CN114855241B - Preparation method of refractory medium-high entropy alloy surface in-situ self-generated wear-resistant ceramic coating - Google Patents
Preparation method of refractory medium-high entropy alloy surface in-situ self-generated wear-resistant ceramic coating Download PDFInfo
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Classifications
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Abstract
The invention belongs to a preparation method of a medium-high entropy alloy ceramic coating, and in particular relates to a preparation method of an in-situ self-generated ceramic coating on the surface of a refractory medium-high entropy alloy. The invention provides a method for improving the friction resistance and corrosion resistance of a product by a micro-arc oxidation technology and a heat treatment technology aiming at refractory medium-high entropy alloy for the first time. In the invention, a constant voltage power supply is adopted and the forward voltage is controlled to be less than or equal to 400V during micro-arc oxidation; in the heat treatment, the heat treatment temperature is controlled to be 450-600 ℃. When the alloy is TiNbZr refractory medium entropy alloy, the friction coefficient of the ceramic coating obtained after heat treatment is less than or equal to 0.26; and the Ecorr of the obtained product is more than or equal to-0.2V SCE (closer to 0), icorr of 1.7X10 or less ‑5 A/cm 2 (closer to 0).The process is simple and controllable, and the obtained product has excellent friction resistance and corrosion resistance, and is convenient for large-scale industrial application.
Description
Technical Field
The invention belongs to a preparation method of a medium-high entropy alloy ceramic coating, and in particular relates to a preparation method of an in-situ self-generated ceramic coating on the surface of a refractory medium-high entropy alloy.
Background
With the rapid development of aerospace technology, high temperature components in aircraft are increasingly exposed to harsher and more severe service environments. Based on the particular use environment of aircraft, a series of materials with special properties, including medium-high entropy alloys, have been developed.
The novel design concept of the medium-high entropy alloy breaks the bottleneck of traditional material design, the concept is more and more perfect, the classification is more and more reasonable, the research scope is gradually expanded from the initial single-phase solid solution alloy with the equimolar ratio to the multi-component multiphase alloy, the multi-component multiphase alloy is further expanded to the complex component alloy, and a brand new thought is developed for the research and development of high-performance metal materials. The Ti-36Nb-5Zr alloy prepared by Meng et al has higher yield strength (720 MPa) and ultimate tensile strength (860 MPa) after cold rolling at 87.5% reduction and annealing at 698K for 25 minutes; the medium-high entropy alloy provides a new thought for the development of high-performance metal materials, and corrosion resistance, friction resistance and high-temperature oxidation resistance are key factors for restricting the application development of the high-performance metal materials. Meanwhile, the medium-high entropy alloy matrix is extremely easy to have the problems of component segregation, coarse structure and the like, and the problem is solved, so that the medium-high entropy alloy matrix becomes one of research hot spots of the current medium-high entropy alloy.
Compared with the traditional alloy, the medium-high entropy alloy has complex composition, but has simple phase composition, usually has a single-phase or double-phase structure, and the four-effect is still the main theoretical basis of the research organization and performance at present. And the research on the mechanical properties and the deformation mechanism of the medium-high entropy alloy is still in the primary stage. Compared with the traditional metal materials, the medium-high entropy alloy has a plurality of excellent performances such as high strength/hardness, high wear resistance, high fracture toughness, good corrosion resistance, oxidation resistance and the like. However, for certain special and extreme service environments, the wear resistance, corrosion resistance and high-temperature oxidation resistance of the medium-high entropy alloy are still to be further improved, and the plating of a ceramic coating is one of effective ways to solve the problems. At present, the preparation of ceramic coatings by micro-arc oxidation on the surface of high-entropy alloys is tried; but the performance of the obtained product has a huge improvement space. Meanwhile, no related report on the improvement of the friction resistance and the corrosion resistance of products by a micro-arc oxidation technology and a heat treatment technology aiming at refractory medium-high entropy alloy exists so far.
Disclosure of Invention
The invention aims to overcome the defect of corrosion resistance and wear resistance of refractory intermediate entropy alloy in extreme application environment, and provides a preparation method of an intermediate entropy alloy oxide ceramic coating which has strong bonding force with a substrate, high surface hardness, high wear resistance and corrosion resistance and excellent high-temperature oxidation resistance and is bonded with the substrate through diffusion bonding, micro-metallurgical bonding and chemical bonding for the first time.
The invention discloses a preparation method of an in-situ self-generated ceramic coating on the surface of a refractory medium-high entropy alloy, which comprises the following steps:
(a) Pretreating the surface of the TiNbZr refractory medium-high entropy alloy; obtaining the TiNbZr refractory medium-high entropy alloy with clean and dry surface;
(b) Preparing an in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with a clean and dry surface by utilizing a micro-arc oxidation technology; when micro-arc oxidation is carried out, a constant voltage power supply is adopted, and the forward voltage is controlled to be 150-400V;
(c) Carrying out structure regulation and control and friction resistance on the TiNbZr refractory medium-high entropy alloy surface ceramic coating through subsequent heat treatment; in the heat treatment, the heat treatment temperature is controlled to be 450-600 ℃.
As a preferable scheme, the TiNbZr refractory medium-high entropy alloy comprises a TiNbZr refractory medium-entropy alloy and a TiNbZr-containing high entropy alloy.
In the invention, in the TiNbZr refractory medium entropy alloy, ti is as follows: nb: zr=0.95 to 1.05:0.95 to 1.05:0.95 to 1.05.
In the invention, the refractory high-entropy alloy containing TiNbZr is prepared from Hf, nb, ta, zr, ti and Hf in an atomic ratio: nb: ta: zr: ti=0.95 to 1.05:0.95 to 1.05:0.95 to 1.05:0.95 to 1.05:0.95 to 1.05.
In the invention, the aim of pretreatment of the surface of the TiNbZr refractory medium-high entropy alloy is mainly to remove organic matters, oil stains and oxide layers, the operation can be the operation of the existing surface cleaning treatment, and the following process can be selected during laboratory operation:
(a1) For smelting (vacuum degree 6.0X10) -3 Pa) preparing a component close to the medium-high entropy alloy refractory to TiNbZr with equal atomic ratio, preparing a plurality of wafers with diameters of 5-20mm and thicknesses of 0.5-3mm by wire cutting, and penetrating a small hole with diameters of 1-2mm at the edge of the wafer.
(a2) Ultrasonic treating with acetone and alcohol to remove impurities such as organic solvent.
(a3) Polishing step by using sand paper, and polishing the two sides of the sample to 1500# to 80# respectively. Alcohol ultrasonic and drying for standby.
Further, in the invention, when the micro-arc oxidation technology is utilized to prepare the in-situ native oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with clean and dry surface, the electrolyte comprises the following components:
Na 2 (EDTA) 24 to 48g/L, preferably 30 to 42g/L, further preferably 36.0 to 36.1g/L;
6 to 30g/L, preferably 12 to 24g/L, and more preferably 18.8 to 18.9g/L of calcium oxalate;
NaOH 5-15 g/L, preferably 8-12 g/L, more preferably 10.7-10.8 g/L;
Na 2 SiO 3 4 to 8g/L, preferably 5 to 7g/L, more preferably 6.0 to 6.1g/L.
The above drugs are dissolved in deionized water as solutes, most preferably in electrolyte concentration. In industrial applications, it is generally required that the above-mentioned medicines be dissolved in this way before use. However, one of the difficulties in this experiment is that the electrolyte is not sufficiently dissolved, and the coagulation phenomenon is very easy to occur. In order to sufficiently chelate the elements in the electrolyte, it is preferable to dissolve NaOH, then to stir it electromagnetically at 1000-2000 r/min for 24-28 hours, and finally to add Na 2 SiO 3 . By the operation, the occurrence of the coagulation sedimentation phenomenon can be effectively avoided.
In industrial applicationIt is generally desirable that the electrolyte be used on the same day after it is prepared, preferably at the end of Na 2 SiO 3 The dissolution was completed and used. In order to ensure uniform mixing of the electrolyte and further improve the effect, na is generally firstly distributed according to the design group 2 (EDTA), calcium oxalate and NaOH are mixed uniformly, and then are added with designed Na before use 2 SiO 3 And stirred uniformly.
In the invention, when an in-situ native oxide ceramic coating is prepared on the surface of a TiNbZr refractory medium-high entropy alloy with a clean and dry surface by utilizing a micro-arc oxidation technology, the forward voltage is controlled to be 150-350V; the negative voltage is 8-12V, preferably 10V, the working frequency is 350-650 Hz, preferably 500Hz, the positive-negative duty ratio is 30-50%, preferably 40%, and the number of positive and negative pulses is 1-3, preferably 1.
In the practical application process, when the in-situ self-generated oxide ceramic coating is prepared on the surface of the TiNbZr refractory medium-high entropy alloy with a clean and dry surface, the time of micro-arc oxidation is influenced by positive voltage, negative voltage, positive and negative duty ratio, working frequency and the thickness of the designed ceramic coating. When the thickness of the ceramic coating is 5-25 micrometers, the working time is generally controlled to be 4-8 min, more preferably 5min under preferable conditions.
In practical application, when the alloy is TiNbZr refractory medium entropy alloy, the positive voltage is 150V-300V, preferably 250-300V, the negative voltage is 10V, the working frequency is 500Hz, the positive and negative duty ratio is 40%, the number of positive and negative pulses is 1, and the working time is 5min.
In practical application, when the alloy is a refractory high-entropy alloy containing TiNbZr, the alloy adopts positive voltage 300V-350V, negative voltage 10V, working frequency 500Hz, positive and negative duty ratio 40%, positive and negative pulse number 1 and working time 5min.
In the invention, the micro-arc oxidation technology is utilized, and in order to improve the quality of the ceramic coating, the temperature of the system is generally controlled to be less than or equal to 40 ℃. The temperature of the system can be controlled to improve the quality of the ceramic coating, reduce the production risk and facilitate the comfort of the production environment.
In the invention, the micro-arc oxidation sample obtained after the micro-arc oxidation technology is used for processing is respectively cleaned by deionized water and absolute ethyl alcohol in an ultrasonic manner, and then is dried in the air.
Further, in the step (c), the structure regulation of the micro-arc oxidation ceramic coating on the surface of the medium-high entropy alloy by the subsequent heat treatment mainly comprises the following steps:
(c1) And (c) placing the sample prepared in the step (b) in a vacuum box type atmosphere furnace, sintering the samples prepared under different micro-arc oxidation power supply voltages, and taking out after slow cooling.
(c2) And respectively ultrasonically cleaning the taken sample with deionized water and absolute ethyl alcohol, and then airing in air.
Further, the surface of the medium-high entropy alloy prepared in the step (c) contains ZrO 2 、TiO 2 Ceramic coating of Zr-Ti mixed oxide.
In the invention, the heat treatment system is as follows: placing the sample subjected to micro-arc oxidation with clean and dry surface in an atmosphere furnace, heating to 500-700 ℃, and preserving heat for at least 60min to obtain the product.
Preferably, the heat treatment system in the present invention is as follows: placing the sample subjected to micro-arc oxidation with clean and dry surface in an atmosphere furnace, heating to 280-350 ℃ at 2-3 ℃/min, preserving heat, heating to 500-600 ℃ at 5-10 ℃/min, and preserving heat for 60-120 min to obtain the product.
Preferably, when the alloy is a TiNbZr refractory medium entropy alloy; after the micro-arc oxidation, the ceramic coating with the thickness of 10-15 mu m can be obtained by matching with the later 600 ℃ and 2h heat treatment.
Preferably, when the alloy is a refractory high-entropy alloy containing TiNbZr, the ceramic coating with the thickness of 10-15 mu m can be obtained by matching with the later 600 ℃ after micro-arc oxidation and 2h heat treatment.
When the alloy is a TiNbZr refractory medium entropy alloy, obtaining a ceramic coating by adopting an optimized process; the better the abrasion resistance is: si according to 4mm diameter 3 N 4 The ceramic beads are used as a friction pair, the applied load is 5N, the rotating speed is 120r/min, the friction rotating radius is 2mm, and the friction test time is 2000 standard measurement. Its friction coefficient is less than or equal to 0.26 (warp inThe optimized one-step can be 0.14-0.26; for the present invention, in the case of consistent corrosion performance; the smaller the coefficient of friction, the better); and has excellent corrosion resistance. The better the corrosion resistance in the invention is: the corrosion behavior in seawater was simulated according to a NaCl solution with a concentration of 3.5%. The current range was set to 2mA and the sampling frequency was 2Hz. record-0.5V at a scan rate of 1.0mv/s SCE To 1.5V SCE Polarization curve in the potential range of (2); the Ecorr of the obtained product is more than or equal to-0.20V SCE And 0 or less VSCE and 1.7X10 or less Icorr -5 A/cm 2 . After optimization, the Ecorr of the obtained product is more than or equal to-0.20V SCE And 0 or less VSCE and 8×10 or less Icorr -6 A/cm 2 。
As a further preferable scheme, when the alloy is TiNbZr refractory medium entropy alloy, adopting positive voltage 300V, negative voltage 10V, working frequency 500Hz, positive and negative duty ratio 40%, positive and negative pulse number 1, working time 5min, and matching with the later 600 ℃ for 2h heat treatment; the performance of the product can be improved to be far superior to other schemes, such as the friction coefficient of the product after heat treatment is 0.14, and the corrosion resistance is: ecorr= -0.194V SCE ，Icorr＝7.28×10 -6 A/cm 2 。
When the alloy is a refractory high-entropy alloy containing HfNbTaZrTi, obtaining a ceramic coating by adopting an optimized process; the better the abrasion resistance is: si according to 4mm diameter 3 N 4 The ceramic beads are used as a friction pair, the applied load is 5N, the rotating speed is 120r/min, the friction rotating radius is 2mm, and the friction test time is 2000 standard measurement. The friction coefficient is less than 0.32 (0.17-0.32 after further optimization; under the condition of consistent corrosion performance, the friction coefficient is of course smaller and better); and has excellent corrosion resistance. The better the corrosion resistance in the invention is: the corrosion behavior in seawater was simulated according to a NaCl solution with a concentration of 3.5%. The current range was set to 2mA and the sampling frequency was 2Hz. record-0.5V at a scan rate of 1.0mv/s SCE To 1.5V SCE Polarization curve in the potential range of (2); the Ecorr of the obtained product is more than or equal to-0.21V SCE And less than or equal to 0VSCE, icorr less than or equal toAt 2.0X10 -5 A/cm 2 。
As a further preferable scheme, when the alloy is a refractory high-entropy alloy containing HfNbTaZrTi, micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 2 hours at 600 ℃, the friction resistance coefficient is 0.17; corrosion resistance: ecorr is-0.21V SCE Icorr is 1.26X10 -5 A/cm 2 。
The ceramic coating thickness is 10-15 μm by adopting the optimization process of the invention.
The beneficial effects are that:
the medium-entropy alloy TiNbZr and the high-entropy alloy HfNbTaZrTi used in the invention are both composed of several metal elements as principal elements, and under the same condition, the oxidation tendency and degree of the principal elements of Ti, nb, zr, hf, ta are different. In addition, the electrochemical oxidation behaviors of different elements can be influenced by factors such as an electrolyte system and process parameters in the micro-arc oxidation process, and the power supply voltage in the micro-arc oxidation process is controlled to be in the range of 150-350V (preferably 300-350V when the alloy is a refractory high-entropy alloy containing TiNbZr, and preferably 250-300V when the alloy is a refractory medium-entropy alloy containing TiNbZr), so that the electrochemical oxidation behaviors of the medium-entropy alloy TiNbZr and the high-entropy alloy HfNbTaZrTi are hopefully influenced, and further the phase composition and the related performance of the ceramic coating are influenced. The ceramic coating after the micro-arc oxidation is further heat-treated at 450 to 600 ℃ (preferably 600 ℃), so that the surface TiO is formed 2 、ZrO 2 、Nb 2 O 5 The oxide is further oxidized at the heat treatment temperature, so that the purposes of regulating and controlling the surface crystallinity and the phase composition of the oxide are achieved, and the most obvious is that: the product obtained after micro-arc oxidation is composed of binary oxide TiO 2 、ZrO 2 、Nb 2 O 5 And the like, and the surface corrosion resistance, friction resistance and high-temperature oxidation resistance are further improved by the characteristics of the newly generated multi-element composite oxide.
According to the invention, through micro-arc oxidation with proper parameters and heat treatment with proper parameters for the first time, the synchronous improvement of corrosion resistance, friction resistance and high-temperature oxidation resistance of the product is realized. The lifting amplitude is far greater than that of the prior art, especially for the medium-entropy alloy TiNbZr.
Drawings
FIG. 1 is a schematic diagram of a micro-arc oxidation system apparatus required for sample preparation according to the present invention;
FIG. 2 is a sample view of a portion of the HfNbTaZrTi high-entropy alloy of examples 1-4 of the present invention;
FIG. 3 is an SEM image of a sample surface of a micro-arc oxidized portion of a HfNbTaZrTi high-entropy alloy according to examples 1-4 of the present invention;
FIG. 4 is a XRD analysis chart of different voltage microarc oxidation of entropy alloy in TiNbZr according to examples 5-9 of the invention;
FIG. 5 is a graph showing differential voltage differential arc oxidation friction wear test curves before heat treatment of the entropy alloy in examples 5-9 TiNbZr according to the invention;
FIG. 6 is a graph showing the coefficient of friction at 2000s for different voltages and 1000s for different voltages before heat treatment of the entropy alloy in TiNbZr according to examples 5-9 of the present invention;
FIG. 7 is a graph showing the differential voltage differential arc oxidation friction wear test after 600 ℃ heat treatment of the entropy alloy in TiNbZr according to examples 5-9 of the invention;
FIG. 8 is a graph showing the coefficient of friction at different voltages for 2000s and the first 1000s after heat treatment at 600℃for the entropy alloy of TiNbZr according to examples 5 to 9 of the present invention;
FIG. 9 is a graph showing differential voltage differential arc oxidation polarization prior to heat treatment of a portion of samples of entropy alloy in TiNbZr according to examples 5-9 of the present invention;
FIG. 10 is a graph showing differential voltage micro-arc oxidation polarization after heat treatment at 600℃for partial samples of the entropy alloy in TiNbZr according to examples 5-9 of the present invention.
The basic structure and composition of the micro-arc oxidation system can be seen in fig. 1.
The actual overall situation of the samples of the high entropy alloy parts of examples 1-4 HfNbTaZrTi can be seen from FIG. 2, wherein a is an ingot, b is a product obtained by micro-arc oxidation, and c is a product obtained by combining micro-arc oxidation with heat treatment at 600 ℃.
From fig. 3, the surface morphology of the sample of the micro-arc oxidized part of the high-entropy alloy of the HfNbTaZrTi of examples 1-4 can be seen.
From FIG. 4, XRD phase analysis of the entropy alloys of examples 5 to 9TiNbZr subjected to differential voltage microarc oxidation can be seen.
From FIG. 5, it can be seen that the entropy alloys in examples 5 to 9TiNbZr were subjected to micro-arc oxidation under different voltages, and the frictional wear test curves before heat treatment were obtained. The wear resistance of the micro-arc oxidation samples subjected to different voltages is reacted. (corresponding to FIG. 7 after heat treatment at 600 ℃ C.)
From FIG. 6, it can be seen that the entropy alloy in examples 5 to 9TiNbZr was subjected to micro-arc oxidation under different voltages, and a friction coefficient histogram was obtained after a 2000s friction experiment before heat treatment. (after heat treatment at 600 ℃ C., corresponding to FIG. 8), it can be seen from FIG. 7 that the entropy alloys in examples 5 to 9TiNbZr were subjected to micro-arc oxidation at different voltages, in combination with the friction and wear test curves of the subsequent heat treatment at 600 ℃ C. The reaction is subjected to differential arc oxidation with different voltages, and the wear resistance after heat treatment at 600 ℃ is further combined.
From fig. 8, it can be seen that the entropy alloys in examples 5 to 9TiNbZr undergo micro-arc oxidation under different voltages, and undergo a friction coefficient histogram of 2000s friction experiment in combination with subsequent heat treatment at 600 ℃.
From FIG. 9, it can be seen that the entropy alloys in examples 5 to 9TiNbZr were subjected to micro-arc oxidation under different voltages, and polarization curves before heat treatment. The corrosion resistance of the micro-arc oxidation samples subjected to different voltages is reacted.
From fig. 10, it can be seen that the entropy alloys in examples 5 to 9TiNbZr undergo micro-arc oxidation at different voltages, in combination with polarization graphs of subsequent 600 ℃ heat treatments. The reaction is subjected to differential arc oxidation with different voltages, and the corrosion resistance after heat treatment at 600 ℃ is further combined.
Detailed Description
The invention discloses a preparation method of an in-situ self-generated wear-resistant ceramic coating on the surface of a refractory medium-high entropy alloy, which is characterized in that the medium-high entropy alloy cast according to design components is prepared by taking the obtained as-cast medium-high entropy alloy as a raw material, carrying out linear cutting, degreasing and degreasing, polishing 80-1500# and clear drying on the surface to obtain a micro-arc oxidized alloy matrix, and preparing samples under different power supply voltages on the surface in situ by utilizing a micro-arc oxidation method. The surface phase composition and crystallinity are further controlled through heat treatment, and the friction resistance of the medium-high entropy alloy is further improved.
Example 1
In this example, the constituent elements of the high-entropy alloy include Ti, nb, ta, zr, hf, and are subjected to micro-arc oxidation treatment and heat treatment.
The operation comprises the following steps:
(a) And (3) preprocessing the surface of the HfNbTaZrTi high-entropy alloy.
(a1) For a high-entropy alloy (namely, the ratio of Hf, nb, ta, zr, ti in the alloy is 1:1:1:1 in terms of mole ratio) with a composition close to equal atomic ratio HfNbTaZrTi refractory prepared by smelting (the vacuum degree is 6.0X10-3 Pa), a plurality of wafers with the diameter of 10mm and the thickness of 1mm are prepared by linear cutting, and a small hole with the diameter of 1mm is formed at the 1mm position at the edge of the wafer.
(a2) Ultrasonic treating with acetone and alcohol to remove impurities such as organic solvent.
(a3) Polishing step by using sand paper, and polishing the two sides of the sample to 1500# to 80# respectively. Alcohol ultrasonic and drying for standby.
(b) And preparing an in-situ native oxide ceramic coating on the surface of the HfNbTaZrTi refractory high-entropy alloy by utilizing a micro-arc oxidation technology. The method specifically comprises the following steps:
(b1) And preparing micro-arc oxidation experimental electrolyte 24 hours before the experiment. (in 1L of deionized water, 0.10M Na was dissolved in this way 2 (EDTA)、0.10M Ca(CH 3 COO) 2 ·H 2 O, 0.25M NaOH. The whole process of electrolyte preparation needs to be stirred by a magnetic stirrer. Stirring the above medicines for 24 hr, and adding 0.02Mna before experiment 2 SiO 3 ·9H 2 O. To Na (sodium carbonate) 2 SiO 3 ·9H 2 After complete dissolution of O, experiments were performed. )
(b2) 1mm thick titanium wires are penetrated into the small holes of the HfNbTaZrTi alloy wafer pretreated in the step (a). Placing the sample in an electrolytic tank, fully immersing the sample in electrolyte, and performing a micro-arc oxidation experiment.
(b3) The micro-arc oxidation power supply parameters are a constant voltage power supply, positive voltage 350V, negative voltage 10V, working frequency 500Hz, positive and negative duty ratio 40%, positive and negative pulse number 1 and working time 5min. (in the experimental process, a circulating cooling water device and an electrolyte stirring device are started, and the control temperature is less than or equal to 40 ℃)
(b4) And respectively ultrasonically cleaning the micro-arc oxidation sample by deionized water and absolute ethyl alcohol, and then airing in air.
(c) Through subsequent heat treatment, different process parameters are utilized to carry out tissue regulation and control on the ceramic coating on the surface of the HfNbTaZrTi high-entropy alloy, so that the friction resistance of the alloy is further optimized. The method specifically comprises the following steps:
(c1) Placing the micro-arc oxidation sample prepared in the step (b) in a vacuum box type atmosphere furnace, heating to 280-350 ℃ at 2-3 ℃/min, and preserving heat for a moment. Heating to 400-800 ℃ at 5-10 ℃/min, and preserving heat for 60-120 min to obtain the product.
(c2) The samples taken out are respectively washed by deionized water and absolute ethyl alcohol in an ultrasonic mode, and then are dried in the air. The abrasion resistance was prepared for testing.
The ceramic coating prepared by adopting the micro-arc oxidation technology has an antifriction coefficient of 0.51 before heat treatment.
In this embodiment:
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 2 hours at 400 ℃, the friction resistance coefficient is 0.46;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 2 hours at 500 ℃, the friction resistance coefficient is 0.22;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after 2h of heat treatment at 600 ℃, the friction resistance coefficient is 0.17; corrosion resistance: ecorr is-0.21V SCE Icorr is 1.26X10 -5 A/cm 2 。
Micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 2 hours at 700 ℃, the friction resistance coefficient is 0.61;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 2 hours at 800 ℃, the friction coefficient is 0.72;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 1h at 500 ℃, the friction resistance coefficient is 0.52;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 1h at 600 ℃, the friction resistance coefficient is 0.23;
micro-arc oxidation is carried out under the power supply voltage of 350V, and after heat treatment for 1h at 700 ℃, the friction resistance coefficient is 0.60;
micro-arc oxidation is carried out under 350V power supply voltage, and after heat treatment for 1h at 800 ℃, the friction resistance coefficient is 0.79;
through the experiment, when the heat treatment temperature is higher than 600 ℃, the friction coefficient of the product is obviously increased; it was also found that when the heat treatment temperature was lower than 500 ℃, the coefficient of friction of the product was not greatly reduced by the heat treatment.
Example 2
Other conditions were identical to example 1 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 250V; the friction coefficient was 0.61 before heat treatment, and 0.32 after 2 hours heat treatment at 600 ℃. Corrosion resistance: ecorr= -0.205V SCE ，Icorr＝1.60×10 -5 A/cm 2 。
Example 3
Other conditions were identical to example 1 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 200V; the friction coefficient of the material is 0.58 before heat treatment, and the friction coefficient of the material is 0.24 after heat treatment at 600 ℃ for 2 hours. Corrosion resistance: ecorr= -0.184V SCE ，Icorr＝1.98×10 -5 A/cm 2 。
Example 4
Other conditions were identical to example 1 except that: the arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 300V; the friction coefficient was 0.69 before heat treatment, and 0.20 after 2 hours heat treatment at 600 ℃. Corrosion resistance: ecorr= -0.191V SCE ，Icorr＝1.85×10 -5 A/cm 2 。
Example 5
In the example, the constituent elements of the high-entropy alloy comprise three of Ti, nb and Zr, and the product is obtained by micro-arc oxidation treatment and then heat treatment.
(a) And (3) preprocessing the TiNbZr alloy surface.
(a1) A plurality of wafers with the diameter of 10mm and the thickness of 1mm are prepared from TiNbZr refractory alloy with the composition close to the equal atomic ratio prepared by smelting (the vacuum degree is 6.0X10-3 Pa) through linear cutting, and a small hole with the diameter of 1mm is perforated at the position of 1mm at the edge of the wafer.
(a2) Ultrasonic treating with acetone and alcohol to remove impurities such as organic solvent.
(a3) Polishing step by using sand paper, and polishing the two sides of the sample to 1500# to 80# respectively. Alcohol ultrasonic and drying to obtain TiNbZr alloy wafer with diameter of 10mm, thickness of 1mm, small holes, clean surface and smooth drying.
(b) And preparing an in-situ self-generated oxide ceramic coating on the surface of the entropy alloy in TiNbZr by utilizing a micro-arc oxidation technology. The method specifically comprises the following steps:
(b1) And preparing micro-arc oxidation experimental electrolyte 24 hours before the experiment. (in 1L of deionized water, 0.10M Na was dissolved in this way 2 (EDTA)、0.10M Ca(CH 3 COO) 2 ·H 2 O, 0.25M NaOH. The whole process of electrolyte preparation needs to be stirred by a magnetic stirrer. Stirring the above medicines for 24 hr, and adding 0.02Mna before experiment 2 SiO 3 ·9H 2 O. To Na (sodium carbonate) 2 SiO 3 ·9H 2 After complete dissolution of O, experiments were performed. )
(b2) 1mm thick titanium wires are penetrated into the small holes of the TiNbZr alloy discs pretreated in the step (a). Placing the sample in an electrolytic tank, fully immersing the sample in electrolyte, and performing a micro-arc oxidation experiment.
(b3) The micro-arc oxidation power supply parameters are a constant voltage power supply, a positive voltage of 250V, a negative voltage of 10V, a working frequency of 500Hz, a positive and negative duty ratio of 40%, a positive and negative pulse number of 1 and a working time of 5min. (in the experimental process, a circulating cooling water device and an electrolyte stirring device are started, and the control temperature is less than or equal to 40 ℃)
(c) And through subsequent heat treatment, different process parameters are utilized to carry out structure regulation and control on the ceramic coating on the surface of the TiNbZr alloy, so that the friction resistance of the alloy is further optimized. The method specifically comprises the following steps:
and (c) placing the sample prepared in the step (b) in a vacuum box type atmosphere furnace, sintering the sample at 600 ℃, and taking out the sample after slow cooling. The samples taken out are respectively washed by deionized water and absolute ethyl alcohol in an ultrasonic mode, and then are dried in the air. The abrasion resistance was prepared for testing.
Such as: the ceramic coating prepared by adopting the micro-arc oxidation technology has an antifriction coefficient of 0.80 before heat treatment,
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 2 hours at 400 ℃, the friction resistance coefficient is 0.55;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 2 hours at 500 ℃, the friction resistance coefficient is 0.26;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 2 hours at 600 ℃, the friction resistance coefficient is 0.19; corrosion resistance: ecorr= -0.187V SCE ，Icorr＝4.86×10 -6 A/cm 2
Micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 2 hours at 700 ℃, the friction resistance coefficient is 0.60;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 2 hours at 800 ℃, the friction coefficient is 0.81;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 1h at 500 ℃, the friction resistance coefficient is 0.23;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 1h at 600 ℃, the friction resistance coefficient is 0.21;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 1h at 700 ℃, the friction resistance coefficient is 0.42;
micro-arc oxidation is carried out under the power supply voltage of 250V, and after heat treatment for 1h at 800 ℃, the friction resistance coefficient is 0.78;
through the experiment, when the heat treatment temperature is higher than 600 ℃, the friction coefficient of the product is obviously increased, the width of the grinding mark is increased, and the abrasion loss is increased; it was also found that the coefficient of friction of the product after heat treatment was still at a higher value when the heat treatment temperature was below 500 ℃.
Example 6
Other conditions were identical to example 5 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 350V; the friction coefficient was 0.79 before heat treatment, and after 2 hours heat treatment at 600 ℃, the friction coefficient was 0.76. Corrosion resistance: ecorr= -0.192V SCE ，Icorr＝1.74×10 -5 A/cm 2 。
Example 7
Other conditions were identical to example 5 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 200V; the friction coefficient of the material is 0.23 before heat treatment, and the friction coefficient of the material is 0.17 after heat treatment at 600 ℃ for 2 hours.
Example 8
Other conditions were identical to example 5 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 300V; the friction coefficient of the material is 0.15 before heat treatment, and the friction coefficient of the material is 0.14 after heat treatment at 600 ℃ for 2 hours. Corrosion resistance: ecorr= -0.194V SCE ，Icorr＝7.28×10 -6 A/cm 2 。
Example 9
Other conditions were identical to example 5 except that: the micro-arc oxidation power supply parameter is a constant voltage power supply, and the forward voltage is 150V; the friction coefficient was 0.58 before heat treatment, and 0.15 after 2 hours heat treatment at 600 ℃.
Table 1 shows the friction coefficient comparison table (heat treatment temperature 600 ℃ C., time 2 h) of TiNbZr micro arc oxidation samples under different voltages in examples 5-9
Claims (10)
1. A preparation method of an in-situ self-generated ceramic coating on the surface of a refractory medium-high entropy alloy is characterized by comprising the following steps of; the method comprises the following steps:
(a) Pretreating the surface of the TiNbZr refractory medium-high entropy alloy; obtaining the TiNbZr refractory medium-high entropy alloy with clean and dry surface;
(b) Preparing an in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with a clean and dry surface by utilizing a micro-arc oxidation technology; when micro-arc oxidation is carried out, a constant voltage power supply is adopted, and the forward voltage is controlled to be 150-350V;
when the micro-arc oxidation technology is utilized to prepare the in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with clean and dry surface, the electrolyte comprises the following components:
Na 2 (EDTA) 24~48g/L；
6-30 g/L of calcium oxalate;
NaOH 5~15g/L；
Na 2 SiO 3 ;
when preparing an in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with a clean and dry surface by utilizing a micro-arc oxidation technology, controlling the negative voltage to be 8-12V; the working frequency is 350-650 Hz; positive and negative duty ratios are 30-50%; 1-3 positive and negative pulses;
when in micro-arc oxidation, the working time is controlled to be 4-8 min, and the temperature is less than or equal to 40 ℃;
(c) Carrying out structure regulation and control and friction resistance on the TiNbZr refractory medium-high entropy alloy surface ceramic coating through subsequent heat treatment; in the heat treatment, the heat treatment temperature is controlled to be 450-600 ℃.
2. The method for preparing the refractory medium-high entropy alloy surface in-situ authigenic ceramic coating according to claim 1, which is characterized by comprising the following steps: the TiNbZr refractory medium-high entropy alloy comprises a TiNbZr refractory medium-entropy alloy and a TiNbZr-containing high entropy alloy;
in the TiNbZr refractory intermediate entropy alloy, the molar ratio of Ti: nb: zr=0.95 to 1.05: 0.95-1.05: 0.95-1.05;
the refractory high-entropy alloy containing TiNbZr comprises Hf, nb, ta, zr, ti and Hf in atomic ratio: nb: ta: zr: ti=0.95 to 1.05: 0.95-1.05: 0.95-1.05: 0.95-1.05: 0.95-1.05.
3. The method for preparing the refractory medium-high entropy alloy surface in-situ authigenic ceramic coating according to claim 1, which is characterized by comprising the following steps: when the micro-arc oxidation technology is utilized to prepare the in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with clean and dry surface, the electrolyte comprises the following components:
Na 2 (EDTA) 30~42g/L；
6-30 g/L of calcium oxalate;
NaOH 5~15g/L；
Na 2 SiO 3 4~8g/L。
4. a method for preparing an in-situ self-generated ceramic coating on the surface of a refractory medium-high entropy alloy according to claim 3, which is characterized in that: firstly, na is prepared 2 (EDTA), calcium oxalate and NaOH are mixed uniformly, and then added with the prepared Na before use 2 SiO 3 And stirred until uniform.
5. The method for preparing the refractory medium-high entropy alloy surface in-situ authigenic ceramic coating according to claim 1, which is characterized by comprising the following steps: when the micro-arc oxidation technology is utilized to prepare an in-situ self-generated oxide ceramic coating on the surface of the TiNbZr refractory medium-high entropy alloy with a clean and dry surface, the negative voltage is controlled to be 10V; the working frequency is 500Hz; positive and negative duty cycle 40%; the number of positive and negative pulses is 1.
6. The method for preparing the refractory medium-high entropy alloy surface in-situ self-generated ceramic coating according to claim 5, which is characterized in that: and in the micro-arc oxidation, the working time is controlled to be 4-8 min, and the temperature is less than or equal to 40 ℃.
7. The method for preparing the refractory medium-high entropy alloy surface in-situ self-generated ceramic coating according to claim 5, which is characterized in that: when the alloy is a TiNbZr refractory medium entropy alloy, the alloy adopts positive voltage 150V-300V, negative voltage 10V, working frequency 500Hz, positive and negative duty ratio 40%, positive and negative pulse number 1 and working time 5min.
8. The method for preparing the refractory medium-high entropy alloy surface in-situ self-generated ceramic coating according to claim 5, which is characterized in that: when the alloy is a refractory high-entropy alloy containing TiNbZr, adopting positive voltage 300V-350V, negative voltage 10V, working frequency 500Hz, positive and negative duty ratio 40%, positive and negative pulse number 1 and working time 5min.
9. The method for preparing the refractory medium-high entropy alloy surface in-situ authigenic ceramic coating according to claim 1, which is characterized by comprising the following steps: the heat treatment system is as follows: and placing the sample subjected to micro-arc oxidation with the clean and dry surface in an atmosphere furnace, heating to 500-700 ℃, and preserving heat for at least 60min to obtain the product.
10. The method for preparing the refractory medium-high entropy alloy surface in-situ authigenic ceramic coating according to claim 9, which is characterized in that:
when the alloy is TiNbZr refractory medium entropy alloy, the friction coefficient of the ceramic coating obtained after heat treatment is less than or equal to 0.26; and the Ecorr of the obtained product is more than or equal to-0.20V SCE Icorr less than or equal to 1.7X10 -5 A/cm 2 ；
When the alloy is a refractory high-entropy alloy containing HfNbTaZrTi, the friction coefficient of the ceramic coating obtained after heat treatment is less than 0.32, and the Ecorr of the obtained product is more than or equal to-0.21V SCE Icorr less than or equal to 2.00×10 -5 A/cm 2 。
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