CN114032595A - Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy - Google Patents
Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy Download PDFInfo
- Publication number
- CN114032595A CN114032595A CN202111449892.XA CN202111449892A CN114032595A CN 114032595 A CN114032595 A CN 114032595A CN 202111449892 A CN202111449892 A CN 202111449892A CN 114032595 A CN114032595 A CN 114032595A
- Authority
- CN
- China
- Prior art keywords
- alloy
- anodic oxidation
- nickel
- micro
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- 229910000599 Cr alloy Inorganic materials 0.000 title abstract description 7
- 239000000788 chromium alloy Substances 0.000 title abstract description 7
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 137
- 239000000956 alloy Substances 0.000 claims abstract description 137
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000002048 anodisation reaction Methods 0.000 claims description 19
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 16
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 238000007743 anodising Methods 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000010297 mechanical methods and process Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Landscapes
- 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 invention discloses a preparation method of micro-nano holes on the surface of a nickel-containing iron-chromium alloy, which comprises the following steps of firstly, pretreating the alloy to remove impurities on the surface; performing first anodic oxidation treatment on the surface of the alloy, performing first anodic oxidation by taking the alloy as an anode and taking a graphite sheet as a cathode, cleaning by using ethanol, and drying for later use; and then, carrying out secondary anodic oxidation treatment on the alloy surface after the primary anodic oxidation treatment, taking the alloy as an anode and a graphite flake as a cathode, carrying out secondary anodic oxidation in sodium dihydrogen phosphate dihydrate solution, then washing with ethanol, and drying to obtain the flexible compound gold surface with obvious micro-nano pores. According to the invention, the alloy surface is subjected to flexible treatment by adopting a two-time anodic oxidation method, the universality of the anodic oxidation alloy is expanded, micro-nano holes on the surface of the nickel-containing iron-chromium alloy are ideally arranged through secondary anodic oxidation, and the application of the nickel-containing iron-chromium alloy in the fields of 3C, electronic appliances and the like is promoted.
Description
Technical Field
The invention belongs to the technical field of metal alloy surface flexible treatment, and particularly relates to a preparation method of micro-nano holes on a nickel-iron-chromium-containing alloy surface.
Background
There are many methods for metal surface treatment, mainly including mechanical method, chemical etching method, ion implantation surface modification research, anodic oxidation and other methods. The mechanical methods generally used for treating metal surfaces include sand blast cleaning, roughening, cleaning with a brush, etc., and the main purpose is to remove contamination such as oil stains from the metal surfaces, and to increase the roughness of the metal surfaces and improve the adhesion effect. And iron sand grains, quenched and annealed iron sand and corundum or silicon carbide can be used for treatment during sand blasting cleaning. Some pits and surface roughness can be obviously seen on the metal surface after the sand blasting treatment is carried out on the metal surface, but the mechanical method only can roughen the metal surface generally, and micro-nano holes cannot be prepared.
The metal surface is further subjected to nanocrystallization by a chemical etching method. The general chemical etching method is acid etching or alkali etching, different shapes are formed on the metal surface through chemical reaction with the metal surface, different bosses or pits are usually etched on the metal surface by using hydrochloric acid, sulfuric acid, phosphoric acid or sodium hydroxide, and potassium hydroxide, which is not beneficial to preparing a metal resin composite material by nano injection molding or preparing a nano array one-dimensional nano material as a template.
The anodic oxidation method is commonly used for preparing a porous structure by treating the surface of a metal, and comprises the steps of taking a pretreated metal or alloy product as an anode, taking an inert electrode as a cathode (such as graphite), applying direct current or direct current voltage in a proper electrolyte, enabling ions in an electrolyte solution to make directional motion under the action of an electric field, and enabling the surface of the anode electrode and the contact surface of the solution to generate corresponding chemical changes. In addition, the metal micro-nano pore membrane after anodic oxidation is used as a template to prepare the nano-array one-dimensional nano material, and the nano-array one-dimensional nano material is successfully applied to the fields of electronic appliances, aerospace, automobile transportation and the like.
In early research work, the regularity of the alumina alloy nanopore array structure prepared by one-time anodic oxidation is found to be poor; this is caused by defects in the lattice arrangement in the parent anode porous alumina from which it is used as a starting material. In recent studies, we have found that almost ideal alignment of nanopore arrays can be achieved under appropriate anodization conditions by a secondary anodization process. The first step of anodic oxidation can generate random alumina which can be removed by treatment under acidic conditions, and the alumina can generate nano cavities on the surface of the aluminum, which are called nano dents. These nanoindentions serve as templates during the second step anodization, forming porous alumina with good alignment and long range order. The secondary anodic oxidation is a method for changing reaction conditions to carry out anodic oxidation again on the basis of the primary oxidation of the alloy, so that the alloy nano-pores present an open and orderly-arranged structure, even a large-pore-sleeve-small-pore structure. The nanochannel fabrication method should provide the nanocomposite with the desired combination of properties, which is a difficult goal to achieve by conventional one-step embedding methods. One important aspect of two-step anodization, which differs from the traditional one-step intercalation method, is that it allows the pore array of the anodic porous alumina to be fully replicated with the desired material. Thus, the defects of insufficient chemical stability and thermal stability, low mechanical strength and the like of the porous aluminum oxide alloy can be overcome.
Disclosure of Invention
The invention aims to provide a preparation method of micro-nano holes on the surface of nickel-containing ferrochromium alloy, which aims to solve the problems, and the micro-nano holes on the surface of the nickel-containing ferrochromium alloy are ideally arranged through secondary anodic oxidation, so that the application of the nickel-containing ferrochromium alloy in the fields of 3C, electronics and the like is promoted.
The invention is mainly realized by the following technical scheme:
a preparation method of micro-nano holes on the surface of a nickel-iron-chromium-containing alloy comprises the following steps:
step S100: pretreating the alloy to remove surface impurities;
step S200: performing first anodic oxidation treatment on the alloy surface treated in the step S100, performing first anodic oxidation by using the alloy as an anode and a graphite sheet as a cathode, cleaning with ethanol, and drying for later use;
step S300: and performing secondary anodic oxidation treatment on the surface of the alloy treated in the step S200, wherein the alloy is used as an anode and a graphite flake is used as a cathode, and the secondary anodic oxidation is performed in sodium dihydrogen phosphate dihydrate solution, and then the alloy is cleaned by ethanol and dried for standby.
In order to better implement the present invention, further, in step S100, the alloy is placed in an acetone solution for 30min by ultrasound, and then is washed with ethanol and dried at 60 ℃ for standby.
In order to better implement the present invention, in step S200, the electrolyte for the first anodization is an ammonium fluoride/ethylene glycol electrolyte, and the concentration of ammonium fluoride is 0.05mol/L to 0.2 mol/L.
In order to better implement the invention, further, the concentration of the ammonium fluoride is 0.15 mol/L.
In order to better implement the present invention, in step S200, the voltage of the first anodization is 20V, and the time is 60 min.
In order to better implement the present invention, further, in step S300, the voltage of the second anodization is 20V and the time is 60 min.
The invention has the beneficial effects that:
(1) according to the invention, the alloy surface is subjected to flexible treatment by adopting a two-time anodic oxidation method, the universality of the anodic oxidation alloy is expanded, micro-nano holes on the surface of the nickel-containing iron-chromium alloy are ideally arranged through secondary anodic oxidation, and the application of the nickel-containing iron-chromium alloy in the fields of 3C, electronic appliances and the like is promoted;
(2) the metal surface treated by the method can be prepared into a uniform and regular micro-nano pore structure, and the method for treating the alloy surface is simple and easy to operate and has low cost;
(3) the invention can prepare regular and uniform micro-nano holes only by carrying out anodic oxidation twice, can prepare micro-nano holes with a certain scale on the surface of metal, can be used as a substrate for preparing a metal resin composite material by nano injection molding, and can also be used as a template for preparing a one-dimensional nano material array structure, so that the micro-nano holes become a multifunctional application material.
Drawings
FIG. 1 is a flow chart of an experiment according to the present invention;
FIG. 2 is a Mapping spectrogram of alloy surface components obtained by EDS surface scanning before the alloy surface is not anodized;
FIG. 3 is an SEM image of the surface of an alloy subjected to primary anodic oxidation in electrolyte with different concentrations;
FIG. 4 is an SEM image of the surface of the alloy after the first anodization at different temperatures;
FIG. 5 is an SEM image of the surface of the alloy after the primary anodization in example 1, the secondary anodization and the anodization in comparative example 2.
Detailed Description
Example 1:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at 20 ℃ and 0.1mol/L of ammonium fluoride/ethylene glycol electrolyte at a voltage of 20V, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 2:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at 20 ℃ and 0.05mol/L of ammonium fluoride/ethylene glycol electrolyte at a voltage of 20V, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 3:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at 20 ℃ and 0.15mol/L of ammonium fluoride/ethylene glycol electrolyte at a voltage of 20V, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 4:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at 20 ℃ and 0.2mol/L of ammonium fluoride/ethylene glycol electrolyte at a voltage of 20V, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 5:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at a voltage of 20V in 0.1mol/L ammonium fluoride/ethylene glycol electrolyte at a temperature of 0 ℃, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 6:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at a voltage of 20V in 0.1mol/L ammonium fluoride/ethylene glycol electrolyte at a temperature of 10 ℃, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Example 7:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃ for later use.
(2) Primary anodic oxidation of the alloy surface: and (2) taking the alloy block obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at the voltage of 20V in 0.1mol/L ammonium fluoride/ethylene glycol electrolyte at the temperature of 30 ℃, washing with ethanol, and drying the surface to obtain the primary oxidation treatment alloy block.
(3) Performing secondary anodic oxidation treatment on the alloy surface: and (3) anodizing the alloy block with the surface subjected to the primary anodizing treatment in the step (2) as an anode in 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte at the voltage of 20V for 60min, washing with ethanol, and drying to obtain the secondary anodized metal block.
Comparative example 1:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the metal alloy into an acetone solution, performing ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃.
(2) Anodizing the alloy surface: and (2) taking the alloy obtained in the step (1) as an anode and a graphite sheet as a cathode, anodizing for 60min at 20 ℃ and 0.1mol/L of ammonium fluoride/ethylene glycol electrolyte at a voltage of 20V, washing with ethanol, and drying the surface to obtain an oxidized alloy block.
Comparative example 2:
a preparation method of micro-nano holes on the surface of nickel-iron-chromium-containing alloy is shown in figure 1 and comprises the following steps:
(1) alloy surface pretreatment: and putting the alloy into an acetone solution, carrying out ultrasonic treatment for 30min, cleaning with ethanol, and drying at 60 ℃.
(2) Anodizing the alloy surface: and (2) anodizing the wrench tool obtained in the step (1) as an anode and the graphite flake as a cathode at 20 ℃ and 0.1mol/L of sodium dihydrogen phosphate dihydrate electrolyte at 20V for 60min, washing the anode with ethanol, and drying the surface of the anode to obtain an oxidized alloy block.
TABLE 1
TABLE 2
As shown in tables 1 and 2, the following analyses were carried out in accordance with the methods of example 1 to example 7 and comparative example 1 to comparative example 2:
as shown in FIG. 2, the initial alloy was subjected to EDS surface scanning to obtain Mapping chart, from which it can be seen how the surface mainly contains elements such as nickel and the like, and also a small amount of Fe and Co elements.
As shown in fig. 3, fig. 3 (a), 3 (b), 3 (c) and 3 (d) are SEM images of the alloy surfaces prepared by the first anodization in example 2, example 1, example 3 and example 4, respectively. The concentrations of the electrolytes of the first anodizing of examples 1 to 4 were 0.1mol/L, 0.05mol/L, 0.15mol/L, and 0.2mol/L, respectively. Wherein FIG. 3 (a) is at 0.05mol/L NH4The appearance graph is obtained by anodizing in the F/EG electrolyte for 60min, and it can be seen that at the moment, part of the surface of the alloy is subjected to an anodic oxidation reaction, the formed porous structure does not cover the surface of the alloy, and the shape is extremely irregular; and FIG. 3 (b) is a graph showing that the alloy is at 0.1mol/L NH4The morphology graph is obtained by anode oxidation in the F/EG electrolyte for 60min, and at the moment, the alloy surface is covered by a porous structure and the porous structure is distributed more uniformly; FIG. 3 (c) is at 0.15mol/L NH4The morphology graph obtained by anodic oxidation in the F/EG electrolyte for 60min shows that the alloy surface is uniformly covered by a porous structure and is distributed more uniformly; FIG. 3 (d) is a graph showing that the alloy is at 0.2mol/L NH4According to a morphology graph obtained by anodic oxidation in the F/EG electrolyte for 60min, the porous structure on the surface of the alloy is damaged, mainly due to the fact that the concentration is too high and the oxidation speed is too high, and the porous structure formed on the surface of the alloy is damaged to a certain extent due to transitional oxidation. In summary, in the first anodizing process, when the electrolyte concentration is low, it will react with the surface of the alloy to initially form a small amount of relatively dispersed micro-nano pores with small depth; but when the electrolyte concentration is further increased, it will continue to interact with the micro-nano pores.
As shown in fig. 4, SEM images of the alloy surfaces of the first anodizing in examples 5 to 7 and comparative example 1 at different temperatures, the temperatures of the first anodizing in fig. 4 (a) to 4 (d) were 0 ℃, 10 ℃, 20 ℃ and 30 ℃. SEM images obtained by anodizing the alloy surface at the same voltage (20V) at different temperatures for 60min in the first anodizing. As is clear from fig. 4 (a) -4 (d), the change in the micropores on the alloy surface becomes more pronounced as the temperature is gradually increased. Similarly, as the temperature increases, the number and regularity of the holes gradually increase, and the holes gradually increase from the beginning to the micro-nano holes with more uniform whole surface. As shown in fig. 4 (a), when the temperature is 0 ℃, the pore size of the porous structure on the surface of the alloy is small and the distribution is not uniform at this time; as shown in fig. 4 (b), when the temperature is 10 ℃, it can be seen that a porous structure exists on the surface of the alloy, and the porous structure covers the surface of the alloy, and the porous structure of the alloy is still unevenly distributed; as shown in fig. 4 (c), when the temperature is 20 ℃, it can be seen that the porous structure covers the alloy surface and is distributed regularly and uniformly, and the difference of the pore sizes is small; as shown in fig. 4 (d), when the reaction temperature reaches 30 ℃, the micro/nano pores on the surface of the alloy are reduced, and the temperature is not uniform and regular any more, which is unfavorable for the formation of the porous structure on the surface of the alloy.
As shown in fig. 5, fig. 5 (a) is an SEM image of the alloy surface after the first anodization in example 1, which is obtained by anodizing the alloy ingot at 20 ℃ and 0.1mol/L ammonium fluoride/ethylene glycol electrolyte for 60min at 20V using a graphite sheet as an anode and a graphite sheet as a cathode, and as can be seen from fig. 5 (a), only a very small portion of the alloy surface is oxidized and the pores are sparsely distributed; FIG. 5 (b) is an SEM image obtained by anodizing the alloy as an anode and the graphite sheet as a cathode at 20 ℃ for 60min at a voltage of 20V in 0.1mol/L sodium dihydrogenphosphate electrolyte in comparative example 2, and it can be seen from FIG. 5 (b) that the surface of the alloy is partially oxidized, but the formed pores are not uniform in size and are different in pore diameter depth; fig. 5 (c) is a morphology diagram obtained after the first anodization is performed on the 0.1mol/L ammonium fluoride/ethylene glycol electrolyte and the second anodization is performed on the 0.1mol/L sodium dihydrogen phosphate dihydrate electrolyte in example 1, and it is obvious from the SEM image that most of the alloy surface is covered by the porous structure and the pores with uniform size are formed after the two anodization, which fully embodies the advantages of the second oxidation method.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. A preparation method of micro-nano holes on the surface of a nickel-iron-chromium-containing alloy is characterized by comprising the following steps:
step S100: pretreating the alloy to remove surface impurities;
step S200: performing first anodic oxidation treatment on the alloy surface treated in the step S100, performing first anodic oxidation by using the alloy as an anode and a graphite sheet as a cathode, cleaning with ethanol, and drying for later use;
step S300: and performing secondary anodic oxidation treatment on the surface of the alloy treated in the step S200, wherein the alloy is used as an anode and a graphite flake is used as a cathode, and the secondary anodic oxidation is performed in sodium dihydrogen phosphate dihydrate solution, and then the alloy is cleaned by ethanol and dried for standby.
2. The method for preparing micro-nano holes on the surface of a nickel-iron-chromium-containing alloy according to claim 1, wherein in the step S100, the alloy is placed into an acetone solution for ultrasonic treatment for 30min, then washed with ethanol, and dried at 60 ℃ for later use.
3. The method according to claim 1, wherein in step S200, the electrolyte for the first anodization is ammonium fluoride/ethylene glycol electrolyte, and the concentration of ammonium fluoride is 0.05mol/L-0.2 mol/L.
4. The method for preparing micro-nano holes on the surface of nickel-iron-chromium-containing alloy according to claim 3, wherein the concentration of ammonium fluoride is 0.15 mol/L.
5. The method for preparing micro-nano holes on the surface of nickel-containing ferrochrome alloy according to claim 1, wherein in the step S200, the voltage of the first anodization is 20V, and the time is 60 min.
6. The method for preparing micro-nano holes on the surface of nickel-containing ferrochrome alloy according to claim 1, wherein in the step S300, the voltage of the second anodization is 20V, and the time is 60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111449892.XA CN114032595A (en) | 2021-12-01 | 2021-12-01 | Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111449892.XA CN114032595A (en) | 2021-12-01 | 2021-12-01 | Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114032595A true CN114032595A (en) | 2022-02-11 |
Family
ID=80139374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111449892.XA Pending CN114032595A (en) | 2021-12-01 | 2021-12-01 | Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114032595A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100132546A1 (en) * | 2007-04-05 | 2010-06-03 | Yi Hua Ma | Composite Structures with Porous Anodic Oxide Layers and Methods of Fabrication |
| US20120125786A1 (en) * | 2010-11-22 | 2012-05-24 | MetCon LLC | Electrolyte solution and electrochemical Surface Modification Methods |
| CN108048894A (en) * | 2017-12-08 | 2018-05-18 | 广东工业大学 | A kind of preparation method of metal-surface nano hole array film |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | A kind of preparation method of titanium oxide perforated membrane SERS substrates |
| CN111803252A (en) * | 2020-08-27 | 2020-10-23 | 广东工业大学 | Stainless steel, preparation method thereof and drug eluting stent |
| CN112064090A (en) * | 2020-09-16 | 2020-12-11 | 山东大学 | Microstructure surface preparation method with high blood compatibility and microstructure |
-
2021
- 2021-12-01 CN CN202111449892.XA patent/CN114032595A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100132546A1 (en) * | 2007-04-05 | 2010-06-03 | Yi Hua Ma | Composite Structures with Porous Anodic Oxide Layers and Methods of Fabrication |
| US20120125786A1 (en) * | 2010-11-22 | 2012-05-24 | MetCon LLC | Electrolyte solution and electrochemical Surface Modification Methods |
| CN108048894A (en) * | 2017-12-08 | 2018-05-18 | 广东工业大学 | A kind of preparation method of metal-surface nano hole array film |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | A kind of preparation method of titanium oxide perforated membrane SERS substrates |
| CN111803252A (en) * | 2020-08-27 | 2020-10-23 | 广东工业大学 | Stainless steel, preparation method thereof and drug eluting stent |
| CN112064090A (en) * | 2020-09-16 | 2020-12-11 | 山东大学 | Microstructure surface preparation method with high blood compatibility and microstructure |
Non-Patent Citations (1)
| Title |
|---|
| 李淑华等: "《机械制造现场实用经验丛书 热处理技术经验》", 30 October 2015 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101962792B (en) | Method for preparing pore diameter controllable through hole anodized aluminum oxide film | |
| CN109913923B (en) | Surface treatment liquid and method for surface treatment of magnesium alloy aluminum alloy composite part | |
| CN105088309B (en) | A kind of energy-efficient anode oxidative treatment method of pack alloy | |
| CN105239133A (en) | Titanium and titanium alloy surface anodic oxidation coloring method | |
| CN112609218A (en) | Preparation method of super-hydrophobic micro-arc oxidation composite membrane | |
| CN101831682A (en) | Method for preparing highly ordered aluminum oxide template by asymmetric two-step anodization | |
| CN108193250A (en) | A kind of sulfuric acid+nitration mixture mixing anode oxidation process | |
| CN111101164B (en) | Preparation method of high-bonding-force coating with anodized aluminum as base material | |
| KR102337928B1 (en) | Method for forming anodized film and anodized aluminum containing anodized film formed thereby | |
| CN111286770B (en) | Composite material with high binding force | |
| CN106676619B (en) | A kind of preparation method of glassy metal nano-porous structure | |
| KR100695999B1 (en) | Anodizing method for matal surface using high-frequency pluse | |
| CN112853456B (en) | Method for manufacturing high-pressure high-specific-volume corrosion foil | |
| CN104451819A (en) | Method for constructing superhydrophobic aluminum surface with high stability | |
| CN114032595A (en) | Preparation method of micro-nano holes on surface of nickel-containing iron-chromium alloy | |
| CN110552044A (en) | Steel anodic oxidation electrolyte and anodic oxidation method thereof | |
| CN107893232A (en) | A kind of surface etching method before titanium plate anodic coating | |
| CN113436891A (en) | Method for inducing medium-high voltage anode foil to uniformly corrode and form pores by adopting nano pits after anodic oxidation | |
| CN110565145B (en) | Pure titanium surface super-hydrophobic anodic oxidation coloring film and preparation method and application thereof | |
| JPH09184094A (en) | Surface treated aluminum material and its production | |
| CN104103428A (en) | Manufacturing method for high-voltage high-dielectric formed foil for aluminium electrolytic capacitor | |
| KR100489640B1 (en) | Electrolyte solution for anodizing and corrosion-resisting coating method of magnesium alloy using the same | |
| CN111235579A (en) | Metal polishing method | |
| Zhao et al. | Micro-arc Oxidation Coating Formed on Anodized Aluminum Surface under Different Pulse Frequencies | |
| CN110117809B (en) | Preparation method of oxide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220211 |