CN112030210A - Method for improving wear resistance of near-alpha titanium alloy micro-arc oxidation film by adding zirconium carbonate into electrolyte - Google Patents
Method for improving wear resistance of near-alpha titanium alloy micro-arc oxidation film by adding zirconium carbonate into electrolyte Download PDFInfo
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Abstract
The invention discloses a method for improving the wear resistance of a micro-arc oxidation film of a near-alpha titanium alloy by adding zirconium carbonate into electrolyte, which comprises the following steps: (1) pretreating a near-alpha titanium alloy sample; (2) preparing micro-arc oxidation electrolyte; (3) and (5) micro-arc oxidation treatment. Zirconium carbonate is added into the electrolyte, and the zirconium carbonate is gradually decomposed to generate H under the action of micro-arc oxidation at high temperature and high pressure2O、CO2And ZrO2，CO2More tiny discharge holes are created while the gas overflows, so that the dissipation of redundant heat generated by micro-arc oxidation is facilitated, and the growth rate of a micro-arc oxidation film layer is increased; ZrO (ZrO)2The coating can enter the film layer to fill the discharge holes and cracks under the action of adsorption and meshing, and is dispersed and distributed at the discharge holes and surface depressions to form effective filling, so that the diameter of the discharge holes is reduced, the roughness of the film layer is reduced, and the compactness of the film layer is improved.
Description
Technical Field
The invention relates to the technical field of titanium alloy micro-arc oxidation films. In particular to a method for improving the wear resistance of a micro-arc oxidation film of near-alpha titanium alloy by adding zirconium carbonate into electrolyte.
Background
The titanium alloy is classified into five types, namely alpha type, near alpha type, alpha + beta type, metastable beta type and beta type, from the perspective of the metastable state phase composition of the titanium alloy. The near-alpha titanium alloy has excellent corrosion resistance and creep resistance, excellent weldability, formability, oxidation resistance and good thermal stability, the use temperature can reach 600 ℃, and the near-alpha titanium alloy is often applied to aerospace, military fields and ships. However, titanium alloys have poor wear resistance due to their inherent characteristics, and are particularly sensitive to adhesive wear and fretting wear, and are susceptible to crevice corrosion, galvanic corrosion and wear corrosion when used in various complex environments, thereby limiting their wide application.
At present, there are many techniques for improving the wear resistance and corrosion resistance of titanium alloys, such as electroplating and chemical plating, surface alloying, thermal spraying and plasma spraying, magnetron sputtering, surface nanocrystallization and other processing techniques. However, these techniques have problems, such as requiring inert gas protection in a vacuum environment, complicated equipment, easy damage, or poor coating effect.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a method for improving the wear resistance and corrosion resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte.
In order to solve the technical problems, the invention provides the following technical scheme:
the method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte comprises the following steps:
(1) pretreating a near-alpha titanium alloy sample;
(2) preparing micro-arc oxidation electrolyte;
(3) and (5) micro-arc oxidation treatment.
The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte comprises the following steps in step (1):
(1-1) cutting: cutting the near-alpha titanium alloy into cuboid flaky samples with the size of 30mm multiplied by 20mm multiplied by 5mm by using a numerical control linear cutting instrument, and cleaning in time to remove oil stains on the surface of an alloy substrate after cutting;
(1-2) drilling: drilling the cut cuboid flaky sample for hanging the alloy sample, wherein the position of the hole is controlled at the middle position of the top of the test piece, and the size of the hole is phi 3.2 mm;
(1-3) polishing the top point and the edge of the tip of a cuboid sample into a fillet by using a grinding wheel machine, wherein the sample surface is polished by using water-milled metallographic abrasive paper, and the metallographic abrasive paper is sequentially polished by using metallographic abrasive paper models of 80#, 400#, 1000# and 2000 #;
(1-4) ultrasonic cleaning: firstly, ultrasonic cleaning is carried out in acetone for 10min, the cleaned alloy is put into alcohol for ultrasonic cleaning for 10min, grease and other impurities on the surface of the base alloy are removed, and the base alloy is sealed for standby after being dried.
In the step (2), zirconium carbonate particles or modified zirconium carbonate particles are added into silicate system electrolyte, wherein the silicate system electrolyte comprises Na2SiO3、Na2HPO4And Na2EDTA, zirconium carbonate particles are ZrCO3(OH)2·ZrO2。
Method for improving wear resistance of near-alpha titanium alloy micro-arc oxidation film by adding zirconium carbonate into electrolyte, and Na in system2SiO3Has a concentration of 16g/L, Na2HPO4Has a concentration of 10.0g/L, Na2The concentration of EDTA was 2.0g/L, and the concentration of the fine zirconium carbonate particles or the fine modified zirconium carbonate particles added to the electrolyte was 0 to 4 g/L.
The method for improving the wear resistance of the near-alpha titanium alloy micro-arc oxidation film by adding zirconium carbonate into the electrolyte comprises the following steps:
(A) concentrated sulfuric acid is dripped into the zirconium hydroxide solution to lead SO4 2-：ZrO2In a ratio of 0.6 to 0.7, and then reactingHeating the reaction system to 90-100 ℃, keeping the reaction temperature of 90-100 ℃ for 2-2.5h at the heating speed of 1 ℃/min, carrying out vacuum filtration, and washing a filter cake with deionized water to obtain basic zirconium sulfate;
(B) slowly adding 25-30% by mass of sodium carbonate aqueous solution into the basic zirconium sulfate prepared in the step (A) to ensure that the pH of the reaction mixture is 9-10, continuously stirring for reaction for 2-2.5h, carrying out vacuum filtration, washing a filter cake with deionized water, and carrying out vacuum filtration to obtain crude zirconium carbonate;
(C) dropwise adding dilute hydrochloric acid into the crude zirconium carbonate, adjusting the pH value of the system to 6.0-7.0, carrying out vacuum filtration, and washing a filter cake with deionized water to obtain zirconium carbonate;
(D) and (C) adding 20-30g of zirconium carbonate in the step (C) into 30-50mL of absolute ethyl alcohol, uniformly stirring, adding 0.5-1mL of silane coupling agent, stirring at 80-90 ℃ for reaction for 5-6h, drying at 100 ℃, and crushing to obtain the modified zirconium carbonate particles.
The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte is characterized in that a silane coupling agent is KH550 or KH 560.
In the step (3), the outer wall of the micro-arc oxidation electrolytic tank (1) is a stainless steel electrolytic tank, the outer wall of the electrolytic tank (1) is a hollow interlayer outer wall (2), the hollow interlayer outer wall (2) is in fluid communication with the cooling water circulation system (3), and the bottom of the electrolytic tank (1) is provided with a stirrer (4).
In the step (3), a constant voltage method is adopted for micro-arc oxidation treatment, the anode of the multifunctional power supply (5) is connected with the near alpha titanium alloy pattern (7), and the cathode of the multifunctional power supply (5) is connected with the electrolytic bath (1); the parameters of the micro-arc oxidation treatment are a positive working voltage of 420V, a negative working voltage of 80V, a frequency of 100Hz, a duty ratio of 50 percent and an oxidation time of 15 min.
The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte has the advantage that the temperature of the electrolyte in the electrolytic bath (1) is 20-60 ℃ in the micro-arc oxidation treatment process.
The technical scheme of the invention achieves the following beneficial technical effects:
1. zirconium carbonate is added into the electrolyte, and the zirconium carbonate is gradually decomposed to generate H under the action of micro-arc oxidation at high temperature and high pressure2O、CO2And ZrO2，CO2More tiny discharge holes are created while the gas overflows, so that the dissipation of redundant heat generated by micro-arc oxidation is facilitated, and the growth rate of a micro-arc oxidation film layer is increased; ZrO (ZrO)2The coating can enter the film layer to fill the discharge holes and cracks under the action of adsorption and meshing, and is dispersed and distributed at the discharge holes and surface depressions to form effective filling, so that the diameter of the discharge holes is reduced, the roughness of the film layer is reduced, and the compactness of the film layer is improved.
2. By changing the addition amount of zirconium carbonate in the electrolyte, the addition of the zirconium carbonate enables the sizes of cracks and holes on the surface of the film layer to be reduced, and the discharge holes and surface depressions are effectively filled; when the adding amount is 1g/L, the maximum thickness of the film layer is 110 mu m, and the minimum roughness is 13.5 mu m; when the addition amount of the zirconium carbonate is 4g/L, the number of holes in the film layer is the largest, and the compactness is poor.
3. The modified zirconium carbonate particles use zirconium hydroxide as a starting material, firstly prepare basic zirconium sulfate, then prepare zirconium carbonate with stable particle size and high crosslinking activity, then add silane coupling agents KH550 and KH560 to modify the zirconium carbonate, so that the defects of zirconium carbonate crystals are increased, Si-OH in the inner layer of the silane coupling agent can form hydrogen bonds with OH-on the surface of the zirconium carbonate, so that the silane coupling agent is connected with or coated on the surface of the zirconium carbonate to form a modified coating layer, the particle size distribution of the zirconium carbonate particles is relatively uniform, which can not only obstruct the agglomeration of calcium carbonate particles, improve the dispersibility of the zirconium carbonate in electrolyte, reduce the deposition of the zirconium carbonate at the bottom of an electrolytic bath, but also can effectively avoid the agglomeration of the zirconium carbonate particles in the electrolyte on the surface of a composite film and obstruct the interaction of the electrolyte and a sample, thereby improving the performance of a micro-arc oxidation film layer, the oxide film is more uniform and compact, and the grinding loss-weight ratio is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of the micro-arc oxidation operation of the present invention;
FIG. 2 is a graph comparing the thickness of films with different amounts of added zirconium carbonate;
FIG. 3 is a graph comparing the roughness of films with different amounts of added zirconium carbonate;
FIG. 4a shows the current change (positive current) in the differential arc oxidation process with different amounts of added zirconium carbonate;
FIG. 4b shows the current change (reverse current) during the differential arc oxidation process with different amounts of added zirconium carbonate;
FIG. 5a is SEM images of the surfaces of the micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 0 g/L;
FIG. 5b is SEM images of the surfaces of the micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 1 g/L;
FIG. 5c is SEM images of the surfaces of the micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 2 g/L;
FIG. 5d is SEM images of the surfaces of the micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 3 g/L;
FIG. 5e is SEM images of the surfaces of the micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of zirconium carbonate is 4 g/L;
FIG. 6a is a three-dimensional view of the surface of a micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 0 g/L;
FIG. 6b is a three-dimensional view of the surface of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 1 g/L;
FIG. 6c is a three-dimensional view of the surface of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 2 g/L;
FIG. 6d is a three-dimensional view of the surface of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 3 g/L;
FIG. 6e is a three-dimensional view of the surface of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of zirconium carbonate is 4 g/L;
FIG. 7a is SEM images of sections of micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 0 g/L;
FIG. 7b is SEM images of sections of micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 1 g/L;
FIG. 7c is SEM images of sections of micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 2 g/L;
FIG. 7d is SEM images of sections of micro-arc oxidation film layers with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 3 g/L;
FIG. 7e is a SEM image of the cross section of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of zirconium carbonate is 4 g/L;
FIG. 8a is a cross-sectional line scan of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 0 g/L;
FIG. 8b is a cross-sectional line scan of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 1 g/L;
FIG. 8c is a cross-sectional line scan of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 2 g/L;
FIG. 8d section line scanning of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of the zirconium carbonate is 3 g/L;
FIG. 8e is a cross-sectional line scan of the micro-arc oxidation film layer with different zirconium carbonate addition amounts: the adding amount of zirconium carbonate is 4 g/L;
FIG. 9 XRD patterns of micro-arc oxidation film layers with different zirconium carbonate addition amounts.
The reference numbers in the figures denote: 1-an electrolytic cell; 2-outer wall of hollow interlayer; 3-a cooling water circulation system; 4-a stirrer; 5-a multifunctional power supply; 6-thermometer; 7-near alpha titanium alloy pattern; 8-insulating matrix.
Detailed Description
First part, adding zirconium carbonate into electrolyte to prepare near alpha titanium alloy micro-arc oxidation film
1. Preparation of near-alpha titanium alloy
The matrix sample is Ti-5Al-1V-1Sn-4Zr-0.8Mo alloy (the early research result shows that the film obtained after the alloy is micro-arc oxidized has better bonding force and wear resistance), and the preparation method adopts a vacuum consumable arc melting furnace (VAR) to carry out vacuum consumable melting. And detecting and analyzing the actual components of the ingot prepared by smelting by adopting an inductively coupled plasma atomic emission spectrometry, wherein the actual components are shown in table 1, and the measured values of the chemical components of the ingot obtained from the test results are close to the nominal components of the alloy, so that the experimental requirements are met.
TABLE 2-1 chemical composition of alloy (wt.%)
2. Pretreatment of near-alpha titanium alloy sample
(1) Cutting: the four matrix alloys are cut into cuboid flaky samples with the size of 30mm multiplied by 20mm multiplied by 5mm by a numerical control linear cutting instrument, and oil stains on the surfaces of the alloy matrixes are timely cleaned and removed after cutting.
(2) Drilling: and drilling the top of the cut cuboid sheet sample for suspending the alloy sample. The position of the hole is controlled at the middle position of the top of the test piece, the size is phi 3.2mm, and the purpose is to connect the test piece by using a power-on lead and hang and soak the test piece in electrolyte.
(3) Polishing a sample: the tip discharge effect exists in the initial stage of micro-arc oxidation reaction, so that the vertex and the edge of the tip of the cuboid sample are firstly polished into round corners by using a grinding wheel machine. In the experimentation, the sample surface is polished and is adopted the water mill metallography abrasive paper, uses the metallography abrasive paper model to be: 80#, 400#, 1000#, 2000 #.
(4) Ultrasonic cleaning: an ultrasonic cleaning machine CJ-030 of Shenzhen super clean science and technology industries Limited is used, firstly, ultrasonic cleaning is carried out in acetone for 10min, the cleaned ultrasonic cleaning is carried out in alcohol for 10min, grease and other impurities on the surface of the matrix alloy are removed, and the substrate alloy is sealed for later use after being dried.
3. Preparation of micro-arc oxidation electrolyte
The micro-arc oxidation experiment adopts electrolyte as a silicate system, and the composition ratio is as follows:
Na2SiO3(16g/L)+Na2HPO4(10.0g/L)+Na2EDTA(2.0g/L)。
zirconium carbonate fine particles were added to the silicate system electrolyte. Chemical formula is ZrCO3(OH)2·ZrO2The amounts of zirconium carbonate added are shown in Table 2.
TABLE 2 experimental protocol for zirconium carbonate addition
| Numbering | ZrCO3(OH)2·ZrO2/(g/L) |
| S4-0 | 0 |
| S4-1 | 1 |
| S4-2 | 2 |
| S4-3 | 3 |
| S4-4 | 4 |
4. Micro arc oxidation treatment
(1) Micro-arc oxidation power supply
The experiment adopts a T-MAO-B30 micro-arc oxidation treatment power supply and a cooling water circulation system which are produced by the New science and technology Limited company of Xian Tianao, and the main technical parameters of the power supply are shown in Table 3.
TABLE 3 micro-arc oxidation power supply main technical parameters
| Parameters of power supply | Output parameter |
| Output power | 0-30KW |
| Forward voltage | 0-700V |
| Negative voltage | 0-50A |
| Forward current flow | 0-250V |
| Negative current | 0-50A |
| Output frequency | 30-10000Hz |
(2) Electrolytic cell, as shown in FIG. 1
The outer wall of the micro-arc oxidation electrolytic cell (1) is a stainless steel electrolytic cell, the capacity of the electrolytic cell is 16L, the outer wall of the electrolytic cell (1) is a hollow interlayer outer wall (2), and the hollow interlayer outer wall (2) is in fluid communication with the cooling water circulation system (3), so that the temperature of electrolyte in the electrolytic cell is reduced, the temperature is controlled to be 20-60 ℃, the growth rate of a micro-arc oxidation film layer is improved, and the compactness and uniformity of the film layer are kept at a good level.
The bottom of the electrolytic cell (1) is provided with a stirrer (4): the components of the electrolyte are uniform through stirring, and the medicine is prevented from being deposited at the bottom of the electrolytic tank. In addition, the heat conduction rate in the electrolyte can be improved through stirring, so that the temperature in the electrolytic cell is stable, and the temperature of the electrolyte is controlled at a reasonable level by matching with a cooling water circulation system.
(3) Micro arc oxidation treatment parameters
Micro-arc oxidation treatment is carried out by adopting a constant voltage method, the anode of the multifunctional power supply (5) is connected with the near alpha titanium alloy pattern (7), and the cathode of the multifunctional power supply (5) is connected with the electrolytic bath (1); the parameters of the micro-arc oxidation treatment are a positive working voltage of 420V, a negative working voltage of 80V, a frequency of 100Hz, a duty ratio of 50 percent and an oxidation time of 15 min.
Second part, influence of zirconium carbonate on micro-arc oxidation film layer characteristics
Zirconium carbonate is a white powdery inorganic compound with the chemical formula of ZrCO3(OH)2·ZrO2Easily soluble in organic and inorganic acids, insoluble in water and organic solvents, easily decomposable by heating, and decomposable at a temperature below 200 deg.C to produce H2O, gradually decomposing above 500 ℃ to form ZrO2It can be widely used in the high and new technical fields of functional ceramics, structural ceramics, optical storage materials, catalysts and the like. Adding zirconium carbonate particles into the electrolyte, and decomposing zirconium carbonate to generate ZrO by utilizing the action of micro-arc oxidation at high temperature and high pressure2When the film grows, the ZrO enters the ceramic film and is utilized2Excellent characteristics and a toughening and reinforcing mechanism, thereby improving the performance of the micro-arc oxidation film layer.
1. Film thickness and roughness
Measuring the thickness of the micro-arc oxidation ceramic membrane by using an OxFORD INSTRUMENTS CMI 233 type magnetic induction/eddy current dual-purpose thickness gauge, wherein ten positions are taken as measurement sampling points, five points are respectively taken on the front surface and the back surface, and the average value of the thicknesses measured by the ten points is taken as the final thickness measurement value at four points which are 5mm away from the top point of the sample and are positioned at the central parts of the front surface and the back surface of the sample.
The roughness of the micro-arc oxidation film layer is measured by adopting a Zeiss laser scanning confocal microscope LSM700, the scanning area of the microscope is 1.3mm multiplied by 1.3mm, three points are respectively taken at equal intervals on the horizontal and vertical coordinates in the scanning area of the microscope for line scanning to obtain 6 groups of roughness data, and the average value of the measured data is taken as the final measured value of the roughness of the film layer.
The thickness and the roughness of the micro-arc oxidation film layer prepared by adding zirconium carbonate into the electrolyte are shown in figures 2 and 3, and the change of positive and negative current in the micro-arc oxidation process is shown in figures 4a and 4 b. As can be seen from FIG. 2, after the zirconium carbonate is added to the electrolyte, the thickness of the micro-arc oxidation film layer is obviously increased, the thickness of the ceramic film layer is increased by 24.9 μm when the addition amount of the zirconium carbonate is 1g/L compared with that of the zirconium carbonate which is not added, the thickness change amplitude of the film layer is smaller as the addition amount of the zirconium carbonate is larger, and the total thickness of the ceramic film layer is kept within the range of 100-one-film thickness of 110 μm; as can be seen from FIG. 3, the addition of zirconium carbonate to the electrolyte significantly reduced the surface roughness of the film, with the minimum roughness of 13.5 μm for a film added at 1g/L, and the roughness gradually increased as the amount of zirconium carbonate added increased, but was always less than 40.22 μm for a film without zirconium carbonate.
From the positive and negative current change diagrams (fig. 4a and 4b) in the reaction process, it can be found that the positive and negative currents of the sample without adding zirconium carbonate in the electrolyte are obviously higher than those of the sample with adding zirconium carbonate, because the resistivity of the electrolyte is increased by adding zirconium carbonate, the current density of the sample is reduced, the micro-arc oxidation process is mild, the film generation rate is high, and the thickness is increased. Under the action of micro-arc oxidation, zirconium carbonate is gradually decomposed to generate ZrO2And a large amount of gas, the reaction heat on the surface of the sample is taken away while the gas overflows, so that the dissolving speed and the surface temperature of the film layer are reduced, and the thickness of the film layer is obviously increased under the combined action of the dissolving speed and the surface temperature of the film layer; ZrO (ZrO)2Then enters into the film, the discharge hole and the film pit to reduce the roughness of the micro-arc oxidation film, and ZrO is utilized2High strength, high resistivity, good wear resistance, corrosion resistance and other excellent characteristics and a self toughening and reinforcing mechanism, thereby improving the compactness, wear resistance and corrosion resistance of the micro-arc oxidation film.
2. Microscopic morphology of film surface
And observing the micro-morphology of the surface and the section of the prepared micro-arc oxidation film layer by using a Hitachi S-3400N II type scanning electron microscope, and analyzing and measuring the element content and the element distribution of the surface and the section of the film layer by using an EMAX energy spectrometer of Horiba company, wherein a gold spraying instrument is JEOL, JFC-1600.
FIGS. 5a to 5e are micro-topography images of the surface of the micro-arc oxidation film layer of zirconium carbonate with different contents. As can be seen from the figure, when zirconium carbonate is not added into the electrolyte, the size of the discharge hole on the surface of the micro-arc oxidation film layer is larger, the depth and the size of the crack are both larger, and the whole thickness of the film layer is thinner and the roughness is larger. The thickness of the film layer is increased after the electrolyte is added into the zirconium carbonate, and the change is not large along with the increase of the adding amount of the zirconium carbonate; the roughness decrease is evident, slightly greater with increasing zirconium carbonate addition.
As can be seen from fig. 5a to 5e, the surface of the film layer without the added zirconium carbonate has more cracks, larger sizes of the width and the depth of the cracks, deeper discharge holes and loose integral structure of the film layer. After the zirconium carbonate is added, the width of the cracks on the surface of the film layer is narrowed, the internal film layer grows out of the cracks to fill the cracks, the diameter of the holes is reduced, and the holes grow and are filled compactly. The reason is that the zirconium carbonate is gradually decomposed to generate H under the action of micro-arc oxidation high temperature and high pressure2O、CO2And ZrO2，CO2More tiny discharge holes are created while the gas overflows, so that the dissipation of redundant heat generated by micro-arc oxidation is facilitated, and the growth rate of a micro-arc oxidation film layer is increased; ZrO (ZrO)2The coating can enter the film layer to fill the discharge holes and cracks under the action of adsorption and meshing, and is dispersed and distributed at the discharge holes and surface depressions to form effective filling, so that the diameter of the discharge holes is reduced, the roughness of the film layer is reduced, and the compactness of the film layer is improved.
Fig. 6a to 6e show three-dimensional surface morphologies of the micro-arc oxide films with different contents, and it can be seen from the graphs that the difference between the non-added zirconium carbonate film layer and the added zirconium carbonate film layer is large in height fluctuation, the non-added zirconium carbonate film layer is severe in height fluctuation, and the added zirconium carbonate film layer is flat, which is consistent with the roughness result of fig. 3. The position of the film layer protrusion corresponds to fused oxide on the surface and zirconium dioxide generated by zirconium carbonate decomposition, and the position of the pit corresponds to a hole left by discharge.
3. Microscopic morphology and element distribution of film section
FIGS. 7a to 7e show the micro-morphology of the cross section of the micro-arc oxidation film layer with different zirconium carbonate contents.
As can be seen from FIGS. 7a to 7e, the number of holes in the micro-arc oxidation film layer without adding zirconium carbonate is smaller than that of holes in the zirconium carbonate film layer, and the size of the discharge holes in the micro-arc oxidation film layer is increased after adding zirconium carbonate into the electrolyte, because zirconium carbonate is decomposed into zirconium oxide and carbon dioxide under the action of the micro-arc oxidation at high temperature and high pressure, and the gas generated by decomposition increases with the addition of zirconium carbonate in the electrolyte, so that the number of holes in the film layer is increased, and a large amount of CO is generated2Gas accumulation resulting in pore sizeBecomes larger. When the film layer grows under the action of electrolyte convection and electric field, ZrO2And the metal oxide film is embedded into the discharge micropores of the oxide film and the surface of the film layer by virtue of adsorption engagement. In the process, the zirconium carbonate particles which move violently absorb and take away the reaction heat generated on the surface of the film layer, and the reaction heat on the surface of the film layer is also taken away while a large amount of gas overflows, so that the melting and cooling rate is increased when the temperature on the surface of the film layer is reduced, the thickness of the film layer is increased, and the roughness is reduced.
FIGS. 8a to 8e are sectional line scanning element distribution diagrams of micro-arc oxidation film layers with different zirconium carbonate contents. As can be seen from the figure, the content of Al and Ti elements in the matrix is obviously higher than that of the film layer, and the distribution in the film layer is gradually reduced from inside to outside; zr and O elements are uniformly distributed in the film layer and the content of the Zr and O elements is obviously higher than that of the matrix, because a large amount of calcium carbonate powder is decomposed by means of micro-arc oxidation high-temperature high-pressure action to generate ZrO when the film layer grows2Then the obtained product is embedded into the oxide film discharge micropores and the surface of the film layer through the adsorption and meshing action, so that the content of Zr and O elements in the film layer is higher.
Comparing fig. 8b, fig. 8c, fig. 8d and fig. 8e, it is found that the addition amount of zirconium carbonate is 1g/L, 2g/L and 3g/L, the content of Zr and O elements in the film layer is more and is distributed uniformly, and the addition amount of zirconium carbonate is 4g/L, the content of Zr and O elements in the film layer is reduced, because the zirconium carbonate is added excessively and is easy to agglomerate and deposit to the bottom of the electrolytic cell, the effective concentration of the electrolyte is improved less, and the quality of the micro-arc oxidation film layer is directly influenced.
4. Film composition and phase distribution
The phase composition of the micro-arc oxidation film layer is measured and analyzed by using a Japanese physical D \ max-2500PC type X-ray diffractometer, the maximum power of an X-ray generator is 18kW, the tube voltage is 20-60kV, and the tube current is 10-300 mA. The main measurement technical parameters are Cu target, tube voltage 40kV, tube current 100mA, scanning angle 20-80 degrees and scanning speed 2/min.
The EDS surface scanning results of different calcium carbonate micro-arc oxidation film layers are shown in Table 4. As can be seen from Table 4, the main constituent elements of the film layer were O, Al, Si, Ti, and Zr. Wherein Zr mainly comes from ZrO generated by zirconium carbonate particles decomposed under the action of micro-arc oxidation at high temperature and high pressure2The increase in Zr content with increasing zirconium carbonate addition indicates thatThe Zr element content in the film layer is directly influenced by the adding amount of zirconium carbonate in the electrolyte.
TABLE 4 surface element content of micro-arc oxidation film layer with different zirconium carbonate addition
As shown in fig. 9, XRD patterns of the obtained films with different amounts of added zirconium carbonate. According to XRD (X-ray diffraction) pattern, the main phases of the film layer are anatase phase and rutile phase, when no zirconium carbonate is added into the electrolyte, the peak values of the anatase phase and the rutile phase in the micro-arc oxidation film layer are lower, and ZrO is formed2The phase has only weak diffraction peak, which indicates that the content is less; anatase phase and ZrO when zirconium carbonate is added in an amount of 1g/L2The peak strength of the phase is obviously improved, and the peak strength of the rutile phase is slightly improved when the addition amount of the zirconium carbonate is 2g/L and 3g/L, but the peak strength of the corresponding phase is reduced when the addition amount of the zirconium carbonate is 4g/L, the excessive added zirconium carbonate is easy to agglomerate and deposit at the bottom of an electrolytic bath, the difference between the effective concentration of the electrolyte and the theoretical concentration is increased, and meanwhile, the excessive added calcium carbonate particles agglomerate and agglomerate on the surface of the composite film layer to form spheres, so that the interaction between the electrolyte and a sample is prevented, and the quality of the micro-arc oxidation film layer is directly influenced. In conclusion, the zirconium carbonate added into the electrolyte is helpful for the film layer to generate anatase phase, rutile phase and ZrO2Phase, but should not be added in excess.
Influence of zirconium carbonate of a third part and different sources on corrosion resistance, film bonding force and wear resistance of the micro-arc oxidation film
Based on the conclusion of the second part, it is found that zirconium carbonate is added into the electrolyte, and the zirconium carbonate is gradually decomposed to generate H under the action of micro-arc oxidation at high temperature and high pressure2O、CO2And ZrO2，CO2More tiny discharge holes are created while the gas overflows, so that the dissipation of redundant heat generated by micro-arc oxidation is facilitated, and the growth rate of a micro-arc oxidation film layer is increased; ZrO (ZrO)2Can enter the film layer by virtue of the adsorption and meshing action to fill the discharge holes and cracks, and is dispersed and distributed at the discharge holes and the surface depressions to form effective filling, so that the discharge holesThe diameter is reduced, the roughness of the film is reduced, and the compactness is improved.
But also find that the excessive zirconium carbonate is easy to agglomerate and deposit at the bottom of the electrolytic bath, the effective concentration of the electrolyte is improved a little, and the quality of the micro-arc oxidation film layer is directly influenced. Therefore, the problem of agglomeration and deposition of zirconium carbonate in the electrolyte is improved by modifying zirconium carbonate in the part, and the influence of the zirconium carbonate on the corrosion resistance, the film bonding force and the wear resistance of the micro-arc oxidation film is researched.
The preparation method of the modified zirconium carbonate particles comprises the following steps:
(A) concentrated sulfuric acid is dripped into the zirconium hydroxide solution to lead SO4 2-：ZrO2The mass ratio of the substances is 0.7, then the reaction system is heated to 90 ℃, the heating speed is 1 ℃/min, the reaction temperature of 90 ℃ is kept for 2.5h, vacuum filtration is carried out, and the filter cake is washed by deionized water to obtain basic zirconium sulfate;
(B) slowly adding a sodium carbonate aqueous solution with the mass fraction of 25% into the basic zirconium sulfate prepared in the step (A) to ensure that the pH of the reaction mixture is 10, continuously stirring and reacting for 2.5h, carrying out vacuum filtration, washing a filter cake with deionized water, and carrying out vacuum filtration to obtain crude zirconium carbonate;
(C) dropwise adding dilute hydrochloric acid into the crude zirconium carbonate, adjusting the pH value of the system to 6.0, carrying out vacuum filtration, and washing a filter cake with deionized water to obtain zirconium carbonate;
(D) and (3) adding 50mL of absolute ethyl alcohol into 30g of zirconium carbonate obtained in the step (C), uniformly stirring, adding 1mL of silane coupling agent KH550, stirring at 90 ℃ for reacting for 6 hours, drying at 100 ℃, and crushing to obtain the modified zirconium carbonate particles.
Modified zirconium carbonate was added to the electrolyte solution in such a manner that the amount of the added modified zirconium carbonate in the electrolyte solution was 1g/L, 2g/L, 3g/L, and 4g/L, respectively, according to the method of adding commercially available zirconium carbonate, and the samples were marked as S4-1 modification, S4-1 modification, S4-1 modification, and S4-1 modification, respectively.
1. Film bonding force test
The method comprises the steps of using a WS-2005 type coating adhesion automatic scratch instrument produced by Kekachikoku technology development Limited in Lanzhou to test the film layer bonding force, adopting a mode of combining acoustic emission and friction force to measure the film layer bonding force, comprehensively judging the film layer bonding force through two signals, adopting a dynamic load operation mode, adopting a single scratch mode, and obtaining the film layer bonding force with the loading rate of 40N/m, the test load of 40N and the scratch length of 3 mm. As shown in table 5.
TABLE 5
| Test specimen | Combining force (N) |
| S4-0 | 25.1 |
| S4-1 | 26.3 |
| S4-2 | 27.8 |
| S4-3 | 26.9 |
| S4-4 | 22.6 |
| Modification of S4-1 | 26.5 |
| Modification of S4-2 | 28.3 |
| Modification of S4-3 | 29.5 |
| Modification of S4-4 | 27.3 |
2. Film abrasion resistance test
A DZ-322TABER abrasion resistance tester developed by Dazhong instruments Co., Ltd, Dongguan is adopted to test the abrasion resistance of the ceramic film, the pressure load is 500g, the rotating speed is 60r/min, the test is 1000r, and the abrasion resistance of the film is judged by measuring the weight reduction of the ceramic film before and after friction. As shown in table 6.
TABLE 6
The silane coupling agent KH550 modifies zirconium carbonate to cause the defects of zirconium carbonate crystals to be increased, Si-OH in the inner layer of the silane coupling agent can form hydrogen bonds with OH-on the surface of the zirconium carbonate, so that the silane coupling agent is connected with or coated on the surface of the zirconium carbonate to form a modified coating layer, the particle size distribution of zirconium carbonate particles is uniform, the agglomeration of calcium carbonate particles can be prevented, the dispersibility of the zirconium carbonate in electrolyte is improved, the deposition of the zirconium carbonate on the bottom of an electrolytic tank is reduced, more importantly, the agglomeration of the zirconium carbonate particles in the electrolyte on the surface of a composite membrane to form balls can be effectively avoided, and the interaction between the electrolyte and a sample is hindered, so that the performance of a micro-arc oxidation film layer is improved, the film layer is uniform and compact, the bonding force between the film layer and a matrix is improved, and the wear resistance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (9)
1. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte is characterized by comprising the following steps of:
(1) pretreating a near-alpha titanium alloy sample;
(2) preparing micro-arc oxidation electrolyte;
(3) and (5) micro-arc oxidation treatment.
2. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding the zirconium carbonate into the electrolyte according to claim 1, wherein the step (1) comprises the following steps:
(1-1) cutting: cutting the near-alpha titanium alloy into cuboid flaky samples with the size of 30mm multiplied by 20mm multiplied by 5mm by using a numerical control linear cutting instrument, and cleaning in time to remove oil stains on the surface of an alloy substrate after cutting;
(1-2) drilling: drilling the cut cuboid flaky sample for hanging the alloy sample, wherein the position of the hole is controlled at the middle position of the top of the test piece, and the size of the hole is phi 3.2 mm;
(1-3) polishing the top point and the edge of the tip of a cuboid sample into a fillet by using a grinding wheel machine, wherein the sample surface is polished by using water-milled metallographic abrasive paper, and the metallographic abrasive paper is sequentially polished by using metallographic abrasive paper models of 80#, 400#, 1000# and 2000 #;
(1-4) ultrasonic cleaning: firstly, ultrasonic cleaning is carried out in acetone for 10min, the cleaned alloy is put into alcohol for ultrasonic cleaning for 10min, grease and other impurities on the surface of the base alloy are removed, and the base alloy is sealed for standby after being dried.
3. The method for improving the wear resistance of the micro-arc oxide film of the near-alpha titanium alloy by adding the zirconium carbonate into the electrolyte according to claim 1, wherein in the step (2), zirconium carbonate particles or modified zirconium carbonate particles are added into a silicate system electrolyte, and the silicate system electrolyte comprises Na2SiO3、Na2HPO4And Na2EDTA, zirconium carbonate particles are ZrCO3(OH)2·ZrO2。
4. Electrolysis according to claim 3The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the solution is characterized in that Na is contained in the system2SiO3Has a concentration of 16g/L, Na2HPO4Has a concentration of 10.0g/L, Na2The concentration of EDTA was 2.0g/L, and the concentration of the fine zirconium carbonate particles or the fine modified zirconium carbonate particles added to the electrolyte was 0 to 4 g/L.
5. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding the zirconium carbonate into the electrolyte according to claim 3, wherein the preparation method of the modified zirconium carbonate particles comprises the following steps:
(A) concentrated sulfuric acid is dripped into the zirconium hydroxide solution to lead SO4 2-：ZrO2The mass ratio of the substances is 0.6-0.7, then the reaction system is heated to 90-100 ℃, the heating rate is 1 ℃/min, the reaction temperature of 90-100 ℃ is kept for 2-2.5h, vacuum filtration is carried out, and the filter cake is washed by deionized water to obtain basic zirconium sulfate;
(B) slowly adding 25-30% by mass of sodium carbonate aqueous solution into the basic zirconium sulfate prepared in the step (A) to ensure that the pH of the reaction mixture is 9-10, continuously stirring for reaction for 2-2.5h, carrying out vacuum filtration, washing a filter cake with deionized water, and carrying out vacuum filtration to obtain crude zirconium carbonate;
(C) dropwise adding dilute hydrochloric acid into the crude zirconium carbonate, adjusting the pH value of the system to 6.0-7.0, carrying out vacuum filtration, and washing a filter cake with deionized water to obtain zirconium carbonate;
(D) and (C) adding 20-30g of zirconium carbonate in the step (C) into 30-50mL of absolute ethyl alcohol, uniformly stirring, adding 0.5-1mL of silane coupling agent, stirring at 80-90 ℃ for reaction for 5-6h, drying at 100 ℃, and crushing to obtain the modified zirconium carbonate particles.
6. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding the zirconium carbonate into the electrolyte according to claim 5, wherein the silane coupling agent is KH550 or KH 560.
7. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte according to claim 1, wherein in the step (3), the outer wall of the micro-arc oxidation electrolytic tank (1) is a stainless steel electrolytic tank, the outer wall of the electrolytic tank (1) is a hollow interlayer outer wall (2), the hollow interlayer outer wall (2) is in fluid communication with the cooling water circulation system (3), and a stirrer (4) is arranged at the bottom of the electrolytic tank (1).
8. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding zirconium carbonate into the electrolyte according to claim 7, wherein in the step (3), the micro-arc oxidation treatment is carried out by adopting a constant voltage method, the anode of the multifunctional power supply (5) is connected with the near-alpha titanium alloy pattern (7), and the cathode of the multifunctional power supply (5) is connected with the electrolytic cell (1); the parameters of the micro-arc oxidation treatment are a positive working voltage of 420V, a negative working voltage of 80V, a frequency of 100Hz, a duty ratio of 50 percent and an oxidation time of 15 min.
9. The method for improving the wear resistance of the micro-arc oxidation film of the near-alpha titanium alloy by adding the zirconium carbonate into the electrolyte according to claim 7, wherein the temperature of the electrolyte in the electrolytic bath (1) is 20-60 ℃ in the micro-arc oxidation treatment process.
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