CN112391659A - Method for preparing oxide film containing alpha-alumina and vessel - Google Patents
Method for preparing oxide film containing alpha-alumina and vessel Download PDFInfo
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- CN112391659A CN112391659A CN201910748557.6A CN201910748557A CN112391659A CN 112391659 A CN112391659 A CN 112391659A CN 201910748557 A CN201910748557 A CN 201910748557A CN 112391659 A CN112391659 A CN 112391659A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000010407 anodic oxide Substances 0.000 claims abstract description 60
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000007743 anodising Methods 0.000 claims description 16
- 238000002048 anodisation reaction Methods 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- 230000007704 transition Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention provides a method for preparing an oxide film containing alpha-alumina, comprising the steps of: s1: preparing an anodic oxide film on the surface of the aluminum or the aluminum alloy through anodic oxidation; s2, roasting the anodic oxide film on the surface of the aluminum alloy with the anodic oxide film formed by the aluminum alloy with the high energy density heat source at the temperature of more than 1500 ℃ to enable the aluminum oxide in the anodic oxide film to generate alpha phase change to form an oxide film containing alpha-aluminum oxide; the heat source is preferably an acetylene-pure oxygen flame, a plasma arc, a laser, or a combination thereof. The anode oxide film is roasted by a high-temperature and high-energy-density heat source, so that the gamma-alumina and the hydrated alumina in the anode oxide film can be converted into alpha-alumina at high temperature. The oxidation film after alpha phase change has a porous layer structure, the hardness reaches more than 1000HV, and the obtained oxidation film is more wear-resistant. Meanwhile, the chemical stability of the alpha-alumina is the best, so that the corrosion resistance of the oxide film is improved. The invention also provides a vessel containing the alpha-alumina oxide film.
Description
Technical Field
The invention relates to the technical field of inorganic material manufacturing, in particular to a method for preparing an oxide film containing alpha-alumina and a vessel containing the oxide film prepared by the method.
Background
Alpha-alumina (alpha-Al)2O3) Has the advantages of high hardness,has wide industrial application. Alpha-alumina (corundum) is industrially produced, and is generally obtained by roasting ordinary alumina produced by a Bayer process. Under normal conditions, the aluminum alloy is subjected to anodic oxidation treatment to form gamma-alumina (gamma-Al) with lower hardness2O3) Alumina hydrate (AlOOH), aluminum sulfate hydrate (Al (OH) SO4) An oxide film of the composition.
The aluminum alloy can form an oxidation film containing a certain amount of alpha-alumina through micro-arc oxidation under the condition of high voltage and high current and high temperature generated by micro-arc. However, in the micro-arc oxidation process, very high voltage (200-800V) and very high current density (10-30A/dm) are often required2) An oxide film layer containing alpha-alumina is formed. The heat generated by the high voltage and high current is mostly absorbed by the solution used in the process, resulting in low efficiency of energy utilization and the need to cool the solution, resulting in additional consumption of electrical energy. In the prior art, the micro-arc oxidation of aluminum alloy under the conditions of high voltage and high current requires high equipment investment and high preparation cost, and the industrial application of the micro-arc oxidation for preparing alpha-alumina is always limited. Therefore, there is a need for an industrial method for producing an oxide film containing α -alumina, which is simple to operate and low in cost.
Disclosure of Invention
An aspect of the present invention provides a method for preparing an oxide film containing α -alumina, which can greatly reduce the cost of preparing an oxide film containing α -alumina on the surface of an aluminum alloy. The method is simple and easy to implement, has small equipment investment, and can be used for preparing the oxide film containing the alpha-alumina on a large scale.
The method for preparing the oxide film of the alpha-alumina comprises the following steps:
s1: forming an anodic oxide film on the surface of the aluminum or aluminum alloy by anodic oxidation;
s2: the temperature is more than 1500 ℃, and the energy density is 10W/mm2The heat source mentioned above is used to bake the anodic oxide film to cause alpha-transformation of alumina in the anodic oxide film, thereby forming an oxide film containing alpha-alumina。
The energy density refers to the output power of the high-temperature heat source per se per unit area of the energy beam (e.g., flame, laser beam, etc.). In this application, high energy density means that the output power of the high-temperature heat source per unit area of the energy beam is 10W/mm2The above.
In step S2 of the method of the present invention, the heat source is a combustible gas combustion flame plasma arc, a laser, or a combination thereof.
The gamma-aluminum oxide (gamma-Al) in the anodic oxide film can be obtained by roasting with a high energy density heat source at a temperature of 1500 ℃ or higher2O3) The conversion of hydrated alumina (AlOOH) to alpha-alumina (alpha-Al) at high temperatures2O3). The high temperature of the heat source allows this phase change reaction to occur. The heat source must rapidly sweep the surface of the anodized film to cause the alumina in the anodized film to change phase into alpha-alumina (alpha-Al) after absorbing a certain amount of heat (e.g., 10KJ, 15KJ, 20KJ, 30KJ, 40KJ, 50KJ, 60KJ)2O3) But the aluminum alloy substrate below the oxide film does not melt (for acetylene-pure oxygen flame) and the anodized film is not visually damaged (for plasma arc, laser). The hardness of the oxide film after alpha phase change is greatly improved and generally reaches more than 1000HV, and the obtained oxide film is more wear-resistant. Meanwhile, the chemical stability of the alpha-alumina is the best, so that the corrosion resistance of the oxide film is improved.
In an embodiment of the method of the present invention, the heat source in step S2 is a natural gas-pure oxygen flame, an acetylene-pure oxygen flame, an ethylene-pure oxygen flame, or a combination thereof, and when the anodic oxide film is baked by using the natural gas-pure oxygen flame, the baking time per square decimeter of the anodic oxide film is 15 to 25 seconds. The temperature of the natural gas-pure oxygen flame is related to the components of the natural gas, and the temperature of the natural gas-pure oxygen flame is 1500-2500 ℃. Generally, the temperature of the natural gas-pure oxygen flame can be 1500-1800 ℃, 1800-2200 ℃, 2200-2500 ℃. And when the anodic oxide film is roasted by adopting acetylene-pure oxygen flame, the roasting time of the anodic oxide film per square decimeter is 5-20 seconds. The temperature of the flame of acetylene-pure oxygen and/or ethylene-pure oxygen can reach 2500-3000 ℃. In practical use, the temperature of the flame of acetylene-pure oxygen and/or ethylene-pure oxygen is 2500-2700 ℃, 2700-2800 ℃ and 2800-3000 ℃.
In one embodiment of the method of manufacturing the present invention, the heat source in step S2 is a plasma arc, and when the anodic oxide film is baked by the plasma arc, the baking time per square decimeter of the anodic oxide film is 5 to 15 seconds. The plasma arc temperature can be very high, reaching more than 4000 ℃. However, in the method of the present invention, too high a temperature may cause the aluminum or aluminum alloy to burn through in a short time, and therefore, the temperature of the plasma arc is preferably 4000 to 6000 ℃. For example, the plasma arc temperature is 4000-4500 deg.C, 4500-5000 deg.C, 5000-5500 deg.C, 5500-6000 deg.C.
In one embodiment of the method of manufacturing the present invention, the heat source in step S2 is a laser, and when the anodic oxide film is baked by the laser, the baking time per square decimeter of the anodic oxide film is 20 to 200 seconds. When the laser is used for roasting, the temperature of the laser is 4000-6000 ℃, for example, the temperature of the laser is 4000-4500 ℃, 4500-5000 ℃, 5000-5500 ℃, 5500-6000 ℃. Compared with the combustible gas-pure oxygen flame, the laser temperature is high, but the laser beam sectional area is small, the output power is small, therefore, when the laser is adopted for roasting, the roasting time needs to be longer, and the specific roasting time is determined according to the thickness of the anodic oxide film.
Further, the anodic oxidation is sulfuric acid anodic oxidation, and the thickness of an oxidation film after the sulfuric acid anodic oxidation is 15-30 micrometers.
Further, the anodic oxidation is oxalic acid anodic oxidation, and the thickness of an oxide film after the oxalic acid anodic oxidation is 15-30 microns.
Further, the anodic oxidation is hard anodic oxidation, and the thickness of an oxide film after the hard anodic oxidation is 25-100 micrometers.
Furthermore, the porosity of the anodic oxide film is 10-20%, and the porosity of the oxide film after alpha phase transition is 30-40%.
Another aspect of the present invention provides an oxide film containing α -alumina, which is prepared by the method of the present invention.
Further, the oxide film has an α -alumina porous layer structure. Further, the hole penetrates through the entire oxide film thickness.
Further, the hardness of the oxide film is 1000HV or more.
Further, the density of the oxide film is 3.2-3.98 g/cm3The above.
Further, the porosity of the oxide film is 30-40%.
The method for preparing the oxide film containing the alpha-alumina does not need equipment for generating high voltage and high current, and the equipment cost investment is low; and in the process of preparing the alpha-alumina-containing oxide film, the heat source loss is small, and the energy utilization rate is high. In addition, the method is simple to operate and easy to industrialize.
The invention further provides a vessel, which comprises a vessel base body and an oxide film arranged on the surface of the vessel base body, wherein the oxide film is prepared by the method and contains alpha-alumina, the porosity of the oxide film is 30-40%, and the oxide film has high hardness and strong corrosion resistance.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow diagram of the process of the present invention;
FIG. 2 is a schematic diagram of the phase transition of alumina at different temperatures;
FIG. 3 is a schematic illustration of a process for dehydrating hydrated alumina at elevated temperatures;
FIG. 4 is an SEM image of a cross section of an oxide film having a porous layer structure;
FIG. 5 is an SEM image of a plan view of an oxide film having a porous layer structure.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below by way of specific examples.
As shown in fig. 1, fig. 1 shows a method for preparing an oxide film containing α -alumina according to the present invention, comprising the steps of:
s1: forming an anodic oxide film on the surface of the aluminum alloy through anodic oxidation;
s2: adopts the temperature of more than 1500 ℃ and the energy density of 10W/mm2The heat source described above is used to bake the anodic oxide film, and alpha-phase transformation is performed on the alumina in the anodic oxide film, thereby forming an oxide film containing alpha-alumina.
In this application, energy density refers to the output power per unit area of the high temperature heat source itself in its energy beam (e.g., flame, laser beam, etc.); wherein the area refers to the (cross-sectional) area of the energy beam (e.g. flame or laser beam) itself of the heat source. The temperature and energy density of the heat source are important parameters for the alpha phase transformation of the alumina in the anodic oxide film. When a high energy density heat source is used, the anodic oxide film can absorb enough energy in a short time, so that alpha phase change occurs. It is difficult to cause the alpha-phase change of alumina in the anodic oxide film even when the temperature of the heat source is not high enough or the energy density of the heat source is not high enough. The energy density of the heat source is related to the kind of the heat source. For the energy density of the combustible gas type heat source, the energy density can be obtained by conversion according to the flow velocity of flame and the combustion heat of the combustible gas; for the laser or plasma arc heat source, the conversion can be obtained according to the output power of the laser or plasma arc device mark.
Industrially, commonly used high energy density heat sources include natural gas-pure oxygen flame, acetylene-pure oxygen, ethylene pure oxygen flame, plasma arc, laser. The energy density of the heat sources can reach 10W/mm2The above can satisfy the energy density requirement for the alpha phase transition of alumina. Thus, in step S2 of the method of the present invention, the heat is appliedThe source may be a natural gas-pure oxygen flame, an acetylene-pure oxygen and/or ethylene-pure oxygen flame, a plasma arc, a laser, or a combination thereof.
In S1 of the method of the present invention, the anodization may be a sulfuric acid anodization, an oxalic acid anodization, or a hard anodization, which is conventional in the art. When the anodic oxidation is carried out, the procedures of alkaline etching, neutralization and ash removal and the like are needed to be carried out on the aluminum alloy. The sealing process may not be performed after the anodic oxidation.
The passing temperature is more than 1500 ℃, and the energy density is 10W/mm2The heat source is quickly swept, so that a larger temperature gradient can be formed between the surface of the oxide film and the aluminum alloy substrate, the temperature gradient is favorable for alpha phase change of the anodic oxide film, and the aluminum alloy substrate is not melted. Thicker anodized films help provide a relatively large temperature gradient. Therefore, if the sulfuric acid anodizing process is used in step S1, the thickness of the anodized oxide film is preferably 15 to 30 μm. If the oxalic acid anodizing process is adopted in step S1, the thickness of the oxide film after the oxalic acid anodizing is preferably 15 to 30 μm. If the hard anodizing process is used in step S1, the thickness of the hard film is preferably 25 to 100 μm.
Typical sulfuric acid anodization processes, oxalic acid anodization processes, and hard anodization processes are as follows:
a typical sulfuric acid anodizing process is as follows:
sulfuric acid: 120-150 g/L;
temperature: 18-22 ℃;
current density: 1.0 to 2.0A/dm2；
Process voltage: 16-19V;
time: 30-60 min;
a typical oxalic acid anodization process is as follows:
oxalic acid: 40-60 g/L;
temperature: 25-30 ℃;
current density: 1.0 to 2.0A/dm2；
Process voltage: 50-60V;
time: 30-60 min.
A typical hard anodizing process is as follows:
sulfuric acid: 180-250 g/l;
temperature: -2 ℃ to 12 ℃;
current density: 2.0 to 4.0A/dm2；
Process voltage: 25-70V;
time: 30-50 min.
The anodization of step S1 of the method of the present invention may be performed by any of the above processes, so as to form an anodized film on the surface of the aluminum alloy.
In step S2 of the method of the present invention, the temperature for baking the anodized film must be higher than 1500 ℃, otherwise the alumina in the anodized film cannot be converted into alpha-phase alumina. The high energy density heat source can be high temperature heat source in the forms of acetylene-pure oxygen flame, plasma arc, laser and the like, and heat sources in different forms can be alternately combined according to specific conditions. The phase of alumina in the anodic oxide film is changed to alpha-alumina (alpha-Al)2O3) It is necessary to absorb a certain amount of heat, for example, 10KJ, 15KJ, 20KJ, 30KJ, 40KJ, 50KJ, 60 KJ). The phase of alumina in the anodic oxide film is changed to alpha-alumina (alpha-Al)2O3) The amount of heat required depends on the thickness of the anodized film, the type of heat source, and the firing time. For an anodized film having a small thickness, less heat is required to phase-convert alumina in the anodized film into α -alumina.
In order to make gamma-alumina (gamma-Al) in the anodic oxide film2O3) The hydrated alumina (AlOOH) generates alpha phase change, and when the anodic oxide film is roasted by adopting acetylene-pure oxygen flame, the roasting time of the anodic oxide film per square decimeter is 5-20 seconds; when the anodic oxide film is roasted by adopting plasma arcs, the roasting time of the anodic oxide film per square decimeter is 5-15 seconds; and when the anodic oxide film is roasted by laser, the roasting time of the anodic oxide film per square decimeter is 20-200 seconds. When the anodic oxide film is roasted by adopting a high-energy-density heat source, roasting is carried outToo short a time to effectively make gamma-alumina (gamma-Al) in the anodic oxide film2O3) The alpha phase transition of the hydrated aluminum oxide (AlOOH) occurs, and the long time causes the aluminum or aluminum alloy substrate to which the anodic oxide film is adhered to melt due to the high temperature or causes the anodic oxide film to be burned.
The alumina in the anodic oxide film that undergoes the α -phase transition may be a part (for example, alumina near the heat source) or the whole. Overall, the alumina in which the alpha phase transformation occurs in the anodized film may be 1/3, 1/2 or 2/3 of total alumina, and the proportion of alumina in which the alpha phase transformation occurs depends on the kind of heat source, temperature and firing time.
The hardness of the oxide film is related to the composition and porosity of the oxide film, and γ -alumina itself has a certain hardness, and generally, the hardness is decreased as the porosity is higher. However, the hardness of the oxide film containing α -alumina obtained by the treatment according to the present invention is much higher than that of the anodic oxide film before the treatment, mainly because α -alumina formed after the α -transformation has a much higher hardness than γ -alumina, and even if the porosity of the oxide film after the α -transformation is increased, the hardness of the entire oxide film after the α -transformation is higher than that of the anodic oxide film without the α -transformation. Therefore, the hardness of the oxide film subjected to alpha phase change is greatly improved, and the hardness generally reaches over 1000HV, so that the oxide film is more wear-resistant. In addition, the change in the hardness of the oxide film is also an important criterion for judging the occurrence of the α -phase transition of alumina in the anodized film. In some cases, the alpha phase change of alumina in the anodic oxide film is difficult to calculate, but the conversion of alumina in the anodic oxide film into alpha-alumina can be judged by measuring the great difference in the hardness of the oxide film.
After being roasted by a high-temperature and high-energy-density heat source, the gamma-aluminum oxide (gamma-Al) in the anodic oxide film2O3) And the hydrated alumina (AlOOH) is subjected to alpha phase change to become alpha-alumina. The density of the common anodic oxide film (sulfuric acid, oxalic acid) is 2.0-2.4 g/cm3The density of the hard anodic oxide film is 2.4-2.8 g/cm3The density of the gamma-alumina was 3.2g/cm3After being roasted by a high-temperature and high-energy-density heat source, the thickness of the oxide film is not changedThe density of the obtained oxide film containing alpha-alumina was 3.98g/cm3. This means that as the alpha phase change occurs, the alpha alumina in the oxide film will become more dense. Figure 3 shows a schematic of the dehydration of hydrated alumina at high temperature.
In addition, before the high-temperature, high-energy-density heat source firing, the anodized film has a porous layer structure as shown in fig. 4, and has a certain porosity ratio. Along with the occurrence of alpha phase change, the oxide film is more densified, and the porosity of the oxide film is greatly improved. Generally, the porosity of various anodic oxide films is 10-20%, and the porosity of the obtained oxide film is 30-40% after alpha phase change treatment.
The pores of the anodic oxide film are formed by gamma-alumina with active chemical properties in the anodic oxide film, and the pores are easily and spontaneously closed to cause the pores to disappear. However, the oxide film after the alpha phase change treatment has stable chemical properties, and the pores can be maintained for a long time. In the application occasion of abrasion, the oxide film with higher porosity can store lubricating oil, and the wear resistance of the oxide film is more outstanding by matching with harder alpha-alumina.
When the oxide film prepared by the method is used as a coating of the aluminum alloy cooker, the oxide film with more stable chemical property can enable the edible oil to permeate into the pores, so that the aluminum alloy cooker can achieve the effect of non-sticking under the condition of not arranging the non-sticking coating.
In order to further demonstrate the advantages of the method of the present invention, the following description will be made by taking preferred embodiments, but the aluminum alloy workpiece is not limited to aluminum alloy cookware or aluminum alloy pistons.
Example 1: an aluminum alloy cooker is made of 3003 materials, sulfuric acid is used for anodic oxidation, a heat source is acetylene-pure oxygen flame, wherein the temperature of the heat source is 2800 ℃, and the energy density of the heat source is 15W/mm2。
Example 2: an aluminum alloy cooker is made up of 1050 raw materials through anodic oxidation of oxalic acid, and features that the heat source is acetylene-pure oxygen flame at 3000 deg.C and 20W/mm of energy density2。
Example 3: aluminium alloyThe gold cooker comprises 3003 of material, hard anode oxidation, and ethylene-pure oxygen flame as heat source, wherein the temperature of the heat source is 2700 deg.C, and the energy density of the heat source is 40W/mm2。
Example 4: the aluminum alloy cooker comprises 3003 as material component, hard anode oxidation, and plasma arc as heat source, wherein the heat source has temperature of 4000 deg.C and energy density of 50W/mm2。
Example 5: an aluminum alloy cooker is prepared from 3003 materials by hard anodizing, and laser as heat source, wherein the heat source has a temperature of 4900 deg.C and energy density of 50W/mm2。
Example 6: an aluminum alloy piston is prepared from 6063 materials by hard anodizing, wherein the heat source is acetylene-pure oxygen flame, the temperature of the heat source is 2500 ℃, and the energy density of the heat source is 60W/mm2。
Example 7: an aluminum alloy piston, material composition 6063, hard anodizing and plasma arc as a heat source, wherein the temperature of the heat source is 4200 ℃, and the energy density of the heat source is 50W/mm2。
Example 8: the aluminum alloy cooker comprises 3003 of materials, sulfuric acid is used for anodic oxidation, and a heat source is natural gas-pure oxygen flame, wherein the temperature of the heat source is 1500 ℃, and the energy density of the heat source is 10W/mm2。
Example 9: an aluminum alloy cooker is made up of 1050 raw materials through anodic oxidation of oxalic acid, and features that the heat source is acetylene-pure oxygen flame at 3000 deg.C and 30W/mm of energy density2。
Example 10: the aluminum alloy cooker comprises 3003 as material component, hard anode oxidation, and plasma arc as heat source, wherein the heat source temperature is 6000 deg.C, and the energy density is 60W/mm2。
Example 11: the aluminum alloy cooker comprises 3003 of material components, and is prepared by hard anodizing, wherein a heat source is natural gas-pure oxygen, the temperature of the heat source is 2200 ℃, and the energy density of the heat source is 15W/mm2。
Example 12: the aluminum alloy cooker comprises 3003 serving as a material component, hard anodizing and a heat source of laser, wherein the temperature of the heat source is 6000 ℃,the energy density of the heat source is 50W/mm2。
Example 13: an aluminum alloy piston is prepared from 6063 materials by hard anodizing, wherein the heat source is acetylene-pure oxygen flame, the temperature of the heat source is 2500 ℃, and the energy density of the heat source is 40W/mm2。
Example 14: an aluminum alloy piston, material composition 6063, hard anodizing and plasma arc as a heat source, wherein the temperature of the heat source is 4200 ℃, and the energy density of the heat source is 50W/mm2。
The material components of examples 1 to 14 were anodized and fired using a high temperature heat source to effect phase change. The process conditions and test results of examples 1 to 14 are shown in table 1 below.
TABLE 1
TABLE 1 (continuation)
Note: in table 1, the treatment time means the time per square decimeter of the oxide film treated (baked) under the high temperature heat source, and the unit is seconds(s). The treatment time is in units of time for baking the oxide film per square decimeter, which can make the treatment time length in seconds for convenient statistics and calculation.
As can be seen from table 1 above, the hardness of the oxide film subjected to the α -phase transformation treatment is greatly improved by comparing the hardness before and after the treatment.
Comparing the thickness before and after the treatment in the examples, it is understood that the thickness of the oxide film after the alpha-phase transformation treatment is not changed, but the density of the alumina is increased and the volume is shrunk due to the existence of the alpha-phase alumina, which means that the porosity of the oxide film is greatly improved. Such changes in the oxide film will contribute to the improvement of wear resistance and corrosion resistance.
Claims (10)
1. A method of preparing an oxide film comprising alpha-alumina, comprising the steps of:
s1: forming an anodic oxide film on the surface of the aluminum and/or aluminum alloy by anodic oxidation;
s2: the temperature is more than 1500 ℃, and the energy density is 10W/mm2The heat source described above is used to bake the anodic oxide film, and alpha-phase transformation is performed on the alumina in the anodic oxide film, thereby forming an oxide film containing alpha-alumina.
2. The method according to claim 1, wherein in step S2, the heat source is a combustible gas combustion flame, a plasma arc, a laser, or a combination thereof.
3. The method according to claim 1, wherein in step S2, the heat source is a natural gas-pure oxygen flame, an acetylene-pure oxygen flame and/or an ethylene-pure oxygen flame, and the baking time per square decimeter of the anodic oxide film is 5 to 20 seconds.
4. The method according to claim 1, wherein in step S2, the heat source is a plasma arc, and the baking time per square decimeter of the anodic oxide film is 5 to 15 seconds.
5. The method according to claim 1, wherein in step S2, the heat source is laser, and the baking time per square decimeter of the anodic oxide film is 20 to 200 seconds.
6. The method according to any one of claims 1 to 5, wherein the anodization is sulfuric acid anodization, oxalic acid anodization or hard anodization.
7. The method according to claim 6, wherein when the anodic oxide film is formed by sulfuric acid anodizing or oxalic acid anodizing, the anodic oxide film has a thickness ranging from 15 to 30 μm; when the anodic oxide film is formed by hard anodic oxidation, the thickness of the anodic oxide film ranges from 25 micrometers to 100 micrometers.
8. The vessel comprises a vessel base body, wherein the surface of the vessel base body is made of aluminum and/or aluminum alloy, and is characterized in that the surface of the aluminum/aluminum alloy is provided with an oxidation film containing alpha-alumina, and the porosity of the oxidation film containing alpha-alumina is 30-40%.
9. The vessel according to claim 8, wherein the oxide film containing α -alumina is prepared by: anodizing the surface of the aluminum and/or aluminum alloy material to obtain an anodized film, and then adopting a temperature of more than 1500 ℃ and an energy density of 10W/mm2The above heat source is used to bake the anodic oxide film.
10. The vessel according to claim 9, wherein the heat source is a combustible gas combustion flame, a plasma arc or a laser.
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