 之電鑄技術製作出不同形狀的具有非均勻磁場強度的金屬成品，提供 近代電子與生化·Χ業的需要ϋ發這些近代卫業的更新紐展。 如同在先前技術中述說的，奈米科技的發展引領出奈米級的規則 .性六角蜂寫多孔性减齡金之氧化朗磁性金屬電鑛，—般銘陽極 處理後的氧化膜孔洞寬約為5至25G奈米，孔敝小隨施加電壓而增， 約有2.5奈米/伏特的關係，例如磷酸電解質需施加較高之電壓而可獲 • 取較大之孔洞，孔洞長度可隨電解時間而加長，也能利用擴孔條件以 增加孔洞的孔徑。調整此些氧化膜孔洞的深寬比而電鍍出深寬比不同 的磁性金屬奈米線，也就獲取磁場強度不同的磁性金屬奈米線，在固 定溫度下更利用磁性金屬奈米線的磁滯迴線之測定而求得頑磁性 (retentivity)與抗磁性(coercivity^本發明即進一步利用此磁性金屬奈米 線的高磁場強度之特性，以規則性六角蜂窩多孔性的鋁或鋁合金氧化 膜為電鑄模版而電鑄出含有奈米金屬線結構的金屬電鑄件，亦即能使 金屬電鑄件於選擇性的部分表面上含有磁性金屬奈米線，更由磁性金 1304843 屬奈米線深寬比_異而呈現關磁場強度的躲，形成金屬電鱗件 於選擇性的部分表面上呈現不_磁場酸，獲得具有非均勻磁場強 度的金屬電鑄件。 鋁或鋁合金為傳統的電鑄模版之材料，容易加工成各種形狀，也容 易以驗液溶解絲’配合此磁性金屬奈米線的製作當然可電鑄出各種 複雜形狀的金屬電鑄件，並使金屬電鑄件具有非均勻磁場強度的特性。 【實施方式】 本發明主要分為電鑄模版的製作與磁性金屬的電禱。喊銘合金 氧化膜電鑄模版的製作除了控制多孔性贼齡金之氧化·洞的深 寬比外也要機電賴版健表面的導電性。陽極處理的酸性電解質 採用硫酸、草酸與磷酸，使用不同的酸性電解質就需施加不同的陽極 處理電壓’從H)伏特至伏特，例如採_酸之酸性電解質就需施 加較高的輕，阿獲得德較大的_性六辨窩氧簡孔洞。本 發明之雜處理_二酸式，將初顿得_紐合金之氧化膜去 除後再進彳了第二謂極處理轉取較完整的規職六肖蜂寫多孔性氧 化膜。陽極處_溶液溫度—般為攝氏零度至35度，陽極處理時須 使溶液有充分勝財雜喊科產賴録。使驗性溶液做氧 化膜孔洞的擴孔處理時’可提猶性溶贿度、處理的時間與溫度以 增加孔洞徑，此舰_孔_氧⑽深度_峨子顯微鏡 測定。銘或齡金的形狀與其要陽極處理的面積皆可依需要而事先調 1304843 整，整個鱗模版表面的導電性可糊濺鍍導電材質或化學鍵而加以 改善，陽極處理時之陰極可採用鋁、鉛、不銹鋼或不溶性陽極。至於 磁性金屬的電鑄除了注意—般電鑄的需求外也需控制電鑄溶液的潤濕 性，較高潤濕性的電鑄溶液較能滲入奈米級的氧化膜孔洞内以電鑄出 含有完整奈米金屬線結構的金屬電鑄件，電鑄結束後以強鹼性溶液去 除鋁或鋁合金以及其氧化膜。除了利用電子顯微鏡觀察磁性金屬奈米 線的形狀與大小並利用高斯計（gauss meter)測定其磁性外，也利用 X-射線能量光譜分析儀(energy-dispersive x_ray anaiysis)測定金屬奈米 線的成份’並利用X-射線繞射光譜(XRD)測定金屬奈米線的結晶度，磁 性金屬奈米線的微結構皆顯示有較高的結晶度。 [實例一]純度為99.9 %銘片（20 X 20 X 7 mm)於進行機械拋光和電解抛 光後進行第一次陽極處理1小時，陽極處理電壓為161伏特，陽極處 理是以不溶性氧化銥為陰極於〇°C之磷酸電解質中進行的，而後將處 理後的氧化層以0.5M濃度的磷酸在45 〇C腐蝕30分鐘並清洗後再進行 第二次陽極處理2小時，陽極處理的磷酸濃度可為〇·3 μ或〇.6M，此 獲取的氧化膜於0.5M濃度的磷酸及45 °C條件下進行擴孔腐姑15分鐘 後皆可獲取規則性六角蜂窩多孔性氧化膜。第(1)圖即顯示磷酸濃度為 0.6 Μ時所獲取之規則性六角蜂窩多孔性氧化鋁膜的一萬倍電子顯微 鏡照片’顯示出規則性六角蜂窩多孔性的氧化鋁膜孔洞，適於後續的 電鑄工作。 1304843 [實例二]如同實例一之多孔性氧化銘膜製程，第二次陽極處理的磷醆 濃度増至1 Μ，處理時間也增至7.5小時，也可獲取規則性六角蜂窩多 孔性氧化鋁膜。第(2)圖即顯示此多孔性氧化鋁膜的一萬倍電子顯微鏡 照片’顯示出的規則性六角蜂窩多孔性之氧化銘膜孔洞，孔洞大小寬 約4〇〇奈米，而高約為62微米，亦即有⑸的深寬比，.非常適於後 續的鎳電鑄工作。Please disclose the chemical formula that best shows the characteristics of the invention: IX. Description of the invention: [Technical field of the invention] The invention relates to an electroforming method for manufacturing a metal member having a non-uniform magnetic field strength, in particular, π is obtained by anodizing The regular hexagonal honeycomb porous aluminum-aluminum oxide film is used as an electroforming template for the magnetic metal, so that the electroformed metal member has a magnetic metal nanowire structure on the selected portion. The electroformed metal parts have a high magnetic field strength in a selective area, and form a non-uniform magnetic field. [Prior Art] Magnetic materials are increasingly used in the modern electronics and biochemical industries. They are used in hard disks of high density magnetic data storage devices, and thin magnetic films (thin-film magnetics). Head) is an example. In addition, the development of Nano Technology has created a new generation of technologies and applications, the well-known $1304843-meter regular hexagonal honeycomb porous oxide film (an〇dic p〇r〇us plus) in the new nano-era It also triggered new discussions and applications. The bee-shaped hole of the oxide film of aluminum or its alloy according to the present invention takes a six-dimensional shape, but the condition for forming a hole is not in an ideal equilibrium state, so it is often a hexagonal deformation like a pentagonal or quadrangular shape. However, in the industry and scientific articles, it is called a six-Shape shape, so an oxide film of aluminum or a alloy thereof having a honeycomb porosity is referred to as a "regular hexagonal honeycomb porous aluminum oxide film" in the present invention. In the industry, a regular hexagonal honeycomb porous oxide film which is electrolyzed in an acidic electrolyte using aluminum as an anode has hard, wear-resistant and corrosion-resistant properties, and this aluminum anode treatment has been widely used in the industry for many years. In addition to the conditions, the pore size of the oxide film is determined by the electrolyte composition. Different acid electrolytes can be used to obtain pores of various sizes in combination with different oxidation and electrolysis conditions. The pore size of the pores can be from 5 to 25 G, and the length can be as large as several. A hundred micron, it is also possible to obtain nano-level holes with different aspect ratios. This aspect ratio can also be changed by subsequent reaming treatment. In addition, the aluminum alloy can also obtain the same result of the anodizing treatment and is suitable for use in the present invention, as indicated in the 2nd year of J〇umal 〇f Applied Physics, vol. 87(9), pp. 4-21. Like aluminum, the anodizing of aluminum-magnesium alloys is like aluminum. In addition to aluminum-magnesium alloys, RA. L〇wenheim also pointed out that anodized aluminum was also published in the EleetIOplating book published by IG978 in McGmw-Hill, New York, USA. The alloy also includes an aluminum-magnesium-bismuth alloy, an aluminum-magnesium alloy, an aluminum-manganese alloy, an aluminum-cerium alloy, and an aluminum-magnesium-bismuth-copper-chromium alloy. The barrier layer of the oxide film of the above-mentioned nano-scale pores is thin and electrically conductive. Therefore, metal nano-particles or nanowires can be plated at the deep bottom of the pores of the oxide film, for example, in the Electrochimica Acta magazine 1304843 of 1997. [Invention] In the metal material Langxian sex table production (four) magnetic surface More complex 'feasible material' is made by electroplating or other _ coating method on the selective surface of the metal material. + Magnetic material with the same magnetic field strength, so that the surface of the metal part has a non-uniform magnetic field strength. This method has its own blind spots, especially when the shape of the metal material is special, for example, in a tubular metal to obtain a special portion of the area with a high magnetic field strength, this method cannot be made at all. To solve these problems This novel invention is proposed to make use of electroforming technology which has been used for many years in the industry to produce metal products with different shapes and strengths of non-uniform magnetic field, and to provide the needs of modern electronics and biochemical industry. As described in the prior art, the development of nanotechnology leads to the nano-scale rule. The sex hexagonal bee writes the porous age-reducing gold oxide metal oxide mine, the pore width of the oxide film after the alum treatment About 5 to 25G nanometers, the pore size increases with the applied voltage, and has a relationship of about 2.5 nm/volt. For example, the phosphoric acid electrolyte needs to apply a higher voltage to obtain a larger hole, and the length of the hole can be The electrolysis time is lengthened, and the reaming conditions can also be utilized to increase the pore size of the pores. Adjusting the aspect ratio of the pores of the oxide film and plating the magnetic metal nanowires with different aspect ratios, thereby obtaining the magnetic metal nanowires with different magnetic field strengths, and magnetically using the magnetic metal nanowires at a fixed temperature. Determination of hysteresis and reductivity (coercivity) The invention further utilizes the high magnetic field strength of the magnetic metal nanowire to oxidize aluminum or aluminum alloy with regular hexagonal honeycomb porosity. The film is an electroformed stencil and electroformed a metal electroforming part containing a nanowire structure, that is, the metal electroforming part can contain a magnetic metal nanowire on a selective part of the surface, and the magnetic gold 1304843 is a nanowire. The aspect ratio _ is different from the hiding of the magnetic field strength, forming a metal electric scale member to exhibit a non-magnetic field acid on a selective partial surface, and obtaining a metal electroforming member having a non-uniform magnetic field strength. Aluminum or aluminum alloy is a conventional electric The material of the mold plate is easy to process into various shapes, and it is easy to dissolve the silk with the test liquid. The production of the magnetic metal nanowire can of course electroform a variety of complex shapes of metal electricity. And the metal electroformed part has the characteristics of non-uniform magnetic field strength. [Embodiment] The present invention is mainly divided into the production of electroforming stencil and the electric prayer of magnetic metal. In addition to controlling the porosity of the electro-molding stencil of the alloy The oxidation of the age of the thief, the depth-to-width ratio of the hole must also be the electrical conductivity of the electroplated surface. The anodized acid electrolyte uses sulfuric acid, oxalic acid and phosphoric acid. Different acid electrolytes are required to apply different anode treatment voltages. H) Volt to volts, for example, the acid electrolyte of acid-like acid needs to be applied with a higher lightness, and A. The miscellaneous treatment-diacid type of the invention removes the oxide film of the initial alloy and then enters the second pre-polarization process to transfer a relatively complete syllabus to write a porous oxide film. At the anode, the temperature of the solution is generally between 0 and 35 degrees Celsius. When the anode is treated, the solution must be fully spurred by the company. When the test solution is used for the reaming treatment of the oxide film hole, the brittleness, the treatment time and the temperature can be increased to increase the hole diameter. The ship_hole_oxygen (10) depth is determined by the microscope. The shape of the inscription or the age of gold and the area to be anodized can be adjusted to 1304843 as needed. The conductivity of the surface of the entire scale plate can be improved by sputtering the conductive material or chemical bond. The anode can be made of aluminum when the anode is processed. Lead, stainless steel or insoluble anode. As for the electroforming of magnetic metal, in addition to the demand for electroforming, it is also necessary to control the wettability of the electroforming solution. The electrowetting solution with higher wettability can be infiltrated into the pore of the nanometer oxide film to be electroformed. A metal electroforming product containing a complete nanowire structure, after the electroforming is finished, the aluminum or aluminum alloy and its oxide film are removed by a strong alkaline solution. In addition to observing the shape and size of the magnetic metal nanowire by an electron microscope and measuring the magnetic properties using a gauss meter, the composition of the metal nanowire is also determined by an energy-dispersive x-ray anaiysis. 'The crystallinity of the metal nanowire was measured by X-ray diffraction spectroscopy (XRD), and the microstructure of the magnetic metal nanowire showed high crystallinity. [Example 1] The purity of 99.9 % (20 X 20 X 7 mm) was subjected to the first anodizing treatment for 1 hour after mechanical polishing and electrolytic polishing, the anode treatment voltage was 161 volts, and the anodizing treatment was based on insoluble cerium oxide. The cathode was carried out in a phosphoric acid electrolyte of 〇 ° C, and then the treated oxide layer was etched with 0.5 M phosphoric acid at 45 〇 C for 30 minutes and washed for a second anodic treatment for 2 hours. It can be 〇·3 μ or 〇.6M, and the obtained oxide film can obtain a regular hexagonal honeycomb porous oxide film after being expanded for 15 minutes at a concentration of 0.5 M phosphoric acid and 45 ° C. Figure (1) shows a 10,000-fold electron micrograph of a regular hexagonal honeycomb porous alumina film obtained with a phosphoric acid concentration of 0.6 ', which shows a regular hexagonal honeycomb porous aluminum oxide film hole, which is suitable for subsequent Electroforming work. 1304843 [Example 2] As in the porous oxidation film process of Example 1, the second anodized phosphonium concentration was increased to 1 Μ, the treatment time was also increased to 7.5 hours, and a regular hexagonal honeycomb porous alumina film was also obtained. . Figure (2) shows the 10,000-fold electron micrograph of the porous alumina film, which shows the regular hexa-cell porous porosity of the oxide film, the pore size is about 4 〇〇 nanometers, and the height is about 62 microns, which has an aspect ratio of (5), is very suitable for subsequent nickel electroforming work.
[實例三]如同實例-之多孔性氧化紹膜製程，但是陽極處理用的酸性 電解質採用草酸溶液，當草酸濃度由α3 M至，陽極處理電壓由2〇 至40伏特，第二次陽極處理時間由!至4小時的—系列探討中，皆如 同實例-的能獲取酬性蜂窩多孔性的氧化_孔洞，但是孔洞較 小，例如0.3 Μ的輕溶液在陽極處理⑽伏特時的孔洞大小之寬 約90奈米，一樣地適於後續的電鑄工作。 [實例叫如同實例-之多孔性氧脑膜製程，但是陽極處理用的酸性 電解質硫酸溶液，同樣地做-系列探討，硫酸濃度由咖至齢 陽極處理電壓由10至30伏特’第二次陽極處理時間由i至5小時， 也如同實例-罐取規雕蜂窩纽性的氧倾職洞，是孔洞更 小，例如0.3 Μ的硫酸溶液在陽極處理健25伏特時的孔洞大小之寬 約45奈米，一樣也遶於後續的電鑄工作。 但是陽極處理用的酸 變酸電解質成分與濃 [比較例一]如同實例一之多孔性氧化鋁膜製程， 性電解質採用硼酸或酒石酸，則在—系列的改 1304843 度、陽極處理電壓與陽極處理時間之變數下皆無法獲取規則性六角蜂 窩多孔性氧化膜的孔洞，不能成為本發明的電鑄模版。 [實例五]如同實例-之多孔性氧化膜製程，但是陽極處理用的陽極材 料採用紹鎂合金(#5〇52)，一樣可獲取規則性蜂寫多孔性的氧化膜，適 於後續的電鑄工作。[Example 3] As the example - the porous oxidation process, but the acid electrolyte for the anode treatment uses oxalic acid solution, when the concentration of oxalic acid is from α3 M to, the anode treatment voltage is from 2 〇 to 40 volts, the second anode treatment time From ! to 4 hours - in the series, as in the case - the oxidation hole that can obtain the porosity of the honeycomb, but the hole is small, for example, the light solution of 0.3 Μ has a wide hole size at the anode treatment (10) volt. About 90 nm, the same is suitable for subsequent electroforming work. [The example is called the example of the porous oxygen meninges process, but the acidic electrolyte sulfuric acid solution for the anodizing treatment, the same is done - series discussion, the sulfuric acid concentration from the coffee to the anodic anode treatment voltage is from 10 to 30 volts' second anodizing treatment The time is from i to 5 hours, and it is also like the example - the oxygen dumping hole of the potting honeycomb, which is smaller, for example, the 0.3 Μ sulfuric acid solution has a pore size of about 45 Å when the anode is treated at 25 volts. Rice, as well as the subsequent electroforming work. However, the acid-acid electrolyte component for the anodizing treatment and the concentrated [Comparative Example 1] are as in the porous alumina membrane process of Example 1, and the boric acid or tartaric acid is used as the electrolyte, and the series is changed to 1304843 degrees, the anode treatment voltage and the anode treatment. The pores of the regular hexagonal honeycomb porous oxide film cannot be obtained under the variation of time, and cannot be the electroformed stencil of the present invention. [Example 5] As the example - the porous oxide film process, but the anode material for the anode treatment is made of Shaomei alloy (#5〇52), which can obtain the regular oxide film of the porous bee, suitable for subsequent electricity. Cast work.
[實例六]制實例二之多錄氧化賴，但是在1M _酸濃度下其 第二次陽極處辦間只施行小時，則孔顺淺，只有約116微米， 亦即深寬比对29。乡孔性氧化賴的啡層不太厚，可透過電流進 行電沈積，但是氧她_外層表面並料電，愈近表面的氧化賴 層愈不導電，賴在製備的氧化娜上濺鍍黃金3()秒，因為愈近表面[Example 6] The second example of the preparation of the oxidation of the second, but at the 1M _ acid concentration of the second anode between the implementation of only hours, the hole is shallow, only about 116 microns, that is, the aspect ratio of 29. The layer of porphyrin oxide is not too thick, and it can be electrodeposited by current, but the surface of the outer layer of oxygen is oxidized. The closer the surface of the oxidized layer is, the less conductive it is. 3 () seconds because the closer the surface
的濺鍵黃金層較厚，晴反向的克服朗表_不導電性，成為整面 適於電鑄的模版。將此電鑄模版置於含胺基續酸錄與棚酸電解質中， 每升電解質巾也含0.2克_關，在5G 〇c及丨安餅方公寸的電流 密度下進行鎳電鑄6小時，而後錢％氫氧化納溶液去除電禱後. 與氧化娜後獲取的賴就有—面含齡鱗，此鎳奈米線的成 分也利用X-射線能量光譜分析儀測定。此些鎳奈米線在又_射線繞射 光.曰之(111) (2GG)和(220)晶面的繞射峰齡有高結晶度，高結晶度 的磁性奈米線有較整齊的砸排列會顯示較高的磁場強度，所以在含 鎳奈米線的電鑄樹|面上測得獨強為2. 4高顺叫。 11 1304843 [比較例二]士°同實例六的電鑄錄箱，但是減版並未施行陽極處理， 就如同氧化軸孔_深寬比值為零，所以如同實例六電鑄後所獲得 的電鑄錄社就無鎳奈米線的存在m齡電鑄鎳本純質的磁場 強度，測得磁場強度值僅有〇. 6高斯。 [實例七]細實例二之多孔性氧化賴，同時也依照實例六之方式電 鑄鎳4 ’但疋第二次陽極處理時間增為7. 5小時，所以有62微米的孔 洞厚度’亦即氧化铭膜孔洞的深寬比提升至155，電鑄後之電鑄鎳猪就 有面含有較尚深寬比的鎳奈米線。第(3)圖即顯示以10 %氫氧化鈉 溶液去除電鑄後德純他驗所獲取之電鑄職面義奈米線之 萬七電子顯微鏡照片，顯示出規則性六角柱形的鎳奈米線，將第(3) 圖放大成二萬倍電子顯微鏡照片的第⑷圖就更清楚的顯示此些規則性 八角柱形的錄奈米線。帛(5)圖為第(4)圖的示意圖。因為高深寬比的 磁吐金屬奈米線有較高的磁場強度，所以在含鎳奈米線的電鑄鎳落面 上測得之磁場強度增至21.6高斯(gauss)。與實例六比較後可清楚 的m明磁性金屬之奈米金屬線的磁場強度與其深寬比有關，並且隨深 寬比而加大，所以改變鋁氧化膜孔洞的深寬比並施行電鑄，就可改變 電鑄件表面的磁場強度，穫得具有非均勻磁場強度的電鑄件。 [實例八]採用實例二之多孔性氧化鋁膜，同時也依照實例七之方式電 鑄鎳金屬，但是鋁陽極處理前以防鍍膠帶貼住部分的鋁表面，使鋁表The splash-bonded gold layer is thicker, and the sunny reverse overcomes the sleek _ non-conductivity and becomes a stencil suitable for electroforming. The electroformed stencil is placed in an amine-containing acid-receiving and arsenic acid electrolyte, and each liter of the electrolyte towel also contains 0.2 g-off, and nickel electroforming is carried out at a current density of 5 G 〇c and 丨an cake square inch. Hours, and then the money % sodium hydroxide solution to remove the electric prayer. After the oxidation of Na Na, there is a surface-scale scale, the composition of the nickel nanowire is also determined by X-ray energy spectrum analyzer. These nickel nanowires have high crystallinity at the diffraction peak age of the (111) (2GG) and (220) crystal planes, and the magnetic crystal nanowires with high crystallinity have a relatively uniform flaw. The arrangement will show a higher magnetic field strength, so the surface of the electroformed tree containing the nickel nanowires is measured to be 2. 4 high. 11 1304843 [Comparative Example 2] The electrocasting box of the same example as the sixth example, but the reduced version is not subjected to anodizing, just like the oxidation shaft hole _the aspect ratio is zero, so the electricity obtained after the example six electroforming The Casting Society has the magnetic field strength of the age-old electroformed nickel in the presence of a nickel-free nanowire. The measured magnetic field strength is only 〇. 6 Gauss. [Example 7] The porous oxide of the second example was electroformed, and the nickel 4' was electroformed according to the method of Example 6. However, the second anode treatment time was increased to 7.5 hours, so there was a hole thickness of 62 μm. The aspect ratio of the oxidized Ming film hole is raised to 155, and the electroformed nickel pig after electroforming has a nickel nanowire with a relatively deep aspect ratio. Figure (3) shows the electron micrograph of the electro-casting face-named nano-line taken by Dechun Heji after removing electroforming at 10% sodium hydroxide solution, showing the regular hexagonal column of nickel naphthalene In the rice noodle, the (4) image which magnifies the (3) figure into a 20,000-fold electron microscope photograph more clearly shows the regular octagonal column-shaped nanowires.帛(5) is a schematic diagram of the figure (4). Because the high aspect ratio magnetic spit metal nanowire has a higher magnetic field strength, the magnetic field strength measured on the electroformed nickel falling surface of the nickel-containing nanowire increases to 21.6 gauss. Comparing with Example 6, it is clear that the magnetic field strength of the magnetic metal nanowire is related to its aspect ratio and increases with the aspect ratio, so the aspect ratio of the aluminum oxide film hole is changed and electroforming is performed. The strength of the magnetic field on the surface of the electroformed part can be changed to obtain an electroformed part having a non-uniform magnetic field strength. [Example 8] The porous aluminum oxide film of Example 2 was used, and nickel metal was electroformed in the same manner as in Example 7, except that the aluminum surface was adhered to the aluminum surface before the aluminum anode treatment, so that the aluminum surface was made.
12 1304843 面只有選擇的部分面積有陽極處理，則其獲得之電鑄鎳金屬也只有相 對的部分表面含有鎳奈米金屬線，所以使電鑄的鎳金屬件也只有部分 表面有高磁場強度，是具有非均勻磁場強度的電鑄件。 [實例九]採用實例二之多孔性氧化鋁膜，同時也依照實例七之方式電 鑄鎳金屬，但是陽極處理之鋁材為直徑為3毫米而長為6公分的圓柱 體，鋁材於陽極處理前以2公分寬之防鍍膠帶環狀貼在鋁材圓柱體上 丨 下兩端，使鋁材只呈現寬為2公分之中央環狀的陽極處理面積，於陽 極處理後去除防鍍膠帶並進行電鑄，鎳電鑄後去除鋁與氧化鋁膜後就 可獲得管狀的電鑄鎳，相對於環狀的陽極處理面積此管狀電鑄鎳件的 内壁中央呈現有寬為2公分之環狀部分的高磁場強度，是具有非均勻 磁場強度的電鑄件。 [實例十]依實例四的在硫酸電解質中以10伏特電壓獲取之多孔性氧 1 化銘膜’於填酸溶液中擴孔後製取氧化紹膜的孔洞孔徑約為20奈米而 長約為600奈米，並於硫酸钻及硼酸之電鑄溶液中電鑄鈷金屬，使鈷 金屬面上flb有/未寬比30的銘金屬奈米線，測其抗磁性(C〇erCivity)高達 1550 奥斯特(〇e，oersteds)。 [實例十一]類似實例三的在草酸電解質中以20伏特電壓獲取之多孔 性氧化鋁膜，於磷酸溶液中擴孔後的氧化鋁膜孔洞孔徑約為5〇奈米而 長約為350奈米，並於硫酸亞鐵及硼酸之電鑄溶液中電鑄鐵金屬，使 13 1304843 電鑄的鐵金屬表面上能有深寬比7的鐵金屬奈米線，測其抗磁性高達 1250奥斯特。 [比較例三]如同實例十一的電鑄鐵金屬但是銘模版並未進行陽極處 理就如同氧化銘膜孔洞的深寬比值為零，所以如同實例十一電禱後 所獲得的電鑄鐵社就無鐵奈鱗的存在n齡電鑄鐵本身材質 的磁性，測其抗磁性只有100奥斯特。 [貝例十—]採用實例二之纽性氧化賴，同時也賴實例六之方式 於胺基續_、胺基俩亞鐵及概之電鑄溶液中電鑄出錄鐵高導磁 合金(pemmlby) ’測得磁場強度值達3G 6高斯。 [實例十一]知用實例二之多孔性氧化紹膜，但是依照實例七之方式於 含胺基s酸鎳、職細鋪電解質巾進行制内健鑄2小時後並 且經清洗乾额才贿金難，絲於雜额銅輯雜巾進行銅 電鑄達6〇从米厚’而後以1G %氫氧化鈉溶液去除電鑄後之贿氧化銘 懈树鑄件的選擇 «上能有高磁韻度的性f，_奈錄的成分也彻儀測定。 進一步地，此鋼電鑄件的含錄奈米線之面可進行銅電鍍加厚至填平鎳 奈米線的厚度’並進行拋平工作，使鎳奈米線端與平面齊，形成在銅 金屬電鑄件的—面有高磁場強度_奈米線鑲埋細，蚁具有非均 勻磁場強度的電鎿件。 14 1304843 上述實例係說明本發明的實用性，但此些實例無意限制本發明的 可行性。贼地，本發明涵魏有可能包括在所”請專利範圍所界 定之精神及範圍之替代、修正及其相等者。 【圖式簡單說明】 所 第⑴圖、齡屬於顧濃度〇·6Μ時進行2小時的第二次陽極處理 獲取之規雜六鱗窩多孔性氧傾朗1倍電子驗鏡照片圖 第⑵圖、齡屬於姉農度1Μ時進行7.5小時的第二次陽極處理所 獲取之賴性六鱗窩純幽咖的1倍轩驗鏡照片圖。 第⑶圖、深寬比⑸的規則性六角柱形錄奈米線之一萬倍電子顯微 鏡照片圖。 微 第⑷圖、綠t⑸職丨性六妹_奈鱗之三萬倍電子顯 鏡照片圖。 第（5)圖、為第4圖的示意圖’係在電鑄鎳箔 白10上的規則性六角柱形 鎳奈米線11。 ‘ 代表符號說明 10電鑄鎳箔 11規則性六角柱形鎳奈米線 1512 1304843 Only the selected part of the surface is anodized, and the electroformed nickel metal obtained by the surface only contains the nickel nanowires on the opposite part of the surface, so that the electroformed nickel metal parts have only a part of the surface with high magnetic field strength. It is an electroformed part with a non-uniform magnetic field strength. [Example 9] The porous alumina film of Example 2 was used, and the nickel metal was electroformed according to the method of Example 7, but the anodized aluminum material was a cylinder having a diameter of 3 mm and a length of 6 cm, and the aluminum was at the anode. Before the treatment, the anti-plating tape of 2 cm width is attached to the lower end of the aluminum cylinder, so that the aluminum material only exhibits a central annular anodized area of 2 cm wide, and the anti-plating tape is removed after the anode treatment. And electroforming, after removing the aluminum and aluminum oxide film by nickel electroforming, a tubular electroformed nickel can be obtained, and the inner wall of the tubular electroformed nickel piece has a width of 2 cm in width with respect to the annular anode treated area. The high magnetic field strength of the shaped portion is an electroformed part having a non-uniform magnetic field strength. [Example 10] According to the fourth example, the porous oxygen obtained in the sulfuric acid electrolyte at a voltage of 10 volts is used to refine the pores in the acid solution to obtain a pore diameter of about 20 nm and a length of about 20 nm. It is 600 nm, and electroformed cobalt metal in the electroforming solution of sulfuric acid drill and boric acid, so that the cobalt metal surface has a flb with/without width ratio of 30 metal nanowires, and its magnetic resistance (C〇erCivity) is as high as 1550 Oster (〇e, oersteds). [Example 11] A porous alumina film obtained by using a voltage of 20 volts in an oxalic acid electrolyte similarly to Example 3, the pore diameter of the alumina film after reaming in a phosphoric acid solution is about 5 Å and the length is about 350 Å. Meter, and electric cast iron metal in the electroforming solution of ferrous sulfate and boric acid, so that 13 1304843 electroformed iron metal surface can have an aspect ratio of 7 iron metal nanowires, measuring its diamagnetic resistance up to 1250 Oersted . [Comparative Example 3] Like the electric cast iron metal of the eleventh example, but the inscription plate is not anodized, just as the aspect ratio of the pores of the oxidized inscription film is zero, so the electric cast iron company obtained after the example eleven electric prayers has no The existence of the iron scales is the magnetic properties of the n-age electric cast iron itself, and its diamagnetic resistance is only 100 Oersted. [Bei Shi Shi-] The use of the second example of the oxidation of Lai, but also rely on the example of the six methods in the amine continued _, the amine two ferrous iron and the electroforming solution electrocasted iron recording high magnetic alloy ( Pemmlby) 'Measured magnetic field strength values up to 3G 6 Gauss. [Example 11] It is known to use the porous oxidized film of the second example, but according to the method of the seventh embodiment, the nickel-containing s-acid sulphate and the fine-layered electrolyte towel are used for the inner casting for 2 hours and the cleaned amount is bribed. Difficult, the silk in the miscellaneous copper series of miscellaneous towels for copper electroforming up to 6 〇 from the thickness of the rice and then to remove the electroforming after 1G% sodium hydroxide solution, the choice of bribes and oxidation of the tree castings «There can be high magnetic rhyme The composition of the sex f, _ Nailu is also measured. Further, the surface of the steel electroforming part containing the recorded nanowire can be thickened by copper plating to fill the thickness of the nickel nanowire and perform the flattening work, so that the nickel nanowire end is flush with the plane and formed in the copper. The surface of the metal electroformed part has a high magnetic field strength. The nanowire is inlaid finely, and the ant has a non-uniform magnetic field strength. 14 1304843 The above examples illustrate the utility of the invention, but such examples are not intended to limit the scope of the invention. In the case of thieves, the invention may include substitutions, amendments and equivalents of the spirit and scope defined by the scope of the patent. [Simplified description of the schema] The figure (1) and the age belong to the concentration of 〇·6Μ Obtained in the second anodizing treatment obtained by the second anodizing treatment for 2 hours, and obtained by the second anodizing treatment of the hexavalent fossil porous oxygen oxidized 1x electron inspection photograph (2) and the age of 1 姊Photograph of the 1x Xuan Mirror of the 6th-six-spot pure café. The (3), the aspect ratio (5) of the regular hexagonal column of the nanowire is a million times electron micrograph. Micro (4), Green t (5) professional six-sex _ 30,000 scale electronic photomicrograph of Nai scale. The (5) picture, the schematic diagram of Figure 4 is a regular hexagonal cylindrical nickel-neon on electroformed nickel foil white 10 Rice noodles 11. ' Representative symbol description 10 electroformed nickel foil 11 regular hexagonal cylindrical nickel nanowires 15