CN110055496B - Preparation process for preparing Cr coating on surface of nuclear zirconium alloy substrate - Google Patents

Preparation process for preparing Cr coating on surface of nuclear zirconium alloy substrate Download PDF

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CN110055496B
CN110055496B CN201910517214.9A CN201910517214A CN110055496B CN 110055496 B CN110055496 B CN 110055496B CN 201910517214 A CN201910517214 A CN 201910517214A CN 110055496 B CN110055496 B CN 110055496B
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sputtering
zirconium alloy
coating
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CN110055496A (en
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张瑞谦
刘春海
杨红艳
韦天国
彭小明
杜沛南
王昱
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Nuclear Power Institute of China
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

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Abstract

The invention discloses a preparation process for preparing a Cr coating on the surface of a zirconium alloy substrate for a core, which comprises the steps of grinding the zirconium alloy substrate, polishing the zirconium alloy substrate on a metallographic polishing machine by using polishing paste, and cleaning oil stains on the surface of a zirconium alloy sheet after the zirconium alloy substrate is polished to be smooth; placing in a vacuum furnace cavity of an ultrahigh vacuum magnetron sputtering device until the vacuum degree reaches the background vacuum of 2 multiplied by 10‑4After Pa, introducing gas and cleaning for 10 minutes by bias back-sputtering; after the surface of the substrate is cleaned by back sputtering, rapidly glowing the Cr target by adopting a radio frequency power supply, closing the baffle, and pre-sputtering the surface of the target for 10 minutes to remove surface oxides or adsorbed impurities; opening a Cr target baffle plate to deposit a Cr coating; and cooling the zirconium alloy to below 100 ℃ along with the furnace under the condition of not closing a vacuum system, and performing stress removal and deformation correction treatment. The invention adopts the magnetron sputtering technology to deposit the Cr coating with strong binding force and high thickness on the zirconium alloy substrate for the core.

Description

Preparation process for preparing Cr coating on surface of nuclear zirconium alloy substrate
Technical Field
The invention relates to the field of metal surface modification, in particular to a preparation process for preparing a Cr coating on the surface of a nuclear zirconium alloy substrate.
Background
The zirconium alloy cladding shows good radiation resistance and corrosion resistance, and is successfully applied to a Light Water Reactor (LWR), but under the conditions of a cooling water loss of coolant accident (LOCA) and a super design basis accident (BDBA) of the cladding material, the zirconium alloy cladding releases a large amount of hydrogen and heat through high-temperature oxidation, so that a serious nuclear accident is caused, a large amount of radioactive substances leak, and disastrous consequences are brought to the living environment of human beings, such as 'Fudao nuclear power station accident' in 2011. The research on the accident-resistant cladding material mainly focuses on developing a novel accident-tolerant material (ATF) for replacing the traditional zirconium alloy, wherein the accident-tolerant material is required to be used under the normal working condition of a reactor or can improve the performance of the zirconium alloy, and the most important point is that the stability of the reactor core can be maintained within a certain time when the reactor core loss accident occurs, so that enough time is provided for taking accident measures. The accident fault-tolerant material needs to protect the zirconium alloy surface coating, so that the high-temperature oxidation resistance and strength of the zirconium alloy cladding material are improved, and the safety and the economy of the nuclear reactor are further improved.
The metal coating material can form a compact oxide film in a high-temperature water vapor and water corrosion environment, can effectively prevent oxygen from diffusing into the substrate, and has high bonding strength with a matrix interface, so that the metal coating is modified on the surface of the zirconium alloy to become one of the most promising accident tolerance candidate materials.
However, the Cr coating in the metal coating is the most promising accident-tolerant cladding coating material for the surface modification of zirconium alloy, the current Cr coating preparation mainly adopts the technologies of arc ion plating, atmospheric plasma spraying, cold spraying and 3D laser coating, but in the preparation process of the existing Cr coating on the surface of the zirconium alloy, after the deposition thickness exceeds 20 microns, the bonding force between the coating and the substrate is reduced, the coating is not beneficial to being used in the field of nuclear application, and the corrosion resistance and the oxidation resistance of the obtained material at high temperature are also obviously reduced, so that the service life and the efficiency are reduced, and safety accidents are easy to occur.
Disclosure of Invention
The invention aims to solve the technical problems that in the existing preparation process of the Cr coating on the surface of the zirconium alloy, the obtained coating can not keep better bonding force, high-temperature oxidation resistance and corrosion resistance under thicker thickness, and the use efficiency is lower, and aims to provide a preparation process for preparing the Cr coating on the surface of a nuclear zirconium alloy substrate, so as to solve the problem of preparing the Cr coating on the surface of the zirconium alloy.
The invention is realized by the following technical scheme:
a preparation process for preparing a Cr coating on the surface of a zirconium alloy substrate for a core comprises the following steps:
(1) sequentially grinding the zirconium alloy substrate from coarse to fine by using water abrasive paper, finally polishing on a metallographic polishing machine by using polishing paste, and cleaning oil stains on the surface of the zirconium alloy sheet after polishing is smooth;
(2) placing the treated zirconium alloy sheet in a vacuum furnace cavity of ultrahigh vacuum magnetron sputtering equipment, introducing gas to perform bias back-sputtering cleaning for 10 minutes after the vacuum degree reaches the background vacuum of 2 x 10 < -4 > Pa;
(3) after the surface of the substrate is cleaned by back sputtering, rapidly glowing the Cr target by adopting a radio frequency power supply, closing the baffle, and pre-sputtering the surface of the target for 10 minutes to remove surface oxides or adsorbed impurities;
(4) opening a Cr target baffle plate to deposit a Cr coating;
(5) and cooling the zirconium alloy to below 100 ℃ along with the furnace under the condition of not closing a vacuum system, and performing stress removal and deformation correction treatment.
In the preparation process, in the step (1), the zirconium alloy substrate is sequentially ground by using 240#, 600#, 1000#, 1500# and 3000# water grinding sandpaper from coarse to fine. In the step (1), after polishing, ultrasonic cleaning is carried out in acetone and alcohol for 10-20 minutes in sequence. The substrate bias back-sputtering cleaning in the step (2) is performed for 10min under the conditions of-700V bias, Ar atmosphere and 2Pa vacuum degree. In the step (3), the pre-sputtering is performed for 10min under the conditions that the air pressure is 0.4Pa, the sputtering power is 100W, the working atmosphere is Ar and the target base distance is 6 cm. In the deposition parameters in the step (4), the sputtering pressure is 0.3-0.6Pa, the working atmosphere is Ar, the flow rate is 30-60 sccm, the target base distance is 6-7cm, the bias working voltage is 0V-150V, the heating temperature of the deposition substrate is 200-400 ℃, a Cr coating is sputtered on the surface of the Zr-4 substrate, and the sputtering time is determined according to the coating thickness; the target sputtering power is 120-160W. The purity of the Cr target in the step (4) is 99.99%. And (5) after the zirconium alloy is cooled to below 90-120 ℃ along with the furnace, closing the vacuum system, and storing the sample in the vacuum cavity for more than 9-11 hours so as to avoid stress peeling of the coating caused by sudden change of external pressure. And (5) after the zirconium alloy is cooled to below 100 ℃ along with the furnace, closing the vacuum system, and storing the sample in the vacuum cavity for more than 10 hours to avoid stress peeling of the coating caused by sudden change of external pressure. The thickness of the obtained Cr coating is 5-50 mu m.
Furthermore, the invention adopts the magnetron sputtering technology physical vapor deposition technology, obtains the Cr coating with strong binding force and high thickness by changing the sputtering power of the Cr target, the substrate bias voltage, the substrate temperature and the deposition air pressure, and realizes the preparation of the Cr coating meeting the high temperature and high pressure in the nuclear field on the surface of the zirconium alloy; in the preparation method, stress removal and deformation correction are carried out, all samples are cooled to below 100 ℃ along with a furnace under the condition that a vacuum system is not closed, then the vacuum system is closed, and the samples are stored in a vacuum cavity for more than 10 hours, so that the stress stripping of the coating caused by the sudden change of the external pressure is avoided.
The research has been carried out to prepare Cr coating on the surface of zirconium alloy by adopting ion plating technology, the surface coating may have the phenomena of liquid drops and large particles, and the quality control of the surface film of the metal Cr coating prepared by adopting magnetron sputtering technology is better, and the metal Cr coating has better corrosion resistance. The surfaces of the sample and the target are cleaned before the coating is prepared, and the film base has good binding force after the coating is deposited. The deposition is carried out at a certain temperature, the deposition power is determined, and the rapid deposition can be realized, so that the ultra-thick Cr coating with good film-substrate binding force and compact surface is obtained, and the coating has better oxidation resistance under the high-temperature condition.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention relates to a preparation process for preparing a Cr coating on the surface of a nuclear zirconium alloy substrate, which adopts a magnetron sputtering technology to deposit a Cr coating with strong bonding force and high thickness on the nuclear zirconium alloy substrate, not only has better performance than the traditional electroplated hard chromium coating, but also overcomes the serious pollution to the environment caused by the contained metal chromium ions with strong oxidizing property in the traditional electroplated hard chromium technology;
2. the invention relates to a preparation process for preparing a Cr coating on the surface of a nuclear zirconium alloy substrate, which adopts a process for preparing the Cr coating on the surface of the zirconium alloy substrate by magnetron sputtering, and has the advantages of simple operation, accurate control of sputtering power of a target material, adjustable coating thickness, compact and uniform surface of the prepared Cr coating and excellent binding force;
3. according to the preparation process for preparing the Cr coating on the surface of the zirconium alloy substrate for the core, the material obtained by the invention is effectively subjected to stress removal and deformation correction treatment, so that the material prepared by the invention has better performance, is more suitable for the environment with corrosivity under high temperature and high pressure for the core, is safer to use and has higher efficiency.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a surface micro-topography characterization of the prepared Cr coating by SEM at a bias voltage of 0V (a picture) and a bias voltage of-50V (b picture);
FIG. 2 is a cross-sectional micro-topography characterization of the prepared Cr coating by SEM at a bias voltage of 0V (a picture) and a bias voltage of-50V (b picture);
FIG. 3 is a graph showing the bonding force test of the present invention at a bias voltage of 0V (graph a) and a bias voltage of-50V (graph b);
FIG. 4 is a SEM image of the profile of a scratch of the coating of the present invention at a bias voltage of 0V (a view) and a bias voltage of-50V (b view), and a c view is an enlarged view of the small image in a view.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
As shown in FIGS. 1 to 4, the preparation process for preparing the Cr coating on the surface of the zirconium alloy substrate for the core comprises the following steps:
(1) sequentially grinding zirconium alloy square sheets from coarse to fine by using No. 240, No. 600, No. 1000, No. 1500 and No. 3000 water grinding abrasive paper, finally polishing on a metallographic polishing machine by using polishing paste, and ultrasonically cleaning for 15-20min by using acetone and alcohol after polishing;
(2) placing the treated zirconium alloy sheet in a vacuum furnace cavity of ultrahigh vacuum magnetron sputtering equipment, and after the vacuum degree reaches the background vacuum of 2 multiplied by 10-4After Pa, introducing gas, and cleaning for 10 minutes by using bias voltage back sputtering, wherein the back sputtering bias voltage is-700V, the working atmosphere is Ar, and the working vacuum degree is 2 Pa;
(3) after the surface of the substrate is subjected to back sputtering cleaning, rapidly glowing the Cr target by using a radio frequency power supply, closing the baffle plate, and carrying out pre-sputtering on the surface of the target for 10 minutes to remove surface oxides or adsorb impurities, wherein the pre-sputtering is carried out for 10 minutes under the conditions that the air pressure is 0.4Pa, the sputtering power is 100W, the working atmosphere is Ar and the target base distance is 6 cm.
(4) After sputtering parameters are adjusted to set parameters, a Cr target baffle is opened to deposit a Cr coating, the sputtering pressure is 0.5Pa, the working atmosphere is Ar, the flow is 50sccm, the target base distance is 7cm, the bias working voltage is 120V, the heating temperature of the deposition substrate is 350 ℃, the Cr coating is sputtered on the surface of the Zr-4 substrate, and the sputtering time is 6 hours; the target sputtering power is 140W; the purity of the Cr target is 99.99%.
(5) The method comprises the steps of cooling a sample of the zirconium alloy material along with a furnace until the temperature is below 100 ℃ under the condition that a vacuum system is not closed, then closing the vacuum system, and storing the sample in a vacuum cavity for more than 10 hours so as to avoid stress peeling of a coating caused by sudden change of external pressure.
Example 2
(1) Polishing and cleaning the surface of the substrate: sequentially using 800-5000 meshes of water sand paper and polishing flannelette to grind and polish the surface of the substrate sample until the surface roughness Ra is less than 10 nm; then, sequentially putting the substrate sample into a detergent powder aqueous solution with the concentration of 40%, a saturated Na2CO3 aqueous solution, acetone, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 15min respectively, and then blowing the substrate sample to dry by using N2 gas;
(2) placing the cleaned substrate sample in a vacuum chamber for plasma bias back-splash cleaning, wherein the process parameters are as follows: background vacuum 5X 10-4Pa, the back splash bias voltage is 200V, the back splash air pressure is 1.0Pa, and the back splash time is 20 min;
(3) depositing a nano gradient coating on the surface of a substrate by adopting an ultrahigh vacuum multi-target magnetron sputtering coating machine, wherein the background vacuum degree of the coating machine is 5 multiplied by 10-4Pa, deposition temperature 200 ℃, specifically comprising the following 3 consecutive time periods: in the first sputtering time period, after the vacuum chamber is pumped to reach the background vacuum degree, introducing Ar gas into the vacuum chamber, wherein the gas flow is 32sccm, the working gas pressure is 0.3Pa, then starting Cr, Al and Si targets for sputtering, wherein the power of the Al target is gradually and linearly increased from 20W to 100W, and realizing the co-sputtering of the Cr target, the Al target and the Si target, thereby obtaining Cr with gradually increased Al content in a gradient mannerxAlySi1-x-yAnd (4) coating.
Example 3
(1) Polishing and cleaning the surface of the substrate: sequentially using 800-5000 meshes of water sand paper and polishing flannelette to grind and polish the surface of the substrate sample until the surface roughness Ra is less than 10 nm; then, sequentially putting the substrate sample into a detergent powder aqueous solution with the concentration of 40%, a saturated Na2CO3 aqueous solution, acetone, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 15min respectively, and then blowing the substrate sample to dry by using N2 gas;
(2) placing the cleaned substrate sample in a vacuum chamber for plasma bias back-splash cleaning, wherein the process parameters are as follows: background vacuum 5X 10-4Pa, the back splash bias voltage is 200V, the back splash air pressure is 1.0Pa, and the back splash time is 20 min;
(3) depositing a nano gradient coating on the surface of a substrate by adopting an ultrahigh vacuum multi-target magnetron sputtering coating machine, wherein the background vacuum degree of the coating machine is 5 multiplied by 10-4Pa, deposition temperature 200 deg.C, introducing Ar gas into the vacuum chamber when the vacuum chamber reaches background vacuum degree, wherein the gas flow is 32sccm, and the working gasThe pressure was 0.3Pa, and then sputtering was performed by turning on a Cr target with a Cr target power of 100W.
Example 4
(1) Polishing and cleaning the surface of the substrate: sequentially using 800-5000 meshes of water sand paper and polishing flannelette to grind and polish the surface of the substrate sample until the surface roughness Ra is less than 10 nm; then, sequentially putting the substrate sample into a detergent powder aqueous solution with the concentration of 40%, a saturated Na2CO3 aqueous solution, acetone, absolute ethyl alcohol and deionized water, and ultrasonically cleaning for 15min respectively, and then blowing the substrate sample to dry by using N2 gas;
(2) placing the cleaned substrate sample in a vacuum chamber for plasma bias back-splash cleaning, wherein the process parameters are as follows: background vacuum 5X 10-4Pa, the back splash bias voltage is 200V, the back splash air pressure is 1.0Pa, and the back splash time is 20 min;
(3) depositing a nano gradient coating on the surface of a substrate by adopting an ultrahigh vacuum multi-target magnetron sputtering coating machine, wherein the background vacuum degree of the coating machine is 5 multiplied by 10-4Pa and the deposition temperature is 200 ℃, after the vacuum chamber is pumped to reach the background vacuum degree, introducing Ar gas into the vacuum chamber, wherein the gas flow is 32sccm, the working gas pressure is 0.3Pa, and then starting a Cr target for sputtering, wherein the power of the Cr target is 100W.
(4) The method comprises the steps of cooling a sample of the zirconium alloy material along with a furnace until the temperature is below 100 ℃ under the condition that a vacuum system is not closed, then closing the vacuum system, and storing the sample in a vacuum cavity for more than 10 hours so as to avoid stress peeling of a coating caused by sudden change of external pressure.
Example 5
(1) Sequentially grinding zirconium alloy square sheets from coarse to fine by using No. 240, No. 600, No. 1000, No. 1500 and No. 3000 water grinding abrasive paper, finally polishing on a metallographic polishing machine by using polishing paste, and ultrasonically cleaning for 15-20min by using acetone and alcohol after polishing;
(2) placing the treated zirconium alloy sheet in a vacuum furnace cavity of ultrahigh vacuum magnetron sputtering equipment, and after the vacuum degree reaches the background vacuum of 2 multiplied by 10-4After Pa, introducing gas, and cleaning for 10 minutes by using bias voltage back sputtering, wherein the back sputtering bias voltage is-700V, the working atmosphere is Ar, and the working vacuum degree is 2 Pa;
(3) after the surface of the substrate is subjected to back sputtering cleaning, rapidly glowing the Cr target by using a radio frequency power supply, closing the baffle plate, and carrying out pre-sputtering on the surface of the target for 10 minutes to remove surface oxides or adsorb impurities, wherein the pre-sputtering is carried out for 10 minutes under the conditions that the air pressure is 0.4Pa, the sputtering power is 100W, the working atmosphere is Ar and the target base distance is 6 cm.
(4) Depositing a nano gradient coating on the surface of a substrate by adopting an ultrahigh vacuum multi-target magnetron sputtering coating machine, wherein the background vacuum degree of the coating machine is 5 multiplied by 10-4Pa, deposition temperature 200 ℃, specifically comprising the following 3 consecutive time periods: in the first sputtering time period, after the vacuum chamber is pumped to reach the background vacuum degree, introducing Ar gas into the vacuum chamber, wherein the gas flow is 32sccm, the working gas pressure is 0.3Pa, then starting Cr, Al and Si targets for sputtering, wherein the power of the Al target is gradually and linearly increased from 20W to 100W, and realizing the co-sputtering of the Cr target, the Al target and the Si target, thereby obtaining Cr with gradually increased Al content in a gradient mannerxAlySi1-x-yAnd (4) coating.
(5) The method comprises the steps of cooling a sample of the zirconium alloy material along with a furnace until the temperature is below 100 ℃ under the condition that a vacuum system is not closed, then closing the vacuum system, and storing the sample in a vacuum cavity for more than 10 hours so as to avoid stress peeling of a coating caused by sudden change of external pressure.
Opening a Cr target baffle of the ultrahigh vacuum magnetron sputtering equipment to deposit a Cr coating, and respectively setting the following parameters to obtain the following table 1:
Figure BDA0002095425290000061
TABLE 1
In the process steps of the invention, the zirconium complex is prepared according to the sputtering parameter preparation patterns in Table 1 and the methods of examples 1-5
Gold-based Cr coating, the following data were obtained:
Figure BDA0002095425290000062
the ranges of the parameters in table 1 are outside the range of the present invention, and the samples 1 to 4 were prepared according to the procedure of example 1, and since the parameters are outside the range of the present invention, the binding force and the high temperature oxidation resistance at high temperature were poor.
Example 2 is an existing manufacturing process, and example 3 is also an existing manufacturing process, and the Cr, Al, Si targets are changed to only Cr targets; example 4 is also the prior art, and example 5 is the process of the present invention, in which the target material is changed to the prior art three-target sputtering;
from the above data analysis, it can be seen that the performance of examples 2-5 is inferior to the coating obtained in example 1 of the present invention, especially the oxidation resistance at high temperature. The coating prepared under the technological parameters of the invention has good film-substrate bonding quality, compact film surface, high deposition efficiency and good oxidation resistance under high temperature. Therefore, the process is a preparation technology of the oxidation resistant coating on the surface of the material in the reactor with development prospect.
And (3) performing surface and section microscopic morphology characterization on the prepared Cr coating by using an SEM (scanning Electron microscope), wherein the surface of the prepared Cr coating is dense and continuous, no obvious defect is observed in a larger range, and the section SEM image shows that the coating has uniform thickness.
The bonding strength of the coating is estimated using an automatic scratch tester, a scratch test is performed under linear dynamic increasing load, and simultaneously a scanning electron microscope is used to observe the scratch morphology. The bonding force test result is shown in fig. 3, fig. 4 is a coating scratch morphology SEM image, the bonding force of the Cr coating biased at 0V exceeds 30N, the Cr coating biased at-50V exceeds 100N, no acoustic emission signal is observed at 0-100N, and the scratch is relatively small, no obvious delamination or peeling occurs, and it can be found that all coatings are tightly bonded to the substrate, and the interface between the coating and the substrate is fuzzy, indicating that the coating has strong mutual adhesion ability with the substrate surface and the coating has excellent bonding performance with the substrate. The coating prepared by the invention has the thickness of about 20-30 microns, has better high-temperature oxidation resistance, corrosion resistance, binding force and strength, is superior to the coating obtained by the existing preparation process, and the obtained material is more suitable for the nuclear field.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (1)

1. A preparation process for preparing a Cr coating on the surface of a zirconium alloy substrate for a core is characterized by comprising the following steps of:
(1) sequentially grinding the zirconium alloy substrate from coarse to fine by using water abrasive paper, finally polishing on a metallographic polishing machine by using polishing paste, and cleaning oil stains on the surface of the zirconium alloy sheet after polishing is smooth;
(2) placing the treated zirconium alloy sheet in a vacuum furnace cavity of ultrahigh vacuum magnetron sputtering equipment, and after the vacuum degree reaches the background vacuum of 2 multiplied by 10-4After Pa, introducing gas and cleaning for 10 minutes by bias back-sputtering;
(3) after the surface of the substrate is cleaned by back sputtering, rapidly glowing the Cr target by adopting a radio frequency power supply, closing the baffle, and pre-sputtering the surface of the target for 10 minutes to remove surface oxides or adsorbed impurities;
(4) opening a Cr target baffle plate to deposit a Cr coating;
(5) cooling the zirconium alloy to below 100 ℃ along with the furnace under the condition of not closing a vacuum system, and performing stress removal and deformation correction treatment;
the detailed process comprises the following steps:
(1) sequentially grinding zirconium alloy square sheets from coarse to fine by using No. 240, No. 600, No. 1000, No. 1500 and No. 3000 water grinding abrasive paper, finally polishing on a metallographic polishing machine by using polishing paste, and ultrasonically cleaning for 15-20min by using acetone and alcohol after polishing;
(2) placing the treated zirconium alloy sheet in a vacuum furnace cavity of ultrahigh vacuum magnetron sputtering equipment until the vacuum degree reachesTo background vacuum 2X 10-4After Pa, introducing gas, and cleaning for 10 minutes by using bias voltage back sputtering, wherein the back sputtering bias voltage is-700V, the working atmosphere is Ar, and the working vacuum degree is 2 Pa;
(3) after the surface of the substrate is subjected to back sputtering cleaning, rapidly glowing a Cr target by using a radio frequency power supply, closing a baffle plate, and carrying out pre-sputtering on the surface of the target for 10 minutes to remove surface oxides or adsorb impurities, wherein the pre-sputtering is carried out for 10 minutes under the conditions that the air pressure is 0.4Pa, the sputtering power is 100W, the working atmosphere is Ar and the target base distance is 6 cm;
(4) after sputtering parameters are adjusted to set parameters, a Cr target baffle is opened to deposit a Cr coating, the sputtering pressure is 0.5Pa, the working atmosphere is Ar, the flow is 50sccm, the target base distance is 7cm, the bias working voltage is 120V, the heating temperature of the deposition substrate is 350 ℃, the Cr coating is sputtered on the surface of the Zr-4 substrate, and the sputtering time is 6 hours; the target sputtering power is 140W; the purity of the Cr target is 99.99 percent;
(5) cooling a sample of the zirconium alloy material to below 100 ℃ along with a furnace under the condition of not closing a vacuum system, then closing the vacuum system, and storing the sample in a vacuum cavity for more than 10 hours so as to avoid stress peeling caused by sudden change of external pressure of the coating;
the thickness of the prepared zirconium alloy substrate Cr coating is 28 mu m.
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CN110499494A (en) * 2019-09-05 2019-11-26 西安交通大学 It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof
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