CN115012012A - Aluminum oxide doped composite coating for medical metal base material and preparation method thereof - Google Patents
Aluminum oxide doped composite coating for medical metal base material and preparation method thereof Download PDFInfo
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 19
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Abstract
The invention belongs to the technical field of materials, and particularly relates to an aluminum oxide doped composite coating for a medical metal substrate and a preparation method thereof. The aluminum oxide doped composite coating provided by the invention comprises Cr and Al 2 O 3 And PTFE. The invention is prepared by mixing Al 2 O 3 Evenly mix to the coating in, produced the effect that fine grain strengthens, made the structure of coating denser, strengthened the hardness and the wear resistance of coating, simultaneously, the introduction of PTFE, can make the coating that obtains produce one deck lubricating film at the friction in-process, improves the blocking resistance of coating from this.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an aluminum oxide doped composite coating for a medical metal substrate and a preparation method thereof.
Background
With the continuous development of medical technology, composite electrosurgical devices, mainly high-frequency surgical instruments, have been developed. The tissue thermal effect generated in the process of contacting the medical instruments and the human tissues can cut and stop bleeding, but the tissue eschar is carbonized and adhered to the electric knife head, so that the advance of medical work is influenced. Therefore, the cutting effect, anti-adhesion and wear resistance of the cutting head need to be considered.
Electroplating is a surface treatment technique for surface modification, and different coatings are applied to the surface of materials to meet different performance requirements, so that electroplating has been widely used in various fields of medical instruments, industrial production, and scientific research. The common electroplating solution for the prior electroplated coating is a BSC12 type trivalent chromium hard chromium electroplating solution, and although the problem of poor bonding force between the coating and a substrate is solved by using the pure Cr coating obtained by electroplating with the electroplating solution, the wear resistance and the blocking resistance need to be further improved.
Disclosure of Invention
In view of the above, the present invention provides an alumina-doped composite coating for a medical metal substrate and a preparation method thereof, and the composite coating provided by the present invention has good wear resistance and blocking resistance.
In order to achieve the aim, the invention provides an aluminum oxide doped composite coating for a medical metal substrate, which comprises Cr and Al 2 O 3 And PTFE.
Preferably, the thickness of the aluminum oxide doped composite coating is 3-4 μm.
The invention also provides a preparation method of the aluminum oxide doped composite coating, which comprises the following steps:
pretreating the base material to obtain a pretreated base material;
electroplating the pretreated substrate surface by using a plating solution to obtain the aluminum oxide doped composite coating;
the plating solution comprises trivalent chromium hard chromium working solution and Al 2 O 3 Particles and PTFE emulsions.
Preferably, Al in the plating solution 2 O 3 The mass concentration of the particles is 0.5 to 3 g/L.
Preferably, the volume ratio of the PTFE emulsion to the trivalent chromium hard chromium working solution is 1.25: 100.
Preferably, the electroplating temperature is 40-50 ℃, the time is 15-25 min, and the current density is 30-40A/dm 2 。
Preferably, the pretreatment is polishing treatment, ultrasonic cleaning, degreasing treatment and acid washing in sequence.
Preferably, the temperature of the oil removing treatment is 70-80 ℃, and the time is 10-15 min.
Preferably, the acid-washing agent comprises hydrochloric acid; the volume concentration of the acid washing reagent is 40-60%, and the acid washing time is 3-5 min.
Preferably, after the electroplating, the method further comprises the step of carrying out heat treatment on the coating obtained by the electroplating; the temperature of the heat treatment is 180-220 ℃, and the time is 50-70 min.
The invention provides an aluminum oxide doped composite coating for a medical metal substrate, which comprises Cr and Al 2 O 3 And PTFE. The invention is prepared by mixing Al 2 O 3 The coating is uniformly doped in the coating, so that a fine-grain strengthening effect is generated, the structure of the coating is more compact, and the hardness and the wear resistance of the coating are enhanced; meanwhile, the introduction of PTFE enables the coating to generate a lubricating film during the friction process, thereby improving the anti-blocking property of the coating.
The invention also provides a preparation method of the aluminum oxide doped composite coating, which comprises the following steps: pretreating the base material to obtain a pretreated base material; electroplating the pretreated substrate surface by using a plating solution to obtain the aluminum oxide doped composite coating; the plating solution comprises trivalent chromium hard chromium working solution and Al 2 O 3 Particles and PTFE emulsions. The preparation method provided by the invention has the advantages of simple process, high deposition speed and good bonding strength.
Drawings
FIG. 1 is an XRD spectrum of coatings 1-7 prepared in examples 1-7;
FIGS. 2-8 are SEM images of coatings 1-7 prepared in examples 1-7, respectively;
FIG. 9 is a microhardness map of coatings 1-7 prepared in examples 1-7;
FIG. 10 is a graph of the coefficient of friction of coatings 1-7 prepared in examples 1-7;
FIG. 11 is a graph of the wear resistance of coatings 1-7 prepared in examples 1-7;
FIG. 12 is a graph of the microhardness effect of coatings prepared in examples 1 and 5 at different heat treatment temperatures;
FIG. 13 is a surface energy spectrum of the coating prepared in example 5;
FIG. 14 is an SEM cross-sectional view of the coating prepared in example 5.
Detailed Description
The invention provides an aluminum oxide doped composite coating for a medical metal substrate, which comprises Cr and Al 2 O 3 And PTFE.
In the invention, the thickness of the aluminum oxide doped composite coating is preferably 3-4 μm, and more preferably 3.2-3.5 μm.
The invention also provides a preparation method of the aluminum oxide doped composite coating, which comprises the following steps:
pretreating the base material to obtain a pretreated base material;
electroplating the pretreated substrate surface by using a plating solution to obtain the aluminum oxide doped composite coating.
The plating solution comprises trivalent chromium hard chromium working solution and Al 2 O 3 Particles and PTFE emulsions.
In the present invention, the base material is preferably made of stainless steel.
In the present invention, the pretreatment is preferably a polishing treatment, an ultrasonic cleaning, an oil removal treatment and an acid washing in this order.
The polishing process is not particularly limited in the present invention, and may be performed by an operation known to those skilled in the art. In the invention, the reagent for ultrasonic cleaning preferably comprises acetone, and the power for ultrasonic cleaning is preferably 80-100W, and more preferably 90W; the ultrasonic cleaning time is preferably 25-35 min, and more preferably 30 min. In the invention, the agent for oil removal treatment is preferably NaOH or Na 2 CO 3 And Na 3 PO 4 The mixed solution of (1); the concentration of NaOH in the mixed solution is preferably 20g/L, Na 2 CO 3 The concentration of (B) is preferably 30g/L, Na 3 PO 4 The concentration of (B) is preferably 30 g/L. In the invention, the temperature of the oil removing treatment is preferably 70-80 ℃, and more preferably 75 ℃; the time for the oil removing treatment is preferably 10-15 min, and more preferably 12-13 min. In the present invention, the agent for acid washing preferably comprises hydrochloric acid, and the acid washingThe volume concentration of the reagent (2) is preferably 40-60%, and more preferably 50%; in the present invention, the temperature of the acid washing is preferably room temperature; the time is preferably 3 to 5min, and more preferably 4 min. In the present invention, the pickling is preferably performed by immersing the substrate in a pickling agent.
After the pretreated base material is obtained, electroplating is carried out on the surface of the pretreated base material by using plating solution, so as to obtain the aluminum oxide doped composite coating.
In the invention, the plating solution preferably comprises trivalent chromium hard chromium working solution and Al 2 O 3 Particles and PTFE emulsions. In the invention, the trivalent chromium hard chromium working solution preferably comprises 23-27 g/LCr 2 (SO 4 ) 3 ·6H 2 O、50g/LNa 2 SO 4 ，60g/LAl 2 (SO 4 ) 3 ·18H 2 O, 20g/L of catalyst, 120g/L of buffering agent and 35g/L of composite coordination agent, wherein in the embodiment of the invention, the trivalent chromium hard chromium working solution is preferably purchased from Beijing Lanli scientific and technological center.
In the invention, the plating solution is preferably prepared by self-control, and the preparation method of the plating solution is to add Al into the trivalent chromium hard chromium working solution 2 O 3 And (3) uniformly mixing the particles and the PTFE emulsion by ultrasonic.
In the present invention, Al is contained in the plating solution 2 O 3 The mass concentration of the particles is preferably 0.5 to 3g/L, more preferably 1 to 2 g/L. The volume ratio of the PTFE emulsion to the trivalent chromium hard chromium working solution is preferably 1.25: 100.
In the invention, the electroplating temperature is preferably 40-50 ℃, and more preferably 45 ℃; the time is preferably 15-25 min, and more preferably 20 min; the current density is preferably 30 to 40A/dm 2 More preferably 35A/dm 2 。
After the electroplating, the invention preferably further comprises heat treating the coating obtained by the electroplating.
In the invention, the temperature of the heat treatment is preferably 180-220 ℃, more preferably 200 ℃, and the time is preferably 50-70 min, more preferably 60 min.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The apparatus used in the examples of the invention was as follows:
x-ray diffractometer model D8Advance, Bruker, germany;
QuantaFEG450 type scanning electron microscope, FEI usa;
NANO indentor model NANO Indenter G200, agilent technologies, usa;
an HSR-2M reciprocating friction abrasion tester, Kaikaya Huakejiu development Co., Ltd, Lanzhou;
WS-2005 coating automatic scratch tester, Kaikayaki Huakejiu development, Inc. of Nakangzhou;
a high-frequency rectifier, fushuntai science and technology ltd, shenzhen, inc;
DHG 101-COB type box furnace, shangyi instrument and equipment plant;
XP6 analytical balance, METTLER TOLEDO, Switzerland.
Example 1
Putting a stainless steel substrate (with the length of 40mm, the width of 40mm and the thickness of 0.3mm) into a beaker containing 100mL of acetone, and carrying out ultrasonic cleaning for 10min with the power set to be 90W; then, removing oil from the matrix by using the following reagents: the concentration of Na is 20g/LNaOH and 30g/L 2 CO 3 And 30g/L of Na 3 PO 4 The mixed solution of (1); the oil removing temperature is 70 ℃, and the time is 10 min; and then, carrying out acid washing and activation on the base material for 4min by using hydrochloric acid with the volume fraction of 40% to obtain the pretreated base material.
Preparing a plating solution:
adding 12.5ml of TFE emulsion into 1L of trivalent chromium hard chromium working solution, and uniformly mixing by ultrasonic.
Under the condition of slow stirring by a magnetic stirrer, electroplating the pretreated substrate surface by using a plating solution, wherein the electroplating temperature is as follows: current at 45 deg.CThe density is 35A/dm 2 And the deposition time is 20min, and the aluminum oxide doped composite coating is obtained and is marked as a coating 1.
Example 2
This embodiment differs from embodiment 1 only in that: 0.5gAl is also added into 1L of the trivalent chromium hard chromium working solution 2 O 3 Particles, resulting in coating 2.
Example 3
This embodiment differs from embodiment 2 only in that: al in plating solution 2 O 3 Was 1g/L, to obtain a coating layer 3.
Example 4
This embodiment differs from embodiment 2 only in that: al in plating solution 2 O 3 Was 1.5g/L, giving a coating 4.
Example 5
This embodiment differs from embodiment 2 only in that: al in plating solution 2 O 3 Was 2.0g/L, to obtain a coating 5.
Example 6
This embodiment differs from embodiment 2 only in that: al in plating solution 2 O 3 Was 2.5g/L, giving a coating 6.
Example 7
This embodiment differs from embodiment 2 only in that: al in plating solution 2 O 3 Was 3.0g/L, giving a coating 7.
The XRD spectrograms of the coatings 1-7 prepared in the embodiments 1-7 are measured, the measurement result is shown in figure 1, and different Al can be seen from figure 1 2 O 3 The pattern shapes of the coatings under the concentration are similar, and different Al is prepared under the condition that the current density, the electroplating time, the PTFE concentration, the pH value and the temperature are kept unchanged in the electroplating process 2 O 3 The XRD lines of the coatings at the concentration of 44.3 degrees show a diffraction peak of Cr. According to XRD pattern, along with Al in the plating solution 2 O 3 The increasing concentration increases and then decreases the intensity of the diffraction peak of the coating, i.e. the crystalline intensity of the coating increases and then decreases. In Al 2 O 3 Has a concentration of 2.0 g-When the amount of the compound is L, the diffraction peak of trivalent chromium is strongest, and other Al 2 O 3 The intensity of the diffraction peak of the trivalent chromium with concentration is relatively weaker, which shows that the crystallinity of the Cr phase formed in the electroplating coating is better; however, PTFE and Al were not observed in the XRD pattern 2 O 3 Due to PTFE and Al in the coating 2 O 3 The content of nanoparticles is small.
FIGS. 2 to 8 are SEM images of coatings 1 to 7 prepared by the present invention. As can be seen from FIGS. 2 to 8, when Al is contained in the trivalent chromium plating solution 2 O 3 When the concentration of the particles is between 0 and 2.0g/L, Al is wrapped in the coating 2 O 3 Particles and PTFE particles, and with Al 2 O 3 Gradual increase of particles, Al 2 O 3 The embedding amount of the particles in the coating is increased continuously and is distributed in the coating more uniformly, and the embedding amount of the PTFE particles is gradually reduced along with the Al 2 O 3 The concentration continues to increase, during the electroplating process, Al 2 O 3 The probability of particles becoming embedded in the coating increases, thereby allowing Al to enter the surface of the electroplated coating 2 O 3 The amount of particles also increases when Al 2 O 3 The rate of particle entry into the electroplated coating surface is equal to Al 2 O 3 Al in the coating at the rate of particles becoming embedded in the coating 2 O 3 The particles reach the highest value, i.e. Al 2 O 3 Al in the coating at a particle concentration of 2.0g/L 2 O 3 The particle recombination reaches the optimum, and the coating surface is flat and has no obvious cracks. With Al 2 O 3 Further increase of particles, i.e. from a concentration of 2.0g/L to 3.0g/L, Al in the coating 2 O 3 The amount of recombination of particles starts to decrease because at this concentration, Al 2 O 3 Too many particles make the collision of particles during movement to be intensified, Al 2 O 3 And PTFE particles are polymerized and settled in the trivalent chromium plating solution, do not present a suspension uniform state, but are colloidal, so that the particles are prevented from moving to a cathode, the adsorption quantity of the particles on the surface of the coating is reduced, the composite quantity is not increased or even reduced, the quality of the surface of the coating is gradually reduced, the appearance is poor, and as shown in figures 7-8, the composite coating is formedCracks are evident.
The microhardness of the coatings 1-7 prepared in examples 1-7 was measured and fitted to a curve, as shown in FIG. 9, which is seen from the curve of FIG. 9 along with Al 2 O 3 The increase in particle concentration increases the hardness of the coating first and then decreases. The hardness of the composite coating is related to the content and distribution of the second phase particles therein, i.e. by Al in the coating 2 O 3 And PTFE particles. When Al is in trivalent chromium plating solution 2 O 3 When the concentration is increased from 0g/L to 2.0g/L, the concentration is changed along with Al 2 O 3 Added to the trivalent chromium bath, the hardness of the coating increases because of Al 2 O 3 High hardness of particles, Al in plating solution 2 O 3 The particles enter the surface of the coating and become embedded therein, and Al in the coating 2 O 3 Increased content, reduced content of PTFE particles, Al 2 O 3 And PTFE particles are uniformly distributed in the coating, thereby producing the function of fine crystal strengthening and enabling the structure of the coating to be more compact, namely Al 2 O 3 At a concentration of 2.0g/L, the coating hardness reaches a maximum. When the concentration is increased from 2.0g/L to 3.0g/L, the concentration is changed along with Al 2 O 3 Further increase of particles, at which point Al in the bath 2 O 3 The excessive particles generate a large amount of bubbles in the cathode coating through hydrogen evolution reaction, hydrogen on the surface of the coating cannot escape completely, the internal stress of the coating is increased, cracks appear on the surface of the coating, the appearance quality of the coating is reduced, and the hardness is also reduced.
The friction coefficients of the coatings 1 to 7 prepared in examples 1 to 7 were measured and fitted to a friction coefficient curve, as shown in fig. 10, as can be seen from fig. 10: with Al 2 O 3 The increase in concentration increases the coefficient of friction of the coating and decreases the lubricity. The coefficient of friction of the coating is significantly affected by the PTFE particles, which have a very low coefficient of friction, and a uniform lubricating film can be formed during frictional wear. From Al 2 O 3 When the concentration of 0g/L is increased to 2.0g/L, Al in the trivalent chromium plating solution 2 O 3 The suspension amount of the nano particles is correspondingly increased, so that the surface Al of the coating is increased 2 O 3 The adsorption amount of the particles is increased, the composite amount of PTFE particles in the composite coating is gradually reduced, and the friction coefficient of the coating is increased more slowly because of the Al along with the electroplating process 2 O 3 Increasing the particle concentration, stirring to remove Al 2 O 3 The more particles are transported to the surface of the plated part, Al 2 O 3 The probability of embedding the particles into the coating is increased, the embedding of PTFE particles is influenced, the ratio of adsorbing the PTFE particles on the surface of the plating piece is reduced, and the PTFE particles in the coating are gradually reduced. When Al in trivalent chromium plating solution 2 O 3 When the concentration is further increased, Al in the plating solution is present 2 O 3 Too high concentration of particles, Al during electroplating 2 O 3 The particle collision is intensified, the stability of the composite plating solution is obviously reduced, and Al 2 O 3 And PTFE nano particles are difficult to maintain a uniform and stable suspension state, so that the effective concentration of PTFE in the plating solution is reduced, the lubricating property is further reduced, and the friction coefficient is increased.
The abrasion resistance of the coatings 1 to 7 prepared in examples 1 to 7 was measured and fitted to a wear characteristic curve, as shown in fig. 11. As can be seen from FIG. 11, with Al in the trivalent chromium plating bath 2 O 3 The increase of the content causes the abrasion loss of the coating to decrease and then increase, and the abrasion resistance to increase and then decrease. This is because the wear resistance of the coating is greatly affected by the hardness and the friction coefficient of the coating. When Al is present 2 O 3 When the concentration of (A) is 0 to 2.0g/L, the hardness of the coating layer increases, and the friction coefficient is maintained at a low level even though it increases, so that the shear strength of the plating layer increases, the wear resistance increases, and Al is added 2 O 3 The concentration of (A) is 2.0g/L to reach an optimal value. With Al 2 O 3 The concentration of (C) continues to increase in Al 2 O 3 When the concentration of (B) is 2.0 to 3.0g/L, the stability of the plating solution is lowered. As can be seen from FIGS. 3 to 4, in Al 2 O 3 When the concentration of (2.0-3.0 g/L) is used, the hardness of the coating is reduced, the friction coefficient is greatly increased, and cracks are generated, so that the shear strength of the coating is reduced, and the wear resistance is reduced.
The coatings prepared in example 1 and example 5 were appliedThe layers were heat treated at 50 deg.C, 100 deg.C, 150 deg.C, 200 deg.C, 250 deg.C, holding for 60min, cooled in furnace, and the resulting coating was measured for microhardness and fitted to a curve, see FIG. 12. As can be seen from FIG. 12, Al is not added 2 O 3 The hardness of the coating layer of the particles is continuously increased along with the continuous increase of the heat treatment temperature, and the increasing speed is higher, because the coating layer has carbide precipitation during the heat treatment process, and the coating layer can generate the crystallization phenomenon, the phenomenon can prevent the slippage of crystal dislocation by the grain boundary existing between the crystallized particles, thereby leading the micro hardness of the coating layer to increase, and the hardness of the coating layer has a maximum value at 200 ℃. Thereafter, with further increase in temperature, the hardness of the coating decreases, possibly due to grain growth of the coating and oxide agglomeration within the coating. Al (Al) 2 O 3 The change trend of the microhardness of the coating with the concentration of 2.0g/L and 0g/LAl 2 O 3 The trivalent chromium composite coating of the particle is basically consistent, and the microhardness is firstly increased and has a maximum value at 200 ℃ and then is reduced along with the continuous increase of the heat treatment temperature. But differs therefrom in that 2.0g/LAl 2 O 3 The increase of the microhardness of the concentrated coating is obviously smaller, and the increase of the hardness is not 4GPa, because the coating follows Al 2 O 3 Addition of particles due to Al 2 O 3 Pinning of particles to cause Al 2 O 3 The crystal lattice around the particles is distorted, thereby hindering the diffusion of carbide, and the carbide formation rate is slow compared with that without Al 2 O 3 The rate of increase of the hardness of the coating of the particles with temperature is correspondingly slowed down. Thus, Al 2 O 3 The addition of 3 seeds improves the thermal stability of the coating to a certain extent.
FIG. 13 is a surface energy spectrum of the coating prepared in example 5; as can be seen from fig. 13: five elements of F, C, O, Al and Cr exist, and the content of the F and Al elements is small, which indicates that PTFE and Al enter the composite coating 2 O 3 The amount of the complex is less, which is not detected by PTFE and Al in the XRD pattern 2 O 3 And (4) the same.
FIG. 14 is a SEM cross-sectional view of the coating prepared in example 5; as can be seen from fig. 14: to observe the doping of Al in the bath during the electroplating of trivalent chromium 2 O 3 The amount of 2.0g/L, PTFE was 12.5ml/L in concentration and the current density was 35A/dm 2 And when the PH value is about 2.0, the temperature is 45 ℃ and the deposition time is 20min, the thickness of the composite coating is 3.49um and the composite coating is tightly combined with the substrate.
The above examples, by comparison of different Al 2 O 3 The influence of doping on the microstructure and mechanical properties of the coating clearly shows that the concentration of PTFE is 12.5ml/L and the current density is 35A/dm 2 The optimal Al of the coating is obtained when the pH value is 2.0, the temperature of the plating solution is 45 ℃, the deposition time is 20min, and the heat treatment time is 60min at 200 DEG C 2 O 3 The doping amount is 2.0 g/L. The coating prepared under the doping amount has a compact structure, uniform grain size, tight combination between the coating and the substrate and optimal surface wear resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
1. The aluminum oxide doped composite coating for the medical metal base material is characterized by comprising Cr and Al 2 O 3 And PTFE.
2. The aluminum oxide-doped composite coating according to claim 1, wherein the thickness of the aluminum oxide-doped composite coating is 3-4 μm.
3. The method for preparing the aluminum oxide doped composite coating according to any one of claims 1 to 2, characterized by comprising the following steps:
pretreating the base material to obtain a pretreated base material;
electroplating the pretreated substrate surface by using a plating solution to obtain the aluminum oxide doped composite coating;
the plating solution comprises trivalent chromium hard chromium working solution and Al 2 O 3 Particles and PTFE emulsions.
4. The method according to claim 3, wherein Al in the plating solution 2 O 3 The mass concentration of the particles is 0.5 to 3 g/L.
5. The preparation method according to claim 3, wherein the volume ratio of the PTFE emulsion to the trivalent chromium hard chromium working solution is 1.25: 100.
6. The method according to claim 3, wherein the electroplating temperature is 40 to 50 ℃, the time is 15 to 25min, and the current density is 30 to 40A/dm 2 。
7. The production method according to claim 3, wherein the pretreatment is polishing treatment, ultrasonic cleaning, degreasing treatment, and acid washing in this order.
8. The preparation method according to claim 4, wherein the temperature of the oil removing treatment is 70-80 ℃ and the time is 10-15 min.
9. The method of claim 4, wherein the acid-washing reagent comprises hydrochloric acid; the volume concentration of the acid washing reagent is 40-60%, and the acid washing time is 3-5 min.
10. The method according to claim 3, wherein after the electroplating, the method further comprises heat-treating the coating obtained by the electroplating; the temperature of the heat treatment is 180-220 ℃, and the time is 50-70 min.
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