CN110938855A - Zirconium alloy surface ZrO2Preparation method of/FeCrAl composite coating and zirconium alloy - Google Patents

Zirconium alloy surface ZrO2Preparation method of/FeCrAl composite coating and zirconium alloy Download PDF

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CN110938855A
CN110938855A CN201911057293.6A CN201911057293A CN110938855A CN 110938855 A CN110938855 A CN 110938855A CN 201911057293 A CN201911057293 A CN 201911057293A CN 110938855 A CN110938855 A CN 110938855A
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zirconium alloy
fecral
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贾斌
赵小方
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Chengdu Jichuang Technology Co Ltd
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    • 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
    • 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
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    • 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
    • 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
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
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    • G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

Zirconium alloy surface ZrO2A preparation method of a/FeCrAl composite coating, in particular to the related application field of nuclear reactor materials; the invention comprises the following steps: s1, performing zirconium alloy surface treatment; s2 preparation of ZrO on surface of zirconium alloy by micro-arc oxidation2A layer forming a substrate; s3, preparing an FeCrAl layer on the substrate by utilizing a magnetron sputtering mode. The high-temperature oxidation resistance of the zirconium alloy is obviously improved after the buffer layer is added, and the buffer layer plays a good role in protecting the zirconium matrix in the oxidation process.

Description

Zirconium alloy surface ZrO2Preparation method of/FeCrAl composite coating and zirconium alloy
Technical Field
The invention relates to the field of nuclear reactor material application, in particular to ZrO on the surface of a zirconium alloy2A preparation method of a/FeCrAl composite coating and a zirconium alloy.
Background
Zirconium alloy as a light water reactor cladding material shows good radiation resistance and corrosion resistance, and has been successfully used in a pressurized water reactor of a nuclear power station for decades. The zirconium alloy reacts violently with water vapor at high temperature, and releases a large amount of hydrogen and heat when the temperature is higher than 1200 ℃, thereby bringing great potential safety hazard. How to further improve the safety and reliability of the light water reactor nuclear fuel element under the accident condition becomes a problem to be solved urgently by nuclear science researchers, therefore, the reactor design provides higher safety margin requirement for the fuel performance, and a breakthrough of the light water reactor nuclear fuel element facing the challenge is to develop a novel accident-resistant fuel element.
The direction of research on accident-resistant fuels (ATF) proposed by scientists includes accident-resistant fuel cores and accident-resistant cladding materials. The accident-resistant cladding material aims to improve the accident-resistant capability of the cladding material, provides a larger safety margin as far as possible under the accident condition, and avoids the problem of severe melting of the reactor core. The zirconium alloy surface coating is a main direction for the development of accident-resistant cladding materials, and aims to improve the oxidation resistance of the zirconium alloy cladding in a high-temperature water vapor environment and improve the corrosion resistance of the zirconium alloy cladding under normal working conditions.
However, in the prior published art research, although some cladding material surface coating preparation is disclosed, no coating and coating structure for improving the above problems is available.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides ZrO on the surface of a zirconium alloy2A preparation method of a/FeCrAl composite coating and a zirconium alloy.
In order to achieve the above object, the first aspect of the present invention provides ZrO on the surface of a zirconium alloy2The preparation method of the/FeCrAl composite coating comprises the following steps:
s1, performing zirconium alloy surface treatment;
s2, preparing ZrO on the surface of the zirconium alloy by using a micro-arc oxidation mode2A layer forming a substrate;
s3, preparing an FeCrAl layer on the substrate by utilizing a magnetron sputtering mode.
Further, the zirconium alloy surface treatment method comprises the following steps:
ultrasonically cleaning the surface of the zirconium alloy by using an acetone solution, and then washing for 30min by using deionized water;
and (3) putting the zirconium alloy washed by the deionized water into a vacuum drying chamber, and drying at 110 ℃ for 30 min.
Further, the ZrO2The layer preparation method comprises the following steps:
preparing an electrolyte;
micro-arc oxidation treatment, namely connecting the surface-treated zirconium alloy with an anode, immersing the zirconium alloy in the electrolyte, turning on a cooling water and stirring device, adjusting power supply parameters, and then switching on a power supply for oxidation;
and cleaning the zirconium alloy subjected to micro-arc oxidation by using deionized water and absolute ethyl alcohol in sequence, and then placing the cleaned zirconium alloy in a 50 ℃ drying oven for drying.
Further, the electrolyte includes:
NaAlO20.05-0.30mol L-1；
NaOH 0.05-0.30mol L-1。
further, the electrolyte includes:
Na2SiO3·9H2O 0.05-0.30mol L-1；
NaOH 0.05-0.30mol L-1。
further, the forward voltage in the micro-arc oxidation process is 50V, and the current density is not more than 150mA cm-2The boosting speed of (2) is increased to a desired voltage.
Further, the specific method for preparing the FeCrAl layer on the substrate by utilizing a magnetron sputtering mode comprises the following steps:
cleaning a substrate: ultrasonically cleaning with anhydrous ethanol for 15-30min, and cleaning with deionized water for 15-30 min; and drying in a 50 ℃ oven after cleaning.
Vacuum preparation: vacuumizing the vacuum chamber to 6X 10-4And when Pa is reached, heating to a set temperature of 300 ℃ and then preserving heat for 2 h.
Bias cleaning: and introducing argon after the heat preservation time is reached, adjusting the pressure of the empty chamber to 3-5 Pa, then adjusting the bias voltage to 300-400V, and carrying out surface cleaning on the substrate for 10-20 min.
Sputtering deposition: starting sputtering, adjusting to the required power, adjusting the pressure of the vacuum chamber to 0.5Pa after smooth glow starting, pre-sputtering for 5-10min, and performing sputtering deposition on the substrate for 2 h.
Taking the sample out of the bin: and after the sputtering is finished, the heating temperature is gradually adjusted downwards until the heating temperature is closed.
In a second aspect, the present invention provides a zirconium alloy having ZrO on the surface thereof2Layer of the ZrO2The outside of the layer has a FeCrAl coating to form a composite coating, and the composite coating is formed by the zirconium alloy surface ZrO of the first aspect of the invention2A preparation method of a/FeCrAl composite coating.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares ZrO by micro-arc oxidation technology2The layer is used as a buffer layer, the high-temperature oxidation resistance of the zirconium alloy is obviously improved, and the buffer layer plays a good role in protecting the zirconium matrix in the oxidation process. ZrO (ZrO)2the/FeCrAl composite coating has good high-temperature oxidation resistance and is an accident-resistant fault-tolerant coating cladding material with development prospect.
In the prior art, the compatibility of FeCrAl serving as a zirconium alloy surface coating and a zirconium alloy matrix in a high-temperature steam environment is poor, the Fe element and the zirconium alloy are seriously diffused with each other to cause failure of the coating, and the key factor of failure of the FeCrAl coating on the surface of the zirconium alloy at high temperature is the problem of high-temperature diffusion between the zirconium alloy matrix and the FeCrAl coating.
The surface coating is suitable for accident-resistant cladding materials, such as zirconium alloy (N36, Zr-4 and the like) cladding materials, and is also suitable for other structural materials in a reactor, such as grid materials, conduit materials and the like, and the application range is wide.
Drawings
FIG. 1 is an overall flow chart of the present embodiment;
FIG. 2 shows a single FeCrAl coating and ZrO of the specific example 1 of the present application2The cross-sectional shape of the/FeCrAl composite coating before and after oxidation at different temperatures is shown in the figure 2a, wherein a single FeCrAl coating is shown in the figure 2b, and ZrO is shown in the figure 2b2FIG. 2c is a backscattering image of a single FeCrAl coating after oxidation at 1000 deg.C2d is ZrO2a/FeCrAl composite coating backscattering image;
FIG. 3 is a graph showing oxidation kinetics curves of a single FeCrAl coating of a Zr-4 alloy matrix and a ZrO2/FeCrAl composite coating of example 1, FIG. 3a is a graph showing a weight gain curve at 800 ℃ at 14400s, FIG. 3b is a graph showing a weight gain curve at 800 ℃ at 14400s squared, FIG. 3c is a graph showing a weight gain curve at 1000 ℃ at 3600s, and FIG. 3d is a graph showing a weight gain curve at 1000 ℃ at 3600s squared.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention without any creative efforts shall fall within the protection scope of the present invention.
Example 1
ZrO on the outer surface of the Zr-4 alloy2The preparation method of the/FeCrAl composite coating mainly comprises the following steps:
s1, zirconium-based body external surface pretreatment:
the zirconium alloy finished tube meeting the technical index requirements of the reactor cladding material is adopted, acetone solution is firstly subjected to ultrasonic cleaning for 30 minutes, then deionized water is adopted for washing in a large quantity, and then the zirconium alloy finished tube is placed into a special high-vacuum drying chamber for drying at 110 ℃ for 30 minutes.
S2 preparation of micro-arc oxidation ZrO from sodium aluminate system electrolyte2Layer (b):
preparing electrolyte: the electrolyte component is NaAlO20.05mol L-1，NaOH 0.05mol L-1；
Micro-arc oxidation treatment: the electrolyte was first poured into the cell and then the Zr-4 alloy coupon was connected to the anode metal fixture and immersed in the electrolyte to the appropriate position. Cooling water is turned on, the stirring device is turned on, power supply parameters are adjusted to required values, and finally the power supply is turned on to start oxidation (the forward voltage in the constant voltage mode is 50V, and the current density is not more than 150mA cm)-2The boost speed of (c) up to the required voltage).
Cleaning and drying: and after the micro-arc oxidation is finished, sequentially closing the equipment. Taking out the micro-arc oxidized Zr-4 alloy, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol, and finally drying in a 50 ℃ oven.
S3, preparing a FeCrAl layer through magnetron sputtering:
cleaning a substrate: firstly, absolute ethyl alcohol is cleaned for 15-30min by ultrasonic, and then deionized water is cleaned for 15-30 min; and drying in a 50 ℃ oven after cleaning.
Base body installation: fixed on the substrate platform by a clamp.
Vacuum preparation: vacuumizing the vacuum chamber to 6X 10-4And heating at the temperature of 300 ℃ at Pa, and keeping the temperature for 2 h.
Bias cleaning: and introducing argon after the heat preservation time is sufficient, adjusting the pressure of the vacuum chamber to 3-5 Pa by adjusting the gate valve, then opening the baffle, adjusting the bias voltage to 300-400V, and performing surface cleaning on the substrate for 10-20 min.
Sputtering deposition: and after the bias cleaning is finished, the bias is closed, the baffle plate is closed, and then sputtering is started to adjust to the required power. Adjusting the gate valve to adjust the pressure of the vacuum chamber to 0.5Pa after smoothly starting, and pre-sputtering for 5-10 min. The shutter was then opened and the substrate was sputter deposited for 2 h.
Taking the sample out of the bin: and after the sputtering is finished, the heating temperature is gradually adjusted downwards until the substrate is closed, and then the substrate is taken out after the chamber is opened.
Zirconium alloy with ZrO on surface2Layer of the ZrO2The outside of the layer has a FeCrAl coating forming a composite coating from the zirconium alloy surface ZrO described in example 12Preparing a preparation method of a/FeCrAl composite coating;
the FeCrAl alloy can keep excellent oxidation resistance in the range of 1400 ℃, so that the FeCrAl coating on the surface of the zirconium alloy can be used as an accident fault-tolerant coating. However, the zirconium alloy and FeCrAl coating diffuse with each other at high temperature and generate intermetallic compounds, which can have serious influence on the matrix performance and the film-substrate binding force. Therefore, buffer layers must be added to avoid FeCrAl coating caused by diffusionThe layer fails. The buffer layer needs to have high temperature stability, high bonding strength, and match the thermal expansion coefficient of the FeCrAl coating. Preparation of ZrO on zirconium alloy surface by micro-arc oxidation (MAO) technology2A buffer layer is formed, and an FeCrAl coating is deposited on the surface of the ZrO2 buffer layer by utilizing the magnetron sputtering technology, so that the ZrO with accident fault tolerance capability meeting the requirements can be obtained2the/FeCrAl composite coating.
Example 2
ZrO on the outer surface of the Zr-4 alloy2The preparation method of the/FeCrAl composite coating mainly comprises the following steps:
s1, zirconium-based body external surface pretreatment:
the zirconium alloy finished tube meeting the technical index requirements of the reactor cladding material is adopted, acetone solution is firstly subjected to ultrasonic cleaning for 30 minutes, then deionized water is adopted for washing in a large quantity, and then the zirconium alloy finished tube is placed into a special high-vacuum drying chamber for drying at 110 ℃ for 30 minutes.
S2 preparation of micro-arc oxidation ZrO from sodium silicate system electrolyte2Layer (b):
preparing electrolyte: the electrolyte component is Na2SiO3·9H2O 0.1mol L-1，NaOH 0.1mol L-1；
Micro-arc oxidation treatment: the electrolyte was first poured into the cell and then the Zr-4 alloy coupon was connected to the anode metal fixture and immersed in the electrolyte to the appropriate position. Cooling water is turned on, the stirring device is turned on, power supply parameters are adjusted to required values, and finally the power supply is turned on to start oxidation (the forward voltage in the constant voltage mode is 50V, and the current density is not more than 150mA cm)-2The boosting speed of (1) up to the required voltage);
cleaning and drying: and after the micro-arc oxidation is finished, sequentially closing the equipment. Taking out the micro-arc oxidized Zr-4 alloy, firstly washing with deionized water, then ultrasonically cleaning with absolute ethyl alcohol, and finally drying in a 50 ℃ oven.
S3, preparing a FeCrAl layer through magnetron sputtering:
cleaning a substrate: firstly, absolute ethyl alcohol is cleaned for 15-30min by ultrasonic, and then deionized water is cleaned for 15-30 min; and drying in a 50 ℃ oven after cleaning.
Base body installation: fixed on the substrate platform by a clamp.
Vacuum preparation: vacuumizing the vacuum chamber to 6X 10-4And heating at the temperature of 300 ℃ at Pa, and keeping the temperature for 2 h.
Bias cleaning: and introducing argon after the heat preservation time is sufficient, adjusting the pressure of the vacuum chamber to 3-5 Pa by adjusting the gate valve, then opening the baffle, adjusting the bias voltage to 300-400V, and performing surface cleaning on the substrate for 10-20 min.
Sputtering deposition: and after the bias cleaning is finished, the bias is closed, the baffle plate is closed, and then sputtering is started to adjust to the required power. Adjusting the gate valve to adjust the pressure of the vacuum chamber to 0.5Pa after smoothly starting, and pre-sputtering for 5-10 min. The shutter was then opened and the substrate was sputter deposited for 2 h.
Taking the sample out of the bin: and after the sputtering is finished, the heating temperature is gradually adjusted downwards until the substrate is closed, and then the substrate is taken out after the chamber is opened.
Zirconium alloy with ZrO on surface2Layer of the ZrO2The outside of the layer has a FeCrAl coating forming a composite coating from the zirconium alloy surface ZrO described in example 22A preparation method of a/FeCrAl composite coating.
In order to verify the specific embodiment of the present invention, the zirconium alloy of the coating prepared in example 1 is detected, and the detection results are as follows:
firstly, micro-morphology characterization:
uniform distribution of the coating, ZrO2The thickness of the/FeCrAl composite coating is about 12 μm. Some quality characterization results of the coating are given in fig. 1 and fig. 2, respectively. As can be seen from fig. 1, the zirconium alloy surface coating layer was obtained with good adhesion, and the film-substrate interface adhesion was good.
II, high-temperature oxidation test:
zirconium alloy surface ZrO made by the method of the invention example 12the/FeCrAl composite coating, the single FeCrAl coating on the surface of the zirconium alloy and the zirconium alloy matrix are oxidized in high-temperature steam at 800 ℃ for 4 hours and 1000 ℃ for 1 hour. High temperature oxidation results show, ZrO2The surface of the/FeCrAl composite coating formsThe compact protective film has a complete and good material structure. The test result shows that the high-temperature oxidation resistance of the zirconium alloy is obviously improved after the buffer layer is added, and the buffer layer plays a good role in protecting the zirconium matrix in the oxidation process.
In the specific embodiment of the invention, Zr-4 alloy is taken as a matrix, and micro-arc oxidation technology and magnetron sputtering technology are adopted to prepare the ZrO on the surface2The test result of the/FeCrAl composite coating material shows that the high-temperature oxidation resistance of the zirconium alloy is obviously improved after the buffer layer is added, and the buffer layer plays a good role in protecting the zirconium matrix in the oxidation process. ZrO (ZrO)2the/FeCrAl composite coating has good high-temperature oxidation resistance and is an accident-resistant fault-tolerant coating cladding material with development prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention should be covered by the scope of the present invention.

Claims (8)

1. Zirconium alloy surface ZrO2The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the method comprises the following steps:
s1, performing zirconium alloy surface treatment;
s2, preparing ZrO on the surface of the zirconium alloy by using a micro-arc oxidation mode2A layer forming a substrate;
s3, preparing an FeCrAl layer on the substrate by utilizing a magnetron sputtering mode.
2. The ZrO surface of claim 12The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the zirconium alloy surface treatment method comprises the following steps:
ultrasonically cleaning the surface of the zirconium alloy by using an acetone solution, and then washing for 30min by using deionized water;
and (3) putting the zirconium alloy washed by the deionized water into a vacuum drying chamber, and drying at 110 ℃ for 30 min.
3. The ZrO surface of claim 12The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the ZrO2The layer preparation method comprises the following steps:
preparing an electrolyte;
micro-arc oxidation treatment, namely connecting the surface-treated zirconium alloy with an anode, immersing the zirconium alloy in the electrolyte, turning on a cooling water and stirring device, adjusting power supply parameters, and then switching on a power supply for oxidation;
and cleaning the zirconium alloy subjected to micro-arc oxidation by using deionized water and absolute ethyl alcohol in sequence, and then placing the cleaned zirconium alloy in a 50 ℃ drying oven for drying.
4. The ZrO surface of claim 32The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the electrolyte includes:
NaAlO20.05-0.30mol L-1；
NaOH 0.05-0.30mol L-1。
5. the ZrO surface of claim 32The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the electrolyte includes:
Na2SiO3·9H2O 0.05-0.30mol L-1；
NaOH 0.05-0.30mol L-1。
6. the ZrO surface of claim 32The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: the forward voltage in the micro-arc oxidation process is 50V, and the current density is not more than 150mA cm-2The boosting speed of (2) is increased to a desired voltage.
7. The ZrO surface of claim 12The preparation method of the/FeCrAl composite coating is characterized by comprising the following steps: specific method for preparing FeCrAl layer on substrate by magnetron sputtering modeThe method comprises the following steps:
cleaning a substrate: ultrasonically cleaning with anhydrous ethanol for 15-30min, and cleaning with deionized water for 15-30 min; and drying in a 50 ℃ oven after cleaning.
Vacuum preparation: vacuumizing the vacuum chamber to 6X 10-4And when Pa is reached, heating to a set temperature of 300 ℃ and then preserving heat for 2 h.
Bias cleaning: and introducing argon after the heat preservation time is reached, adjusting the pressure of the empty chamber to 3-5 Pa, then adjusting the bias voltage to 300-400V, and carrying out surface cleaning on the substrate for 10-20 min.
Sputtering deposition: starting sputtering, adjusting to the required power, adjusting the pressure of the vacuum chamber to 0.5Pa after smooth glow starting, pre-sputtering for 5-10min, and performing sputtering deposition on the substrate for 2 h.
Taking the sample out of the bin: and after the sputtering is finished, the heating temperature is gradually adjusted downwards until the heating temperature is closed.
8. A zirconium alloy, characterized by: the surface of the zirconium alloy has ZrO2Layer of the ZrO2The outside of the layer has a FeCrAl coating forming a composite coating consisting of a zirconium alloy surface ZrO according to any of claims 1 to 72A preparation method of a/FeCrAl composite coating.
CN201911057293.6A 2019-11-01 2019-11-01 Zirconium alloy surface ZrO2Preparation method of/FeCrAl composite coating and zirconium alloy Pending CN110938855A (en)

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CN108624882A (en) * 2018-05-18 2018-10-09 天津师范大学 Zr alloy surface zirconium oxide/chromium nitride composite membrane and the preparation method and application thereof
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