TWI588300B - Sealing equipment and method for sealing pores of anodic oxide film by using vacuum and injection steam - Google Patents

Description

Sealing device for sealing anodized film by vacuum and jet steam and method thereof

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

The present invention also illustrates the following feature points:

(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) 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) The anodized film is sealed in a vapor to keep the surface of the anodized film clean.

(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) 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) AlO(OH) has better corrosion resistance and wear resistance than Al(OH) ₃ .

(7) Sealing reaction formula: alumina trihydrate → alumina monohydrate 2Al(OH) ₃ +3H ₂ O → 2AlO(OH)+3H ₂

(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%)

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.

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.

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.

In a preferred embodiment of the invention, the furnace maintains the temperature within the sealed chamber between 80 ° C and 150 ° C.

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.

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.

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.

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.

In a preferred embodiment of the invention, the ion comprises an ion having a transition element.

In a preferred embodiment of the invention, the molecule comprises a hydrophobic alkyl molecule or a hydrophilic hydroxyl molecule.

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.

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‧‧‧sealing equipment

1001‧‧‧Anode treated workpiece

1002‧‧‧ Sealing cavity

1003‧‧‧vacuum pressure port

1004‧‧‧ positive pressure port

1005‧‧‧Vacuum connecting tube

1006‧‧‧First air pressure valve

1007‧‧‧vacuum pump

1008‧‧‧ positive pressure connecting pipe

1009‧‧‧Second air pressure valve

1010‧‧‧Steaming machine

1011‧‧‧heating furnace

3001‧‧‧Aluminum parts

3002‧‧‧ barrier layer

3003‧‧‧Anodized film

S10~S60‧‧‧Steps

A-A’‧‧‧ corresponds to the section line of Figure 3B

R‧‧‧ hole radius

W‧‧‧ wall thickness

Ψ‧‧‧ hole diameter

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.

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.

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.

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).

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.

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.

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.

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.

First embodiment:

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.

Second embodiment:

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‧‧‧sealing equipment

1001‧‧‧Anode treated workpiece

1002‧‧‧ Sealing cavity

1003‧‧‧vacuum pressure port

1004‧‧‧ positive pressure port

1005‧‧‧Vacuum connecting tube

1006‧‧‧First air pressure valve

1007‧‧‧vacuum pump

1008‧‧‧ positive pressure connecting pipe

1009‧‧‧Second air pressure valve

1010‧‧‧Steaming machine

1011‧‧‧heating furnace

Claims (11)

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 for maintaining the sealing cavity a specific temperature between 80 ° C and 150 ° C; a vacuum pump connected to the plugging cavity for drawing the inside of the plugging cavity to a negative pressure state below 0.01 torr; a jet steamer is connected to the plugging cavity for injecting a hole into the plugging cavity to convert the negative cavity into a positive pressure state greater than 1.1 atm. Wherein the sealing agent fills a hole of the anodized film of the anode-treated workpiece. The sealing device according to claim 1, wherein the anodized film comprises: the anodized film produced by anodizing, hardening, or micro-arc anodic treatment of aluminum or aluminum alloy. The sealing device of claim 1, wherein the jetting machine sprays the liquid or gaseous plugging agent into the sealing cavity to seal the anodized film of the anode treated workpiece. Hole handling. The sealing device according to claim 1, wherein the sealing agent comprises water, water vapor, an aqueous solvent containing ions, an aqueous solvent containing a molecule, or a solvent containing a suspension. The sealing device of claim 4, wherein the ion comprises an ion having a transition element. The sealing device of claim 4, wherein the molecule comprises a hydrophobic alkyl molecule or a hydrophilic hydroxyl molecule. The sealing device according to claim 4, wherein the suspension comprises Teflon, alumina powder, titanium dioxide powder, ceramic pool powder, metal powder, polymer powder, or diamond powder. A sealing method using vacuum and jetting steam, the sealing method comprises: placing an anodized workpiece having an anodized film in a cavity; maintaining the sealing cavity at 80 by using a heating furnace a specific temperature between ° C and 150 ° C; using a vacuum pump to pump the inside of the plugging cavity to a negative pressure state below 0.01 torr; closing between the vacuum pump and the plugging cavity a first pneumatic valve; opening a second pneumatic valve between a jet steamer and the plugging cavity to connect the jet steamer and the plugging cavity; and using the jet steamer to seal the sealant The sealing cavity is inserted into the sealing cavity to change from the negative pressure state to a positive pressure state greater than 1.1 atm, and the anodized film of the anode-treated workpiece is sealed. The method of sealing according to claim 8, wherein the anodized film comprises: the anodized film produced by anodizing, hardening, or micro-arc anodic treatment of aluminum or an aluminum alloy. The sealing method of claim 8, wherein the jetting machine sprays the liquid or gaseous plugging agent into the sealing cavity to seal the anodized film of the anode treated workpiece. Hole handling. The method for sealing a hole according to claim 10, wherein the sealing agent comprises water and steam a gas, an aqueous solvent containing ions, an aqueous solvent containing a molecule, or a solvent containing a suspension; wherein the ion comprises an ion having a transition element; wherein the molecule comprises a hydrophobic alkyl molecule or a hydrophilic hydroxyl molecule; And wherein the suspension comprises Teflon, alumina powder, titanium dioxide powder, ceramic pool powder, metal powder, polymer powder, or diamond powder.