CN109207936A - Zr alloy surface nitridation and ion plating composite coating and preparation method thereof - Google Patents
Zr alloy surface nitridation and ion plating composite coating and preparation method thereof Download PDFInfo
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- CN109207936A CN109207936A CN201810202163.6A CN201810202163A CN109207936A CN 109207936 A CN109207936 A CN 109207936A CN 201810202163 A CN201810202163 A CN 201810202163A CN 109207936 A CN109207936 A CN 109207936A
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/06—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
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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
- 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
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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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
- 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
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
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Abstract
The invention discloses Zr alloy surface nitridation and ion plating composite coating technology of preparing, preparing Zr alloy surface nitridation and the method for ion plating composite coating includes: that zirconium base material is carried out surface preparation by (1)；(2) zirconium base material obtained by step (1) is subjected to tufftride processing；(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；(4) TiAlSiN work coating is formed on the surface of the Cr tie coat, to obtain the composite coating.This method is remarkably improved the high-temperature oxidation resistance and film-substrate cohesion of zircaloy by carrying out tufftride processing in Zr alloy surface and forming the composite coating of Cr tie coat and TiAlSiN work coating.
Description
Technical field
The present invention relates to materials science fields, specifically, the present invention relates to Zr alloy surface nitridation is compound with ion plating
Coating and preparation method thereof.
Background technique
Zircaloy is widely used in nuclear reactor material because having good comprehensive performance.In all core structures
In material, the operating condition of cladding nuclear fuels pipe is the harshest, and cladding nuclear fuels pipe is in nuclear reactor nuclear energy fission reaction, core
It can be converted into the release position of thermal energy, while it is the first road barrier for preventing reactor radioactive fission product from escaping outward, needed
It is subjected to high temperature, oxidation, burn into wash away, the test of radiation environment.The hydrogen and fuel generated under corrosion reaction and radiation effects
Hydrogen present in element material involucrum may cause cladding nuclear fuels pipe and inhale hydrogen embrittlement, seriously affect the safety of pile core.Normal work
Cladding nuclear fuels pipe surface hot spot design temperature is more than 600 DEG C under the conditions of condition, the cladding nuclear fuels pipe surface temperature under loss of-coolant accident (LOCA)
Degree will be further increased to 1000~1200 DEG C, and a large amount of thermal acceleration fuel element can be released when it is reacted with vapor
Failure.
However, existing Zirconium alloy material can not still be competent at harsh working condition requirement.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies, extend making for zircaloy
Use the service life.For this purpose, an object of the present invention is to provide the methods of Zr alloy surface nitridation and ion plating composite coating.The party
Method is worked the composite coating of coating by carrying out tufftride processing in Zr alloy surface and forming Cr tie coat and TiAlSiN,
It is remarkably improved the high-temperature oxidation resistance and film-substrate cohesion of zircaloy.
In the first aspect of the present invention, Zr alloy surface nitridation and ion plating composite coating are prepared the invention proposes a kind of
Method characterized by comprising (1) by zirconium base material carry out surface preparation；(2) zirconium base material obtained by step (1) is carried out soft
Nitrogen treatment；(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；(4) on the surface of the Cr tie coat
TiAlSiN work coating is formed, to obtain the Zr alloy surface nitridation and ion plating composite coating.
The method of Zr alloy surface nitridation and ion plating composite coating according to an embodiment of the present invention, by by surface
Pretreated zirconium base material carries out tufftride processing, and the hardness of substrate surface can be improved, and reduces the difference of hardness between substrate and coating
Value improves film-substrate cohesion to reduce the presence of residual stress；And then zirconium substrate surface sequentially form Cr tie coat and
TiAlSiN work coating, directly forms the technique of work coating in substrate surface compared with the existing technology, the present invention is by passing through
The Cr tie coat that high rigidity is set between nitrogen treatment and zirconium base material and TiAlSiN work coating is crossed, material can be made to be formed
By zirconium base material to Cr tie coat, TiAlSiN work coating hardness gradually increases and the hardness distribution trend of change of gradient, thus
Improve the film-substrate cohesion and high-temperature oxidation resistance of TiAlSiN work coating.It will be used to prepare as a result, using the method for the present invention
The cladding nuclear fuels pipe surface of nuclear reactor is remarkably improved the intensity and oxidation resistance of cladding tubes, reduces reactor dehydration
The high-temperature oxydation rate of zirconium alloy cladding pipe, improves the safety allowance of reactor under accident.
In addition, the Zr alloy surface according to the above embodiment of the present invention for preparing is nitrogenized with the method for ion plating composite coating also
It can have following additional technical characteristic:
In some embodiments of the invention, in step (1), the zirconium base material is Zr4 alloy.
In some embodiments of the invention, in step (1), the surface preparation includes: sand paper polishing, polishing, surpasses
Sound wave cleaning.
In some embodiments of the invention, in step (2), the condition of the tufftride processing includes: treatment temperature 520
~600 DEG C, the processing time is 30~3600min, and ammonia flow is 100~8000L/min, and methanol dripping quantity is 0.5~13mL/
Min, cooling medium are aqueous rust preventive.
In some embodiments of the invention, in step (3), by multi-arc ion plating process on the surface of the zirconium base material
Cr tie coat is formed, the technological parameter of the multi-arc ion plating process includes: that bias is -200~0V, and electric current is 30~95A,
Air pressure is 1~2Pa, and temperature is room temperature to 400 DEG C.
In some embodiments of the invention, in step (4), by multi-arc ion plating process in the Cr tie coat
Surface forms TiAlSiN work coating, and the technological parameter of the multi-arc ion plating process includes: that bias is -300~0V, electric current
For 10~90A, air pressure is 1~3Pa, and temperature is room temperature to 300 DEG C.
In some embodiments of the invention, the Cr tie coat with a thickness of 5~6 μm.
In some embodiments of the invention, 5~6 μm of thickness of the TiAlSiN work coating.
In the second aspect of the present invention, the invention proposes a kind of nitridations of Zr alloy surface and ion plating composite coating.Root
According to the embodiment of the present invention, which is to prepare Zr alloy surface nitridation and ion plating composite coating by above-described embodiment
Method be prepared.
Zr alloy surface nitridation according to an embodiment of the present invention and ion plating composite coating, zirconium substrate surface is through tufftride
Processing has higher hardness, and the hardness difference between substrate and coating is small, thus can reduce the presence of residual stress, improves
Film-substrate cohesion.Zirconium substrate surface is sequentially formed with Cr tie coat and TiAlSiN work coating, compared with the existing technology directly
The technique of work coating is formed in substrate surface, the present invention by nitrogen treatment and the work of zirconium base material and TiAlSiN by applying
The Cr tie coat of high rigidity is set between layer, material can be made to be formed and applied by zirconium base material to Cr tie coat, TiAlSiN work
Layer hardness gradually increases and the hardness distribution trend of change of gradient, so that TiAlSiN work coating be made to have higher film base junction
Resultant force and high-temperature oxidation resistance.Zr alloy surface nitridation of the invention is used with ion plating preparation method of composite coating as a result,
In the cladding nuclear fuels pipe surface for preparing nuclear reactor, it is remarkably improved the intensity and oxidation resistance of cladding tubes, reduces reaction
The high-temperature oxydation rate of zirconium alloy cladding pipe, improves the safety allowance of reactor under heap loss of-coolant accident (LOCA).
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method stream according to an embodiment of the invention for preparing Zr alloy surface nitridation and ion plating composite coating
Journey schematic diagram；
Fig. 2 is Zr alloy surface nitridation ion plating composite coating preparation process flow according to an embodiment of the invention
Figure；
Fig. 3 is substrate according to an embodiment of the invention/nitridation/chromium/TiAlSiN composite coating scratch test friction
Power acoustical signal figure；
Fig. 4 is that substrate/TiAlSiN coating scratch test frictional force acoustical signal is prepared in a kind of technique in the prior art
Figure；
Fig. 5 is another substrate/TiAlSiN coating scratch test frictional force acoustical signal figure in the prior art；
Fig. 6 is substrate/nitridation/TiAlSiN coating scratch test friction that a kind of technique is prepared in the prior art
Power acoustical signal figure；
Fig. 7 is that substrate/nitridation/TiAlSiN coating scratch test that another technique is prepared in the prior art is rubbed
Wipe power acoustical signal figure；
Fig. 8 is substrate according to an embodiment of the invention/nitridation/chromium/TiAlSiN composite coating oxidation weight gain experiment
Oxidizing dynamics curve；
Fig. 9 is that substrate/nitridation/chromium/TiAlSiN composite coating oxidation weight gain of further embodiment according to the present invention is real
Test oxidizing dynamics curve.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In the first aspect of the present invention, Zr alloy surface nitridation and ion plating composite coating are prepared the invention proposes a kind of
Method characterized by comprising (1) by zirconium base material carry out surface preparation；(2) zirconium base material obtained by step (1) is carried out soft
Nitrogen treatment；(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；(4) it is formed on the surface of Cr tie coat
TiAlSiN work coating, to obtain composite coating in Zr alloy surface.
It should be noted that, in this document, " Zr alloy surface nitridation and ion plating composite coating " is also referred to as " substrate/nitrogen
Change/chromium/TiAlSiN composite coating ".
The method according to an embodiment of the present invention for preparing composite coating is described in detail below with reference to Fig. 1.According to this
The embodiment of invention, this method comprises:
S100: surface preparation
In the step, zirconium base material is subjected to surface preparation.
According to an embodiment of the invention, zirconium base material can be Zr4 alloy.
According to an embodiment of the invention, may include: sand paper polishing, polishing, ultrasonic wave to the surface preparation of zirconium base material
Cleaning.
S200: tufftride processing
In the step, zirconium base material obtained by S100 is subjected to tufftride processing.According to an embodiment of the invention, passing through tufftride
Processing carries out nitriding to zirconium base material, and the hardness of substrate surface can be improved, so that the hardness difference between substrate and coating is reduced,
Reduce different materials between residual stress presence, improve film-substrate cohesion, while can also improve zirconium base material corrosion resistance and
Wear-resisting property.
According to an embodiment of the invention, the condition that the condition of above-mentioned tufftride processing includes: the tufftride processing includes:
Treatment temperature is 520~600 DEG C, and the processing time is 30~3600min, and ammonia flow is 100~8000L/min, and methanol is added dropwise
Amount is 0.5~13mL/min, and cooling medium is aqueous rust preventive.In some embodiments of the invention, the temperature of tufftride processing is
590 ± 10 DEG C, the processing time is 360min, and ammonia flow is 1500~2000L/min, and methanol dripping quantity is 7~8mL/min.
Thus, it is possible to further be conducive to improve intensity, corrosion resistance and the wear-resisting property of zirconium substrate surface.
S300: Cr tie coat is formed
In the step, the surface of the zirconium base material obtained by S200 forms Cr tie coat.According to an embodiment of the invention, passing through
Hardness is formed therebetween between the zirconium base material by tufftride processing and the TiAlSiN work coating being subsequently formed
Cr tie coat can make zirconium base material to Cr tie coat, TiAlSiN work coating formation hardness gradually increases and change of gradient
Hardness distribution trend, by be arranged Cr tie coat, can make TiAlSiN work coating have higher film-substrate cohesion and
High-temperature oxidation resistance, to improve the performance of Zr alloy surface nitridation and ion plating composite coating.
According to an embodiment of the invention, Cr tie coat can be formed in the surface of zirconium base material by multi-arc ion plating process.It is more
The technological parameter of arc ion plating includes: that bias is -200~0V, and electric current is 30~95A, and air pressure is 1~2Pa, and temperature is room
Temperature is to 400 DEG C.In some embodiments of the invention, the bias in technological parameter be -200V, electric current 65A, air pressure 1Pa,
Temperature is 380 DEG C.Thus, it is possible to further advantageously form the suitable Cr tie coat of intensity.
According to an embodiment of the invention, the thickness of above-mentioned Cr tie coat can be 5~6 μm.
S400: TiAlSiN work coating is formed
In the step, TiAlSiN work coating is formed on the surface of Cr tie coat, to obtain composite coating.According to
The embodiment of the present invention, by the surface of Cr tie coat be further formed TiAlSiN work coating, can make zirconium base material with
TiAlSiN work coating before there is more preferably hardness gradient distribution trend, thus improve work coating film-substrate cohesion and
High-temperature oxidation resistance.
According to an embodiment of the invention, TiAlSiN work coating can be formed in Cr tie coat by multi-arc ion plating process
Surface.The technological parameter of multi-arc ion plating process include: bias be -300~0V, electric current be 10~90A, air pressure be 1~
3Pa, temperature are room temperature to 300 DEG C.In some embodiments of the invention, the bias in technological parameter is -100V, and electric current is
60A, air pressure 2.2Pa, temperature are 300 DEG C.Thus, it is possible to further advantageously form high-intensitive TiAlSiN work coating.
According to an embodiment of the invention, inventor has found in an experiment, the thickness of TiAlSiN work coating is no more than 12
μm, if TiAlSiN work coating layer thickness is excessive, the binding force that may result in the coating and Cr tie coat declines, and influences
Properties of product.Preferred embodiment in accordance with the present invention, the thickness of above-mentioned TiAlSiN work coating can be 5~6 μm.As a result, may be used
Make that there is suitable binding force between TiAlSiN work coating and Cr tie coat, and guarantees that TiAlSiN work coating has foot
Enough intensity and high-temperature oxidation resistance.
According to a particular embodiment of the invention, after TiAlSiN work coating is formed, rapid evaluation can be carried out to sample,
Whether consistent observe entire coating surface color, weighing, measurement test size, failed test sample return to form Cr transition zone work
Sequence.Qualified sample further progress chemical constituents determination, phase structure analysis, coating morphology, thickness, microstructure observation's test
Analysis, bond strength test, surface hardness test and high-temperature oxidation test, failed test sample return to form Cr tie coat work
Sequence.
The method of Zr alloy surface nitridation and ion plating composite coating according to embodiments of the present invention as a result, by passing through
The zirconium base material of surface preparation carries out tufftride processing, and the hardness of substrate surface can be improved, and reduces hard between substrate and coating
Difference is spent, to reduce the presence of residual stress, improves film-substrate cohesion；And then Cr transition is sequentially formed in zirconium substrate surface and is applied
Layer and TiAlSiN work coating, directly form the technique of work coating in substrate surface compared with the existing technology, the present invention passes through
In the Cr tie coat by high rigidity is arranged between nitrogen treatment and zirconium base material and TiAlSiN work coating, material can be made
It is formed and is gradually increased and the hardness distribution trend of change of gradient by zirconium base material to Cr tie coat, TiAlSiN work coating hardness,
To improve the film-substrate cohesion and high-temperature oxidation resistance of TiAlSiN work coating.Zircaloy of the invention will be used as a result,
The surfaces nitrided cladding nuclear fuels pipe surface that nuclear reactor is used to prepare with ion plating composite coating technology of preparing, is remarkably improved
The intensity and oxidation resistance of cladding tubes reduce the high-temperature oxydation rate of zirconium alloy cladding pipe under reactor loss of-coolant accident (LOCA), improve
The safety allowance of reactor.
In the second aspect of the present invention, the invention proposes a kind of nitridations of Zr alloy surface and ion plating composite coating.Root
According to the embodiment of the present invention, Zr alloy surface nitridation and ion plating composite coating are to prepare zircaloy table by above-described embodiment
What the method for face nitridation and ion plating composite coating was prepared.
Zr alloy surface nitridation according to an embodiment of the present invention and ion plating composite coating, zirconium substrate surface is through tufftride
Processing has higher hardness, and the hardness difference between substrate and coating is small, thus can reduce the presence of residual stress, improves
Film-substrate cohesion.Zirconium substrate surface is sequentially formed with Cr tie coat and TiAlSiN work coating, compared with the existing technology directly
The technique of work coating is formed in substrate surface, the present invention by nitrogen treatment and the work of zirconium base material and TiAlSiN by applying
The Cr tie coat of high rigidity is set between layer, material can be made to be formed and applied by zirconium base material to Cr tie coat, TiAlSiN work
Layer hardness gradually increases and the hardness distribution trend of change of gradient, so that TiAlSiN work coating be made to have higher film base junction
Resultant force and high-temperature oxidation resistance.Zr alloy surface nitridation of the invention is used to prepare core with ion plating composite coating as a result,
The cladding nuclear fuels pipe of reactor is remarkably improved the intensity and oxidation resistance of cladding tubes, reduces under reactor loss of-coolant accident (LOCA)
The high-temperature oxydation rate of zirconium alloy cladding pipe, improves the safety allowance of reactor.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
With reference to Fig. 2, surfaces nitrided and ion plating composite coating is carried out to zircaloy according to the following steps:
(1) zirconium base material is subjected to surface preparation；
(2) zirconium base material obtained by step (1) is subjected to tufftride processing；
Soft-nitriding process parameter: 590 ± 10 DEG C of nitriding temperature, nitridation time 360min, 1500~2000L/ of ammonia flow
Min, methanol dripping quantity 7-8mL/min, cooling medium is aqueous rust preventive；
(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；
Cr tie coat coating process parameter are as follows: bias -200V, electric current 65A, air pressure 1.2Pa, 380 DEG C of temperature；
(4) TiAlSiN work coating is formed on the surface of Cr tie coat；
TiAlSiN work coating coating process parameter: bias -100V, electric current 60A, air pressure 2.2Pa, 300 DEG C of temperature.
Embodiment 2
With reference to Fig. 2, surfaces nitrided and ion plating composite coating is carried out to zircaloy according to the following steps:
(1) zirconium base material is subjected to surface preparation；
(2) zirconium base material obtained by step (1) is subjected to tufftride processing；
Soft-nitriding process parameter: 590 ± 10 DEG C of nitriding temperature, nitridation time 360min, 1500~2000L/ of ammonia flow
Min, methanol dripping quantity 7-8mL/min, cooling medium is aqueous rust preventive；
(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；
Cr tie coat coating process parameter are as follows: bias -200v, electric current 65A, air pressure 1.2Pa, 400 DEG C of temperature；
(4) TiAlSiN work coating is formed on the surface of Cr tie coat；
TiAlSiN works coating coating process parameter: bias -100v, electric 60A, air pressure 2.2Pa, and 260 DEG C of temperature.
Embodiment 3
Investigate Zr alloy surface nitridation and the ion plating composite coating (substrate/nitridation/compound painting of chromium/TiAlSiN of the application
Layer) and existing substrate/TiAlSiN coating, substrate/nitridation/TiAlSiN coating film-substrate cohesion performance, instrument is using WS-
The automatic scratching instrument of 2005 coating adhesion.The result shows that:
(1) as shown in figure 3, the Zr alloy surface nitridation of the application is believed with ion plating composite coating scratch test frictional force sound
Number figure, acoustical signal occur first crest location frictional force be coating binding force, be 38N；
(2) as shown in Figures 4 and 5, substrate made from different technology conditions/TiAlSiN coating, coating film-substrate cohesion are 23
~32N；
(3) as shown in figs. 6-7, substrate/nitridation/TiAlSiN coating made from different technology conditions, coated film base junction are closed
Power is 29~32N；
It is obtained by comparing, relative to existing other techniques, the application substrate/nitridation/chromium/TiAlSiN technique is made
Composite coating film-substrate cohesion is higher.
Embodiment 4
Investigate the high-temperature oxidation resistance of the Zr alloy surface nitridation and ion plating composite coating of the application, 800 DEG C of oxidations
Weight gain experiment carries out in chamber type electric resistance furnace, weighs in precision electronic balance after oxidation.As can be seen that nitrogen from Fig. 8 and Fig. 9
Change/chromium/TiAlSiN composite coating high-temperature oxidation resistance is best, and oxidation test initial phase oxidation rate is low, oxidation weight gain mistake
Cheng Pingwen, increase weight 7g/cm after oxidation 120 minutes2。
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. a kind of method for preparing Zr alloy surface nitridation and ion plating composite coating characterized by comprising
(1) zirconium base material is subjected to surface preparation；
(2) zirconium base material obtained by step (1) is subjected to tufftride processing；
(3) surface of the zirconium base material obtained by step (2) forms Cr tie coat；
(4) TiAlSiN is formed on the surface of the Cr tie coat to work coating, so as to obtain Zr alloy surface nitridation with
Ion plating composite coating.
2. the method according to claim 1, wherein the zirconium base material is Zr4 alloy in step (1).
3. the method according to claim 1, wherein the surface preparation includes: that sand paper is beaten in step (1)
Mill, polishing, ultrasonic cleaning.
4. the method according to claim 1, wherein in step (2), the condition of the tufftride processing includes:
Treatment temperature is 520~600 DEG C, and the processing time is 30~3600min, and ammonia flow is 100~8000L/min, and methanol is added dropwise
Amount is 0.5~13mL/min, and cooling medium is aqueous rust preventive.
5. the method according to claim 1, wherein in step (3), by multi-arc ion plating process in the zirconium
The surface of substrate forms Cr tie coat, and the technological parameter of the multi-arc ion plating process includes: that bias is -200~0V, electric current
For 30~95A, air pressure is 1~2Pa, and temperature is room temperature to 400 DEG C.
6. the method according to claim 1, wherein in step (4), by multi-arc ion plating process in the Cr
The surface of tie coat forms TiAlSiN work coating, and the technological parameter of the multi-arc ion plating process includes: that bias is -300
~0V, electric current are 10~90A, and air pressure is 1~3Pa, and temperature is room temperature to 300 DEG C.
7. the method according to claim 1, wherein the Cr tie coat with a thickness of 5~6 μm.
8. the method according to claim 1, wherein the TiAlSiN works coating with a thickness of 5~6 μm.
9. a kind of Zr alloy surface nitridation and ion plating composite coating, which is characterized in that the Zr alloy surface nitridation and ion
Plating composite coating is prepared by method according to any one of claims 1 to 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293374A (en) * | 2021-05-07 | 2021-08-24 | 上海核工程研究设计院有限公司 | Coating for outer surface of zirconium alloy cladding tube and manufacturing method |
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| US5227129A (en) * | 1990-04-26 | 1993-07-13 | Combustion Engineering, Inc. | Method for applying corrosion resistant metallic coating of zirconium nitride |
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| KR20160005819A (en) * | 2014-07-07 | 2016-01-18 | 한국원자력연구원 | Method for manufacturing of Zirconium alloy cladding tubes and the Zirconium alloy cladding tubes thereby |
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| US5227129A (en) * | 1990-04-26 | 1993-07-13 | Combustion Engineering, Inc. | Method for applying corrosion resistant metallic coating of zirconium nitride |
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| KR20160005819A (en) * | 2014-07-07 | 2016-01-18 | 한국원자력연구원 | Method for manufacturing of Zirconium alloy cladding tubes and the Zirconium alloy cladding tubes thereby |
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| CN113293374A (en) * | 2021-05-07 | 2021-08-24 | 上海核工程研究设计院有限公司 | Coating for outer surface of zirconium alloy cladding tube and manufacturing method |
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