CN112760689B - Micro-arc oxidation layer on surface of aluminum alloy piston and preparation method thereof - Google Patents
Micro-arc oxidation layer on surface of aluminum alloy piston and preparation method thereof Download PDFInfo
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- CN112760689B CN112760689B CN202011536705.7A CN202011536705A CN112760689B CN 112760689 B CN112760689 B CN 112760689B CN 202011536705 A CN202011536705 A CN 202011536705A CN 112760689 B CN112760689 B CN 112760689B
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- 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
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- C25D11/026—Anodisation with spark discharge
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
The invention discloses a micro-arc oxidation layer on the surface of an aluminum alloy piston and a preparation method thereof, wherein an aluminum alloy sample is sequentially subjected to oil and grease removal, grinding and polishing washing; preparing micro-arc oxidation electrolyte containing nano-scale TaC powder; placing the polished and washed aluminum alloy sample into electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer of 10-75 mu m on the surface of the aluminum alloy sample; according to the invention, the nano-scale TaC powder is added into a sodium silicate electrolyte system, and a high-hardness and relatively flat micro-arc oxidation ceramic layer can be prepared on the surface of the aluminum alloy by regulating the concentration and the particle size of TaC in the electrolyte; the wear resistance and hardness of the micro-arc oxidation ceramic layer containing the TaC are obviously higher than those of the traditional aluminum alloy micro-arc oxidation ceramic layer, and the protective performance of the ceramic layer on the aluminum alloy is enhanced.
Description
Technical Field
The invention belongs to the technical field of preparation of functional coatings on the surfaces of aluminum alloys, and particularly relates to a micro-arc oxidation layer on the surface of an aluminum alloy piston and a preparation method thereof.
Background
With the rapid development of the transportation industry, energy conservation and emission reduction are the core driving forces of transportation. For a fuel oil vehicle, the fuel consumption can be reduced by 0.5L per hundred kilometers when the weight of the whole vehicle is reduced by 100 kg; and from the driving performance's of car perspective, the lightweight will greatly promote the acceleration performance, the braking performance and the climbing performance of car. The present "heart" -piston of internal combustion engine is mainly made of aluminium alloy (Al density 2.69 g/cm)3) And conventional cast iron, cast steel pistons (density of Fe 7.86 g/cm)3) Mainly, the idea of light weight, energy conservation and emission reduction is not difficultIt is seen that aluminum alloy pistons are ideal materials for pistons for internal combustion engines.
During high-speed operation of the internal combustion engine, the piston is subjected to a certain impact force, reciprocating inertia force and a large thermal load. However, the aluminum alloy piston has low thermal strength and poor high-temperature mechanical properties, and can generate phenomena such as ablation and corrosion under certain conditions. Therefore, the service capacity of the aluminum alloy piston in a high-temperature environment is particularly important to be improved, the service life of the aluminum alloy piston can be prolonged, and meanwhile, the temperature of the aluminum alloy piston can be widened.
Aiming at the ablation phenomenon of the aluminum alloy piston, an ablation-resistant layer is prepared on the top of the piston by adopting a surface ceramic treatment method at present, and the heat resistance of the ceramic piston is found to be obviously higher than that of the piston subjected to the traditional hard anode oxidation treatment and the untreated piston. However, with the related reports, it is not easy to find that the temperature of the piston is continuously increased, and people hope to adopt a continuous technical process to innovate and prepare a better protective layer so as to improve the surface performance of the aluminum alloy piston and prolong the service life of the aluminum alloy piston.
Disclosure of Invention
The invention aims to provide a micro-arc oxidation layer on the surface of an aluminum alloy piston and a preparation method thereof, which can improve the wear resistance and hardness of the micro-arc oxidation layer on the surface of the aluminum alloy piston.
The invention adopts the following technical scheme: a preparation method of a micro-arc oxidation layer on the surface of an aluminum alloy piston comprises the following steps:
sequentially carrying out oil removal, grease removal, grinding and polishing water washing on the aluminum alloy sample;
preparing micro-arc oxidation electrolyte containing nano-scale TaC powder;
placing the polished and washed aluminum alloy sample into electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer of 10-75 mu m on the surface of the aluminum alloy sample; wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 450-550V, the frequency is 400-1200 Hz, the duty ratio is 8-30%, and the electrifying time is 10-120 min.
Further, the content of Ta element in the micro-arc oxidation layer is 0.5-3.2 at.%.
Further, the concentration of the nano-scale TaC powder in the micro-arc oxidation electrolyte is 1-10 g/L.
Further, the concentration of the nano-scale TaC powder in the micro-arc oxidation electrolyte is 2-6 g/L.
Further, the micro-arc oxidation electrolyte comprises sodium silicate, sodium hexametaphosphate, potassium hydroxide and nano-scale TaC powder;
the concentration of sodium silicate in the micro-arc oxidation electrolyte is 4-35 g/L, the concentration of sodium hexametaphosphate is 5-32 g/L, and the concentration of potassium hydroxide is 4-10 g/L.
The other technical scheme of the invention is as follows: a micro-arc oxidation layer on the surface of an aluminum alloy piston is prepared by the preparation method of the micro-arc oxidation layer on the surface of the aluminum alloy piston;
the thickness of the micro-arc oxidation layer is 10-75 μm, and the content of Ta element is 0.5-3.2 at.%.
The invention has the beneficial effects that: according to the invention, the nano-scale TaC powder is added into a sodium silicate electrolyte system, and a high-hardness and relatively flat micro-arc oxidation ceramic layer can be prepared on the surface of the aluminum alloy by regulating the concentration and the particle size of TaC in the electrolyte; the wear resistance and hardness of the micro-arc oxidation ceramic layer containing the TaC are obviously higher than those of the traditional aluminum alloy micro-arc oxidation ceramic layer, and the protective performance of the ceramic layer on the aluminum alloy is enhanced.
Drawings
FIG. 1 is a schematic structural diagram of a high-performance heat-insulating wear-resistant ceramic layer on the surface of an aluminum alloy piston, which is prepared by the method for preparing the micro-arc oxidation layer on the surface of the aluminum alloy piston according to the embodiment of the invention;
FIG. 2 is an XPS survey of a ceramic layer prepared on an aluminum surface and an XPS high resolution map of Ta element, prepared in an example of the present invention;
FIG. 3 is a micro-topography of a TaC-containing micro-arc oxidized ceramic layer prepared by different processes on an aluminum alloy in an embodiment of the invention;
FIG. 4 is a graph showing the results of surface hardness of aluminum alloys, micro-arc oxidation of aluminum alloys, and TaC micro-arc oxidation ceramic layers doped with different amounts of aluminum alloys in the embodiment of the present invention;
FIG. 5 is a 3D contour diagram of the appearance of wear scars of an aluminum alloy, an aluminum alloy micro-arc oxidation ceramic layer and an aluminum alloy doped TaC micro-arc oxidation ceramic layer with different contents;
FIG. 6 is a graph of wear scar depth results for aluminum alloys, aluminum alloy micro-arc oxidation, and aluminum alloy doped TaC particle micro-arc oxidation ceramic layers of embodiments of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a preparation method of a micro-arc oxidation layer on the surface of an aluminum alloy piston, which comprises the following steps: sequentially carrying out oil removal, grease removal, grinding and polishing water washing on the aluminum alloy sample; the grinding process is carried out by different waterproof abrasive papers according to requirements, and polishing and washing are carried out after grinding for subsequent treatment. Preparing micro-arc oxidation electrolyte containing nano-scale TaC powder; placing the polished and washed aluminum alloy sample into the electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer of 10-75 mu m on the surface of the aluminum alloy sample; wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 450-550V, the frequency is 400-1200 Hz, the duty ratio is 8-30%, and the electrifying time is 10-120 min.
According to the invention, the nano-scale TaC powder is added into a sodium silicate electrolyte system, and a high-hardness and relatively flat micro-arc oxidation ceramic layer can be prepared on the surface of the aluminum alloy by regulating the concentration and the particle size of TaC in the electrolyte; the wear resistance and hardness of the micro-arc oxidation ceramic layer containing the TaC are obviously higher than those of the traditional aluminum alloy micro-arc oxidation ceramic layer, and the protective performance of the ceramic layer on the aluminum alloy is enhanced.
The content of Ta element in the micro-arc oxidation layer is 0.5-3.2 at.%. In order to achieve the above indexes, the concentration of the nano-scale TaC powder in the micro-arc oxidation electrolyte is 1-10 g/L, and more preferably 2-6 g/L.
Specifically, the micro-arc oxidation electrolyte comprises sodium silicate, sodium hexametaphosphate, potassium hydroxide and nano-scale TaC powder; the concentration of sodium silicate in the micro-arc oxidation electrolyte is 4-35 g/L, the concentration of sodium hexametaphosphate is 5-32 g/L, and the concentration of potassium hydroxide is 4-10 g/L. The electrolyte can be prepared into various components according to the requirement, such as sodium metaaluminate, titanium potassium oxalate, sodium tungstate, sodium tetraborate, potassium fluoride and the like.
The micro-arc oxidation technology is a new technology for directly growing ceramic membranes on the surfaces of light metals in situ, and is a surface modification technology for obtaining metal oxide ceramic layers under the combined action of thermochemistry, plasma chemistry and electrochemistry by placing valve metals such as Al, Mg, Ti and the like or alloys thereof in an electrolyte aqueous solution as an anode and generating spark discharge spots on the surfaces of the materials by an electrochemical method.
In the micro-arc oxidation treatment process, the TaC particles can be ensured to exist in the micro-arc oxidation ceramic layer on the surface of the aluminum matrix by adding a dispersing agent, circularly stirring, cooling and other process means, and the addition of the TaC particles plays a role in enhancing the hardness, wear resistance, corrosion resistance and heat insulation of the ceramic layer.
The TaC particles have high melting point (3800 ℃), high hardness, high conductivity (thermal) performance and stable chemical properties, and the TaC particles introduced into the micro-arc oxidation ceramic layer of the aluminum alloy can block micropores generated in the micro-arc oxidation process to a certain extent and improve the hardness, corrosion resistance and wear resistance of the ceramic layer.
The special micro-arc oxidation ceramic layer prepared by the invention overcomes the problems of the traditional spraying and chromium electroplating combination difference, poor environmental protection and the like, improves the performance of the traditional micro-arc oxidation ceramic layer once, and has great application prospect in the aspect of automobile engine aluminum alloy pistons. Meanwhile, if an electrolytic solution system and electrical parameters are blended, further breakthrough can be made in the aspects of oxidation resistance and wear resistance of the aircraft turbine engine (titanium alloy).
The invention also discloses a micro-arc oxidation layer on the surface of the aluminum alloy piston, which is prepared by adopting the preparation method of the micro-arc oxidation layer on the surface of the aluminum alloy piston; the micro-arc oxidation layer has a thickness of 10-75 μm and a content of Ta element of 0.5-3.2 at.%.
The embodiment prepares a novel high-performance heat-insulating wear-resistant ceramic layer suitable for the surface of the aluminum alloy piston, and can improve the wear resistance and the heat insulation of the aluminum alloy piston.
Example 1:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 28 μm on the surface of the aluminum alloy specifically includes the following steps:
step 1: the processed aluminum alloy sample is subjected to oil and grease removing processes, then is ground by different waterproof abrasive paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the aluminum alloy, sodium silicate is taken as the main component (30g/L), and micro-arc oxidation electrolyte of sodium hexametaphosphate (5g/L), potassium fluoride (4g/L), potassium hydroxide (10g/L), sodium dodecyl benzene sulfonate (1g/L) and TaC nano-scale powder (1g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, an aluminum oxide ceramic layer with the thickness of 28 micrometers and the Ta content of 0.8 at.% is generated on the surface of the aluminum alloy by adjusting the voltage of 480V, the frequency of 500Hz, the duty ratio of 25% and the electrifying time of 30min, and rotary stirring is started in the reaction process.
Example 2:
in this embodiment, the preparation of the 36 μm thick TaC micro-arc oxidized ceramic film on the surface of the aluminum alloy specifically includes the following steps:
step 1: the processed aluminum alloy sample is subjected to oil and grease removing processes, then is ground by different waterproof abrasive paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the aluminum alloy, sodium hexametaphosphate and sodium silicate are taken as main materials (32g/L), and sodium silicate (4g/L), potassium fluoride (3g/L), sodium hydroxide (8g/L), sodium dodecyl benzene sulfonate (1g/L) and TaC nano-scale powder (3g/L) are added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, an aluminum oxide ceramic layer with the thickness of 36 micrometers and the Ta content of 1.4 at.% is generated on the surface of the aluminum alloy by adjusting the voltage of 500V, the frequency of 800Hz, the duty ratio of 15% and the electrifying time of 40min, and rotary stirring is started in the reaction process.
Example 3:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 75 μm on the surface of the aluminum alloy specifically includes the following steps:
step 1: the processed aluminum alloy sample is subjected to oil and grease removing processes, then is ground by different waterproof abrasive paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the aluminum alloy, sodium silicate is taken as the main component (35g/L), and micro-arc oxidation electrolyte of sodium hexametaphosphate (5g/L), sodium tungstate (5g/L), potassium hydroxide (4g/L), sodium carboxymethylcellulose (2g/L) and TaC nano-scale powder (9g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, an aluminum oxide ceramic layer with the thickness of 75 micrometers and the Ta content of 3.2 at.% is generated on the surface of the aluminum alloy by adjusting the voltage of 550V, the frequency of 900Hz, the duty ratio of 20% and the electrifying time of 120min, and the circulating stirring is started in the reaction process.
Example 4:
in this embodiment, the preparation of the 35 μm thick TaC micro-arc oxidized ceramic film on the surface of the aluminum alloy specifically includes the following steps:
step 1: the processed aluminum alloy sample is subjected to oil and grease removing processes, then is ground by different waterproof abrasive paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the aluminum alloy, sodium silicate is taken as the main component (30g/L), and micro-arc oxidation electrolyte of sodium hexametaphosphate (5g/L), potassium fluoride (10g/L), sodium hydroxide (10g/L), sodium carboxymethylcellulose (2g/L) and TaC nano-scale powder (8g/L) is added.
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, an aluminum oxide ceramic layer with the thickness of 35 mu m and the Ta content of 3.2 at.% is generated on the surface of the aluminum alloy by adjusting the voltage of 500V, the frequency of 500Hz, the duty ratio of 30% and the electrifying time of 30min, and the circulating stirring is started in the reaction process.
Example 5:
in this embodiment, the preparation of the TaC micro-arc oxidized ceramic film layer with a thickness of 10 μm on the surface of the aluminum alloy specifically includes the following steps:
step 1: the processed aluminum alloy sample is subjected to oil and grease removing processes, then is ground by different waterproof abrasive paper, and then is polished and washed by water for micro-arc oxidation treatment.
Step 2: according to the micro-arc oxidation electrolyte of the aluminum alloy, sodium silicate is taken as the main electrolyte (30g/L), sodium hydroxide (2g/L), sodium carboxymethylcellulose (1g/L) and TaC nano-scale powder (2 g/L).
And step 3: a direct-current pulse micro-arc oxidation power supply is adopted, an aluminum oxide ceramic layer with the thickness of 10 micrometers and the Ta content of 0.5 at.% is generated on the surface of the aluminum alloy by adjusting the voltage of 450V, the frequency of 1200Hz, the duty ratio of 8% and the electrifying time of 15min, and the circulating stirring is started in the reaction process.
The method can realize controllable regulation (0.5-3.2 at.%) of the content of Ta in the micro-arc oxidation ceramic layer by regulating and controlling the content of TaC particles in the electrolyte and micro-arc oxidation electrical parameters (including voltage and oxidation time), and part of TaC particles can be possibly converted into Ta under the action of high temperature and high pressure of micro-arc oxidation reaction2O5But Ta2O5Still has higher melting point (1872 +/-10 ℃) and meets the standard range of the limit temperature of 400 ℃ of the existing aluminum alloy piston.
As shown in FIG. 1, which is a schematic view of the microstructure of the ceramic layer prepared in example 1, it can be observed that a large number of micropores exist in the micro-arc oxidized ceramic layer, but the doping of the TaC particles can just fill the micropores, so that the compactness of the micro-arc oxidized ceramic layer can be changed.
FIG. 2 is an XPS survey of the ceramic layer and a high resolution XPS map of Ta element in example 1, showing that the micro-arc oxidized ceramic layer contains Ta element and the original peaks are subjected to peak fitting to find TaC and Ta2O5The characteristic peak shows that part of TaC is oxidized into Ta in the high-temperature and high-pressure process of micro-arc oxidation2O5. FIG. 3 is a micro-topography of a micro-arc oxidized ceramic layer containing TaC particles in the ceramic layer of example 1, in which the particles in the circle are TaC particles, which demonstrates that calcium particlesThe particles adhere to the surface of the ceramic layer.
FIG. 4 is a graph showing the results of surface hardness of the micro-arc oxidized layer of the aluminum alloy substrate, the aluminum alloy micro-arc oxidized layer and the aluminum alloy doped with TaC particles, wherein the aluminum alloy substrate (Al in the graph) has a hardness of 68HV, the pure micro-arc oxidized ceramic layer has a hardness of 374HV, and the TaC-doped micro-arc oxidized ceramic layer has a hardness of 390-430 HV, for example, the hardness of the micro-arc oxidized ceramic layer prepared in example 1 is 403HV for TaC-1, the hardness of the micro-arc oxidized ceramic layer prepared in example 2 is 429HV for TaC-2, and the hardness of the micro-arc oxidized ceramic layer prepared in example 3 is 432HV for TaC-3.
FIG. 5 is a 3D morphology of the results of frictional wear of aluminum alloy, aluminum alloy micro-arc oxidation and aluminum alloy doped TaC particle micro-arc oxidation ceramic layers, wherein a) is aluminum alloy, b) is a micro-arc oxidation layer, and c) and D) are micro-arc oxidation layers prepared in examples 1 and 2, respectively, according to the graph, the left side and the right side in the graph a) are ready for wear, the middle part in the graph b) is worn, and no obvious wear part exists in the graphs c) and D). Therefore, the wear resistance of the micro-arc oxidation and TaC-doped micro-arc oxidation ceramic layer is much higher than that of the aluminum alloy matrix, and the wear resistance of the TaC-doped micro-arc oxidation ceramic layer shows good wear resistance due to the fact that the TaC-doped micro-arc oxidation ceramic layer has no wear resistance.
FIG. 6 is a graph showing the results of the wear scar depth of the aluminum alloy, the micro-arc oxidation of the aluminum alloy, and the micro-arc oxidation ceramic layer doped with TaC particles of the aluminum alloy of the present example 1 and the example 2, wherein the wear resistance of the micro-arc oxidation and the micro-arc oxidation ceramic layer doped with TaC is much higher than that of the aluminum alloy substrate, and the micro-arc oxidation ceramic layer doped with TaC have good wear resistance.
In conclusion, the wear resistance and hardness of the aluminum alloy doped TaC particle micro-arc oxidation ceramic layer are obviously higher than those of the traditional aluminum alloy micro-arc oxidation ceramic layer.
Claims (4)
1. The preparation method of the micro-arc oxidation layer on the surface of the aluminum alloy piston is characterized by comprising the following steps of:
sequentially carrying out oil removal, grease removal, grinding and polishing water washing on the aluminum alloy sample;
preparing micro-arc oxidation electrolyte containing nano-scale TaC powder; the concentration of the nano-scale TaC powder in the micro-arc oxidation electrolyte is 2-6 g/L;
placing the polished and washed aluminum alloy sample into the electrolyte, and performing micro-arc oxidation on the aluminum alloy sample by adopting a direct-current pulse micro-arc oxidation power supply to obtain a micro-arc oxidation layer of 10-75 mu m on the surface of the aluminum alloy sample; wherein, the micro-arc oxidation electric parameters are as follows: the voltage is 450-550V, the frequency is 400-1200 Hz,
the duty ratio is 8-30%, and the electrifying time is 10-120 min.
2. The method for preparing the micro-arc oxidation layer on the surface of the aluminum alloy piston according to claim 1, wherein the content of the Ta element in the micro-arc oxidation layer is 0.5 to 3.2 at.%.
3. The method for preparing the micro-arc oxidation layer on the surface of the aluminum alloy piston according to claim 1, wherein the micro-arc oxidation electrolyte comprises sodium silicate, sodium hexametaphosphate, potassium hydroxide and nano-scale TaC powder;
the concentration of sodium silicate in the micro-arc oxidation electrolyte is 4-35 g/L, the concentration of sodium hexametaphosphate is 5-32 g/L, and the concentration of potassium hydroxide is 4-10 g/L.
4. The micro-arc oxidation layer on the surface of the aluminum alloy piston is characterized in that the micro-arc oxidation layer is prepared by the preparation method of the micro-arc oxidation layer on the surface of the aluminum alloy piston according to any one of claims 1 to 3;
the thickness of the micro-arc oxidation layer is 10-75 mu m, and the content of Ta element is 0.5-3.2 at.%.
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