TW201843359A - A method for making a tubular anodic aluminum oxide with nanometer or sub-micron pores - Google Patents
A method for making a tubular anodic aluminum oxide with nanometer or sub-micron pores Download PDFInfo
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本發明專利提出一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法用於製作高品質之管狀奈米薄膜，利用此方法所作出的產品能夠應用在能源產業與環保材料，同時也提升了陽極處理技術的附加價值與鋁材在高科技產業上的應用。 The invention proposes a method for manufacturing a tubular aluminum anode treated film having nano or submicron pores for producing a high quality tubular nano film, and the product made by the method can be applied to the energy industry and environmentally friendly materials, and also Increased the added value of anodizing technology and the application of aluminum in high-tech industries.
陽極處理由來被定義為成熟的傳統產業，其主要的應用如表面抗腐蝕、塗裝、裝飾、電絕緣、表面電鍍、耐磨性等表面改質應用，由於陽極氧化膜的多孔性結構，其後續需再經封孔處理步驟，應用時方能具有美觀與多色彩化的緻密膜。近年來由於奈米技術的發展，也使得在陽極氧化膜管胞或奈米管結構的管徑、管長、與管密度在技術上更能完整的掌控。簡便的陽極處理技術，提供成本低廉且快速量產的製程，可實際應用於要求單位表面積大的產品發展，如染料敏化太陽能電池、光觸媒、導熱片、與隔熱片元件之開發。陽極處理技術，隨著工業產品的需求，從早期針對重工業結構物表面的抗腐蝕、抗磨耗、抗撞擊、與耐高溫等表面改質 的需求，近年來更應用於蒸鍍設備之真空腔體內部的鍍膜吸收層，或積體電路內之阻障層，隨著目前最熱門的散熱材、隔熱材、殺菌材、綠建材、與太陽能電池等產業發展，具功能性的陽極處理產品，勢必將成為各產業的熱門應用端。 Anode treatment is defined as a mature traditional industry, its main applications such as surface corrosion resistance, coating, decoration, electrical insulation, surface plating, wear resistance and other surface modification applications, due to the porous structure of the anodized film, The subsequent step of sealing treatment is required, and the dense film with beautiful appearance and multi-color can be applied. In recent years, due to the development of nanotechnology, the tube diameter, tube length, and tube density of the anodized film tube or nanotube structure are technically more complete. The simple anode treatment technology provides a low-cost and fast mass production process, which can be practically applied to product development requiring large surface area per unit area, such as dye-sensitized solar cells, photocatalysts, thermal conductive sheets, and thermal insulation sheet components. Anode treatment technology, with the demand for industrial products, has been applied to the vacuum chamber of vapor deposition equipment in recent years from the early requirements for surface modification of corrosion resistance, abrasion resistance, impact resistance, and high temperature resistance of heavy industrial structures. The coating absorption layer of the part, or the barrier layer in the integrated circuit, with the development of the most popular heat-dissipating materials, heat-insulating materials, germicidal materials, green building materials, and solar cells, with functional anodized products, It is bound to become a popular application end of various industries.
利用電化學技術製作高品質之奈米管結構觸媒板，使觸媒板獲得最大可用之反應表面積，當鋁置於特定的電解液中且控制適當的陽極處理參數，所形成的氧化膜具有規則狀的胞狀(cell)或奈米管結構，奈米管末端與鋁材的介面則形成半球形的阻障層，末端阻障層可利用化學溶液將其溶解，使氧化膜形奈米直通管，奈米管的直徑、管密度、管壁厚度、與管長則依陽極處理之外加電壓、電解液成分、與電解液溫度參數而定，此輕量化、可量化計算評估之大表面積、低成本、化學穩定性與熱穩定性佳之的觸媒薄膜適用於高溫二氧化碳捕獲與轉換所需的材料，可進一步利用凝膠凝固法(sol-gel)、化學鍍(electroless-deposition)、電鍍法(electro-deposition)、或真空沉積法(vacuum-deposition)將二氧化鈦(TiO2)、二氧化鋯(ZrO2)、銅(Cu)、鐵(Fe)、鋅(Zn)、與鉑黑(Pt)、鎳(Ni)、金(Au)、銀(Ag)、或合金(Alloy)置放在觸媒板表面。 Electrochemical technology is used to fabricate high-quality nanotube structure catalyst plates, so that the catalyst plate can obtain the maximum available reaction surface area. When aluminum is placed in a specific electrolyte and the appropriate anode treatment parameters are controlled, the formed oxide film has Regular cell or nanotube structure, the interface between the end of the nanotube and the aluminum material forms a hemispherical barrier layer, and the terminal barrier layer can be dissolved by a chemical solution to form an oxide film-shaped nanometer. Through-tube, the diameter of the nanotube, the tube density, the wall thickness, and the length of the tube are determined by the anode treatment plus voltage, electrolyte composition, and electrolyte temperature parameters. This lightweight, quantifiable calculation evaluates the large surface area. The catalyst film with low cost, good chemical stability and thermal stability is suitable for materials required for high temperature carbon dioxide capture and conversion, and can further utilize sol-gel, electroless-deposition, electroplating (electro-deposition), or vacuum-deposition, titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), copper (Cu), iron (Fe), zinc (Zn), and platinum black (Pt ), nickel (Ni), gold (Au), silver (Ag), or alloy (Alloy) placed on the surface of the catalyst plate.
學術或研究單位在製作小面積奈米結構觸媒板時可簡單地控制所需的實驗條件，但是當樣品尺寸與數量放大至工業界量產時卻常常面臨到電流密度和溫度不穩定的問題，針對大型或大量觸媒薄膜在反應過程中電流密度控制的穩定性，使具有孔洞結構性的鋁陽極處理薄膜在產業上的應用受到了阻礙。 Academic or research units can simply control the required experimental conditions when making small-area nanostructured catalyst plates, but often suffer from current density and temperature instability when sample size and quantity are scaled up to industrial mass production. For the stability of current density control during the reaction of large or large amount of catalyst film, the industrial application of the porous anodized film with pore structure has been hindered.
本發明專利提出一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法用於製作高品質之管狀奈米薄膜，利用此方法所作出的產品能夠應用在能源產業與環保材料，同時也提升了陽極處理技術的附加價值與鋁材在高科技產業上的應用。 The invention proposes a method for manufacturing a tubular aluminum anode treated film having nano or submicron pores for producing a high quality tubular nano film, and the product made by the method can be applied to the energy industry and environmentally friendly materials, and also Increased the added value of anodizing technology and the application of aluminum in high-tech industries.
本發明是關於一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法，主要是利用電解拋光和陽極處理法在鋁管表面成長一層具有孔洞結構性的鋁陽極處理膜，進一步移除部分鋁基材後，可得雙邊具有鋁管連接的管狀鋁陽極處理膜，此孔洞結構排列隨著鋁基材的純度而變化，當陽極膜成長於純度較差的鋁基材時，例如，陽極膜成長於6061鋁材時，孔洞的排列比較散亂，另外，當陽極膜成長於純度較高的鋁基材時，例如，陽極膜成長於99.999%(5N)純度鋁材時，孔洞的排列較整齊，此具有孔洞結構的管狀陽極膜可進一步被應用於能源轉換、光觸媒、或高階過濾所需的載體材料。 The invention relates to a method for manufacturing a tubular aluminum anode treated film having nano or submicron pores, which mainly uses an electrolytic polishing and anodizing method to grow a layer of aluminum anode treated film having a hole structure on the surface of the aluminum tube, and further removes After a part of the aluminum substrate, a tubular aluminum anode treatment film having an aluminum tube connection is obtained, and the pore structure is changed according to the purity of the aluminum substrate, and when the anode film is grown on a poorly-purified aluminum substrate, for example, an anode When the film is grown on the 6061 aluminum material, the arrangement of the holes is relatively disordered. When the anodic film is grown on a highly pure aluminum substrate, for example, when the anodic film is grown in a 99.999% (5N) purity aluminum material, the arrangement of the holes is performed. More tidy, this tubular anode film with a porous structure can be further applied to energy conversion, photocatalyst, or carrier materials required for high-order filtration.
本發明專利之特點在於(1)陽極製程簡單化：利用成熟傳統產業之陽極處理技術可量產化製作具有奈米或次微米孔洞的管狀鋁陽極處理膜、(2)製作材料簡單：僅需鋁管、(3)製作成本低：不須用到任何真空設備就可製作出具有奈米或次微米孔洞的結構性氧化膜、(4)此化學穩定性高的結構性氧化膜可被應用於高附加價值的能源轉換、藥物釋放、濾材、感測、或光觸媒所需的載體材料、(5)管狀外觀立體式與多樣化的設計易於搭配3C產品的設計、(6)管狀立體式與攜帶方便式的設計可提升產品的設計與消費者的購買意願。 The invention patent is characterized in that (1) the anode process is simplified: the tubular aluminum anode treatment film with nano or submicron holes can be mass-produced by using the anode treatment technology of the mature traditional industry, and (2) the production material is simple: only need Aluminum tube, (3) low manufacturing cost: a structural oxide film with nano or sub-micron holes can be produced without using any vacuum equipment, and (4) a structural oxide film with high chemical stability can be applied. High-value-added energy conversion, drug release, filter media, sensing, or carrier materials required for photocatalyst, (5) tubular appearance, three-dimensional and diverse design, easy to match 3C product design, (6) tubular stereo and Carrying a convenient design enhances the design of the product and the willingness of the consumer to purchase.
管狀陽極膜具相較於板狀陽極膜的外觀新穎性與結構應用創新性的特性，結構性之鋁陽極膜，在學術或研究單位屬於一種成熟的技術，但是在產業界卻很少看到此陽極膜在相關研究或產品上的應用，本專利也希望藉由改變大多數人對平面式板狀陽極膜的印象，而提出一創新的立體式管狀陽極膜的構想，使結構性之鋁陽極膜在未來能夠獲得更多學術、研究單位、和產業界的應用。此管狀結構性之鋁陽極膜更可提供乾式氣流和濕式液流在奈米(次微米)管內流通特性的研究，而本專利也將在管狀陽極膜內通入液體來驗證在液體在管狀陽極膜表面滲透的特徵。 The tubular anodic film has a novelty in appearance and structural innovation compared to the appearance of the anodic anodic film. The structural aluminum anodic film is a mature technology in academic or research units, but it is rarely seen in the industry. The application of the anode film in related research or products, this patent also hopes to propose an innovative three-dimensional tubular anode film by changing the impression of most people on the planar plate anode film, so that the structural aluminum Anode films can be used in more academic, research, and industrial applications in the future. The tubular structural aluminum anode film can provide a study of the flow characteristics of dry gas flow and wet liquid flow in a nanometer (submicron) tube, and this patent will also pass a liquid into the tubular anode film to verify that the liquid is in the liquid. The characteristics of the surface penetration of the tubular anodic membrane.
本發明專利之管狀陽極氧化鋁膜分別利用6061鋁管與高純度(99.999%，5N)鋁管製成。習知之平板狀的結構性陽極氧化鋁膜在學術界或產業界上已經被研究開發幾十年了，近年市面上已經開始販售平板狀的結構性陽極氧化鋁膜，例如：InRedox ( http：//www.inredox.com/product/aao-wafers/ )、上海上木科技有限公司 ( http：//www.nano-star.com/show258.html )、Sigma-Aldrich ( http：//www.sigmaaldrich.com/labware/labware-products.html？TablePage=109501875 ) The tubular anodized aluminum oxide film of the present invention is made of a 6061 aluminum tube and a high purity (99.999%, 5N) aluminum tube, respectively. Conventional flat-shaped structured anodized aluminum oxide membranes have been researched and developed in academia or industry for decades. In recent years, flat-shaped structural anodized aluminum oxide films have been sold on the market, for example: InRedox ( http: //www.inredox.com/product/aao-wafers/ ), Shanghai Shangmu Technology Co., Ltd. ( http://www.nano-star.com/show258.html ), Sigma-Aldrich ( http://www. sigmaaldrich.com/labware/labware-products.html?TablePage=109501875 )
針對管狀的結構性陽極氧化鋁膜，目前研究單位或科技公司尚未有任何文獻報告或產品呈現。相較於板狀結構性陽極氧化鋁膜，管狀結構性陽極氧化鋁膜具有其特殊的特徵與應用的價值。針對此一具有高應用附加價值管狀結構性陽極氧化鋁膜，本發明專利提出一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法，該製程中主要包含電解拋光與陽極處理方法。 For tubular structural anodized aluminum membranes, there are currently no literature reports or product presentations by research units or technology companies. Compared with the plate-like structured anodized aluminum film, the tubular structural anodized aluminum film has its special characteristics and application value. In view of the tubular anodic aluminum oxide film having high application added value, the present invention proposes a method for manufacturing a tubular aluminum anode treated film having nano or submicron pores, and the process mainly comprises an electrolytic polishing and an anode treatment method.
此管狀陽極氧化鋁膜兩側具有鋁管連接，陽極氧化鋁膜具有孔徑為5~500nm、孔密度為108~1011孔/cm2、膜厚為5~500μm的顯微結構。陽極膜的表面與底面具有開孔之通道，陽極膜兩側鋁管可連接氣體或液體，該氣體或液體可在兩端開孔的管狀陽極膜的內表面和外表面之間進行氣體或液體的擴散或滲出作用。具有滲出和擴散特徵的管狀AAO材料可進一步用於先進技術，例如，液體(氣體)過濾器，藥物釋放，氫能生產。 The tubular anodized aluminum film has aluminum tubes connected on both sides thereof, and the anodized aluminum film has a microstructure with a pore diameter of 5 to 500 nm, a pore density of 10 8 to 10 11 pores/cm 2 and a film thickness of 5 to 500 μm. The surface of the anode film and the bottom surface have openings, and the aluminum tubes on both sides of the anode film can be connected with a gas or a liquid, and the gas or liquid can be gas or liquid between the inner surface and the outer surface of the tubular anode film with open ends. Diffusion or exudation. Tubular AAO materials with exudation and diffusion characteristics can be further used in advanced technologies such as liquid (gas) filters, drug release, and hydrogen energy production.
根據本發明所提的一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法，該具有奈米或次微米孔洞的管狀鋁陽極處理膜的結構圖如第1圖所示，其中(a)為平面結構圖、(b)為立體結構圖、包含：多孔性鋁陽極氧化膜11、13，鋁管12、12’、14、14，多孔性鋁陽極氧化膜具有使液體或氣體滲透或擴散的功能，鋁管具有機械性連接的功能。第2圖顯示具有氣(液)連接管之管狀鋁陽極處理膜結構圖，包含：多孔性鋁陽極氧化膜21、氣(液)體接頭22、22’、氣(液)體管23、23’，因此液體或氣體可以透過氣(液)體接頭與氣(液)體管在管狀鋁陽極氧化膜的內表面與外表面間進行滲透或擴散的作用。 A method for fabricating a tubular aluminum anodized film having nano or submicron pores according to the present invention, wherein the structural view of the tubular aluminum anodized film having nano or submicron pores is as shown in Fig . 1 , wherein a) is a planar structure diagram, (b) is a three-dimensional structure diagram, and includes: a porous aluminum anodized film 11 , 13 and aluminum tubes 12, 12', 14 , and 14. The porous aluminum anodized film has a liquid or gas permeation. Or the function of diffusion, the aluminum tube has the function of mechanical connection. Fig. 2 is a structural view showing a tubular aluminum anodized film having a gas (liquid) connecting tube, comprising: a porous aluminum anodized film 21, a gas (liquid) body joint 22, 22', and a gas (liquid) body tube 23, 23 ', therefore liquid or gas can penetrate or diffuse through the gas (liquid) body joint and the gas (liquid) body tube between the inner and outer surfaces of the tubular aluminum anodized film.
蓋因，鋁陽極處理過程需要經過多道溶液的反應與清洗，為了能夠大量且快速的製作管狀鋁陽極處理薄膜，鋁陽極處理過程中需經過多道溶液反應與水洗的流程，包括：電解拋光液、陽極處理液、陽極膜去除液、鋁去除液、擴孔液、與水洗液，為了能夠方便的操作陽極處理流程，並且管理要液的品質，本專利也設計了一簡便型的鋁陽極處理薄膜製作流程規劃，包括：將批量化的鋁管置於掛架式的載具內，使批量化的鋁管進行 後續的陽極處理、利用吊架來移動掛架載具，使載具可以在各水槽中進行反應與清洗。 Gain, aluminum anode treatment process requires multiple solutions of reaction and cleaning. In order to produce tubular aluminum anode treatment film in large quantities and quickly, the process of aluminum anode treatment requires multiple solution reaction and water washing processes, including: electrolytic polishing. Liquid, anode treatment liquid, anode membrane removal liquid, aluminum removal liquid, reaming liquid, and water washing liquid, in order to facilitate the operation of the anode treatment process and to manage the quality of the liquid, this patent also designs a simple aluminum anode. Processing the film production process plan, including: placing the batched aluminum tube in the rack-type carrier, performing the subsequent anode treatment on the batch aluminum tube, and using the hanger to move the rack carrier, so that the vehicle can be The reaction and washing were carried out in each water tank.
第3圖顯示具有批次量產特性之陽極處理掛具，此掛具可以輔助管狀鋁陽極氧化膜進行量產，該掛具的結構包含不導電的治具座33，治具座下方具有複數個圓形孔洞，用以安置鋁管用、導電的電極板34，電擊板上具有複數個圓形孔洞，用以固定鋁管用、複數根治具座連接柱35，用以連接治具座與電極板、電極36，用以電解拋光或陽極處理時外加電壓(流)用、鋁管31***電極板孔洞中並安置於治具座下方的圓形孔洞上、矽膠塞32，塞在鋁管下方，鋁管內通入水，使得鋁管在進行電解拋光或陽極處理時可以獲得冷卻用。 Figure 3 shows an anodized rack with batch production characteristics. This rack can assist in the mass production of a tubular aluminum anodized film. The structure of the rack contains a non-conductive fixture holder 33. a circular hole for arranging the aluminum tube and the conductive electrode plate 34. The electric shock plate has a plurality of circular holes for fixing the aluminum tube and the plurality of root holder connecting columns 35 for connecting the fixture seat and the electrode plate. The electrode 36 is used for applying voltage (flow) during electrolytic polishing or anodic treatment, and the aluminum tube 31 is inserted into the hole of the electrode plate and placed on the circular hole below the fixture seat, and the rubber stopper 32 is inserted under the aluminum tube. Water is introduced into the aluminum tube so that the aluminum tube can be cooled for electropolishing or anodizing.
多孔性鋁陽極膜的顯微結構可根據陽極處理製程參數改變，例如，電壓、電解液成份、陽極處理時間的變化，達到控制奈米管的孔徑(5至500nm)、薄膜厚度(5至500μm)、管密度(108至1011管/cm2)，此規則性之奈米管結構將有效地發揮其大比表面積特性，並可提升載體的單位表面積，利用規則多孔性氧化鋁為載體的特點還包含有利於後續源轉換效率的準確計算與評估。半導體晶圓等級要求之高品質奈米管結構氧化鋁薄膜製程包含：機械研磨、應力消除、電解拋光、第一次陽極處理、移除陽極處理膜、第二次陽極處理、鋁管兩端樹脂保護、移除鋁基材、去除阻障層、與擴孔等10步驟。其詳細管狀結構鋁陽極膜製程如下： The microstructure of the porous aluminum anode film can be changed according to the anode treatment process parameters, for example, voltage, electrolyte composition, and anode treatment time, to control the pore diameter (5 to 500 nm) of the nanotube, and the film thickness (5 to 500 μm). ), tube density (10 8 to 10 11 tubes / cm 2 ), this regular nanotube structure will effectively exert its large specific surface area characteristics, and can increase the unit surface area of the carrier, using regular porous alumina as a carrier The features also include accurate calculations and evaluations that facilitate subsequent source conversion efficiencies. High-quality nanotube structure alumina film process required for semiconductor wafer grades includes: mechanical grinding, stress relief, electrolytic polishing, first anodizing, removal of anodized film, second anodizing, resin at both ends of aluminum tube 10 steps of protecting, removing the aluminum substrate, removing the barrier layer, and reaming. The detailed tubular structure of the aluminum anode film process is as follows:
(1)機械研磨：鋁或鋁合金管(10xx、20xx、30xx、40xx、50xx、60xx、70xx、80xx)或高純度5N(99.999%)鋁管經機械研磨至細號砂紙。 (1) Mechanical grinding: aluminum or aluminum alloy tubes (10xx, 20xx, 30xx, 40xx, 50xx, 60xx, 70xx, 80xx) or high purity 5N (99.999%) aluminum tubes are mechanically ground to fine sandpaper.
(2)應力消除：將鋁管置於大氣爐內進行應力消除的退火處理。 (2) Stress relief: The aluminum tube is placed in an atmospheric furnace for stress relief annealing treatment.
(3)電解拋光：將退火後之鋁管置於電解槽中進行電解拋光。 (3) Electropolishing: The annealed aluminum tube is placed in an electrolytic bath for electrolytic polishing.
(4)第一次陽極處理：將電解拋光後之鋁管進行短時間的第一次陽極處理。 (4) First anodizing treatment: The electrolytically polished aluminum tube was subjected to a first anodizing treatment for a short time.
(5)移除陽極處理膜：移除第一次陽極處理膜，使鋁管表面上殘留規則性的圖樣(pattern)。 (5) Removal of the anodized film: The first anodized film was removed to leave a regular pattern on the surface of the aluminum tube.
(6)第二次陽極處理：將表面具有規則性圖樣的鋁管進行長時間的第二次陽極處理。 (6) Second anodizing treatment: The aluminum tube having a regular pattern on the surface was subjected to a second anodizing treatment for a long time.
(7)鋁管兩端樹脂保護：利用浸漬法將鋁管兩端依序浸漬至樹脂中，利用樹脂包護鋁管，使兩端鋁管不參與後續鋁移除液的反應。 (7) Resin protection at both ends of the aluminum tube: Both ends of the aluminum tube are sequentially impregnated into the resin by dipping, and the aluminum tube is covered with the resin so that the aluminum tubes at both ends do not participate in the reaction of the subsequent aluminum removal liquid.
(8)移除鋁基材：將鋁移除液通入鋁管內，移除受樹脂包護以外的鋁管基材，並獲得兩端具有鋁管接觸，且管中間部分不含鋁基材的半透明陽極處理薄膜。 (8) Removing the aluminum substrate: the aluminum removal liquid is introduced into the aluminum tube, the aluminum tube substrate other than the resin coating is removed, and the aluminum tube is contacted at both ends, and the middle portion of the tube does not contain the aluminum base. A translucent anodized film of material.
(9)去除阻障層：將阻障層移除液通入鋁管內，移除管內的阻障層。 (9) Removing the barrier layer: the barrier layer removal liquid is introduced into the aluminum tube, and the barrier layer in the tube is removed.
(10)擴孔：將管狀陽極處理膜浸漬在擴孔液中進行擴孔反應。 (10) Reaming: The tubular anodized film is immersed in a reaming liquid to carry out a pore expanding reaction.
以下更詳細的說明管狀結構鋁陽極膜的製程參數： The process parameters of the tubular aluminum anode film are described in more detail below:
(1)機械研磨：鋁或鋁合金管(10xx、20xx、30xx、40xx、50xx、60xx、70xx、80xx)或高純度5N(99.999%)鋁管經機械研磨至#2000號碳化矽(SiC)砂紙。 (1) Mechanical grinding: aluminum or aluminum alloy tubes (10xx, 20xx, 30xx, 40xx, 50xx, 60xx, 70xx, 80xx) or high purity 5N (99.999%) aluminum tubes are mechanically ground to #2000 No. SiC (SiC) sandpaper.
(2)應力消除：將鋁管置於大氣爐內進行應力消除的退火處理(550℃、1小時)。 (2) Stress relief: The aluminum tube was placed in an atmospheric furnace for stress relief annealing (550 ° C, 1 hour).
(3)電解拋光：將退火後之鋁管置於電解槽中進行電解拋光，電解液的成份 為15vol.% HClO4+15vol.% CH3(CH2)3OCH2CH2OH+70vol.% C2H6O，電解拋光條件為42伏特(V)、15℃、10分鐘。 (3) Electropolishing: The annealed aluminum tube is placed in an electrolytic bath for electrolytic polishing. The composition of the electrolyte is 15 vol.% HClO 4 +15 vol.% CH 3 (CH 2 ) 3 OCH 2 CH 2 OH+70 vol. % C 2 H 6 O, electropolishing conditions were 42 volts (V), 15 ° C, 10 minutes.
(4)第一次陽極處理：將電解拋光後之鋁管進行短時間的第一次陽極處理，電解液的成份為磷酸(H3PO4)、草酸(C2H2O4)、硫酸(H2SO4)、或以上所述酸之混酸水溶液，陽極處理條件為5~300伏特、-10~40℃、5~200分鐘。 (4) The first anodizing treatment: the electrolytically polished aluminum tube is subjected to the first anodizing treatment for a short time, and the composition of the electrolytic solution is phosphoric acid (H 3 PO 4 ), oxalic acid (C 2 H 2 O 4 ), sulfuric acid. (H 2 SO 4 ), or an aqueous mixed acid solution of the above acid, the anode treatment conditions are 5 to 300 volts, -10 to 40 ° C, and 5 to 200 minutes.
(5)移除陽極處理膜：移除第一次陽極處理膜，使鋁管表面上殘留規則性的圖樣(pattern)，移除液成份為1.8wt.%鉻酸(CrO3)+6vol.%磷酸(H3PO4)，操作條件為：將陽極處理後之鋁管材浸漬於移除液中40~90℃、10~360分鐘。 (5) Removing the anodized film: removing the first anodized film, leaving a regular pattern on the surface of the aluminum tube, the removal liquid composition is 1.8 wt.% chromic acid (CrO 3 ) + 6 vol. % phosphoric acid (H 3 PO 4 ), operating conditions are: immersing the anodized aluminum tube in the removal solution at 40-90 ° C for 10 to 360 minutes.
(6)第二次陽極處理：將表面具有規則性圖樣的鋁管進行長時間的第二次陽極處理，電解液的成份為磷酸(H3PO4)、草酸(C2H2O4)、硫酸(H2SO4)、或以上所述酸之混酸水溶液，陽極處理條件為5~300伏特、-10~40℃、5~200分鐘。 (6) The second anodizing treatment: the aluminum tube having a regular pattern on the surface is subjected to a second anodizing treatment for a long time, and the composition of the electrolyte is phosphoric acid (H 3 PO 4 ) and oxalic acid (C 2 H 2 O 4 ). And sulfuric acid (H 2 SO 4 ), or an aqueous mixed acid solution of the above acid, the anode treatment conditions are 5 to 300 volts, -10 to 40 ° C, and 5 to 200 minutes.
(7)鋁管兩端樹脂保護：利用浸漬法將鋁管兩端依序浸漬至樹脂中，利用樹脂包護鋁管，使兩端鋁管不參與後續鋁移除液的反應，操作條件為：將鋁管的一端浸漬在樹脂溶液中，取出乾燥後，再將另一端鋁管浸漬在樹脂溶液中，並取出乾燥。 (7) Resin protection at both ends of the aluminum tube: Both ends of the aluminum tube are sequentially impregnated into the resin by dipping method, and the aluminum tube is sealed by the resin, so that the aluminum tubes at both ends do not participate in the reaction of the subsequent aluminum removal liquid, and the operating conditions are : One end of the aluminum tube is immersed in the resin solution, and after taking out and drying, the other end aluminum tube is immersed in the resin solution, and taken out and dried.
(8)移除鋁基材：將鋁移除液通入鋁管內，移除受樹脂包護以外的鋁管基材，並獲得兩端具有鋁管接觸，且管中間部分不含鋁基材的半透明陽極處理薄膜，移除液成份為8vol.%鹽酸(HCl)+20wt.%氯化銅(Cul2)的水溶液，操作條件為：將陽極處理後之鋁材浸漬於移除液中25℃、2~60分鐘。 (8) Removing the aluminum substrate: the aluminum removal liquid is introduced into the aluminum tube, the aluminum tube substrate other than the resin coating is removed, and the aluminum tube is contacted at both ends, and the middle portion of the tube does not contain the aluminum base. The translucent anodized film of the material is an aqueous solution containing 8 vol.% hydrochloric acid (HCl) + 20 wt.% copper chloride (Cul 2 ), and the operating conditions are: immersing the anodized aluminum material in the removing liquid 25 ° C, 2 to 60 minutes.
(9)去除阻障層：將阻障層移除液通入鋁管內，移除管內的阻障層，阻障層移除液為5vol.%的磷酸水溶液中，25℃、0.1~5小時。 (9) Removing the barrier layer: the barrier layer removal liquid is introduced into the aluminum tube, and the barrier layer in the tube is removed, and the barrier layer removal liquid is in a 5 vol.% phosphoric acid aqueous solution, 25 ° C, 0.1~ 5 hours.
(10)擴孔：將管狀陽極處理膜浸漬在擴孔液中進行擴孔反應，擴孔液為5vol.%的磷酸水溶液中，25℃、0.1~2小時。 (10) Reaming: The tubular anodized membrane was immersed in a reaming liquid to carry out a pore-expanding reaction, and the reaming liquid was a 5 vol.% phosphoric acid aqueous solution at 25 ° C for 0.1 to 2 hours.
鋁陽極膜的顯微結構示意圖如圖4、5、6所示，其中第4圖為含有鋁基材之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。第5圖為去除鋁基材後之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。第6圖為去除鋁基材與阻障層後之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。鋁基材41、44、鋁陽極處理膜表面42、46、51、54、61、64、鋁陽極處理膜側面43、47、52、55、63、66、阻障層45、53、56、鋁陽極處理膜底面62、65。圖4(a)與(b)顯示具有規則性孔洞的鋁陽極膜成長於鋁基材表面上，陽極膜的側面影像為直通管，管末端為半球形之封閉性的阻障層，陽極膜於形成之初為六角型管狀，其乃陽極膜形成時因彼此之間的互相推擠而達應力平衡所致，隨著陽極處理時間的增長，較早形成的AAO受到電解液蝕刻後形成圓形管。圖5(a)與(b)顯示將鋁基材移除後可獲得獨立的鋁陽極膜，陽極膜管末端為明顯的半球形封閉性的阻障層，此阻障層的存在將影響氣流在陽極管內的流通。圖6(a)與(b)顯示將阻障層移除後可得雙邊開口陽極管，陽極膜的結構則是由連續性的管壁支撐著，此具有兩端開口的陽極管將有利於微小的氣流在陽極管內流通。 Aluminum anodic film microstructure as shown in FIG schematic 4,5,6, wherein FIG. 4 is a tubular aluminum anodized film of an aluminum substrate comprising a configuration diagram; (A) a perspective view, (b) a partially enlarged in FIG. FIG 5 is a tubular aluminum anodized film structure view of the aluminum substrate is removed; (A) a perspective view, (b) a partially enlarged in FIG. FIG 6 is a tubular aluminum anodized film structure view of the aluminum substrate is removed and a barrier layer; (A) a perspective view, (b) a partially enlarged in FIG. Aluminum substrates 41, 44, aluminum anodized film surfaces 42, 46, 51, 54, 61, 64, aluminum anodized film sides 43, 47, 52, 55, 63, 66, barrier layers 45, 53, 56, The aluminum anode treats the film bottom surfaces 62, 65 . 4(a) and (b) show that the aluminum anode film having regular pores grows on the surface of the aluminum substrate, the side image of the anode film is a straight tube, and the end of the tube is a hemispherical barrier layer, and the anode film is formed. At the beginning of the formation, it is a hexagonal tube, which is caused by the stress balance of each other when the anode film is formed. As the anode treatment time increases, the AAO formed earlier is etched by the electrolyte to form a circle. Shaped tube. Figures 5(a) and (b) show that the aluminum substrate can be removed to obtain a separate aluminum anode film. The end of the anode film tube is a distinct hemispherical barrier layer. The presence of this barrier layer will affect the gas flow. Circulation in the anode tube. Figure 6 (a) and (b) show that the double-opening anode tube can be obtained after the barrier layer is removed, and the structure of the anode film is supported by the continuous tube wall. The anode tube with open ends will be beneficial. A small air flow circulates in the anode tube.
第7、8、9圖管狀鋁陽極處理膜樣品的實際照片；第7圖 鋁材與鋁陽極處理實際照片；(a)鋁管、(b)表面經過電解拋光後的鋁管、(c)表 面經過陽極處理後的鋁管、(d)局部鋁基材去除後的陽極處理鋁管。第8圖管狀鋁陽極處理膜實際照片。第9圖 管狀鋁陽極處理膜之應用實際照片；(a)具有氣(液)連接管之管狀鋁陽極處理膜、(b)管內裝有水之管狀鋁陽極處理膜，管內的水可經由多孔性陽極膜的特性滲透至管外、(c)管內裝有紅墨水之管狀鋁陽極處理膜，管內的紅墨水可經由多孔性陽極膜的特性滲透至管外。 Actual photographs of tubular aluminum anodized film samples in Figures 7, 8, and 9 ; actual photographs of aluminum and aluminum anodes in Figure 7 ; (a) aluminum tubes, (b) aluminum tubes after electrolytic polishing on the surface, (c) The anodized aluminum tube after the surface is anodized, and (d) the anodized aluminum tube after the partial aluminum substrate is removed. Figure 8 Actual photo of a tubular aluminum anodized film. Figure 9 is a practical photo of the application of a tubular aluminum anodized film; (a) a tubular aluminum anodized film having a gas (liquid) connecting tube, and (b) a tubular aluminum anodized film containing water in the tube, the water in the tube may be The tubular aluminum anodized film containing red ink is infiltrated through the characteristics of the porous anodic film, and (c) the red ink in the tube is infiltrated into the outside of the tube through the characteristics of the porous anodic film.
第10、11圖管狀鋁陽極處理膜樣品的顯微影像；第10圖 利用6061鋁材製作的鋁陽極處理膜顯微結構；(a)背面顯微影像、(a)正面顯微影像。第11圖 利用高純度鋁材製作的鋁陽極處理膜顯微結構；(a)背面顯微影像、(a)正面顯微影像。比較第10與11圖的顯微影像，陽極處理膜的孔洞結構在由純鋁管表面生成相較於在6061鋁管表面生成，有較佳的孔洞排列情形。 10 and 11 are microscopic images of tubular aluminum anodized film samples; Fig. 10 Microstructure of aluminum anodized film made of 6061 aluminum; (a) back microscopic image, (a) frontal microscopic image. Figure 11 Microstructure of an aluminum anodized membrane made of high purity aluminum; (a) microscopic image of the back side, (a) frontal microscopic image. Comparing the microscopic images of Figs. 10 and 11 , the pore structure of the anodized film was formed on the surface of a pure aluminum tube compared to that formed on the surface of the 6061 aluminum tube, and a preferred hole arrangement was obtained.
以下，茲使用第1圖~第11圖來詳細說明本發明相關之一種具有奈米或次微米孔洞的管狀鋁陽極處理膜的製作方法之各實施例。此外，在圖面的說明中，同一要素或具有同一機能的要素係使用同一符號，並省略重複的說明。 Hereinafter, each of the embodiments of the method for producing a tubular aluminum anodized film having nano or submicron pores according to the present invention will be described in detail using Figs. 1 to 11 . In the description of the drawings, the same elements or elements having the same function are denoted by the same reference numerals, and the description thereof will not be repeated.
鋁陽極處理膜的製作技術在許多的學術或研究單位中乃是屬於成熟的研發技術，然而目前鋁陽極膜在推廣至產業界或更進一步的應用之前仍需克服多項實際的工程技術問題，包括：大面積、高厚度、大孔徑、與薄膜成長速率等困難點，隨著鋁陽極膜反應面積的增大陽極處理時的放熱量也隨之增加，因此大大地增加鋁陽極膜燒毀的現象，大孔徑鋁陽極膜 需在高電壓且低溫的條件下成長，然而局部熱的產生卻是常常使得鋁陽極膜薄膜燒毀，由低溫陽極處理使得鋁陽極膜薄膜的成長速率僅略高於溶解速率，因此不易獲得較高厚度的鋁陽極薄膜。蓋因大面積具有實際科學與工業應用價值，高厚度具有較佳的薄膜機械強度，大孔徑具有與目前之次微米技術直接接合的特點，高的薄膜成長速率可縮短陽極處理時間。本專利目前已成功地克服鋁陽極膜在應用上的困難點包括：非平面式薄膜(管狀)、大面積、高厚度、大孔徑、與薄膜成長速率等。 The fabrication technology of aluminum anode film is a mature R&D technology in many academic or research units. However, the current aluminum anode film still needs to overcome many practical engineering problems before it is extended to the industry or further applications, including : Large area, high thickness, large pore size, and film growth rate, etc., as the reaction area of the aluminum anode film increases, the amount of heat released during the anode treatment also increases, thus greatly increasing the phenomenon of burning of the aluminum anode film. The large-aperture aluminum anode film needs to grow under high voltage and low temperature conditions. However, the local heat generation often causes the aluminum anode film to be burned, and the growth rate of the aluminum anode film is only slightly higher than the dissolution rate by the low temperature anode treatment. Therefore, it is difficult to obtain a high-thickness aluminum anode film. Because of its large scientific and industrial application value, the high thickness has better mechanical strength of the film, and the large pore size has the characteristics of direct bonding with the current sub-micron technology. The high film growth rate can shorten the anode treatment time. The patents have successfully overcome the difficulties in the application of the aluminum anode film, including non-planar film (tubular), large area, high thickness, large pore size, and film growth rate.
此範例將表面經過機械研磨後的鋁管進行電解拋光。 This example electropolished the surface of a mechanically polished aluminum tube.
電解拋光的條件為：5~20%過氯酸(HClO4)+5~20%單丁醚乙二脂(CH3(CH2)3OCH2CH2OH)+85~95%乙醇(C2H6O)，電解液溫度為2~40℃，電解電壓為5~50伏特，電解拋光時間為1~10分鐘，較佳的電解拋光操作條件為15%過氯酸(HClO4)+15%單丁醚乙二脂(CH3(CH2)3OCH2CH2OH)+70%乙醇(C2H6O)，電解液溫度為25℃，電解電壓為40伏特，電解拋光時間為10分鐘。 The conditions of electrolytic polishing are: 5~20% perchloric acid (HClO 4 ) + 5~20% monobutyl ether ethylene diester (CH 3 (CH 2 ) 3 OCH 2 CH 2 OH) + 85~95% ethanol (C 2 H 6 O), the electrolyte temperature is 2~40 °C, the electrolysis voltage is 5~50 volts, the electropolishing time is 1~10 minutes, and the preferred electropolishing operation condition is 15% perchloric acid (HClO 4 )+ 15% monobutyl ether ethylene diester (CH 3 (CH 2 ) 3 OCH 2 CH 2 OH) + 70% ethanol (C 2 H 6 O), electrolyte temperature 25 ° C, electrolysis voltage 40 volts, electropolishing time It is 10 minutes.
此範例將表面經過電解拋光後的鋁管進行第陽極處理。陽極處理的電解液主要以1~15vol.%硫酸、0.5~5vol.%磷酸、或0.5~8wt.%草酸為主，或是利用以上所述的酸進一步調配成混酸溶液。 This example performs an anodic treatment of an aluminum tube whose surface has been electrolytically polished. The anodized electrolyte is mainly composed of 1~15 vol.% sulfuric acid, 0.5~5 vol.% phosphoric acid, or 0.5-8 wt.% oxalic acid, or further mixed into a mixed acid solution by using the above-mentioned acid.
利用10vol.%硫酸水溶液為電解液、外加40伏特直流電壓、陽極處理時間1~80小時、電解液溫度為10℃、可使金屬鋁管表面反應產生 半透明的氧化鋁薄膜，再利用飽和氯化銅溶液將殘留的鋁基材移除後可得多孔性透明的氧化鋁薄膜，進一步利用5vol.%磷酸將附著於氧化鋁薄膜表面的阻障層去除與擴孔可的雙邊管道通孔的多孔性(結構性)鋁陽極處理膜，其陽極氧化鋁膜具有孔徑為5~30nm、孔密度為1010~1011孔/cm2、膜厚為5~500μm的顯微結構。 Using a 10 vol.% aqueous solution of sulfuric acid as the electrolyte, adding 40 volts DC voltage, anodizing time of 1 to 80 hours, and an electrolyte temperature of 10 ° C, the surface of the metal aluminum tube can be reacted to produce a translucent aluminum oxide film, and then saturated chlorine is used. The copper solution removes the residual aluminum substrate to obtain a porous transparent aluminum oxide film, and further removes the barrier layer attached to the surface of the aluminum oxide film by using 5 vol.% phosphoric acid. A porous (structural) aluminum anodized film having an anodic aluminum oxide film having a pore structure of 5 to 30 nm, a pore density of 10 10 to 10 11 pores/cm 2 , and a film thickness of 5 to 500 μm.
此範例將表面經過電解拋光後的鋁管進行第陽極處理。 This example performs an anodic treatment of an aluminum tube whose surface has been electrolytically polished.
陽極處理的電解液主要以硫酸、磷酸、或草酸為主。利用3wt.%草酸水溶液為電解液、外加40伏特直流電壓、陽極處理時間1~100小時、電解液溫度為1℃、可使金屬鋁管表面反應產生半透明的氧化鋁薄膜，再利用飽和氯化銅溶液將殘留的鋁基材移除後可得多孔性透明的氧化鋁薄膜，進一步利用5vol.%磷酸將附著於氧化鋁薄膜表面的阻障層去除與擴孔可的雙邊管道通孔的多孔性(結構性)鋁陽極處理膜，其陽極氧化鋁膜具有孔徑為40~100nm、孔密度為109~1010孔/cm2、膜厚為5~500μm的顯微結構。 The anodized electrolyte is mainly composed of sulfuric acid, phosphoric acid, or oxalic acid. Using a 3wt.% aqueous solution of oxalic acid as the electrolyte, adding 40 volts DC voltage, the anode treatment time is 1~100 hours, and the electrolyte temperature is 1 °C, the surface of the metal aluminum tube can be reacted to produce a translucent aluminum oxide film, and then the saturated chlorine is used. The copper solution removes the residual aluminum substrate to obtain a porous transparent aluminum oxide film, and further removes the barrier layer attached to the surface of the aluminum oxide film by using 5 vol.% phosphoric acid. A porous (structural) aluminum anodized film having an anodic aluminum oxide film having a pore structure of 40 to 100 nm, a pore density of 10 9 to 10 10 pores/cm 2 , and a film thickness of 5 to 500 μm.
此範例將表面經過電解拋光後的鋁管進行第陽極處理。 This example performs an anodic treatment of an aluminum tube whose surface has been electrolytically polished.
陽極處理的電解液主要以硫酸、磷酸、或草酸為主。利用1.5vol.%磷酸水溶液為電解液、外加200伏特直流電壓、陽極處理時間1~200小時、電解液溫度為-4℃、可使金屬鋁管表面反應產生半透明的氧化鋁薄膜，再利用飽和氯化銅溶液將殘留的鋁基材移除後可得多孔性透明的氧化鋁薄 膜，進一步利用5vol.%磷酸將附著於氧化鋁薄膜表面的阻障層去除與擴孔可的雙邊管道通孔的多孔性(結構性)鋁陽極處理膜，其陽極氧化鋁膜具有孔徑為200~500nm、孔密度為108~109孔/cm2、膜厚為5~500μm的顯微結構。 The anodized electrolyte is mainly composed of sulfuric acid, phosphoric acid, or oxalic acid. Using a 1.5 vol.% phosphoric acid aqueous solution as an electrolyte, an external DC voltage of 200 volts, an anodic treatment time of 1 to 200 hours, and an electrolyte temperature of -4 ° C, a surface of the metal aluminum tube can be reacted to produce a translucent aluminum oxide film, and reused. The saturated copper chloride solution removes the residual aluminum substrate to obtain a porous transparent aluminum oxide film, and further removes the barrier layer attached to the surface of the aluminum oxide film by using 5 vol.% phosphoric acid. The porous (structural) aluminum anodized film of the pores has an anodic aluminum oxide film having a pore structure of 200 to 500 nm, a pore density of 10 8 to 10 9 pores/cm 2 , and a film thickness of 5 to 500 μm.
11、13、21‧‧‧多孔性鋁陽極氧化膜 11,13,21 ‧‧‧Porous aluminum anodized film
12、12’、14、14’、31‧‧‧鋁管 12, 12', 14, 14', 31 ‧ ‧ aluminum tubes
22、22’‧‧‧氣(液)體接頭 22, 22' ‧ ‧ gas (liquid) body joint
23、23’‧‧‧氣(液)體管 23, 23' ‧ ‧ gas (liquid) body tube
32‧‧‧矽膠塞 32 ‧‧‧ silicone plugs
33‧‧‧治具座 33 ‧‧‧ fixture seat
34‧‧‧電極板 34 ‧‧‧Electrode plate
35‧‧‧治具座連接柱 35 ‧ ‧ 治具座连接柱
36‧‧‧電極 36 ‧‧‧Electrode
41、44‧‧‧鋁基材 41,44 ‧‧‧Aluminum substrate
42、46、51、54、61、64‧‧‧鋁陽極處理膜表面 42,46,51,54,61,64 ‧‧‧ anodized aluminum film surface
43、47、52、55、63、66‧‧‧鋁陽極處理膜側面 43, 47, 52, 55, 63, 66 ‧‧‧Aluminum anodized film side
45、53、56‧‧‧阻障層 45, 53, 56 ‧ ‧ barrier layer
62、65‧‧‧鋁陽極處理膜底面 62,65 ‧‧‧Aluminum anode treatment membrane bottom surface
第1圖 具有奈米或次微米孔洞的管狀鋁陽極處理膜結構圖；(a)平面結構圖、(b)立體結構圖。 Fig. 1 is a structural view of a tubular aluminum anodized film having nano or submicron pores; (a) a planar structure diagram and (b) a three-dimensional structure diagram.
第2圖 具有氣(液)連接管之管狀鋁陽極處理膜結構圖。 Fig. 2 is a structural view of a tubular aluminum anodized film having a gas (liquid) connecting tube.
第3圖 具有批次量產特性之陽極處理掛具。 Figure 3 Anodized rack with batch production characteristics.
第4圖 含有鋁基材之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。 Fig. 4 is a structural view of a tubular aluminum anodized film containing an aluminum substrate; (a) a perspective view, and (b) a partial enlarged view.
第5圖 去除鋁基材後之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。 Fig. 5 is a structural view of a tubular aluminum anodized film after removing an aluminum substrate; (a) a perspective view, and (b) a partial enlarged view.
第6圖 去除鋁基材與阻障層後之管狀鋁陽極處理膜結構圖；(a)立體圖、(b)局部放大圖。 Fig. 6 is a structural view of a tubular aluminum anodized film after removing an aluminum substrate and a barrier layer; (a) a perspective view, and (b) a partial enlarged view.
第7圖 鋁材與鋁陽極處理實際照片；(a)鋁管、(b)表面經過電解拋光後的鋁管、(c)表面經過陽極處理後的鋁管、(d)局部鋁基材去除後的陽極處理鋁管。 Figure 7: Actual photo of aluminum and aluminum anode treatment; (a) aluminum tube, (b) aluminum tube after electrolytic polishing, (c) aluminum tube with anodized surface, (d) partial aluminum substrate removal After the anode treatment of the aluminum tube.
第8圖 管狀鋁陽極處理膜實際照片。 Figure 8 Actual photo of a tubular aluminum anodized film.
第9圖 管狀鋁陽極處理膜之應用實際照片；(a)具有氣(液)連接管之管狀鋁陽極處理膜、(b)管內裝有水之管狀鋁陽極處理膜、(c)管內裝有紅墨水之管狀鋁陽極處理膜。 Figure 9 is a practical photo of the application of a tubular aluminum anodized film; (a) a tubular aluminum anodized film having a gas (liquid) connecting tube, (b) a tubular aluminum anodized film containing water in the tube, and (c) a tube A tubular aluminum anodized film with red ink.
第10圖 利用6061鋁材製作的鋁陽極處理膜顯微結構；(a)背面顯微影像、(a)正面顯微影像。 Figure 10 Microstructure of an aluminum anodized film made of 6061 aluminum; (a) backside microscopic image, (a) frontal microscopic image.
第11圖 利用高純度鋁材製作的鋁陽極處理膜顯微結構；(a)背面顯微影像、(a)正面顯微影像。 Figure 11 Microstructure of an aluminum anodized membrane made of high purity aluminum; (a) microscopic image of the back side, (a) frontal microscopic image.
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