CN115874125A - Magnesium alloy surface modification method - Google Patents
Magnesium alloy surface modification method Download PDFInfo
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- CN115874125A CN115874125A CN202111143466.3A CN202111143466A CN115874125A CN 115874125 A CN115874125 A CN 115874125A CN 202111143466 A CN202111143466 A CN 202111143466A CN 115874125 A CN115874125 A CN 115874125A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 95
- 238000002715 modification method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 46
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 230000003014 reinforcing effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001234 light alloy Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Abstract
A magnesium alloy surface modification method comprises the following steps: 1) Preparing a stirring friction head, namely adding the ceramic reinforced particles into a magnesium alloy material by the volume percentage of 10-30% to prepare a magnesium-based composite material, and processing the magnesium-based composite material into the stirring friction head; the particle size of the ceramic reinforced particles is less than or equal to 2 mu m; 2) Pretreating the surface of the magnesium alloy, polishing and cleaning the surface of the magnesium alloy to obtain a clean surface; 3) The surface of the magnesium alloy is processed by stirring and rubbing with a stirring and rubbing head, the rotating speed of a main shaft is 800-1000 rpm, the reduction of a shaft shoulder is 0.15-0.2 mm, and the feeding speed of the main shaft is 10-15 mm/min. The invention solves the problem of poor surface wear resistance and corrosion resistance of the magnesium alloy material, maintains the obdurability of the magnesium alloy member, improves the surface rigidity of the magnesium alloy and improves the corrosion resistance.
Description
Technical Field
The invention relates to the technical field of magnesium-based materials, in particular to a magnesium alloy surface modification method.
Background
The magnesium alloy is used as the lightest metal material for the structure, has the advantages of high specific strength, high specific stiffness, excellent damping and noise reduction performance, good electromagnetic shielding performance, excellent machining performance, easy recovery and the like, can replace the traditional steel and aluminum alloy, and has wide application prospect in the fields of aviation, aerospace, automobiles, electronics and the like. However, because of strong chemical activity, magnesium alloy is easy to oxidize in air to form a loose porous oxide film, the surface corrosion resistance and the wear resistance are poor, and the Vickers hardness of the commonly used cast magnesium alloy is about 50-80 kg mm -2 And the method cannot be applied to components with harsh service conditions on a large scale.
The surface treatment technology of the magnesium alloy mainly comprises several methods, such as chemical plating, chemical conversion coating, micro-arc oxidation, coating and the like, for corrosion prevention of the surface of the magnesium alloy, wherein the methods can play a good corrosion prevention role on the magnesium alloy, but also have the defects of environmental pollution, difficulty in manufacturing, high cost, incompact coating, large porosity, poor binding force with a matrix and the like.
Chinese patent publication No. CN112359190A discloses a light alloy surface modification device and a modification method integrating stirring friction and ultrasonic rolling, and provides a modification device and a modification method which can improve the strength and plasticity of a workpiece and effectively improve the fatigue resistance, the abrasion resistance and the corrosion resistance. But only provides an experimental setup.
Chinese patent publication No. CN108456878A discloses a method for improving the performance of a conversion film by modifying the surface of nanoparticles, which forms a silane film on the surface of a magnesium alloy in a self-assembly manner by hydrolyzing a silane coupling agent, and then adds nanoparticles to finally obtain a phosphating film with good corrosion resistance by phosphating. But the chemical method is adopted, and the process is more complicated and takes longer time.
Chinese patent publication No. CN103339288B discloses "a magnesium alloy having a dense surface texture and a surface treatment method thereof", a surface modification layer containing Si on the surface of a magnesium alloy base material is prepared, and a coating layer is formed on the surface modification layer. However, the invention aims at specific magnesium alloy materials, the process is complex, and the wear resistance is to be verified.
Disclosure of Invention
The invention aims to provide a magnesium alloy surface modification method, which solves the problem of poor surface wear resistance and corrosion resistance of a magnesium alloy material, maintains the obdurability of a magnesium alloy member, improves the surface rigidity of the magnesium alloy and improves the corrosion resistance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a magnesium alloy surface modification method comprises the following steps:
1) Preparation of stirring friction head
Adding the ceramic reinforced particles with the volume fraction of 10-30% into a magnesium alloy material to prepare a magnesium-based composite material, and processing the magnesium-based composite material into a stirring friction head; the particle size of the ceramic reinforced particles is less than or equal to 2 mu m;
2) Magnesium alloy surface pretreatment
Polishing and cleaning the surface of the magnesium alloy to obtain a clean surface;
3) Surface treatment of magnesium alloy
The surface of the magnesium alloy is processed by stirring friction by a stirring friction head, the rotating speed of a main shaft is 800-1000 rpm, the reduction of a shaft shoulder is 0.15-0.2 mm, and the feeding speed of the main shaft is 10-15 mm/min.
Preferably, the ceramic reinforcing particles are AlN or SiC particles.
Preferably, the ceramic reinforcing particles have a particle size of 1 μm or less.
Preferably, the magnesium alloy surface pretreatment in the step 2) is to polish the surface of the magnesium alloy by using sand paper, then wash the surface by using alcohol, wash the surface by using deionized water and dry the surface by air.
Preferably, in the step 3) of processing the surface of the magnesium alloy, the friction stir head is processed for 1 to 3 times.
The friction stir processing is a novel processing technology, and uses a friction stir head with high thermal hardness to generate violent stirring and friction effects with materials, and the materials in a stirring area generate violent plastic deformation and dynamic recrystallization under the action of a stirring needle, so that the structure becomes fine and uniform.
The light alloy is subjected to friction stir treatment, so that the microstructure of the alloy can be obviously improved, the mechanical property and the ductility are greatly improved, the plastic processing capacity is improved, and the corrosion resistance is improved. The SiC, alN and other ceramic materials have the advantages of stable chemical properties, high heat conductivity coefficient, small thermal expansion coefficient, good wear resistance and the like, and can effectively improve the rigidity, hardness and wear resistance of the metal material when being added into the metal material.
The smaller the grain size of the ceramic reinforced particles is, the more uniform the ceramic reinforced particles are dispersed, and the more excellent the mechanical and corrosion resistance properties of the prepared metal matrix composite material are. However, since particles having a small particle size are difficult to disperse and the production cost is high, it is necessary to consider the kind, particle size and components of the ceramic reinforcing particles in a comprehensive manner. The invention selects ceramic reinforced particles with the particle size less than or equal to 2 mu m.
The invention has the beneficial effects that:
1. compared with the original material, the hardness of the magnesium alloy surface treated by the method is improved by 50-150%. Taking AZ31 magnesium alloy as an example, the surface has hardness improved from 65kgmm compared with the original material -2 To 100kg mm -2 And the surface wear resistance of the magnesium alloy is realized.
2. Compared with the original magnesium alloy matrix, the corrosion resistance of the magnesium-based composite material subjected to surface modification by the method is improved by one order of magnitude. Taking AZ31 magnesium alloy as an example, compared with the original magnesium alloy matrix, the corrosion resistance of the magnesium-based composite material after surface modification, namely the corrosion rate of the magnesium alloy, is improved from 3 mm/year to 0.2 mm/year.
3. According to the invention, the reinforcing particles are added into the stirring friction head, and the reinforcing body particles in the matrix are uniformly and fully dispersed without agglomeration after surface treatment.
4. Compared with the existing stirring friction method of directly paving the reinforcement on the surface of the magnesium alloy, the method of the invention adopts the stirring friction head containing the ceramic reinforcement particles to lead the surface of the magnesium alloy to be ceramic, and has simple process, practicability and feasibility.
5. The stirring friction head adopted by the method can be manufactured in large batch, and the process flow is suitable for large-scale industrial production.
Detailed Description
The technical solution of the present invention is described in detail by the following examples, which are implemented on the premise of the technical solution of the present invention, and the detailed implementation and the specific operation process are given, but the scope of the present invention to be protected is not limited to the following examples.
Examples of the invention magnesium based materials are shown in table 1.
Table 1: magnesium-based material formulations in examples 1-6 and comparative examples
Example 1
A magnesium alloy surface modification method comprises the following steps:
1) Adding SiC particles with the particle size of less than or equal to 1 mu m into AZ31 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 10 percent, and processing the magnesium-based composite material into a stirring friction head;
2) Polishing the surface of the AZ31 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water and then drying in the air;
3) And (3) performing friction stir processing on the surface of the magnesium alloy by using an AZ31-SiC friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 800rpm, the reduction of a shaft shoulder is 0.15mm, the feeding speed of the main shaft is 10 mm/min, and the processing is performed for 1 pass in total.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring and friction is 98kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.2 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Example 2
A magnesium alloy surface modification method comprises the following steps:
1) Adding SiC particles with the particle size of less than or equal to 1 mu m into AZ31 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 25 percent, and processing the magnesium-based composite material into a stirring friction head;
2) Polishing the surface of the AZ91 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water and then drying in the air;
3) And (3) performing friction stir processing on the surface of the magnesium alloy by using an AZ31-SiC friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 900rpm, the reduction of a shaft shoulder is 0.17mm, the feeding speed of the main shaft is 12 mm/min, and the processing is performed for 2 times.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring and friction is 130kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.2 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Example 3
A magnesium alloy surface modification method comprises the following steps:
1) Adding AlN particles with the particle size of less than or equal to 1 mu m into the AZ31 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 30 percent, and processing the magnesium-based composite material into a stirring friction head;
2) Polishing the surface of the AZ31 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water and then drying in the air;
3) And (3) performing friction stir processing on the surface of the magnesium alloy by using an AZ31-AlN friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 950rpm, the reduction of a shaft shoulder is 0.2mm, the feeding speed of the main shaft is 12 mm/min, and the processing is performed for 2 times.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring friction is 104kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.2 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Example 4
A magnesium alloy surface modification method comprises the following steps:
1) Adding AlN particles with the particle size of less than or equal to 1 mu m into ZK60 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 25 percent, and processing the magnesium-based composite material into a stirring friction head;
2) Polishing the surface of the AZ31 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water and then drying in the air;
3) The ZK60-AlN friction stir head is adopted to carry out friction stir processing on the surface of the magnesium alloy, the rotating speed of a main shaft of the friction stir head is 850rpm, the reduction of a shaft shoulder is 0.19mm, the feeding speed of the main shaft is 15 mm/min, and the processing is carried out for 3 times.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring friction is 143kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.2 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Example 5
A magnesium alloy surface modification method comprises the following steps:
1) Adding SiC particles with the particle size of less than or equal to 1 mu m into the AZ31 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 15 percent, and processing the magnesium-based composite material into a stirring friction head;
2) Polishing the surface of the ZK60 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water and then drying by air;
3) And (3) performing friction stir processing on the surface of the ZK60 magnesium alloy by using an AZ31-SiC friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 1000rpm, the reduction of a shaft shoulder is 0.18mm, the feeding speed of the main shaft is 17 mm/min, and the processing is performed for 2 times.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring and friction is 124kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.2 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Example 6
A magnesium alloy surface modification method comprises the following steps:
1) Adding AlN particles with the particle size of less than or equal to 1 mu m into AZ31 magnesium alloy to prepare a magnesium-based composite material, wherein the volume ratio of the ceramic particles is 30 percent, and processing the magnesium-based composite material into a stirring friction head;
2) The WE43 alloy surface is polished by abrasive paper, cleaned by alcohol, washed by deionized water and dried in the air;
3) And (3) performing friction stir processing on the surface of the magnesium alloy by using an AZ31-AlN friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 850rpm, the reduction of a shaft shoulder is 0.16mm, the feeding speed of the main shaft is 10 mm/min, and the processing is performed for 1 pass.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring friction is 143kgmm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method is 0.1 mm/year, and the surface of the magnesium alloy has good corrosion resistance and wear resistance.
Comparative example
And (3) polishing the surface of the AZ31 alloy by using abrasive paper, cleaning by using alcohol, washing by using deionized water, then drying by air, and carrying out friction stir processing on the surface of the magnesium alloy by using an AZ31 friction stir head, wherein the rotating speed of a main shaft of the friction stir head is 800rpm, the reduction of a shaft shoulder is 0.15mm, the feeding speed of the main shaft is 10 mm/min, and the processing is carried out for 3 times in total.
The Vickers hardness of the surface of the magnesium alloy after being processed by stirring friction is 65kg mm -2 The corrosion rate of the magnesium alloy measured by a 1wt.% NaCl solution method was 3 mm/year.
Claims (5)
1. A magnesium alloy surface modification method is characterized by comprising the following steps:
1) Preparation of stirring friction head
Adding the ceramic reinforced particles with the volume fraction of 10-30% into a magnesium alloy material to prepare a magnesium-based composite material, and processing the magnesium-based composite material into a stirring friction head; the particle size of the ceramic reinforced particles is less than or equal to 2 mu m;
2) Magnesium alloy surface pretreatment
Polishing and cleaning the surface of the magnesium alloy to obtain a clean surface;
3) Surface processing of magnesium alloy
The surface of the magnesium alloy is processed by stirring friction by a stirring friction head, the rotating speed of a main shaft is 800-1000 rpm, the reduction of a shaft shoulder is 0.15-0.2 mm, and the feeding speed of the main shaft is 10-15 mm/min.
2. The method for modifying the surface of a magnesium alloy according to claim 1, wherein the ceramic reinforcing particles are SiC or AlN particles.
3. The method for modifying the surface of a magnesium alloy according to claim 1 or 2, wherein the ceramic reinforcing particles have a particle size of 1 μm or less.
4. The method for modifying the surface of a magnesium alloy according to claim 1, wherein the step 2) of pretreating the surface of the magnesium alloy comprises the steps of polishing the surface of the magnesium alloy with sand paper, cleaning the surface with alcohol, washing the surface with deionized water, and then drying the surface in the air.
5. The method for modifying the surface of a magnesium alloy according to claim 1, wherein the friction stir head is processed for 1 to 3 times in the step 3) of processing the surface of the magnesium alloy.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003069001A1 (en) * | 2002-02-15 | 2003-08-21 | Toudai Tlo, Ltd. | Magnesium base composite material and method for production thereof |
| CN104046867A (en) * | 2014-06-26 | 2014-09-17 | 宝山钢铁股份有限公司 | High-plasticity heat-conducting magnesium alloy and preparation method thereof |
| EP3011818A1 (en) * | 2014-10-24 | 2016-04-27 | Rauch Landmaschinenfabrik Gmbh | Spreader machine with a hopper equipped with a stirrer |
| CN106518124A (en) * | 2016-11-21 | 2017-03-22 | 湖南工业大学 | Carbon fiber/sialon ceramic composite as well as preparation method and application |
| CN107805769A (en) * | 2017-11-02 | 2018-03-16 | 西北工业大学 | The rolling of high-performance AlN/AZ91D magnesium-based composite materials and heat treatment method |
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- 2021-09-28 CN CN202111143466.3A patent/CN115874125B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003069001A1 (en) * | 2002-02-15 | 2003-08-21 | Toudai Tlo, Ltd. | Magnesium base composite material and method for production thereof |
| CN104046867A (en) * | 2014-06-26 | 2014-09-17 | 宝山钢铁股份有限公司 | High-plasticity heat-conducting magnesium alloy and preparation method thereof |
| EP3011818A1 (en) * | 2014-10-24 | 2016-04-27 | Rauch Landmaschinenfabrik Gmbh | Spreader machine with a hopper equipped with a stirrer |
| CN106518124A (en) * | 2016-11-21 | 2017-03-22 | 湖南工业大学 | Carbon fiber/sialon ceramic composite as well as preparation method and application |
| CN107805769A (en) * | 2017-11-02 | 2018-03-16 | 西北工业大学 | The rolling of high-performance AlN/AZ91D magnesium-based composite materials and heat treatment method |
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