Patent Publication Number: US-2009233113-A1

Title: Aluminum member or aluminum alloy member with excellent corrosion resistance

Description:
TECHNICAL FIELD 
     The present invention relates to an aluminum alloy material or an aluminum material having excellent gaseous-corrosion resistance and plasma-corrosion resistance, and particularly relates to an aluminum alloy member (aluminum alloy material or aluminum material) suitable for a material of apparatus using gas or plasma containing a corrosive component or element such as apparatus of manufacturing electronic products or instruments of semiconductor or liquid crystal devices or the like, and relates to a vacuum vessel (vacuum chamber) or a reactor vessel (reactor chamber), or a component set in the vessel, the vessel or the component being formed of the member. 
     BACKGROUND ART 
     Corrosion resistance to corrosive gas (hereinafter, called resistance to gaseous corrosion) is required for a vacuum chamber or reactor chamber (hereinafter, chamber), because corrosive gas containing a halogen element such as Cl, F or Br is introduced to the inside of the chamber as reaction gas, etching gas, or cleaning gas. Moreover, in the chambers, since halogenous plasma is often generated in addition to the corrosive gas, corrosion resistance against plasma (hereinafter, called resistance to plasma) is regarded as important. For application as above, a vacuum chamber or reaction chamber made of aluminum or an aluminum alloy, which is lightweight and excellent in heat conductivity, has been used. Furthermore, the aluminum or aluminum alloy is now extensively used for the component set in the chamber. 
     However, since the aluminum or aluminum alloy does not have sufficient resistance to gaseous corrosion and resistance to plasma, various surface modification techniques have been proposed to improve properties of those resistance. 
     As the techniques for improving the resistance to gaseous corrosion and the resistance to plasma, for example, patent literature 1 proposes a technique that an anodic oxide coating in 0.5 to 20 μm is formed, then the coating is subjected to drying by heating at 100 to 150° C. in vacuum so that water content adsorbed in the coating is evaporated and removed. Patent literature 2 proposes a technique that an Al alloy containing copper of 0.05 to 4.0% is subjected to anodizing in an oxalic acid electrolyte, and further dipped in the electrolyte with voltage being dropped. 
     However, since these anodic oxide coatings are significantly different in corrosion resistance to the gas or plasma depending on quality of the coating, they can not meet the requirement of the corrosion resistance in some use environment of a member for semiconductor manufacturing. Moreover, corrosion may cause unstable electrical properties, and particularly in a process using plasma, the properties can not be kept stable, consequently quality control of products may be obstructed. 
     On the other hand, in addition to the anodic oxide coating, as coatings having excellent corrosion resistance to the corrosive gas or plasma, coatings of ceramics such as oxides, nitrides, carbonitrides, borides and silicides are given. Examples that the ceramic coatings are directly provided on a surface of an Al alloy by arc ion plating, sputtering, thermal spraying, CVD or the like are found in patent literature 3 and patent literature 4. However, again in the coatings, while they have excellent corrosion resistance to halogen gas or plasma to some extent, they can not sufficiently respond to the requirement of the corrosion resistance to the gas or plasma, which is now strictly evaluated, similarly as the anodic oxide coating. 
     Furthermore, patent literature 5 and patent literature 6 disclose examples that a ceramic coating is further provided on an anodic oxide coating. However, in this case, there is a particular difficulty in that adhesion between the anodic oxide coating and the ceramic coating is bad. In particular, the members for apparatus of manufacturing the semiconductor or liquid crystal devices are under a severe use environment that the members may be subjected to a number of heat cycles depending on process conditions of manufacturing the semiconductor or liquid crystal devices. Therefore, the members for the apparatus of manufacturing semiconductor or liquid crystal devices are required to have adhesion in a level that separation between the anodic oxide coating and an Al alloy substrate or between the anodic oxide coating and the ceramic coating do not occur even under high-temperature heat cycle or under corrosive environment of gas or plasma. 
     The patent literature 5 discloses a structure having a boron carbide layer coated on an aluminum base substrate, and an anodic oxide layer formed between the substrate and the boron carbide layer, and proposes a measure of roughing a surface of the anodic oxide coating for improving adhesion of the boron carbide layer to the anodic oxide coating. While boron carbide is a ceramic having excellent resistance to gas corrosion and resistance to plasma, adhesion is bad particularly to the anodic oxide coating and insufficient only by roughing the surface, resulting in cracks or separation, consequently sufficient resistance to gas corrosion or resistance to plasma is not obtained. 
     The patent literature 6 proposes a measure that 0.1% or more of one or at least two elements selected from C, N, P, F, B and S are contained in the anodic oxide coating in order to improve adhesion between the ceramic coating and the anodic oxide coating. However, it is insufficient in effect of improving the adhesion, and therefore further excellent resistance to gas corrosion or resistance to plasma is required. 
     [Patent literature 1] JP-B-5-53870 
     [Patent literature 2] JP-A-3-72098 
     [Patent literature 3] JP-B-5-53872 
     [Patent literature 4] JP-B-5-53871 
     [Patent literature 5] JP-A-10-251871 
     [Patent literature 6] JP-A-2000-119896 
     DISCLOSURE OF INVENTION 
     Problems to be Solved by the Invention 
     It is desirable to provide an aluminum alloy (or aluminum) member having an anodic oxide coating formed thereon, the coating having excellent resistance to gaseous corrosion and resistance to plasma and excellent adhesion, and a vacuum vessel (vacuum chamber), a reactor vessel (reactor chamber), or a component set in the vessel (for example, an electrode, a plate or a component for gas diffusion, a shield of preventing scattering of a substance, a ring for unifying or stabilizing plasma or gas), the vessel or the component being formed of such an aluminum alloy member having excellent corrosion resistance. 
     It is further desirable to provide a member having sufficient voltage resistance to stably keep a plasma state in a process using plasma. 
     Means for Solving the Problems 
     As a result of earnest study, the inventors propose the following aluminum or aluminum alloy members (Claims  1  to  4 ). 
     That is, an embodiment of the invention proposes the following: 
     (1) an aluminum alloy (or aluminum) member having excellent corrosion resistance, which has an anodic oxide coating formed on a surface thereof, wherein the anodic oxide coating has impedance of at least 107Ω at a frequency of 10 −2  Hz, and hardness of at least 400 in Vickers hardness (Hv); 
     (2) an aluminum alloy or aluminum member having excellent corrosion resistance, which has an anodic oxide coating formed on a surface thereof, wherein the anodic oxide coating has impedance of at least 10 8 Ω at a frequency of 10 −2  Hz, and hardness of at least 350 in Vickers hardness (Hv); 
     (3) an aluminum alloy or aluminum member wherein the above anodic oxide coating is formed by using an aqueous solution having a sulfuric acid content of 50 g/l or less (assuming that undiluted solution concentration of the sulfuric acid is 98%) and 
     (4) a member for a vacuum apparatus formed of the aluminum alloy or aluminum member having excellent corrosion resistance according to (1) to (3). 
     ADVANTAGES 
     According to an embodiment of the invention, the anodic oxide coating formed on the surface of the aluminum alloy or aluminum member is designed to have the impedance of at least 10 7 Ω at the frequency of 10 −2  Hz, and the hardness of at least 400 in Vickers hardness (Hv), or the impedance of at least 10 8 Ω at the frequency of 10 −2  Hz, and the hardness of at least 350 in Vickers hardness (Hv), thereby a coating having excellent resistance to gaseous corrosion and resistance to plasma and excellent adhesion can be formed, and accordingly an aluminum alloy or aluminum member having excellent corrosion resistance as a material for a vacuum chamber used for CVD apparatus, PVD apparatus, and dry etching apparatus can be provided. 
     Furthermore, the anodic oxide coating having the impedance of at least 10 8 Ω at the frequency of 10 −2  Hz is formed by using the aqueous solution having the sulfuric acid content of 50 g/l or less (assuming that the undiluted solution concentration of the sulfuric acid is 98%), thereby the coating can combine excellent corrosion resistance with excellent voltage resistance. 
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     The inventors have conducted study and analysis in various ways on the difficulty of the anodic oxide coating in the related art, and as a result, as clear from examples described later, found that impedance and hardness of the coating and in addition, adhesion of the coating, are importantly dominant factors in a relation to the resistance to gaseous corrosion and the resistance to plasma; and furthermore found that each of values of them is kept within a certain range, thereby the coating can be improved to have excellent resistance to gaseous corrosion and resistance to plasma, in addition, to have excellent adhesion. 
     For the voltage resistance, the inventors found that an impedance value particularly at low frequency was dominant, and finally the inventors were able to set a value necessary for obtaining stable performance. 
     Specifically, it is necessary to set the impedance and the hardness of the anodic oxide coating to one of (1) and (2) as follows: 
     (1) impedance of at least 107Ω at the frequency of 10 −2  Hz, and hardness of at least 400 in Vickers hardness (Hv). 
     (2) impedance of at least 10 8 Ω at the frequency of 10 −2  Hz, and hardness of at least 350 in Vickers hardness (Hv). 
     Moreover, to ensure sufficient voltage resistance, the coating essentially has impedance indicated in (2) above, of at least 10 8 Ω at the frequency of 10 −2  Hz, and hardness of at least 350 in Vickers hardness (Hv). More preferably, the coating has impedance of at least 10 8 Ω at the frequency of 10 −2  Hz, and hardness of at least 400 in Vickers hardness (Hv). 
     In this case, to stabilize quality of the coating, the coating is effectively formed by using the aqueous solution having the sulfuric acid content of 50 g/l or less. 
     That is, such an anodic oxide coating exhibits a small consumption rate in chloric plasma (BCl 3 +Cl 2 ), and exhibits an excellent property of corrosion resistance in hydrochloric acid (7% HCl solution) (evaluated by time required for hydrogen generation due to corrosion). Furthermore, it has excellent and stable voltage resistance also in practical corrosive environment. 
     The anodic oxide coating that satisfactorily has the impedance and the hardness can be formed on a surface of an aluminum alloy (or aluminum) member by selecting conditions of anodizing and subsequent hydrolytic treatment (sealing), which can be easily understood by embodiments described later. 
     Regarding impedance, for example, a mixed solution of sulfuric acid and oxalic acid is used as an electrolyte in the anodizing, and a mixing ratio of the oxalic acid is increased, thereby an impedance value can be increased and adjusted to be at least a lower limit of an embodiment of the invention. The impedance value can be satisfactorily adjusted by increasing temperature or pressure in the hydrolytic treatment as well. 
     Hardness of the coating can be also increased to be at least a lower limit of the embodiment of the invention by increasing the mixing ratio of the oxalic acid similarly as above. In the hydrolytic treatment, they can be adjusted to be within a range of the embodiment of the invention by controlling temperature in the treatment to be slightly low. Therefore, adjustment of both of the impedance and the hardness into particular range of the embodiment of the invention can be easily carried out and realized by those skilled in the art by considering effects of the conditions on the values, and experimentally confirming the effects as necessary. 
     For the anodizing solution, sulfuric acid of at least 50 g/l is preferably used, and furthermore a mixed solution of adding oxalic acid of 5 g/l or more, and preferably 10 g/l or more to the sulfuric acid is effectively used. In the present invention, sulfuric acid content (g/l) indicates the content of undiluted solution of the sulfuric acid in 1 l (concentration: 98%). 
     While voltage can be appropriately changed depending on purposes during electrolysis, the voltage is set to be 10 to 50 V as an initial value, and set to be 30 to 100 V as a final value, thereby advantages of the embodiment of the invention can be improved. 
     The temperature of the solution is preferably 5° C. or lower particularly in the light of improving plasma resistance (resistance to erosion due to plasma). Moreover, it is preferable that the temperature of the solution is high, at a temperature higher than 10° C., particularly in the light of further improving gas corrosion resistance. 
     For the voltage resistance, sulfuric acid of at most 50 g/l is preferably used, and furthermore a mixed solution of adding oxalic acid of 10 g/l or more, and preferably 20 g/l or more to the sulfuric acid is effectively used. While voltage can be appropriately changed depending on purposes during electrolysis, the voltage is set to be 20 to 60 V as an initial value, and set to be 30 to 100 V as a final value, thereby the advantages of the embodiment of the invention can be improved. Temperature of the solution is preferably −2 to 25° C., and further effectively within a range of 5 to 18° C. 
     The preferable range of the temperature of the anodizing solution is different depending on lights of purposes of the solution as above. Therefore, it is obvious that when anodizing is carried out, the temperature is appropriately selected in the light of a purpose required at that time. 
     For a hydrolytic reaction, water subjected to ion exchange is used. This is to minimize metal ions that may cause malfunction of a semiconductor device and the like. Moreover, as a source of inorganic ions, compounds containing Si are preferably decreased to 15 ppm or less, and more preferably 10 ppm or less. 
     A treatment method is carried out by dipping an object in the water. 
     Temperature of the solution is 60° C. or more, and treatment time is 20 min or more. Particularly, to obtain the advantages of the embodiment of the invention, the temperature of the solution is preferably set to be 90° C. or more, and more preferably 95° C. or more. The treatment can be also performed by using a method of exposing an object to pressurized steam in an atmosphere of the steam, which has been generally used, and in this case, it is recommended that pressure is controlled in a range of normal pressure to about twice the normal pressure. Temperature is preferably 90° C. or more as above, however, when pressure is applied in a region beyond the normal pressure, the advantages are exhibited even at 80 to 85° C. or more. 
     For the voltage resistance, temperature of the solution during hydrolytic reaction is 60° C. or more, and treatment time is 20 min or more, and preferably 30 min or more. Particularly, to obtain the advantages of the embodiment of the invention, the temperature of the solution is preferably set to be 70 to 90° C. The treatment can be also performed by using the method of exposing an object to pressurized steam in an atmosphere of the steam, which has been generally used, and in this case, it is recommended that pressure is controlled in a range of normal pressure to about twice the normal pressure. Temperature is preferably 70 to 90° C. as above, however, when pressure is applied in a region beyond the normal pressure, the advantages are exhibited even at 65 to 85° C. 
     The advantages of the embodiment of the invention can be achieved by specifically controlling the impedance and the hardness of the anodic oxide coating within the ranges of the conditions, which will be proved by giving specific examples below. However, the present invention is not limited thereto. 
     EXAMPLES 
     Example 1 
     Anodizing was carried out at final electrolysis voltage of 30 to 100 V and for treatment time of 20 to 200 min using Al alloy sheets of JIS 6061 or Al alloy sheets of JIS 5052 (50 to 100 mm×50 to 100 mm) as objects, and then hydrolytic treatment (sealing) was carried out, thereby various types of anodic oxide coatings (thickness: 25 to 80 μm) were formed on surfaces of the Al alloy sheets. Impedance (a value of Z at 10 −2  Hz) of the coatings was measured. The impedance was measured in a frequency range of 10 −3  Hz to 10 5  Hz, and the value at 10 −2  Hz was selected as an index of stability of the coating. Moreover, hardness of the coatings was measured using a micro-Vickers hardness tester. 
     Then, aluminum alloy sheets having the anodic oxide coatings formed thereon are irradiated with plasma gas (gas: BCl 3 /50%+Cl 2 /50% sccm, ICP: 800 to 1000 W, bias: 30 to 120 W, gas pressure: 2 mT, and temperature: 30 to 80° C.) for etching of the coatings, and etching rates at that time were investigated. Furthermore, the aluminum alloy sheets were dipped into HCl (7% aqueous solution), and time required for H 2  foaming was measured. 
     Table 1 shows detail of formation and treatment conditions of respective anodic oxide coatings, and Table 2 shows measurement results of impedance values, hardness, plasma etching rates, and H 2  foaming time in HCl dipping of the obtained anodic oxide coatings, respectively. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Example of the 
                 Anodizing 
                 Hydrolytic Treatment 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Invention or 
                   
                   
                   
                 (min) 
                   
                   
                   
                 (min) 
               
               
                   
                 Comparative 
                   
                 Liquid 
                 (V) 
                 Treatment 
                 (μm) 
                   
                   
                 Treatment 
               
               
                 No 
                 Example 
                 Treatment Liquid 
                 Temperature 
                 Voltage 
                 Time 
                 Thickness 
                 Temperature 
                 Method 
                 Time 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 comparative ex 
                 sulfric acid 200 g/l 
                 5° 
                 C. 
                 20~40 
                 100 
                 50 
                 90° 
                 C. 
                 dipping 
                 30 
               
               
                 2 
                 ex of the 
                 ″ 
                 12.5° 
                 C. 
                 20~40 
                 100 
                 50 
                 95° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 invention 
               
               
                 3 
                 comparative ex 
                 ″ 
                 5° 
                 C. 
                 20~40 
                 100 
                 50 
                 100° 
                 C. 
                 ″ 
                 30 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 4 
                 ″ 
                 ″ 
                 ″ 
                 20~40 
                 100 
                 50 
                 90° 
                 C. 
                 pressuring 
                 15 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 5 
                 ″ 
                 sulfric acid 150 g/l 
                 ″ 
                 15~25 
                 100 
                 40 
                 ″ 
                 dipping 
                 30 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 6 
                 ex of the 
                 ″ 
                 13° 
                 C. 
                 15~25 
                 100 
                 40 
                 ″ 
                 ″ 
                 30 
               
               
                   
                 invention 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 7 
                 comparative ex 
                 ″ 
                 5° 
                 C. 
                 15~25 
                 100 
                 40 
                 95° 
                 C. 
                 ″ 
                 30 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 8 
                 ″ 
                 ″ 
                 ″ 
                 15~25 
                 100 
                 40 
                 100° 
                 C. 
                 ″ 
                 30 
               
               
                 9 
                 ″ 
                 ″ 
                 ″ 
                 15~25 
                 100 
                 40 
                 90° 
                 C. 
                 pressuring 
                 15 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 10 
                 ex of the 
                 ″ 
                 13° 
                 C. 
                 15~25 
                 100 
                 40 
                 ″ 
                 pressuring 
                 15 
               
               
                   
                 invention 
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
               
                 11 
                 comparative ex 
                 sulfric acid 200 + 
                 5° 
                 C. 
                 30~50 
                 160 
                 60 
                 ″ 
                 dipping 
                 30 
               
               
                   
                   
                 oxalic acid 5 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 12 
                 ″ 
                 sulfric acid 200 + 
                 ″ 
                 30~50 
                 160 
                 60 
                 95° 
                 C. 
                 ″ 
                 30 
               
               
                   
                   
                 oxalic acid 5 g/l 
               
               
                 13 
                 ″ 
                 sulfric acid 200 + 
                 ″ 
                 30~50 
                 160 
                 60 
                 100° 
                 C. 
                 ″ 
                 30 
               
               
                   
                   
                 oxalic acid 5 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 14 
                 ex of the 
                 sulfric acid 200 + 
                 ″ 
                 40~50 
                 120 
                 50 
                 ″ 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 15 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 15 
                 ex of the 
                 sulfric acid 200 + 
                 11° 
                 C. 
                 40~50 
                 120 
                 50 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 15 g/l 
               
               
                 16 
                 ex of the 
                 sulfric acid 200 + 
                 5° 
                 C. 
                 50~65 
                 120 
                 50 
                 100° 
                 C. 
                 ″ 
                 45 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
               
                 17 
                 ex of the 
                 sulfric acid 200 + 
                 13.5° 
                 C. 
                 50~65 
                 120 
                 50 
                 95° 
                 C. 
                 ″ 
                 45 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 18 
                 comparative ex 
                 sulfric acid 200 + 
                 5° 
                 C. 
                 20~30 
                 100 
                 50 
                 ″ 
                 ″ 
                 40 
               
               
                   
                   
                 oxalic acid 5 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 19 
                 ex of the 
                 sulfric acid 200 + 
                 ″ 
                 20~60 
                 150 
                 70 
                 ″ 
                 ″ 
                 30 
               
               
                   
                 invention 
                 oxalic acid 10 g/l 
               
               
                 20 
                 ex of the 
                 sulfric acid 150 + 
                 ″ 
                 20~60 
                 180 
                 80 
                 ″ 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 15 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 21 
                 ex of the 
                 sulfric acid 150 + 
                 13° 
                 C. 
                 20~60 
                 180 
                 80 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 15 g/l 
               
               
                 22 
                 ex of the 
                 sulfric acid 150 + 
                 5° 
                 C. 
                 30~65 
                 150 
                 60 
                 95° 
                 C. 
                 ″ 
                 50 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 23 
                 ex of the 
                 sulfric acid 150 + 
                 ″ 
                 30~65 
                 150 
                 65 
                 ″ 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 24 
                 ex of the 
                 sulfric acid 150 + 
                 13° 
                 C. 
                 30~65 
                 150 
                 65 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
               
                 25 
                 ex of the 
                 sulfric acid 150 + 
                 5° 
                 C. 
                 40~75 
                 120 
                 70 
                 95° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 26 
                 ex of the 
                 sulfric acid 150 + 
                 ″ 
                 50~65 
                 100 
                 30 
                 90° 
                 C. 
                 ″ 
                 60 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
               
                 27 
                 ex of the 
                 sulfric acid 150 + 
                 ″ 
                 50~65 
                 100 
                 30 
                 98° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
               
                 28 
                 ex of the 
                 sulfric acid 150 + 
                 ″ 
                 50~65 
                 100 
                 30 
                 100° 
                 C. 
                 ″ 
                 50 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 29 
                 ex of the 
                 sulfric acid 150 + 
                 13.5° 
                 C. 
                 50~65 
                 100 
                 30 
                 ″ 
                 ″ 
                 50 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 30 
                 ex of the 
                 sulfric acid 150 + 
                 16° 
                 C. 
                 50~65 
                 100 
                 30 
                 85° 
                 C. 
                 ″ 
                 50 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
               
                 31 
                 comparative ex 
                 sulfric acid 30 + 
                 10° 
                 C. 
                 40~60 
                 160 
                 30 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                   
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 32 
                 ″ 
                 sulfric acid 30 + 
                 ″ 
                 40~60 
                 160 
                 30 
                 95° 
                 C. 
                 ″ 
                 40 
               
               
                   
                   
                 oxalic acid 20 g/l 
               
               
                 33 
                 ″ 
                 sulfric acid 30 + 
                 ″ 
                 35~45 
                 160 
                 25 
                 100° 
                 C. 
                 ″ 
                 30 
               
               
                   
                   
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 34 
                 ex of the 
                 sulfric acid 30 + 
                 14.5° 
                 C. 
                 35~45 
                 160 
                 25 
                 90° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
               
                 35 
                 ex of the 
                 sulfric acid 30 + 
                 15.5° 
                 C. 
                 35~45 
                 160 
                 25 
                 80° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
               
                 36 
                 comparative ex 
                 sulfric acid 30 + 
                 10° 
                 C. 
                 35~45 
                 160 
                 25 
                 80° 
                 C. 
                 pressuring 
                 30 
               
               
                   
                   
                 oxalic acid 20 g/l 
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
               
                 37 
                 ex of the 
                 sulfric acid 30 + 
                 15.5° 
                 C. 
                 35~45 
                 160 
                 25 
                 80° 
                 C. 
                 pressuring 
                 30 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                 Example of the 
                   
                   
                   
                   
               
               
                   
                 Invention or 
                 Impedance Z 
                 Hardness of 
                 BCl3 + Cl2 plasma 
               
               
                   
                 Comparative 
                 Value at 10 −2  Hz 
                 Coating 
                 etching rate 
                 H2 Foaming Time due to 
               
               
                 No 
                 Example 
                 (Ω) 
                 (Hv) 
                 (μm) 
                 HCl Dipping (mm) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 comparative ex 
                 9 × 10 5   
                 380 
                 0.46 
                 3 
               
               
                 2 
                 ex of the 
                 4 × 10 7   
                 410 
                 0.25 
                 40 
               
               
                   
                 invention 
               
               
                 3 
                 comparative ex 
                 2 × 10 7   
                 364 
                 0.29 
                 7 
               
               
                 4 
                 ″ 
                 8 × 10 7   
                 380 
                 0.26 
                 10 
               
               
                 5 
                 ″ 
                 1 × 10 6   
                 390 
                 0.48 
                 3 
               
               
                 6 
                 ex of the 
                 2 × 10 7   
                 405 
                 0.24 
                 35 
               
               
                   
                 invention 
               
               
                 7 
                 comparative ex 
                 1 × 10 7   
                 372 
                 0.30 
                 10 
               
               
                 8 
                 ″ 
                 4 × 10 7   
                 370 
                 0.24 
                 10 
               
               
                 9 
                 ″ 
                 2 × 10 7   
                 380 
                 0.25 
                 7 
               
               
                 10 
                 ex of the 
                 7 × 10 7   
                 405 
                 0.20 
                 45 
               
               
                   
                 invention 
               
               
                 11 
                 comparative ex 
                 5 × 10 6   
                 394 
                 0.36 
                 3 
               
               
                 12 
                 ″ 
                 5 × 10 6   
                 380 
                 0.30 
                 3 
               
               
                 13 
                 ″ 
                 4 × 10 7   
                 380 
                 0.22 
                 10 
               
               
                 14 
                 ex of the 
                 4 × 10 7   
                 410 
                 0.15 
                 15 
               
               
                   
                 invention 
               
               
                 15 
                 ex of the 
                 2 × 10 8   
                 405 
                 0.15 
                 30 
               
               
                   
                 invention 
               
               
                 16 
                 ex of the 
                 2 × 10 7   
                 405 
                 0.18 
                 12 
               
               
                   
                 invention 
               
               
                 17 
                 ex of the 
                 3 × 10 8   
                 405 
                 0.15 
                 40 
               
               
                   
                 invention 
               
               
                 18 
                 comparative ex 
                 2 × 10 7   
                 390 
                 0.24 
                 15 
               
               
                 19 
                 ex of the 
                 1 × 10 7   
                 410 
                 0.20 
                 15 
               
               
                   
                 invention 
               
               
                 20 
                 ex of the 
                 2 × 10 7   
                 415 
                 0.19 
                 12 
               
               
                   
                 invention 
               
               
                 21 
                 ex of the 
                 5 × 10 7   
                 410 
                 0.20 
                 35 
               
               
                   
                 invention 
               
               
                 22 
                 ex of the 
                 3 × 10 7   
                 415 
                 0.12 
                 12 
               
               
                   
                 invention 
               
               
                 23 
                 ex of the 
                 4 × 10 7   
                 410 
                 0.19 
                 15 
               
               
                   
                 invention 
               
               
                 24 
                 ex of the 
                 2 × 10 8   
                 405 
                 0.20 
                 40 
               
               
                   
                 invention 
               
               
                 25 
                 ex of the 
                 2 × 10 7   
                 410 
                 0.22 
                 15 
               
               
                   
                 invention 
               
               
                 26 
                 ex of the 
                 1 × 10 7   
                 415 
                 0.25 
                 15 
               
               
                   
                 invention 
               
               
                 27 
                 ex of the 
                 3 × 10 7   
                 410 
                 0.15 
                 20 
               
               
                   
                 invention 
               
               
                 28 
                 ex of the 
                 4 × 10 7   
                 410 
                 0.12 
                 20 
               
               
                   
                 invention 
               
               
                 29 
                 ex of the 
                 7 × 10 7   
                 400 
                 0.16 
                 40 
               
               
                   
                 invention 
               
               
                 30 
                 ex of the 
                 2 × 10 8   
                 400 
                 0.16 
                 50 
               
               
                   
                 invention 
               
               
                 31 
                 comparative ex 
                 2 × 10 6   
                 390 
                 0.37 
                 10 
               
               
                 32 
                 ″ 
                 8 × 10 6   
                 380 
                 0.30 
                 10 
               
               
                 33 
                 ″ 
                 1 × 10 7   
                 380 
                 0.28 
                 7 
               
               
                 34 
                 ex of the 
                 7 × 10 7   
                 405 
                 0.22 
                 30 
               
               
                   
                 invention 
               
               
                 35 
                 ex of the 
                 5 × 10 7   
                 400 
                 0.25 
                 45 
               
               
                   
                 invention 
               
               
                 36 
                 comparative ex 
                 6 × 10 7   
                 360 
                 0.35 
                 7 
               
               
                 37 
                 ex of the 
                 2 × 10 8   
                 380 
                 0.22 
                 30 
               
               
                   
                 invention 
               
               
                   
               
            
           
         
       
     
     Table 2 shows that Nos. 2, 6, 10, 14 to 17, 19 to 30, 34, 35, 37 included in the scope of the present invention, that is, in the case that the impedance value at the frequency of 10 2 Hz of the anodic oxide coating is 10 7 Ω or more, and the hardness of the coating is 400 or more (Hv), the plasma etching rate is 0.25 μm or less, and the H 2  foaming time in HCl dipping is 12 min or more, excellent results have been obtained. On the other hand, nos. 3, 4, 5, 7 to 9, 11 to 13, 18, 31 to 33, 36 corresponding to comparative examples not satisfying these conditions together show deterioration in resistance to gaseous corrosion and resistance to plasma. 
     Example 2 
     Anodizing was carried out at final electrolysis voltage of 30 to 60 V and for treatment time of 60 to 200 min using Al alloy sheets of JIS 6061 or Al alloy sheets of JIS 5052 (50 to 100 mm×50 to 100 mm) as objects, and then hydrolytic treatment (sealing) was carried out, thereby various types of anodic oxide coatings (thickness: 10 to 60 μm) were formed on surfaces of the Al alloy sheets. Impedance (a value of Z at 10 −2  Hz) of the coatings was measured. The impedance was measured in a frequency range of 10 −3  Hz to 10 5  Hz, and the value at 10 −2  Hz was selected as an index of stability of the coating. Moreover, hardness of the coatings was measured using a micro-Vickers hardness tester. 
     The aluminum alloy sheets were dipped into HCl (7% aqueous solution), and time required for H 2  foaming was measured. Furthermore, dielectric breakdown voltage of the coatings was measured using a DC power supply. 
     Table 3 shows detail of formation and treatment conditions of respective anodic oxide coatings, and Table 4 shows measurement results of impedance values, hardness, H 2  foaming time in HCl dipping, and withstanding voltage (dielectric breakdown voltage) of the obtained anodic oxide coatings, respectively. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Example of the 
                 Anodizing 
                 Hydrolytic Treatment 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Invention or 
                   
                   
                   
                 (min) 
                   
                   
                   
                 (min) 
               
               
                   
                 Comparative 
                   
                 Liquid 
                 (V) 
                 Treatment 
                 (mm) 
                   
                   
                 Treatment 
               
               
                 No 
                 Example 
                 Treatment Liquid 
                 Temperature 
                 Voltage 
                 Time 
                 Thickness 
                 Temperature 
                 Method 
                 Time 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 comparative 
                 sulfric acid 200 g/l 
                 5° 
                 C. 
                 20~40 
                 100 
                 50 
                 90° 
                 C. 
                 dipping 
                 30 
               
               
                   
                 example 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 2 
                 comparative 
                 ″ 
                 ″ 
                 20~40 
                 100 
                 50 
                 100° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 example 
               
               
                 3 
                 comparative 
                 ″ 
                 ″ 
                 20~40 
                 100 
                 50 
                 90° 
                 C. 
                 pressuring 
                 15 
               
               
                   
                 example 
                   
                   
                   
                   
                   
                   
                   
                 5 kgf/mm2 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 4 
                 comparative 
                 sulfric acid 150 g/l 
                 ″ 
                 15~25 
                 100 
                 40 
                 ″ 
                 dipping 
                 30 
               
               
                   
                 example 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 5 
                 comparative 
                 ″ 
                 ″ 
                 15~25 
                 100 
                 40 
                 95° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 example 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 6 
                 comparative 
                 sulfric acid 200 + 
                 ″ 
                 30~50 
                 160 
                 60 
                 ″ 
                 dipping 
                 30 
               
               
                   
                 example 
                 oxalic acid 5 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 7 
                 comparative 
                 sulfric acid 200 + 
                 ″ 
                 30~50 
                 160 
                 60 
                 95° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 example 
                 oxalic acid 5 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 8 
                 example of the 
                 sulfric acid 2 + 
                 15° 
                 C. 
                 40~50 
                 200 
                 50 
                 80° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 9 
                 example of the 
                 sulfric acid 5 + 
                 ″ 
                 40~60 
                 200 
                 50 
                 ″ 
                 ″ 
                 45 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 10 
                 example of the 
                 sulfric acid 2 + 
                 10° 
                 C. 
                 30~40 
                 150 
                 60 
                 85° 
                 C. 
                 ″ 
                 60 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 11 
                 example of the 
                 sulfric acid 50 + 
                 ″ 
                 30~40 
                 120 
                 50 
                 ″ 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
               
                 12 
                 example of the 
                 sulfric acid 20 + 
                 ″ 
                 20~40 
                 120 
                 40 
                 ″ 
                 ″ 
                 50 
               
               
                   
                 invention 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 13 
                 example of the 
                 sulfric acid 5 + 
                 15° 
                 C. 
                 25~50 
                 180 
                 45 
                 ″ 
                 ″ 
                 40 
               
               
                   
                 invention 
                 oxalic acid 25 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 14 
                 example of the 
                 sulfric acid 2 + 
                 ″ 
                 30~60 
                 120 
                 50 
                 80° 
                 C. 
                 ″ 
                 60 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
               
                 15 
                 example of the 
                 sulfric acid 2 + 
                 ″ 
                 30~60 
                 120 
                 50 
                 90° 
                 C. 
                 ″ 
                 60 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
               
                 16 
                 example of the 
                 sulfric acid 5 + 
                 ″ 
                 25~55 
                 90 
                 30 
                 75° 
                 C. 
                 ″ 
                 90 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
               
                 17 
                 example of the 
                 sulfric acid 5 + 
                 ″ 
                 25~55 
                 90 
                 30 
                 90° 
                 C. 
                 ″ 
                 30 
               
               
                   
                 invention 
                 oxalic acid 30 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 18 
                 comparative 
                 sulfric acid 60 + 
                 10° 
                 C. 
                 20~40 
                 70 
                 30 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 example 
                 oxalic acid 20 g/l 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 19 
                 comparative 
                 sulfric acid 30 + 
                 ″ 
                 20~40 
                 160 
                 60 
                 90° 
                 C. 
                 ″ 
                 40 
               
               
                   
                 example 
                 oxalic acid 20 g/l 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                   
                 Example of the 
                   
                   
                   
                   
               
               
                   
                 Invention or 
                   
                   
                 Voltage Resistance 
               
               
                   
                 Comparative 
                 Impedance Z Value at 
                 Hardness of Coating 
                 Dielectric Breakdown 
                 H2 Foaming Time due to 
               
               
                 No 
                 Example 
                 10 −2  Hz (Ω) 
                 (Hv) 
                 Voltage (V/10 μm) 
                 HCl Dipping (min) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 comparative 
                 9 × 10 5   
                 380 
                 200 
                 3 
               
               
                   
                 example 
               
               
                 2 
                 comparative 
                 2 × 10 7   
                 364 
                 170 
                 7 
               
               
                   
                 example 
               
               
                 3 
                 comparative 
                 8 × 10 7   
                 380 
                 140 
                 10 
               
               
                   
                 example 
               
               
                 4 
                 comparative 
                 1 × 10 6   
                 390 
                 170 
                 3 
               
               
                   
                 example 
               
               
                 5 
                 comparative 
                 1 × 10 7   
                 372 
                 170 
                 10 
               
               
                   
                 example 
               
               
                 6 
                 comparative 
                 5 × 10 6   
                 394 
                 140 
                 3 
               
               
                   
                 example 
               
               
                 7 
                 comparative 
                 5 × 10 6   
                 380 
                 140 
                 3 
               
               
                   
                 example 
               
               
                 8 
                 example of the 
                 5 × 10 8   
                 360 
                 270 
                 150 
               
               
                   
                 invention 
               
               
                 9 
                 example of the 
                 3 × 10 8   
                 370 
                 240 
                 200 
               
               
                   
                 invention 
               
               
                 10 
                 example of the 
                 1 × 10 8   
                 390 
                 230 
                 120 
               
               
                   
                 invention 
               
               
                 11 
                 example of the 
                 2 × 10 8   
                 410 
                 210 
                 90 
               
               
                   
                 invention 
               
               
                 12 
                 example of the 
                 1 × 10 8   
                 400 
                 210 
                 80 
               
               
                   
                 invention 
               
               
                 13 
                 example of the 
                 3 × 10 8   
                 380 
                 270 
                 180 
               
               
                   
                 invention 
               
               
                 14 
                 example of the 
                 2 × 10 8   
                 380 
                 275 
                 180 
               
               
                   
                 invention 
               
               
                 15 
                 example of the 
                 1 × 10 8   
                 360 
                 270 
                 150 
               
               
                   
                 invention 
               
               
                 16 
                 example of the 
                 3 × 10 8   
                 370 
                 250 
                 120 
               
               
                   
                 invention 
               
               
                 17 
                 example of the 
                 2 × 10 8   
                 360 
                 210 
                 90 
               
               
                   
                 invention 
               
               
                 18 
                 comparative 
                 8 × 10 6   
                 390 
                 180 
                 15 
               
               
                   
                 example 
               
               
                 19 
                 comparative 
                 5 × 10 6   
                 380 
                 185 
                 15 
               
               
                   
                 example 
               
               
                   
               
            
           
         
       
     
     Table 4 shows that in the case of No. 8 to 17 corresponding to examples of the invention, that is, in the case that the impedance value at the frequency of 10 −2  Hz of the anodic oxide coating is 10 8 Ω or more, and the hardness of the coating is 350 or more (Hv), the H 2  foaming time in HCl dipping is 60 min or more, and the withstanding voltage is 210 V/10 μm or more. Accordingly, it is known that excellent results are obviously obtained in that case compared with the case of No. 1 to 7 and 18 to 19 corresponding to comparative examples that do not satisfy the conditions together. 
     In this way, the aluminum member or the aluminum alloy member of the embodiment of the invention has the anodic oxide coating formed on the surface of the member, which is excellent in both properties of the resistance to plasma and the resistance to gaseous corrosion, that is, has excellent corrosion resistance, therefore the member can be extremely advantageously used for a material of forming the vacuum vessel (vacuum chamber) used for the vacuum apparatuses such as CVD apparatus, PVD apparatus and dry etching apparatus, reactor vessel (reactor chamber), or component set in the vessel.