TWI588300B - Sealing equipment and method for sealing pores of anodic oxide film by using vacuum and injection steam - Google Patents
Sealing equipment and method for sealing pores of anodic oxide film by using vacuum and injection steam Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Description
本發明是關於一種用於將陽極氧化膜封孔的封孔設備及其方法，特別是關於一種利用真空與噴射蒸氣對陽極氧化膜封孔的封孔設備及其方法，使得陽極氧化膜獲得極高的封孔效果。陽極氧化膜經本發明之封孔處理後可獲得更佳的抗乾溼式腐蝕性。真空蒸鍍是綠能產業(例如發光二極體、太陽能電池、超級電容等)製程的重要一環，本發明的封孔設備和方法適用於對半導體電漿設備組件進行表面處理，進而增加電漿設備組件在電漿環境中之使用壽命，進而降低真空鍍膜的成本。 The present invention relates to a sealing device for sealing an anodized film and a method thereof, and more particularly to a sealing device for sealing an anodized film by using a vacuum and a sprayed vapor, and a method thereof, such that an anodized film is obtained High sealing effect. The anodized film is subjected to the sealing treatment of the present invention to obtain better resistance to dry and wet corrosion. Vacuum evaporation is an important part of the process of the green energy industry (such as light-emitting diodes, solar cells, super capacitors, etc.), and the sealing device and method of the present invention are suitable for surface treatment of semiconductor plasma equipment components, thereby increasing plasma The service life of the equipment components in the plasma environment, which in turn reduces the cost of vacuum coating.
近年來，在表面處理領域的發展方興未艾，並且由於表面處理的成功開發與應用著實改善了人們的生活品質，也開創了無限商機。精密表面處理目前正廣泛地被應用於各種產品中，例如：光學產品、電子產品、通訊器材、與筆記型電腦，因此對於表面處理要求品質越來越嚴苛。舉例來說，對於真空電漿腔體而言，陽極氧化表面處理尤其重要。在電化學反應領域中，陽極處理已是一種成熟的傳統產業，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。 In recent years, the development of surface treatment is in the ascendant, and the successful development and application of surface treatment has improved people's quality of life and created unlimited business opportunities. Precision surface treatment is currently being widely used in a variety of products, such as optical products, electronic products, communication equipment, and notebook computers, so the quality of surface treatment is becoming more and more demanding. For example, anodized surface treatments are especially important for vacuum plasma chambers. In the field of electrochemical reactions, anode treatment has become a mature traditional industry, and its main applications are surface modification applications such as surface corrosion resistance, coating, decoration, electrical insulation, surface plating, and abrasion resistance.
陽極氧化鋁最早必須回顧到1932年Setoh和Miyata兩人提出 的假設，他們認為由於有一阻障層(Barrier layer)生成，因此允許皮膜細孔中的水因電極效應而釋放的初生態氧(Nascent oxygen)通過，並且藉此不斷地與鋁結合而生成新的阻障層。此外，細孔的生成主要是溶液中陰離子的腐蝕，導致氧氣滲入細孔中，使得金屬素材因為阻障層的保護而避免與溶液接觸。 Anodized aluminum must first be recalled by Setoh and Miyata in 1932. Hypothesis, they believe that due to the formation of a barrier layer, Nascent oxygen, which is released by the electrode effect, allows the water in the pores of the membrane to pass through, and thereby continuously combines with aluminum to generate new The barrier layer. In addition, the formation of pores is mainly the corrosion of anions in the solution, causing oxygen to penetrate into the pores, so that the metal material is prevented from coming into contact with the solution due to the protection of the barrier layer.
在1934年S.Wernick相繼提出理論，他認為一種帶有負電荷的膠體，經水解後，於陽極生成氫氧化鋁(Aluminum hydroxide)。這種膠體會如海綿網一樣散佈在金屬表面上，當直流電通過時，由於催化泳動現象(Caraphoresis)而將電解質(陰離子)排斥於外；若交流電通過的話，隨著極性變化(正或負)而交互地吸附和驅除電解質。S.Wernick還提出關於電解時間對於皮膜生長和尺寸大小的影響，隨著時間增加膜厚有一最大值。當電流斷斷續續通過時，膜厚隨時間增加而變薄，特別是在使用硫酸當作電解液時，此一現象更為明顯。1936年Rummel提出他的構想，認為阻障層可藉由細孔的生成而讓電流通過，在細孔的底部就有新的一阻障層開始生長，如此一直重覆生長，直到太深的細孔使得現有的電壓不足以維持皮膜繼續生長。 In 1934, S. Wernick came up with the theory that he believed that a negatively charged colloid, after hydrolysis, produced aluminum hydroxide at the anode. This colloid will spread on the metal surface like a sponge mesh. When the direct current is passed, the electrolyte (anion) is repelled due to the catalytic movement phenomenon; if the alternating current passes, the polarity changes (positive or negative). The electrolyte is adsorbed and expelled interactively. S. Wernick also proposed the effect of electrolysis time on film growth and size, with a maximum thickness increase over time. When the current is intermittently passed, the film thickness becomes thinner with time, especially when sulfuric acid is used as the electrolyte. In 1936, Rummel proposed his idea that the barrier layer can pass current through the formation of pores, and a new barrier layer begins to grow at the bottom of the pores, so that it continues to grow until it is too deep. The pores make the existing voltage insufficient to maintain the film's continued growth.
1936年Baumann提出假設在細孔底部的活化層(Active layer)上有一氣層薄膜(Vapor film)的存在；熱量的釋放仍然由於電流和化學反應的關係而在氣體-電解質介面上散佈，因為他假設氧離子是在此一介面上生成的，只要有足夠的電壓迫使氧進入鋁材晶格，氧化皮膜的生成反應便發生，並釋放一熱量；太高的熱量釋放，使陰離子無法進入細孔，電流藉由氧離子傳送，當與鋁結合放電(Discharge)時，造成氧化膜溶解，並使得細孔大小加寬。 In 1936, Baumann proposed the existence of a Vapor film on the active layer at the bottom of the pores; the release of heat is still spread on the gas-electrolyte interface due to the relationship between current and chemical reaction, because he Assuming that oxygen ions are generated at this interface, as long as there is enough voltage to force oxygen into the aluminum lattice, the formation of the oxide film occurs and a heat is released; too much heat is released, so that the anions cannot enter the pores. The current is transmitted by oxygen ions, and when discharged in combination with aluminum, the oxide film is dissolved and the pore size is widened.
近年來由於奈米技術的發展，使得在技術上更能完整的掌控陽極氧化膜管胞或奈米管結構的管徑、管長、與管密度。簡便的陽極處理技術，提供成本低廉且快速量產的製程，可實際應用於單位表面積大的產品發展，如染料敏化太陽能電池、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、綠建材、與太陽能電池等產業發展，具自動化生產特性的陽極處理技術，勢必將成為各產業的製程之一。 In recent years, due to the development of nanotechnology, it is technically more complete to control the tube diameter, tube length, and tube density of the anodized film tube or nanotube structure. The simple anode treatment technology provides a low-cost and fast mass production process, which can be applied to product development with large surface area, such as dye-sensitized solar cells, 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 dissipation materials, heat insulation materials, green building materials, and solar cells, the anodizing technology with automatic production characteristics is bound to be Become one of the processes of various industries.
陽極處理在產業上的應用其中以鋁、鎂、鈦的操作技術最成熟。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，其中奈米管與阻障層的成份均為三氧化二鋁(Al2O3)。鋁於陽極處理主要藉由反應2Al+3+3H2O→Al2O3+6H+而成，因此，需控制pH值低於4以下，即酸性溶液之條件下，且外加電壓需高於-1.8V(SHE)以上，式中H+將藉由H++H+→H2，而生成氫氣，此氫氣由Al2O3內部逸出，進而造成多孔性之氧化鋁形成，因此，控制氫氣逸出之速率，則可控制形成於氧化鋁內部的孔洞，使之成為孔徑均一性之陽極氧化鋁膜。鋁於陽極處理時於表面生成三氧化二鋁(Al2O3)氧化層，該氧化層成長之初以六角形孔洞往上方成長，隨著時間的增加該六角形孔洞周圍原子的排列漸成非規則性(disorder)的排列，所以孔洞漸轉為圓形孔洞，另外孔徑的改變可由C=mV表示之，其中C：孔徑大小(nm)、V：陽極處理電壓(V)、m：常數(2~2.5)。 The application of anodizing in industrial applications is the most mature in the operation technology of aluminum, magnesium and titanium. When the aluminum is placed in a specific electrolyte and the appropriate anode treatment parameters are controlled, the formed oxide film has a regular cell or nanotube structure. The interface between the end of the nanotube and the aluminum material forms a hemispherical barrier layer, wherein the composition of the nanotube and the barrier layer is aluminum oxide (Al 2 O 3 ). The treatment of aluminum in the anode is mainly carried out by reacting 2Al +3 +3H 2 O→Al 2 O 3 +6H + , therefore, it is necessary to control the pH below 4, that is, under the condition of acidic solution, and the applied voltage is higher than -1.8V (SHE) or more, in which H + will generate hydrogen gas by H + +H + →H 2 , which will escape from the inside of Al 2 O 3 , thereby causing the formation of porous alumina, therefore, By controlling the rate at which hydrogen escapes, the pores formed inside the alumina can be controlled to become an anodized aluminum film having a uniform pore size. When the aluminum is anodized, an aluminum oxide (Al 2 O 3 ) oxide layer is formed on the surface, and the oxide layer grows upwards in a hexagonal hole at the beginning of growth, and the arrangement of atoms around the hexagonal hole gradually increases with time. The arrangement of the disorder, so the hole gradually turns into a circular hole, and the change in the aperture can be expressed by C=mV, where C: aperture size (nm), V: anode processing voltage (V), m: constant (2~2.5).
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，應用時除了具有美觀與多色彩化的外觀，同時更能增加陽極膜的機械性質如硬度、耐磨耗等，並能提升陽極薄膜在嚴苛環境中的化學穩定性，如抗溼式溶液中的腐蝕與抗乾式環境中的電漿侵蝕等。 Due to the porous structure of the anodized film, it needs to be subjected to a sealing treatment step in the subsequent application, in addition to having an aesthetically pleasing and multi-colored appearance, and at the same time, it can increase the mechanical properties of the anodic film such as hardness and wear resistance, and can Improve the chemical stability of anodic films in harsh environments, such as corrosion in wet solutions and plasma erosion in dry environments.
為了解決對於表面處理品質嚴苛要求的問題，本發明提出一種利用真空與噴射蒸氣對陽極氧化膜封孔的封孔設備與方法，可使陽極氧化膜獲得極高的封孔效果，進而提升陽極處理工件在乾溼式環境中的使用壽命。 In order to solve the problem of strict requirements on the surface treatment quality, the present invention proposes a sealing device and a method for sealing an anodized film by using a vacuum and a sprayed vapor, so that the anodized film can obtain an extremely high sealing effect, thereby improving the anode. Handle the life of the workpiece in a dry and wet environment.
本發明之目的在於提供一種利用真空與噴射蒸氣對陽極氧化膜封孔的封孔設備及其方法，藉由本發明所提供之封孔設備與方法來提升陽極氧化膜之機械性質與化學穩定性。蓋因鋁陽極氧化膜為管胞狀結構，為了提高鋁件表面的品質和染著色牢固，離子或色料著色後必須將陽極氧化膜的微細孔隙予以封閉，經過封閉處理後表面變的均勻無孔，形成緻密的氧化膜，經封閉後的陽極氧化膜不再具有吸附性，可避免吸附有害物質而被汙染或早期腐蝕，從而提高了陽極氧化膜的防汙染、抗蝕等性能。常用的著色後的封孔方法有水合封孔、無機鹽溶液封孔、透明有機塗層封孔。 SUMMARY OF THE INVENTION An object of the present invention is to provide a sealing device for sealing an anodized film by using a vacuum and a sprayed vapor, and a method thereof for improving the mechanical properties and chemical stability of an anodized film by the sealing device and method provided by the present invention. The aluminum anodized film of Gayin is a tubular structure. In order to improve the quality of the surface of the aluminum part and the coloration of the dyeing, the fine pores of the anodized film must be sealed after the ion or color material is colored, and the surface becomes uniform after the sealing treatment. The pores form a dense oxide film, and the anodized film after sealing is no longer adsorbable, and can avoid contamination or early corrosion by adsorbing harmful substances, thereby improving the anti-pollution and anti-corrosion properties of the anodized film. The commonly used sealing methods after coloring include hydration sealing, inorganic salt solution sealing, and transparent organic coating sealing.
熱封孔技術是在接近沸點的純水中，通過氧化鋁的水合反應，將非晶態氧化鋁轉化成稱為勃姆體(bohmite)的水合氧化鋁，即Al2O3．H2O(AlOOH)。由於水合氧化鋁比原陽極氧化膜的分子體積大，體積膨脹使得陽極氧化膜的微孔填充封閉，陽極氧化膜的抗污染性和耐腐蝕性隨之提 高，同時阻抗增加，陽極氧化膜的介電常數也隨之變大。鋁的陽極氧化膜在水中有兩種形式的反應：其中之一是在較低溫(40℃以下)，pH<4的水中，與水結合成三水合氧化鋁(Bayerite(Al(OH)3))，其反應式為Al+3H 2 O→Al(OH) 3 +1.5H 2 ，此反應在外加電壓(流)下可獲得較高的陽極模成長速率，稱之為陽極處理。另一種是在較高溫(80℃以上)的中性水中，氧化鋁與水化合成一水合氧化鋁(Boehmite AlO(OH))，其反應式為Al 2 O 3 +H 2 O→2AlO(OH)這就是通常所指的水合封孔的反應過程，由於一水合氧化鋁的分子量(60g/mole)比三水合氧化鋁的分子量(78g/mole)的小，因此經過水合封孔處理後的鋁陽極膜體積會膨脹((78-60)/78=23%)(2Al(OH) 3 +3H 2 O→2AlO(OH)+3H 2 )，並且堵塞了管胞狀之陽極氧化膜的孔隙。 The heat sealing technique is to convert amorphous alumina into hydrated alumina called bohmite, ie, Al 2 O 3 , by hydration reaction of alumina in pure water close to the boiling point. H2O (AlOOH). Since the hydrated alumina has a larger molecular volume than the original anodized film, the volume expansion causes the microporous filling of the anodized film to be closed, and the anti-pollution property and corrosion resistance of the anodized film are increased, and the impedance is increased, and the anodized film is interposed. The electrical constant also increases. The anodized film of aluminum has two forms of reaction in water: one of which is combined with water to form alumina trihydrate (Bayerite (Al(OH) 3 ) in water at a lower temperature (below 40 ° C), pH < 4). The reaction formula is Al + 3H 2 O → Al(OH) 3 + 1.5H 2 , and the reaction can obtain a higher anode mold growth rate under an applied voltage (flow), which is called anodization. The other is to synthesize alumina and hydration to synthesize alumina monohydrate (Boehmite AlO(OH)) in neutral water at higher temperature (above 80 °C). The reaction formula is Al 2 O 3 + H 2 O → 2AlO (OH ) this reaction process is commonly referred to hydration sealing, since the molecular weight of a hydrated alumina (60g / mole) ratio of the molecular weight of alumina trihydrate (78g / mole) is small, the sealing treatment is hydrated aluminum The volume of the anodic film expands ((78-60) / 78 = 23%) (2Al(OH) 3 + 3H 2 O → 2AlO(OH) + 3H 2 ) and blocks the pores of the tubular anodized film.
本發明同時說明了以下特徵點： The present invention also illustrates the following feature points:
(1)高壓水蒸氣相較於常壓水蒸氣有較高的溫度與壓力，可以使水分子更容易進入陽極氧化膜內進行封孔。 (1) High-pressure water vapor has a higher temperature and pressure than normal-pressure water vapor, which makes it easier for water molecules to enter the anodized film for sealing.
(2)陽極氧化膜浸泡在熱水中封孔，易使陽極氧化膜表層產生鬆散的片狀結構。 (2) The anodized film is immersed in hot water to seal the pores, which tends to cause a loose sheet-like structure on the surface of the anodized film.
(3)陽極氧化膜置於蒸氣中封孔，可使陽極氧化膜表面保持乾淨的結構。 (3) The anodized film is sealed in a vapor to keep the surface of the anodized film clean.
(4)鋁經陽極處理後會產生鋁陽極氧化膜，其反應式為：Al+3H2O→Al(OH)3+1.5H2 (4) Aluminum is anodized to produce an anodized aluminum film with a reaction formula of: Al+3H 2 O→Al(OH) 3 +1.5H 2
(5)鋁陽極氧化膜經高溫熱水封孔後，陽極氧化膜的成分可由三水合氧化鋁 (Bayerite，(Al(OH)3))轉換成一水合氧化鋁(Boehmite，AlO(OH))。 (5) After the aluminum anodized film is sealed by high temperature hot water, the composition of the anodized film can be converted into alumina monohydrate (Boehmite, AlO(OH)) by alumina trihydrate (Bayerite, (Al(OH) 3 )).
(6)相較於Al(OH)3，AlO(OH)有較佳的抗腐蝕性與耐磨耗性。 (6) AlO(OH) has better corrosion resistance and wear resistance than Al(OH) 3 .
(7)封孔反應式：三水合氧化鋁→一水合氧化鋁 2Al(OH)3+3H2O → 2AlO(OH)+3H2 (7) Sealing reaction formula: alumina trihydrate → alumina monohydrate 2Al(OH) 3 +3H 2 O → 2AlO(OH)+3H 2
(8)一水合氧化鋁的分子量(60g/mole)、三水合氧化鋁的分子量(78g/mole)。經過水合封孔處理後的鋁陽極氧化膜的體積會膨脹((78-60)/78=23%) (8) The molecular weight of alumina monohydrate (60 g/mole) and the molecular weight of alumina trihydrate (78 g/mole). The volume of the aluminum anodized film after hydration sealing treatment will expand ((78-60)/78=23%)
在高溫水中加入某些添加劑如無水碳酸鈉、氨、三乙醇胺等，可增強封孔效果，提高膜層的抗蝕性。水合封孔的另一種方法是蒸汽封孔，其所處理的氧化膜抗蝕性、耐磨性與蒸汽壓力和封孔時間有關。一般隨壓力升高、時間延長、抗蝕性提高、耐磨性降低。 Adding certain additives such as anhydrous sodium carbonate, ammonia, triethanolamine, etc. in high temperature water can enhance the sealing effect and improve the corrosion resistance of the film. Another method of hydration sealing is steam sealing, and the oxidation resistance and wear resistance of the treated oxide film are related to the vapor pressure and the sealing time. Generally, the pressure increases, the time is prolonged, the corrosion resistance is improved, and the wear resistance is lowered.
為達上述目的，本發明提供一種利用真空與噴射蒸氣之封孔設備，該封孔設備包含：一封孔腔體，用於容置一具有陽極氧化膜之陽極處理工件；一加熱爐，用於將該封孔腔體維持在一特定溫度；一真空幫浦，與該封孔腔體連接，用於將該封孔腔體內部抽至負壓狀態；以及一噴射蒸氣機，與該封孔腔體連接，用於將一封孔劑噴射進入該封孔腔體內，以將該封孔腔體內由該負壓狀態轉為正壓狀態，其中該封孔劑填補該陽極處理工件之該陽極氧化膜之孔洞。 In order to achieve the above object, the present invention provides a sealing device using a vacuum and a jetting steam, the sealing device comprising: a hole cavity for accommodating an anodized workpiece having an anodized film; and a heating furnace Maintaining the plugging cavity at a specific temperature; a vacuum pump connected to the plugging cavity for drawing the inside of the plugging cavity to a negative pressure state; and a jetting machine, and the sealing a cavity connection for injecting a hole into the sealing cavity to change the sealing cavity from the negative pressure state to a positive pressure state, wherein the sealing agent fills the anode processing workpiece The pores of the anodized film.
在本發明之一較佳實施例中，該陽極氧化膜包括：藉由將鋁或鋁合金進行陽極處理、硬陽處理、或微弧陽極處理所產生的該陽極氧化膜。 In a preferred embodiment of the present invention, the anodized film comprises: the anodized film produced by anodizing, hardening, or micro-arc anodic treatment of aluminum or aluminum alloy.
在本發明之一較佳實施例中，該加熱爐將該封孔腔體內溫度維持在80℃至150℃之間。 In a preferred embodiment of the invention, the furnace maintains the temperature within the sealed chamber between 80 ° C and 150 ° C.
在本發明之一較佳實施例中，該真空幫浦將該封孔腔體內部抽至0.01torr以下的該負壓狀態。 In a preferred embodiment of the present invention, the vacuum pump draws the inside of the plugging cavity to the negative pressure state of 0.01 torr or less.
在本發明之一較佳實施例中，該噴射蒸氣機將該封孔腔體內 由該負壓狀態轉為1.1atm以上的該正壓狀態。 In a preferred embodiment of the present invention, the jet steamer seals the sealed cavity The negative pressure state is changed to the positive pressure state of 1.1 atm or more.
在本發明之一較佳實施例中，該噴射蒸氣機將液態狀或氣態狀之該封孔劑噴射進入該封孔腔體內，對該陽極處理工件之該陽極氧化膜進行封孔處理。 In a preferred embodiment of the present invention, the jetting machine sprays the sealing agent in a liquid or gaseous state into the sealing cavity, and the anodized film of the anode-treated workpiece is sealed.
在本發明之一較佳實施例中，該封孔劑包含水、水蒸氣、含有離子之水溶劑、含有分子之水溶劑、或含有懸浮物之溶劑。 In a preferred embodiment of the invention, the plugging agent comprises water, water vapor, an aqueous solvent containing ions, an aqueous solvent containing a molecule, or a solvent containing a suspension.
在本發明之一較佳實施例中，該離子包含具有過渡元素之離子。 In a preferred embodiment of the invention, the ion comprises an ion having a transition element.
在本發明之一較佳實施例中，該分子包含具有疏水性之烷基分子或具有親水性之羥基分子。 In a preferred embodiment of the invention, the molecule comprises a hydrophobic alkyl molecule or a hydrophilic hydroxyl molecule.
在本發明之一較佳實施例中，該懸浮物包含鐵氟龍、氧化鋁粉末、二氧化鈦粉末、陶瓷池粉末、金屬粉末、高分子粉末、或鑽石粉末 In a preferred embodiment of the present invention, the suspension comprises Teflon, alumina powder, titanium dioxide powder, ceramic pool powder, metal powder, polymer powder, or diamond powder.
本發明還提供一種封孔方法，包含：將一具有陽極氧化膜之陽極處理工件放置於一封孔腔體內；利用一加熱爐使該封孔腔體維持在一特定溫度；利用一真空幫浦將該封孔腔體內部抽至一負壓狀態；關閉位於該真空幫浦與該封孔腔體之間的一第一氣壓閥門；開啟位於一噴射蒸氣機與該封孔腔體之間的一第二氣壓閥門以連接該噴射蒸氣機和該封孔腔體；以及利用該噴射蒸氣機使封孔劑進入該封孔腔體內，以將該封孔腔體內由該負壓狀態轉為該正壓狀態，並且對該陽極處理工件之該陽極氧化膜進行封孔處理。 The invention also provides a method for sealing a hole, comprising: placing an anodized workpiece having an anodized film in a cavity; maintaining the plugging cavity at a specific temperature by using a heating furnace; using a vacuum pump Pumping the inside of the sealing cavity to a negative pressure state; closing a first gas pressure valve between the vacuum pump and the sealing cavity; opening between a jetting machine and the sealing cavity a second gas pressure valve for connecting the steaming machine and the sealing cavity; and using the steaming machine to cause the sealing agent to enter the sealing cavity to convert the sealing cavity into the negative pressure state The positive pressure state, and the anodized film of the anode-treated workpiece is subjected to a sealing treatment.
1000‧‧‧封孔設備 1000‧‧‧sealing equipment
1001‧‧‧陽極處理工件 1001‧‧‧Anode treated workpiece
1002‧‧‧封孔腔體 1002‧‧‧ Sealing cavity
1003‧‧‧真空氣壓口 1003‧‧‧vacuum pressure port
1004‧‧‧正壓氣壓口 1004‧‧‧ positive pressure port
1005‧‧‧真空連接管 1005‧‧‧Vacuum connecting tube
1006‧‧‧第一氣壓閥門 1006‧‧‧First air pressure valve
1007‧‧‧真空幫浦 1007‧‧‧vacuum pump
1008‧‧‧正壓連接管 1008‧‧‧ positive pressure connecting pipe
1009‧‧‧第二氣壓閥門 1009‧‧‧Second air pressure valve
1010‧‧‧噴射蒸氣機 1010‧‧‧Steaming machine
1011‧‧‧加熱爐 1011‧‧‧heating furnace
3001‧‧‧鋁件 3001‧‧‧Aluminum parts
3002‧‧‧阻障層 3002‧‧‧ barrier layer
3003‧‧‧陽極氧化膜 3003‧‧‧Anodized film
S10~S60‧‧‧步驟 S10~S60‧‧‧Steps
A-A’‧‧‧對應至第3B圖的截線 A-A’‧‧‧ corresponds to the section line of Figure 3B
R‧‧‧孔半徑 R‧‧‧ hole radius
W‧‧‧管壁厚度 W‧‧‧ wall thickness
ψ‧‧‧孔直徑 Ψ‧‧‧ hole diameter
第1圖顯示本發明之封孔設備之示意圖；第2圖顯示本發明之封孔方法之流程圖；第3A圖顯示表面形成有陽極氧化膜之鋁件之示意圖；第3B圖顯示第3A圖中沿A-A’截線之剖面示意圖；第4A圖和第4B圖分別顯示三軸力平衡之示意圖；第5A圖和第5B圖分別顯示陽極氧化膜的之管壁厚度與管內體積或管內表面積之對應圖；第6A圖顯示陽極氧化膜進行封孔處理之前的結構示意圖；第6B圖顯示陽極氧化膜進行封孔處理之後的結構示意圖；第7A圖和第7B圖分別顯示本發明之第一較佳實施例之鋁片藉由草酸溶液進行陽極表面處理前與處理後之微結構示意圖；第8A圖和第8B圖分別顯示本發明第二較佳實施例中鋁片藉由硫酸溶液進行陽極表面處理前與處理後之微結構示意圖。 1 is a schematic view showing a sealing device of the present invention; FIG. 2 is a flow chart showing a sealing method of the present invention; FIG. 3A is a view showing an aluminum member having an anodized film formed on its surface; and FIG. 3B is a view showing a third embodiment; Schematic diagram of the section along the A-A' section line; Figures 4A and 4B show schematic diagrams of the triaxial force balance; Figures 5A and 5B respectively show the wall thickness of the anodized film and the volume inside the tube or Corresponding diagram of the inner surface area of the tube; FIG. 6A is a schematic view showing the structure before the anodized film is subjected to the sealing treatment; FIG. 6B is a schematic view showing the structure after the anodized film is subjected to the sealing treatment; FIGS. 7A and 7B are respectively showing the present invention. A schematic view of the microstructure of the aluminum sheet of the first preferred embodiment before and after the surface treatment of the anode by the oxalic acid solution; and Figs. 8A and 8B respectively show the aluminum sheet of the second preferred embodiment of the present invention by sulfuric acid. The microstructure of the solution before and after the surface treatment of the anode.
以下，茲使用所附圖式來詳細說明本發明相關之一種利用真空與噴射蒸氣對陽極氧化膜封孔的封孔設備與方法之各實施例。此外，在所附圖式的說明中，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, various embodiments of a sealing apparatus and method for sealing an anodized film by vacuum and sprayed vapor according to the present invention will be described in detail using the drawings. In the description of the drawings, the same elements or elements having the same function are denoted by the same reference numerals, and the repeated description is omitted.
本發明為了提升陽極氧化膜的封孔品質，提出了一種利用真空與噴射蒸氣對陽極氧化膜封孔的封孔設備與方法，此種封孔設備與方法，具有生產簡單性與面積變化性大等特性，適用於工業量產上。請參照 第1圖，其顯示本發明之封孔設備1000之示意圖。該封孔設備1000包含封孔腔體1002、真空氣壓口1003、正壓氣壓口1004、真空連接管1005、第一氣壓閥門1006、真空幫浦1007、正壓連接管1008、第二氣壓閥門1009、噴射蒸氣機1010、和加熱爐1011。該封孔腔體1002可承受正壓和/或負壓，係用於將一陽極處理工件1001容置於其內，以對該陽極處理工件1001之陽極氧化膜進行真空與噴射蒸氣之封孔處理。在封孔處理前，該陽極處理工件1001表面形成有一層陽極氧化膜，並且該陽極氧化膜具有未封孔或局部封孔之管胞狀結構，其化學組成一般為三水合氧化鋁(Bayerite(Al(OH)3))。該真空氣壓口1003與該正壓氣壓口1004形成在該封孔腔體1002之表面。該真空連接管1005用於連接在真空氣壓口1003與該真空幫浦1007之間，使得該封孔腔體1002與真空幫浦1007連通。該第一氣壓閥門1006設置在該真空連接管1005內，藉由控制該第一氣壓閥門1006的開啟或關閉，進而控制該封孔腔體1002與真空幫浦1007之間的連通。為了移除該陽極處理工件1001之陽極氧化膜之奈米管內的氣體，使封孔劑更容易進入奈米管內，當該陽極處理工件1001置於該封孔腔體1002時，可藉由該真空幫浦1007對該陽極處理工件1001進行真空抽氣。該正壓連接管1008用於連接在該噴射蒸氣機1010與該正壓氣壓口1004之間，使得該封孔腔體1002與該噴射蒸氣機1010連通。該第二氣壓閥門1009設置在該正壓連接管1008內，藉由控制該第二氣壓閥門1009的開啟或關閉，進而控制該封孔腔體1002與該噴射蒸氣機1010之間的連通。利用該噴射蒸氣機1010將封孔劑高速地注入該封孔腔體1002內，使封孔劑快速地進入該陽極處理工件1001之陽極氧化膜之奈米管內達到封孔的目的。該加熱爐1011 圍繞在該封孔腔體1002之外側，用於使該封孔腔體1002內之溫度維持長時間恆溫的狀態。 In order to improve the sealing quality of the anodized film, the present invention proposes a sealing device and method for sealing an anodized film by using vacuum and jetting steam, and the sealing device and method have the advantages of simple production and large area change. And other characteristics, suitable for industrial production. Please refer to FIG. 1, which shows a schematic view of the sealing device 1000 of the present invention. The sealing device 1000 includes a sealing cavity 1002, a vacuum air port 1003, a positive pressure port 1004, a vacuum connecting pipe 1005, a first pneumatic valve 1006, a vacuum pump 1007, a positive pressure connecting pipe 1008, and a second pneumatic valve 1009. The steam engine 1010 and the heating furnace 1011. The plugging cavity 1002 can withstand a positive pressure and/or a negative pressure for accommodating an anodized workpiece 1001 to vacuum and spray vapor the anodized film of the anode treated workpiece 1001. deal with. Before the sealing treatment, an anodized film is formed on the surface of the anodized workpiece 1001, and the anodized film has a tubular structure which is not sealed or partially sealed, and its chemical composition is generally alumina trihydrate (Bayerite ( Al(OH) 3 )). The vacuum air port 1003 and the positive pressure port 1004 are formed on the surface of the plugging cavity 1002. The vacuum connecting tube 1005 is connected between the vacuum air port 1003 and the vacuum pump 1007 such that the sealing cavity 1002 is in communication with the vacuum pump 1007. The first pneumatic valve 1006 is disposed in the vacuum connecting tube 1005, and controls the communication between the sealing cavity 1002 and the vacuum pump 1007 by controlling the opening or closing of the first pneumatic valve 1006. In order to remove the gas in the anode tube of the anodized film of the anode treated workpiece 1001, the sealing agent is more easily entered into the nanotube tube, and when the anode treated workpiece 1001 is placed in the sealing chamber 1002, the anode can be borrowed The anode treated workpiece 1001 is vacuum evacuated by the vacuum pump 1007. The positive pressure connecting pipe 1008 is connected between the jet steamer 1010 and the positive pressure air port 1004 such that the plugging cavity 1002 communicates with the jet steamer 1010. The second pneumatic valve 1009 is disposed in the positive pressure connecting pipe 1008, and controls the communication between the sealing cavity 1002 and the steaming machine 1010 by controlling the opening or closing of the second pneumatic valve 1009. The sealing agent is injected into the sealing cavity 1002 at a high speed by the jet steamer 1010, so that the sealing agent quickly enters the inner tube of the anodized film of the anode-treated workpiece 1001 to achieve the purpose of sealing. The heating furnace 1011 surrounds the outside of the plugging cavity 1002 for maintaining the temperature in the plugging cavity 1002 for a long time constant temperature.
請參照第2圖，其顯示本發明之封孔方法之流程圖。本發明的封孔方法是藉由如第1圖所示的封孔設備1000利用真空與噴射蒸氣對陽極氧化膜進行封孔處理，其具體步驟包含：首先，進行步驟S10：將該陽極處理工件1001放置於該封孔腔體1002內。接著，進行步驟S20：利用該加熱爐1011使該封孔腔體1002維持在該特定溫度。接著，進行步驟S30：利用該真空幫浦1007將該封孔腔體1002內部抽至該負壓狀態。接著，進行步驟S40：關閉位於該真空幫浦1007與該封孔腔體1002之間的該第一氣壓閥門1006。接著，進行步驟S50：開啟位於該噴射蒸氣機1010與該封孔腔體1002之間的該第二氣壓閥門1009。最後，進行步驟S60：利用該噴射蒸氣機1010使該封孔劑進入該封孔腔體1002內，以將該封孔腔體1002內由該負壓狀態轉為該正壓狀態，並且對該陽極處理工件1001之該陽極氧化膜進行封孔處理。此封孔處理步驟可針對藉由將鋁或鋁合金進行陽極處理、硬陽處理、或微弧陽極處理所產生的陽極氧化膜進行之。在封孔過程中，藉由該加熱爐1011將該封孔腔體1002內的溫度維持在80℃至150℃之間，藉由該真空幫浦1007將該封孔腔體1002內部抽至0.01torr以下的負壓狀態，以及藉由該噴射蒸氣機1010將該封孔腔體1002內由負壓狀態轉為1.1atm以上的正壓狀態。本發明之該封孔劑的種類可包含液態狀或氣態狀之封孔劑，例如，水、水蒸氣、含有離子之水溶劑(如過渡元素之離子)、含有分子之水溶劑(如具有疏水性之烷基分子、具有親水性之羥基分子)、含有懸浮 物之溶劑(如鐵氟龍、氧化鋁粉末、二氧化鈦粉末、陶瓷池粉末、金屬粉末、高分子粉末、或鑽石粉末)。 Please refer to FIG. 2, which shows a flow chart of the sealing method of the present invention. In the sealing method of the present invention, the anodized film is sealed by vacuum and sprayed vapor by the sealing device 1000 as shown in FIG. 1. The specific steps include: first, performing step S10: processing the workpiece by the anode 1001 is placed in the plugging cavity 1002. Next, step S20 is performed to maintain the plugging cavity 1002 at the specific temperature by the heating furnace 1011. Next, step S30 is performed: the inside of the plugging cavity 1002 is evacuated to the negative pressure state by the vacuum pump 1007. Next, step S40 is performed to close the first air pressure valve 1006 between the vacuum pump 1007 and the plugging cavity 1002. Next, step S50 is performed to open the second pneumatic valve 1009 between the jet steamer 1010 and the plugging cavity 1002. Finally, step S60 is performed: the sealing agent is used to enter the sealing cavity 1002 by the steaming machine 1010 to change the inside of the sealing cavity 1002 from the negative pressure state to the positive pressure state, and The anodized film of the anode-treated workpiece 1001 is subjected to a sealing treatment. This sealing treatment step can be carried out for an anodized film produced by anodizing, hardening, or micro-arc anodic treatment of aluminum or aluminum alloy. During the sealing process, the temperature in the sealing cavity 1002 is maintained between 80 ° C and 150 ° C by the heating furnace 1011, and the inside of the sealing cavity 1002 is drawn to 0.01 by the vacuum pump 1007. The negative pressure state below torr and the positive pressure state in which the inside of the plugging cavity 1002 is rotated from the negative pressure state to 1.1 atm or more by the jet steamer 1010. The type of the sealing agent of the present invention may comprise a liquid or gaseous plugging agent, for example, water, water vapor, an aqueous solvent containing ions (such as ions of a transition element), a water solvent containing a molecule (eg, having a hydrophobicity) Alkyl molecule, hydrophilic hydroxyl molecule), containing suspension Solvents (such as Teflon, alumina powder, titanium dioxide powder, ceramic pool powder, metal powder, polymer powder, or diamond powder).
請參照第3A圖和第3B圖，其中第3A圖顯示表面形成有陽極氧化膜之鋁件之示意圖，以及第3B圖顯示第3A圖中沿A-A’截線之剖面示意圖。如第3A圖所示，當將鋁件3001放置於特定的電解液中且控制適當的陽極處理參數，會在該鋁件3001的表面形成具有規則的胞狀(cell)或奈米管結構的陽極氧化膜3003(即氧化鋁)，並且該陽極氧化膜3003之奈米管的末端與鋁3001之間的介面會形成半球形的阻障層3002，其中該陽極氧化膜3003之奈米管與該阻障層3002的成份均為三水合氧化鋁。奈米管的直徑、管密度、管壁厚度、與管長則依陽極處理參數而定。如第3B圖所示，該陽極氧化膜3003之每一奈米管為一上下端連通的中空結構，其孔半徑的大小為R且奈米管的管壁厚度為W。利用奈米管的孔半徑R的大小、管壁厚度W與管密度可計算出在單位樣品上奈米管之表面積與體積值。管密度的理論值可利用下述方法求出：當奈米管之孔直徑為(a)15nm，(b)60nm，與(c)500nm時，其管密度分別為2.6×1011，1.5×1010，與1.5×108pore/cm2。根據以上該等陽極氧化鋁膜之孔直徑與管密度值，可計算出面積為1cm2樣品表面的陽極氧化鋁膜在不同長度下的體積與表面積值。體積與表面積的計算公式分別為πR2×D×ρ與2πR×D×ρ，其中R、D、ρ分別為奈米管的孔半徑、膜厚、與管密度。 Referring to FIGS. 3A and 3B, FIG. 3A shows a schematic view of an aluminum member having an anodized film formed on its surface, and FIG. 3B shows a cross-sectional view taken along line AA' of FIG. 3A. As shown in FIG. 3A, when the aluminum member 3001 is placed in a specific electrolyte and the appropriate anode treatment parameters are controlled, a regular cell or nanotube structure is formed on the surface of the aluminum member 3001. An anodized film 3003 (ie, alumina), and an interface between the end of the nanotube of the anodized film 3003 and the aluminum 3001 forms a hemispherical barrier layer 3002, wherein the anodized film 3003 is formed with a nanotube The barrier layer 3002 is composed of alumina trihydrate. The diameter of the nanotube, tube density, wall thickness, and tube length are determined by the anode processing parameters. As shown in FIG. 3B, each nanotube of the anodized film 3003 is a hollow structure in which the upper and lower ends communicate, and the pore radius is R and the wall thickness of the nanotube is W. Using the pore radius R of the nanotube, the wall thickness W and the tube density, the surface area and volume of the nanotube on the unit sample can be calculated. The theoretical value of the tube density can be obtained by the following method: when the pore diameter of the nanotube is (a) 15 nm, (b) 60 nm, and (c) 500 nm, the tube density is 2.6 × 10 11 , 1.5 ×, respectively. 10 10 , with 1.5 × 10 8 pore/cm 2 . Based on the pore diameter and tube density values of the above anodic aluminum oxide films, the volume and surface area values of the anodic aluminum oxide films having a surface area of 1 cm 2 at different lengths can be calculated. The calculation formulas of volume and surface area are πR 2 ×D×ρ and 2πR×D×ρ, respectively, where R, D and ρ are the pore radius, film thickness and tube density of the nanotube.
理論上，形成在高純度的鋁件上的陽極氧化膜尤其容易形成六角型的管胞狀，其形成原理如第4A圖和第4B圖所示，第4A圖和第4B圖分別顯示三軸力平衡之示意圖。由於陽極氧化膜成長時氫氣逸出與薄膜 互相推擠之力平衡現象會使得陽極氧化膜形成六角型管胞結構。如第4A圖和第4B圖所示，當γAB=γAC=γBC時，γAC與γBC間的夾角可表示為 (第4A圖，根據正弦定律 ()。如第4B圖所示，當各夾角為120°時，進一步將 120°夾角視為管壁的角度，則三個120°夾角的管壁可組合成一六角型結構的管胞。 Theoretically, an anodized film formed on a high-purity aluminum member is particularly easy to form a hexagonal tubular shape, and its formation principle is as shown in FIGS. 4A and 4B, and FIGS. 4A and 4B respectively show three axes. Schematic diagram of force balance. The balance of the force of hydrogen evolution and the pushing of the films during the growth of the anodized film causes the anodized film to form a hexagonal tracheid structure. As shown in Fig. 4A and Fig. 4B, when γ AB = γ AC = γ BC , the angle between γ AC and γ BC can be expressed as (Fig. 4A, according to the sine law ). As shown in Fig. 4B, when the angle is 120°, and the angle of 120° is further regarded as the angle of the tube wall, the tube walls of the three 120° angles can be combined into a hexagonal structure.
請參照第5A圖和第5B圖，其分別顯示陽極氧化膜的之管壁厚度與管內體積或管內表面積之對應圖，其中第5A圖和第5B圖中的數值係基於1cm2面積上的理論計算值。在第5A圖中，顯示陽極氧化鋁膜(Anodic Aluminum Oxide，AAO)的管內體積與孔直徑ψ之對應圖，當陽極氧化鋁膜的管壁厚度為100μm時，孔直徑ψ為15nm、60nm、與500nm之分別對應的管內體積為0.0046cm3、0.0048cm3、0.0069cm3。因為胞狀管壁佔據了部分的管內體積，因此當孔直徑ψ為15nm、60nm、與500nm時，陽極氧化鋁膜的管壁厚度需超過1cm(例如分別達2.18cm、2.09cm與、1.46cm)，胞狀管內體積才會達1cm3。相對於單位體積內陽極氧化鋁膜體積的縮減，陽極氧化鋁膜的管內表面積則大幅的增加。如第5B圖所示，當管壁厚度為100μm時，孔直徑ψ為15nm、60nm、與500nm的陽極氧化鋁膜的管內表面積分別為1225.2cm2、3204.4cm2、與549.7cm2。另外，當管壁厚度為1cm時，孔直徑ψ為15nm、60nm、與500nm的陽極氧化鋁膜的管內表面積分別為1,225,220cm2、320,442cm2、與54,997cm2，即相對於1cm3(管內表面積為6cm2)緻密的塊材，孔直徑ψ為15nm、60nm、與500nm 的1cm3的陽極氧化鋁膜，其管內表面積分別增加了204,203、53,407、與9,166倍。 Please refer to FIG. 5A and FIG. 5B , which respectively show the corresponding relationship between the wall thickness of the anodized film and the volume inside the tube or the surface area inside the tube, wherein the values in FIGS. 5A and 5B are based on an area of 1 cm 2 . Theoretical calculations. In Fig. 5A, the corresponding relationship between the intraluminal volume and the pore diameter ψ of the anodic aluminum oxide film (AAO) is shown. When the wall thickness of the anodic aluminum oxide film is 100 μm, the pore diameter ψ is 15 nm, 60 nm. , and 500nm respectively corresponding to the volume of the inner tube is 0.0046cm 3, 0.0048cm 3, 0.0069cm 3 . Since the cell wall occupies part of the intra-tube volume, when the hole diameter ψ is 15 nm, 60 nm, and 500 nm, the wall thickness of the anodized aluminum film needs to exceed 1 cm (for example, 2.18 cm, 2.09 cm, and 1.46, respectively). Cm), the volume inside the cell tube will reach 1cm 3 . The inner surface area of the anodized aluminum film is greatly increased relative to the reduction in the volume of the anodized aluminum film per unit volume. As shown in FIG. 5B, when the wall thickness is 100 m, ψ pore diameter of 15nm, 60nm, and an anodized aluminum film of the inner tube surface area, respectively 500nm 1225.2cm 2, 3204.4cm 2, and 549.7cm 2. Further, when the tube wall thickness is 1 cm, the pore diameter ψ is 15 nm, 60 nm, and the inner surface area of the 500 nm anodized aluminum film is 1,225,220 cm 2 , 320,442 cm 2 , and 54,997 cm 2 , that is, relative to 1 cm 3 ( The inner surface area of the tube was 6 cm 2 ). The dense bulk material, the pore diameter ψ was 15 nm, 60 nm, and the 500 nm 1 cm 3 anodized aluminum film, and the inner surface area thereof was increased by 204, 203, 53, 407, and 9,166 times, respectively.
請參照第6A圖和第6B圖，其中第6A圖顯示陽極氧化膜進行封孔處理之前的結構示意圖，以及第6B圖顯示陽極氧化膜進行封孔處理之後的結構示意圖。如第6A圖所示，該陽極氧化膜在未進行封孔前具有規則性之管胞狀結構，該陽極氧化膜管內體積與管內表面積的計算方式可依據前述之公式計算。管胞狀之該陽極氧化膜除了具有可與熱水進行體積膨脹之封孔特性外，亦可提供大表面積與空間以供第二相化學物質填充，使得該陽極氧化膜獲得多樣化的表面改質特性。如第6B圖所示，管胞狀之該陽極氧化膜經過熱水體積膨脹之封孔後，呈現封孔狀，以具有緻密的陽極氧化膜特性。 Please refer to FIG. 6A and FIG. 6B, wherein FIG. 6A shows a schematic structural view before the anodized film is subjected to the sealing treatment, and FIG. 6B shows a schematic structural view after the anodized film is subjected to the sealing treatment. As shown in FIG. 6A, the anodized film has a regular tubular structure before sealing, and the calculation method of the inner volume and the inner surface area of the anodized film can be calculated according to the above formula. In addition to the sealing property of volume expansion with hot water, the tubular anodized film can also provide a large surface area and space for the second phase chemical to be filled, so that the anodized film can be diversified. Quality characteristics. As shown in Fig. 6B, the anodized film of the tubular shape is sealed by a volume expansion of hot water, and has a pore-like shape to have a dense anodized film property.
第一實施例： First embodiment:
在此較佳實施例中，將表面經過機械研磨之鋁片再經陽極處理後可使鋁片反應成多孔性之三氧化二鋁薄膜，並利用外加電壓與電解液成份來控制孔密度的分佈與孔洞的大小，陽極處理的電解液主要以草酸為主，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小時、電解液溫度為25℃、可使金屬鋁片表面反應產生多孔性的三氧化二鋁薄膜。請參照第7A圖和第7B圖，其分別顯示本發明之第一較佳實施例之鋁片藉由草酸溶液進行陽極表面處理前與處理後之微結構示意圖。如第7A圖所示，鋁片之陽極氧化膜未封孔前呈現多孔性結構。接著，利用第1圖所示之本發明之該封孔設備1000針對多孔性的三氧化二鋁薄膜進行封孔處理。首先，將未封孔之陽極處理試片置於該封孔腔體內，並使該封孔腔體 保持一特定溫度，例如80~150℃之間，將該封孔腔體施以負壓處理，其真空度保持在0.1torr以下，並使該封孔腔體在此真空度與溫度條件下持續3分鐘以上，再將真空閥門(即，第一氣壓閥門)關閉，接續將開啟噴射蒸氣閥門(即，第二氣壓閥門)，使封孔蒸氣(即，封孔劑)進入封孔腔體內對陽極處理試片進行封孔處理，封孔時間保持在5分鐘以上，經過封孔處理後的陽極氧化膜可呈現出緻密薄膜的微結構，如第7B圖所示，陽極處理試片之陽極氧化膜經短真空與噴射蒸氣封孔後呈現奈米顆粒填充的微結構。 In the preferred embodiment, the surface of the mechanically polished aluminum sheet is subjected to anodization to react the aluminum sheet into a porous aluminum oxide film, and the applied voltage and electrolyte composition are used to control the distribution of the pore density. With the size of the hole, the anode treated electrolyte is mainly oxalic acid, using 3wt% aqueous oxalic acid solution as electrolyte, plus 40 volt DC voltage, anode treatment time 1 hour, electrolyte temperature 25 °C, metal aluminum sheet surface The reaction produces a porous aluminum oxide film. Please refer to FIG. 7A and FIG. 7B, which respectively show the microstructures of the aluminum sheet of the first preferred embodiment of the present invention before and after the surface treatment of the anode by the oxalic acid solution. As shown in Fig. 7A, the anodized film of the aluminum sheet exhibits a porous structure before being sealed. Next, the porous aluminum oxide film is subjected to a sealing treatment by the plugging apparatus 1000 of the present invention shown in Fig. 1. First, an unsealed anodized test piece is placed in the sealed cavity, and the sealed cavity is Maintaining a specific temperature, for example, between 80 and 150 ° C, applying a vacuum treatment to the sealed cavity, the vacuum is maintained below 0.1 torr, and the sealed cavity is continued under the vacuum and temperature conditions. After more than 3 minutes, the vacuum valve (ie, the first air pressure valve) is closed, and the injection steam valve (ie, the second air pressure valve) is opened to make the sealing vapor (ie, the sealing agent) enter the sealing cavity. The anodized test piece is subjected to sealing treatment, and the sealing time is maintained for more than 5 minutes. The anodized film after the sealing treatment can exhibit the microstructure of the dense film, as shown in Fig. 7B, the anodizing of the anodized test piece. The membrane exhibits a nanoparticle-filled microstructure after being sealed by a short vacuum and sprayed vapor.
第二實施例： Second embodiment:
在此較佳實施例中，將表面經過機械研磨之鋁片再經陽極處理後可使鋁片反應成多孔性之三氧化二鋁薄膜，並利用外加電壓與電解液成份來控制孔密度的分佈與孔洞的大小，陽極處理的電解液主要以硫酸為主，利用3wt%硫酸水溶液為電解液、外加35伏特直流電壓、陽極處理時間1小時、電解液溫度為25℃、可使金屬鋁片表面反應產生多孔性的三氧化二鋁薄膜。請第8A圖和第8B圖，其分別顯示本發明第二較佳實施例中鋁片藉由硫酸溶液進行陽極表面處理前與處理後之微結構示意圖。如第8A圖所示，鋁片之陽極氧化膜未封孔前呈現多孔性結構。接著，利用第1圖所示之本發明之該封孔設備1000針對多孔性的三氧化二鋁薄膜進行封孔處理。首先，將未封孔之陽極處理試片置於封孔腔體內，並使該封孔腔體保持一特定溫度，例如80~150℃之間，將該封孔腔體施以負壓處理，其真空度保持在0.1torr以下，並使該封孔腔體在此真空度與溫度條件下持續3分鐘以上，再將真空閥門關閉(即，第一氣壓閥門)，接續開啟噴射蒸氣閥門(即，第二氣壓閥門)，使封孔蒸氣(即，封孔劑)進入該封孔腔體內對陽極處理試片進 行封孔處理，封孔時間保持在1小時以上，經過封孔處理後的陽極氧化膜可呈現出縮孔的微結構。如第8B圖所示，經長時間真空與噴射蒸氣封孔後陽極氧化膜呈現縮孔的微結構。封孔前陽極氧化膜的孔直徑平均為50nm，封孔前陽極氧化膜的孔直徑平均為34nm，其孔經縮孔率為33%。 In the preferred embodiment, the surface of the mechanically polished aluminum sheet is subjected to anodization to react the aluminum sheet into a porous aluminum oxide film, and the applied voltage and electrolyte composition are used to control the distribution of the pore density. The size of the hole, the anode treated electrolyte is mainly sulfuric acid, using 3wt% sulfuric acid aqueous solution as electrolyte, plus 35 volts DC voltage, anode treatment time 1 hour, electrolyte temperature 25 ° C, can make metal aluminum sheet surface The reaction produces a porous aluminum oxide film. Please refer to FIG. 8A and FIG. 8B, which respectively show schematic diagrams of the microstructure of the aluminum sheet before and after the surface treatment of the aluminum sheet by the sulfuric acid solution in the second preferred embodiment of the present invention. As shown in Fig. 8A, the anodized film of the aluminum sheet exhibits a porous structure before being sealed. Next, the porous aluminum oxide film is subjected to a sealing treatment by the plugging apparatus 1000 of the present invention shown in Fig. 1. First, the unsealed anode treated test piece is placed in the sealed cavity, and the sealed cavity is maintained at a specific temperature, for example, between 80 and 150 ° C, and the sealed cavity is subjected to a negative pressure treatment. The vacuum is maintained below 0.1 torr, and the sealing cavity is maintained under the vacuum and temperature conditions for more than 3 minutes, and then the vacuum valve is closed (ie, the first pneumatic valve), and the injection steam valve is continuously opened (ie, , the second air pressure valve), so that the sealing vapor (ie, the sealing agent) enters the sealing cavity to feed the anode treatment piece The sealing treatment is carried out for a period of more than 1 hour, and the anodized film after the sealing treatment can exhibit a microporous structure. As shown in Fig. 8B, the anodized film exhibits a crater microstructure after being sealed with a long time vacuum and sprayed vapor. The pore diameter of the anodized film before sealing was 50 nm on average, and the pore diameter of the anodized film before sealing was 34 nm on average, and the pore shrinkage ratio was 33%.
1000‧‧‧封孔設備 1000‧‧‧sealing equipment
1001‧‧‧陽極處理工件 1001‧‧‧Anode treated workpiece
1002‧‧‧封孔腔體 1002‧‧‧ Sealing cavity
1003‧‧‧真空氣壓口 1003‧‧‧vacuum pressure port
1004‧‧‧正壓氣壓口 1004‧‧‧ positive pressure port
1005‧‧‧真空連接管 1005‧‧‧Vacuum connecting tube
1006‧‧‧第一氣壓閥門 1006‧‧‧First air pressure valve
1007‧‧‧真空幫浦 1007‧‧‧vacuum pump
1008‧‧‧正壓連接管 1008‧‧‧ positive pressure connecting pipe
1009‧‧‧第二氣壓閥門 1009‧‧‧Second air pressure valve
1010‧‧‧噴射蒸氣機 1010‧‧‧Steaming machine
1011‧‧‧加熱爐 1011‧‧‧heating furnace
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| TW105111054A TWI588300B (en) | 2016-04-08 | 2016-04-08 | Sealing equipment and method for sealing pores of anodic oxide film by using vacuum and injection steam |
| CN201610298337.4A CN107268060A (en) | 2016-04-08 | 2016-05-06 | Hole sealing equipment and method for sealing hole of anodic oxide film by using vacuum and jet steam |
| JP2016159837A JP6337052B2 (en) | 2016-04-08 | 2016-08-17 | Sealing device and method for sealing holes in anodized film using vacuum and vapor jet |
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| CN112466512B (en) * | 2020-11-16 | 2023-02-03 | 深圳市铂科新材料股份有限公司 | Inorganic coated insulated copper wire and preparation method thereof |
| CN112725860B (en) * | 2021-01-16 | 2022-02-15 | 江门市钜硕丰五金制品有限公司 | Simple micro-arc oxidation aluminum material treatment method |
| CN114540806B (en) * | 2021-04-11 | 2023-09-05 | 广东兴发铝业有限公司 | Aluminum alloy passivation film treatment method |
| CN113122833B (en) * | 2021-04-11 | 2022-07-15 | 宁波奋达新能源科技有限公司 | Aluminum alloy passivation method |
| CN113913897B (en) * | 2021-10-12 | 2024-01-09 | 长安大学 | Preparation method of ceramic membrane with antibacterial function based on magnesium alloy |
| CN114277418A (en) * | 2021-11-29 | 2022-04-05 | 广东烨兴科技有限公司 | Preparation method of pore-free ceramic membrane covered wire |
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