CN111676475A - Preparation method of high-performance Zr/Al coating - Google Patents

Preparation method of high-performance Zr/Al coating Download PDF

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CN111676475A
CN111676475A CN202010417541.XA CN202010417541A CN111676475A CN 111676475 A CN111676475 A CN 111676475A CN 202010417541 A CN202010417541 A CN 202010417541A CN 111676475 A CN111676475 A CN 111676475A
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coating
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ball milling
electron beam
irradiation
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关庆丰
李雷
季雪素
杜雪泽
田娜娜
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/06—Compressing powdered coating material, e.g. by milling

Abstract

The invention relates to the technical field of aluminum alloy surface modification, and discloses a preparation method of a high-performance Zr/Al coating. The Al block and the required pure zirconium powder are put into a ball mill together for mixing and ball milling, and a layer of coating is prepared on the surface. The method is characterized in that Zr powder is deposited on the surface of an Al matrix in advance to form a Zr film layer under the action of high-pressure impact force, and then the surface organization structure of the alloy layer is adjusted through electron beam treatment, such as density improvement, grain refinement, surface roughness improvement, hardness improvement and the like.

Description

Preparation method of high-performance Zr/Al coating
Technical Field
The invention relates to the technical field of aluminum alloy surface modification, in particular to a preparation method of a high-performance Zr/Al coating, and specifically relates to a method for realizing surface zirconium alloying of the Zr/Al coating prepared by electron beam irradiation ball milling. The invention discloses a method for preparing a Zr coating on the surface of an Al block by block-powder mixed ball milling and combining a high-current pulse electron beam irradiation technology, and an alloying layer with higher hardness and excellent corrosion resistance is prepared on the surface of the Al block, belonging to the technical field of surface modification of metal materials.
Background
Aluminum (Al) and its alloys are widely used in various industries such as automobiles, sports, aerospace, and electronics due to their advantages of high specific strength, good ductility, low density, excellent thermal and electrical conductivity, and the like. However, lower hardness and poor corrosion resistance in some environments have limited their wider use. Therefore, the surface modification treatment is carried out on the aluminum (Al) and the alloy thereof, the surface property of the material is improved, the special comprehensive property of the alloy is kept, and the method has very important effect on the practical application of the alloy.
Common surface modification methods for aluminum alloys include electroplating, anodic oxidation, vapor deposition, thermal spraying, and the like. However, most of them have the problems of thin and brittle coating, discontinuous oxide film, insufficient film layer and substrate binding force, serious oxidation and the like. Therefore, many scholars prefer to focus on elemental alloying. The element alloying means that a surface alloy layer or a permeable layer with excellent comprehensive performance is prepared on the surface of a base material with poor performance by adding alloying elements on the surface of the material and adjusting the processing technology. Zirconium (Zr) is an important strategic material, and the homogeneous Al-Zr alloy layer has the excellent performances of aluminum and zirconium, high strength, higher melting point and excellent corrosion resistance, and also has good ductility, heat conduction property and radiation resistance, thereby being one of the candidate materials for improving the corrosion resistance of armor materials and aerospace engines. However, in the actual casting process, the Al-Zr solidification process is difficult to reach an equilibrium state. Zr element is easy to be deviated and forms coarse primary phase Al3Zr, a precipitated phase depletion region is easily formed near the grain boundary and in the interdendritic region, and the form has great harm to the alloy, so that the traditional processing mode is difficult to avoid. Some researches show that the MA coating preparation method improves the Zr segregation to some extent, but the prepared coating is loose and porous, the surface roughness is inevitably large, and the prepared coating is not metallurgically bonded with a matrix and particularly the corrosion resistance of the material is damaged. In addition, thermal spraying, ion beam injection, laser surface alloying and other techniques have made some progress on aluminum alloys, however, thermal spraying has low bonding strength and has some pores, and ion beam injection has been used to produce aluminum alloysThe production efficiency is low, the injection system is complex and expensive, and the laser surface alloying technology has the problems of low energy utilization rate, high equipment running cost and the like.
High Current Pulsed Electron Beam (HCPEB) surface alloying is a new emerging energy-carrying beam surface modification technique. High energy (10) during electron beam bombardment8～109W/cm2) Instantly depositing on the surface of the material to enable the coating and the matrix to be instantly melted and rapidly solidified, and further forming an alloying layer on the surface; in addition, phase transformation and grain refinement may occur in the process. The metallurgical bonding is realized, and the problem of weak bonding force of the interface between the coating and the substrate is solved. Therefore, the HCPEB technology is used for the Zr/Al coating prepared by the irradiation ball milling to realize the zirconium alloying, the comprehensive performance of the coating can be improved, and the method has an important effect on the application value of the Al-Zr alloy.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide an Al-Zr alloy surface modification technology, so as to improve the surface property of the Al alloy and prolong the service life of the Al alloy in special environments.
The Al block and the required pure zirconium powder are put into a ball mill together for mixing and ball milling, and a layer of coating is prepared on the surface. The method is characterized in that Zr powder is deposited on the surface of an Al matrix in advance to form a Zr film layer under the action of high-pressure impact force, and then the surface organization structure of the alloy layer is adjusted through electron beam treatment, such as density improvement, grain refinement, surface roughness improvement, hardness improvement and the like.
The technical scheme of the invention is as follows:
a processing method for improving comprehensive performance of a Zr/Al coating is characterized in that a high-performance corrosion-resistant Zr/Al coating is prepared by means of a combined process of mechanical ball milling and electron beam processing, a Zr coating is preset on the surface of an Al matrix by means of mechanical mixing ball milling of an Al block and Zr powder, electron beam processing is utilized to improve the surface density of the coating, metallurgical bonding of Al and Zr is realized, and the hardness and the corrosion resistance of a material are improved.
The method specifically comprises the following steps:
(1) pretreatment of the surface of a substrate:
cutting the block pure aluminum into an aluminum block sample, and mechanically grinding, polishing, cleaning and drying the aluminum block sample.
(2) Presetting a Zr coating:
the powder raw material for preparing the coating is Zr powder, and under the protection of high-purity argon (Ar), the aluminum block sample prepared in the step (1) and the Zr powder are uniformly mixed and subjected to ball milling, so that the Zr powder is deposited on the surface of the aluminum block sample serving as the substrate to prepare the pure Zr coating. At the same time, high purity argon is used as a shielding gas to avoid oxidation and contamination.
(3) Irradiation treatment by a high-current pulse electron beam:
fixing an aluminum block sample with a pure Zr coating prepared on the surface on an objective table, and vertically irradiating and presetting the surface of the Zr coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of an Al matrix sample.
In the step (1), the block pure aluminum is 1060 block pure aluminum; cutting into an aluminum block sample refers to cutting into 10 multiplied by 5mm aluminum block samples by utilizing a linear cutting machine; the mechanical grinding and polishing refers to grinding by sequentially adopting SiC sand paper with the specification of 150-3000 meshes, wherein the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent; the cleaning refers to ultrasonic cleaning of the polished aluminum block sample by using acetone and absolute ethyl alcohol; drying refers to drying the aluminum block sample using a blower.
In the step (2), the ball milling process comprises the following steps: quenching steel balls and a stainless steel tank are adopted, the mass ratio of the ball materials is 10: 1-1.5, the rotating speed is 250r/min, and the ball milling time is 1 h; the purity of the Zr powder is 99.9 wt%, and the granularity is 200 meshes; the thickness of the prepared pure Zr coating is 10 mu m; the ball milling is carried out for 20min every time, and then the interval is 10min so as to prevent the temperature in the ball milling tank from being overhigh.
In the step (3), the high current pulse electron beam irradiation technical parameters are as follows: the electron beam acceleration voltage was 23.4kV, and the energy density was 4J/cm2Target source distance 15cm, pulse width 1.5 mus, vacuum degree 5 × 10-3Pa, the irradiation times are respectively 10, 20, 30 and 40.
Compared with the prior art, the invention has the following advantages:
first, the technical scheme of the invention has the advantages of low cost, short period, high efficiency and simple operation process, and plays an extremely important role in the practical application of Zr/Al alloy.
Secondly, the surface alloying of the high-current pulse electron beam is used as a novel surface modification technology, and has the unique advantages of high efficiency, simple operation steps, strong controllability and the like. Compared with the traditional manual coating, the distribution of the ball-milling powder is more uniform, and the surface bonding force between the coating and the surface of the substrate is larger and the coating is not easy to fall off. The HCPEB alloying is realized by utilizing the characteristic of HCPEB irradiation technology to cause chemical reaction between a matrix and alloying elements. After the action of the pulsed electron beam and the material, the temperature of the surface layer is rapidly raised, the substrate and the preset coating are simultaneously melted to form a remelting mixing layer, and then an alloy layer can be formed after rapid solidification, so that the surface mechanical, physical or chemical properties of the substrate, such as surface hardness, wear resistance, corrosion resistance and the like, are improved.
Drawings
FIG. 1 is an XRD spectrum of the sample surface before and after HCPEB irradiation alloying of the present invention;
FIG. 2 is an SEM image of the surface of a sample before and after irradiation with HCPEB of the present invention; (a) ball milling an original sample; (b)10 times; (c)20 times; (d)30 times; (e)40 times and (f) different irradiation times.
FIG. 3 is a cross-sectional SEM and EDS spectra of 30 irradiation alloyed samples of HCPEB of the present invention; (a) the cross-sectional morphology; (b) distribution of Al element and Zr element along the arrow in the figure (a).
FIG. 4 is a graph of surface hardness of samples before and after irradiation alloying of HCPEB in accordance with the present invention;
FIG. 5 is a polarization curve of a sample before and after irradiation alloying of HCPEB in accordance with the present invention;
table 1 shows the corrosion data of the samples before and after the irradiation alloying of the HCPEB of the present invention.
Detailed Description
In order that the invention may be more clearly understood, reference will now be made in detail to the following examples.
Example 1
(1) Preparing an alloy layer:
in the first step, 1060 block pure aluminum is selected as a base material, and the base material is cut into samples of 10X 5mm by a linear cutting machine. And polishing the sample by using sand paper, wherein the type of the adopted sand paper is SiC sand paper with the specification of 150-3000 meshes, the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent, and finally, acetone and absolute ethyl alcohol are used for ultrasonic cleaning for later use.
Secondly, depositing a pure Zr coating on the surface of the sample by utilizing a mechanical mixing ball milling technology, wherein zirconium adopted in the coating is powder with the purity of 99.9 wt% and the granularity of 200 meshes; selecting the ball material according to the technical requirements of ball milling equipment, wherein the mass ratio of the ball material is 10:1, the rotating speed is 250r/min, the ball milling time is 1h, and the thickness of the coating is 10 mu m.
Fixing the sample to be irradiated on an objective table, and vertically irradiating the surface of the preset coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of the Al matrix sample. Wherein, the irradiation technical parameters of the high current pulse electron beam are as follows: the electron beam energy was 23.4KeV and the energy density was 4J/cm2Target source distance 15cm, pulse width 1.5 mus, vacuum degree 5 × 10-3Pa, and the irradiation times are 10 times.
(2) Alloy layer microstructure characterization and performance testing
Phase analysis was performed on the original sample and the 10 times irradiated alloyed sample using an X-ray diffractometer (XRD). As a result, Al was generated in the sample irradiated 10 times as compared with the original sample as shown in FIG. 13And Zr phase, which shows that after electron beam treatment, Al in the ball-milled sample reacts with Zr to generate a new phase, and the new phase has a promoting effect on improving the surface performance of the aluminum alloy. Further, the diffraction peak of Al was broadened, which indicates that the Al crystal grains in the surface layer were refined to some extent after the irradiation alloying treatment. During HCPEB treatment, the surface layer of the sample is rapidly heated to be molten, and the matrix is at normal temperature, so that the temperature between the surface layer and the matrix after the pulse is finishedThe gradient of the degree is very large, heat can be rapidly transferred through the base material, so that extremely rapid cooling is generated, the surface of the molten metal is rapidly solidified, the grains are not grown in time, and the grains of the irradiation surface layer after HCPEB treatment can be obviously refined.
And observing the surface appearance of the treated sample by using a Scanning Electron Microscope (SEM), and finding that a small number of crater-shaped fusion pits with different sizes appear on the surface after the sample is irradiated by HCPEB for 10 times, wherein the size of the crater-shaped fusion pits is about 15-100 mu m. In addition, more particulate matter was observed on the surface of the sample, with a size of about 2-6 μm. The EDS energy spectrum shows that the Zr particles are residual Zr particles on the surface of the Al matrix, namely although the Zr layer prepared by ball milling is melted and dissolved into the Al matrix, the irradiation frequency is less, so that some residual agglomerated Zr powder still exists on the irradiated surface.
The surface microhardness values of the sample before and after irradiation are tested by using a Vickers microhardness tester, and the test result shows that the hardness value of the surface of the sample after irradiation alloying is improved to be about 3.59 times of that of a pure aluminum sample. The corrosion performance of the sample before and after alloying is tested by using a three-electrode electrolytic cell, and the self-corrosion potential of the 10 times of irradiated alloying sample is increased to-0.623V from-0.860V of the ball-milled sample, and the self-corrosion current density is increased from 2.710 mu A/cm2Reduced to 0.821. mu.A/cm2And is reduced by 1 order of magnitude compared with the treatment before. The self-corrosion potential reflects the difficulty of the material in corrosion, and the higher the self-corrosion potential is, the less the material is easy to corrode; the self-corrosion current density reflects the corrosion speed of the metal, and the smaller the self-corrosion current density is, the lower the corrosion speed of the metal is. Therefore, the HCPEB surface alloying treatment improves the corrosion resistance of the Al-Zr alloy surface.
Example 2
(1) Preparing an alloy layer:
in the first step, 1060 block pure aluminum is selected as a base material, and the base material is cut into samples of 10X 5mm by a linear cutting machine. And polishing the sample by using sand paper, wherein the type of the adopted sand paper is SiC sand paper with the specification of 150-3000 meshes, the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent, and finally, acetone and absolute ethyl alcohol are used for ultrasonic cleaning for later use.
Secondly, depositing a pure Zr coating on the surface of the sample by utilizing a mechanical mixing ball milling technology, wherein zirconium adopted in the coating is powder with the purity of 99.9 wt% and the granularity of 200 meshes; selecting the ball material according to the technical requirements of ball milling equipment, wherein the mass ratio of the ball material is 10:1, the rotating speed is 250r/min, the ball milling time is 1h, and the thickness of the coating is 10 mu m.
Fixing the sample to be irradiated on an objective table, and vertically irradiating the surface of the preset coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of the Al matrix sample. Wherein, the irradiation technical parameters of the high current pulse electron beam are as follows: the electron beam energy was 23.4KeV and the energy density was 4J/cm2Target source distance 15cm, pulse width 1.5 mus, vacuum degree 5 × 10-3Pa, and the irradiation times are 20 times.
(2) Alloy layer microstructure characterization and performance testing
Phase analysis was performed on the original sample and the 20-time irradiated alloyed sample using an X-ray diffractometer (XRD). The results show that the Al in the sample was irradiated 20 times more than the 10 times irradiated sample3The Zr peak is slightly strengthened, which shows that Zr particles are gradually dissolved into the matrix and form an intermetallic compound Al3Zr. In addition, the decrease of the diffraction peak intensity of Zr after 20 times of irradiation shows that the Zr content in the surface layer is reduced along with the increase of the irradiation times, and the decrease also indicates that Zr atoms can enter Al crystal lattices to form Al (Zr) supersaturated solid solutions or Al3A Zr phase.
The surface appearance of the sample is observed by adopting a Scanning Electron Microscope (SEM) after 20 times of irradiation, and the number of large melting pits on the surface of the sample is basically reduced to zero, but a small number of small melting pits exist, which is mainly because impurities on the surface layer are gradually sprayed out under the action of electron beams, and the large melting pits formed before are gradually repaired after the electron beams are further irradiated.
The surface microhardness values of the sample before and after irradiation are tested by using a Vickers microhardness tester, and the test result shows that the hardness value of the surface of the sample after irradiation alloying is improved to 4.63 times of that of a pure aluminum sample, and the hardness value is improved compared with that of the sample after 10 times of irradiation. Adopting a three-electrode electrolytic cell to carry out alloying before and afterThe corrosion performance of the samples was tested and it was found that the self-corrosion potential of the 20 irradiated alloyed samples increased from-0.860V as ball milled to-0.605V, while the self-corrosion current density increased from 2.710 μ A/cm2Reduced to 0.622. mu.A/cm2And is reduced by 1 order of magnitude compared with the treatment before. Therefore, the HCPEB surface alloying treatment improves the corrosion resistance of the Al-Zr alloy surface.
Example 3
(1) Preparing an alloy layer:
in the first step, 1060 block pure aluminum is selected as a base material, and the base material is cut into samples of 10X 5mm by a linear cutting machine. And polishing the sample by using sand paper, wherein the type of the adopted sand paper is SiC sand paper with the specification of 150-3000 meshes, the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent, and finally, acetone and absolute ethyl alcohol are used for ultrasonic cleaning for later use.
Secondly, depositing a pure Zr coating on the surface of the sample by utilizing a mechanical mixing ball milling technology, wherein zirconium adopted in the coating is powder with the purity of 99.9 wt% and the granularity of 200 meshes; selecting the ball material according to the technical requirements of ball milling equipment, wherein the mass ratio of the ball material is 10:1, the rotating speed is 250r/min, the ball milling time is 1h, and the thickness of the coating is 10 mu m.
Fixing the sample to be irradiated on an objective table, and vertically irradiating the surface of the preset coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of the Al matrix sample. Wherein, the irradiation technical parameters of the high current pulse electron beam are as follows: the electron beam energy was 23.4KeV and the energy density was 4J/cm2Target source distance 15cm, pulse width 1.5 mus, vacuum degree 5 × 10-3Pa, and the irradiation times are 30 times.
(2) Alloy layer microstructure characterization and performance testing
Phase analysis was performed on the original sample and the 30-time irradiated alloyed sample using an X-ray diffractometer (XRD). The results show that the diffraction peaks of intermetallic compounds in the 30-time irradiation alloyed samples are slightly enhanced compared with the 10-time and 20-time irradiation samples, indicating that Zr is further solid-dissolved in Al as the number of irradiation times increases.
And observing the surface appearance of the sample irradiated for 30 times by adopting a Scanning Electron Microscope (SEM), finding that the molten pit basically disappears, and the surface of the sample is relatively flat, wherein EDS analysis shows that an Al-Zr alloying layer is formed on the surface layer of the Al matrix. Cross-sectional SEM pictures and EDS spectra of the bonded samples revealed that Zr was successfully metallurgically bonded to Al with an Al-Zr alloy layer thickness of about 13 μm.
The surface microhardness values of the sample before and after irradiation are tested by using a Vickers microhardness tester, and the test result shows that the hardness value of the surface of the sample after irradiation alloying is improved to be about 4.96 times of that of a pure aluminum sample. The corrosion performance of the sample before and after alloying is tested by using a three-electrode electrolytic cell, and the self-corrosion potential of the 30 times of irradiation alloying sample is increased from-0.860V of the original ball-milling sample to-0.591V, and the self-corrosion current density is increased from 2.710 mu A/cm2Reduced to 0.443. mu.A/cm2And is reduced by 1 order of magnitude compared with the treatment before. Therefore, the HCPEB surface alloying treatment improves the corrosion resistance of the Al-Zr alloy surface. And as can be seen from the polarization curve, the impedance value of the sample is the highest after 30 times of irradiation alloying, and the corrosion resistance is the best.
Example 4
(1) Preparing an alloy layer:
in the first step, 1060 block pure aluminum is selected as a base material, and the base material is cut into samples of 10X 5mm by a linear cutting machine. And polishing the sample by using sand paper, wherein the type of the adopted sand paper is SiC sand paper with the specification of 150-3000 meshes, the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent, and finally, acetone and absolute ethyl alcohol are used for ultrasonic cleaning for later use.
Secondly, depositing a pure Zr coating on the surface of the sample by utilizing a mechanical mixing ball milling technology, wherein zirconium adopted in the coating is powder with the purity of 99.9 wt% and the granularity of 200 meshes; selecting the ball material according to the technical requirements of ball milling equipment, wherein the mass ratio of the ball material is 10:1, the rotating speed is 250r/min, the ball milling time is 1h, and the thickness of the coating is 10 mu m.
Fixing the sample to be irradiated on an objective table, and vertically irradiating the surface of the preset coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of the Al matrix sample. Wherein, the irradiation technical parameters of the high current pulse electron beam are as follows: the electron beam energy was 23.4KeV and the energy density was 4J/cm2Target sourceDistance of 15cm, pulse width of 1.5 mus, vacuum degree of 5 × 10-3Pa, and the irradiation times are 40 times.
(2) Alloy layer microstructure characterization and performance testing
Phase analysis was performed on the original sample and the 40 times irradiated alloyed sample using an X-ray diffractometer (XRD). The results show that the diffraction peaks of intermetallic compounds in the 40 times irradiated alloyed samples are further enhanced than in the 10 times irradiated, 20 times irradiated and 30 times irradiated samples. After electron beam irradiation, the diffraction peak of the Al (111) crystal face slightly shifts to the high-angle direction, which shows that the crystal face spacing of Al becomes smaller after 40 times of irradiation. It is probably because Zr atoms precipitate from an al (Zr) supersaturated solid solution, and intermetallic compounds are continuously formed, thereby decreasing the interplanar spacing.
And observing the surface appearance of the sample irradiated for 40 times by adopting a Scanning Electron Microscope (SEM), and finding that the surface state of the material is remarkably deteriorated and the number of small melting pits is sharply increased.
The surface microhardness values of the sample before and after irradiation are tested by using a Vickers microhardness tester, and the test result shows that the hardness value of the surface of the sample after irradiation alloying is improved to be about 4.59 times of that of a pure aluminum sample. The corrosion performance of the sample before and after alloying is tested by using a three-electrode electrolytic cell, and the self-corrosion potential of the 40 times of irradiated alloying sample is increased from-0.860V of the original ball-milling sample to-0.584V, and the self-corrosion current density is increased from 2.710 mu A/cm2Reduced to 0.450 muA/cm2And is reduced by 1 order of magnitude compared with the treatment before. Therefore, the HCPEB surface alloying treatment improves the corrosion resistance of the Al-Zr alloy surface. But the 40 irradiation alloying corrosion current was slightly lower than the 30 samples, which is caused by the sharp increase of the number of small craters on the surface of the sample with the increase of the irradiation times.
TABLE 1 Corrosion data for HCPEB radiation alloyed samples
Figure BDA0002495658880000081

Claims (5)

1. A preparation method of a high-performance Zr/Al coating is characterized in that the high-performance corrosion-resistant Zr/Al coating is prepared by means of a combined process of mechanical ball milling and electron beam treatment, a Zr coating is preset on the surface of an Al matrix by a mechanical mixing ball milling method of an Al block and Zr powder, the electron beam treatment is utilized to improve the surface density of the coating, realize the metallurgical bonding of Al and Zr, and improve the hardness and the corrosion resistance of the material; the method comprises the following specific steps:
(1) pretreatment of the surface of a substrate:
cutting block pure aluminum into an aluminum block sample, and mechanically grinding, polishing, cleaning and drying the aluminum block sample;
(2) presetting a Zr coating:
and (2) selecting Zr powder as a powder raw material for preparing the coating, uniformly mixing the aluminum block sample prepared in the step (1) with the Zr powder under the protection of high-purity argon gas, and carrying out ball milling to deposit the Zr powder on the surface of the aluminum block sample serving as the substrate so as to prepare the pure Zr coating. Meanwhile, high-purity argon is used as a protective gas to avoid oxidation and pollution;
(3) irradiation treatment by a high-current pulse electron beam:
fixing an aluminum block sample with a pure Zr coating prepared on the surface on an objective table, and vertically irradiating and presetting the surface of the Zr coating by using a HOPE-1 type high-current pulse electron beam device so as to obtain a Zr/Al alloy layer on the surface of an Al matrix sample.
2. The method for preparing a high performance Zr/Al coating according to claim 1, wherein in step (1), the bulk pure aluminum is 1060 bulk pure aluminum; cutting into an aluminum block sample refers to cutting into 10 multiplied by 5mm aluminum block samples by utilizing a linear cutting machine; the mechanical grinding and polishing refers to grinding by sequentially adopting SiC sand paper with the specification of 150-3000 meshes, wherein the diamond polishing agent with the particle size of 0.5 mu m is selected as the polishing agent; the cleaning refers to ultrasonic cleaning of the polished aluminum block sample by using acetone and absolute ethyl alcohol; drying refers to drying the aluminum block sample using a blower.
3. The method for preparing the high-performance Zr/Al coating according to claim 1, wherein in the step (2), the ball milling process comprises the following steps: quenching steel balls and a stainless steel tank are adopted, the mass ratio of the ball materials is 10: 1-1.5, the rotating speed is 250r/min, and the ball milling time is 1 h; the purity of the Zr powder is 99.9 wt%, and the granularity is 200 meshes; the thickness of the prepared pure Zr coating is 10 mu m; the ball milling is carried out for 20min every time, and then the interval is 10min so as to prevent the temperature in the ball milling tank from being overhigh.
4. The method for preparing the high-performance Zr/Al coating according to claim 1, wherein in the step (3), the technical parameters of the high-current pulsed electron beam irradiation are as follows: the electron beam acceleration voltage is 23.4kV, and the energy density is 4J/cm2Target source distance 15cm, pulse width 1.5 mus, vacuum degree 5 × 10-3Pa, the irradiation times are respectively 10, 20, 30 and 40.
5. The method for preparing a high-performance Zr/Al coating according to claim 4, wherein the irradiation times are 30.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104328431A (en) * 2014-11-14 2015-02-04 重庆理工大学 Aluminum alloy surface modification method
CN106191395A (en) * 2016-08-15 2016-12-07 江苏大学 A kind of high-current pulsed electron beam irradiation 20 steel method for alloying surface
CN107268044A (en) * 2017-05-22 2017-10-20 中国科学院金属研究所 A kind of Pt Zr modified aluminide coating productions
CN107812941A (en) * 2017-10-20 2018-03-20 华中科技大学 A kind of in-situ preparation method of laser gain material manufacture aluminium alloy and products thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104328431A (en) * 2014-11-14 2015-02-04 重庆理工大学 Aluminum alloy surface modification method
CN106191395A (en) * 2016-08-15 2016-12-07 江苏大学 A kind of high-current pulsed electron beam irradiation 20 steel method for alloying surface
CN107268044A (en) * 2017-05-22 2017-10-20 中国科学院金属研究所 A kind of Pt Zr modified aluminide coating productions
CN107812941A (en) * 2017-10-20 2018-03-20 华中科技大学 A kind of in-situ preparation method of laser gain material manufacture aluminium alloy and products thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NANA TIAN ETAL: "The surface modification of aluminum by mechanical milling of Pb coating and high current pulsed electron beam irradiation", 《MATER. RES. EXPRESS 》 *

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Application publication date: 20200918