CN106835067A - A kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating - Google Patents

A kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating Download PDF

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CN106835067A
CN106835067A CN201710026560.8A CN201710026560A CN106835067A CN 106835067 A CN106835067 A CN 106835067A CN 201710026560 A CN201710026560 A CN 201710026560A CN 106835067 A CN106835067 A CN 106835067A
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graphene
passed
reaction chamber
zircaloy
atomic layer
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CN106835067B (en
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章海霞
侯莹
郭俊杰
魏丽乔
王永祯
李中奎
周军
石明华
马琼
黄增鑫
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Taiyuan University of Technology
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/517—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515

Abstract

A kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating is in Zr alloy surface growth in situ Graphene protective layer using MPCVD method; then zircaloy/Graphene sample is placed in the reaction chamber of atomic layer deposition apparatus, the deposition of carborundum is carried out.Because atomic layer passivation particle carborundum is especially sensitive to dangling bond; in the defective locations of Graphene, hole, grain boundaries in Graphene form scattered cluster to meeting preferential deposition, rather than continuous film; the defect of Graphene is passivated, so as to realize completely protection of the Graphene to zircaloy.The simple low cost of this method, the film protective value of acquisition is excellent, has potential application value in the corrosion-resistant field of nuclear-used zirconium alloy.

Description

A kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating
Technical field
The present invention relates to a kind of processing method of Zr alloy surface corrosion-inhibiting coating, specifically using microwave plasma Vapour deposition process is learned in Zr alloy surface growth in situ Graphene protective layer, zircaloy/Graphene sample is then put into atom The reaction chamber of layer depositing device, carries out a kind of side of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating of depositing SiC Method.
Background technology
Nuclear advance, security reliability and economy and cladding materials performance are closely related.Existing zircaloy Corrosion is still faced with acid test in nuclear reactor, can not be ignored, therefore the decay resistance gesture of raising zircaloy exists Must go.Because the corrosion of zircaloy is produced since surface, it is to effectively improve to carry out surface modification treatment to zircaloy The important method of its decay resistance.The modified method of Zr alloy surface has various, such as pre- filming of anodic oxidation, autoclave, The technologies such as plasma electrolytic oxidation, arc evaporation, spraying, sol-gel deposition, the oxidation of air high frequency, ion implanting.But, The diaphragm prepared by current process for treating surface has certain thickness, changes the size of zircaloy, and thickness Diaphragm can reduce the thermal conductivity of zircaloy.Therefore, overcoming the important channel of these problems, to develop a kind of thermal conductivity good Ultra-thin protective layer makes the size of zircaloy and performance change reach minimum.
Graphene is a kind of two-dimentional monoatomic layer carbon material, due to many special performances, being caused in academia Unprecedented research boom.Recent research personnel have found that Graphene can protect metal material as the super thin protective coatings of metal It is not corroded.This provides new approaches for the research of Reactor fuel element cladding Zr alloy surface protective layer.Therefore, the present invention is proposed With Graphene as Zr alloy surface protective layer, while zircaloy thermal conductivity and unaffected shape, size is ensured, will Zircaloy and cooling medium are effectively isolated, and improve the decay resistance of zircaloy.However, Graphene to the degree of protection of metal and Its crystal structure, the number of plies, defect are closely related.High-quality, flawless single crystal graphene can make its protectiveness to metal Can maximize.But, by existing method it is difficult to obtain the single crystal graphene film of large area, zero-fault, received inside Graphene The presence of the defects such as metre hole, crystal boundary seriously limits its improvement to Corrosion Resistance of Zirconium Alloys.Therefore, how to Graphene Defect is passivated treatment, realizes that Zr alloy surface is completely isolated with cooling water, as a problem demanding prompt solution.
The content of the invention
Poor in order to solve the water-fast side corrosive nature of zirconium alloy cladding, the short problem of fuel can service life, the present invention is carried For a kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating.
The present invention the taken technical scheme that solves the above problems is as follows.
A kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating, methods described is to follow these steps to carry out 's：
（1）Zircaloy is first cleaned in acetone, after being soaked in nitric acid and hydrofluoric acid mixed solution, then the ultrasound in absolute ethyl alcohol Vibration 2 times, each 30min removes surface impurity and greasy dirt, then dries in a nitrogen environment；
（2）Zircaloy is placed in the reaction chamber of microwave plasma CVD equipment, by cavity be evacuated to 1Pa with Under, be passed through the hydrogen of 50sccm~200sccm, regulation microwave power to 1000W~6000W, cavity air pressure be maintained at 2kPa~ 9kPa, by hydrogen plasma bombardment zircaloy 10min~180min, substrate is heated and the impurity on surface is further removed；
（3）It is passed through methane and adjusts gas ratio and start to grow graphene film, sedimentation time is 10~120s, and depositing temperature is 300~600 DEG C, gas flow methane/hydrogen is 1/60,1/80,1/100,1/200 or 1/300, cavity air pressure is 2.7~ 7.4kPa, microwave power is 1300~6000 W；
（4）After the completion of deposition, methane gas and microwave power supply are closed, continuing to be passed through hydrogen makes cavity be cooled down with 2~3 DEG C/s speed To less than 100 DEG C, sample is taken out；
（5）The sample of acquisition is placed in the reaction chamber of atomic layer deposition apparatus, the deposition of carborundum passivation particle is carried out, by metal The defect of surface Graphene is passivated treatment；
The deposition of the carborundum passivation particle follow these steps to carry out：
To being passed through argon gas or nitrogen in atomic layer deposition apparatus reaction chamber；
To carbonaceous material is passed through in atomic layer deposition apparatus reaction chamber, makes it that carbon geochemistry occur with sample surfaces and adsorb；
To being passed through silicon-containing material in atomic layer deposition apparatus reaction chamber, the carbon atom of the silicon atom in silicon-containing material and sample surfaces Carbon silicon bonds are formed, after question response is complete, sample surfaces Graphene fault location is to form silicon-carbide particle.
Based on above-mentioned technical proposal, further technical characteristic is as follows.
It is described that zircaloy is placed in the reaction chamber of microwave plasma CVD equipment, cavity is evacuated to During below 1Pa, the hydrogen of 100sccm is further passed through, to 1300W, cavity air pressure is maintained at 2.6kPa to regulation microwave power, by Hydrogen plasma bombards zircaloy 30min, and substrate is heated and the impurity on surface is further removed.
It is described be passed through methane and adjust gas ratio start grow graphene film, further sedimentation time is 120s, Depositing temperature is 550 DEG C, and gas flow methane/hydrogen is 1/60, and cavity air pressure is 4.0kPa, and microwave power is 1300W.
It is carbon tetrachloride that carbonaceous material is passed through in the reaction chamber to atomic layer deposition apparatus, and the flow velocity of carbon tetrachloride is 10sccm~400sccm, inlet period is 0.5s~1s.
It is silane that silicon-containing material is passed through in the reaction chamber to atomic layer deposition apparatus, the flow velocity of silane be 10sccm~ 100sccm, the inlet period of silane is 0.5s~1s.
The method of above-mentioned the provided a kind of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating of the present invention, with existing skill Art is compared, and this method uses MPCVD method in Zr alloy surface direct growth Graphene, by graphite The growth temperature of alkene drops to 300~600 DEG C, so as to not interfere with the microscopic structure of zircaloy；Existed using technique for atomic layer deposition Graphenic surface depositing silicon silicon, atomic layer passivation particle is especially sensitive to dangling bond, defective bit of the meeting preferential deposition in Graphene Put, the hole, grain boundaries in Graphene form scattered cluster, rather than continuous film, the defect of Graphene is carried out blunt Change, so as to realize completely protection of the Graphene to zircaloy.
Brief description of the drawings
Fig. 1 is the schematic diagram that zircaloy sample corrodes in cooling medium.In figure：1 is zircaloy, and 2 is zirconium oxide, and 3 are Hydrone in cooling medium, 4 is zirconium atom.
Fig. 2 is the schematic diagram that zircaloy/Graphene sample corrodes in cooling medium.In figure：1 is zircaloy, and 2 is oxidation Zirconium, 3 is Graphene, and 4 is the hydrone in cooling medium.
Fig. 3 is the schematic diagram that zircaloy/Graphene corrodes in cooling medium after Graphene defect passivation is processed.In figure：1 It is zircaloy, 2 is passivation particle, and 3 is Graphene, and 4 is the hydrone in cooling medium.
Specific embodiment
Specific embodiment of the invention is further illustrated below.
Implement a kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating, the method is to follow these steps to carry out 's：
Step one, by zircaloy be placed in acetone clean, soaked in nitric acid and hydrofluoric acid mixed solution, after again in anhydrous second Sonic oscillation 2 times in alcohol, each 30min, it is therefore an objective to remove impurity and greasy dirt of Zr alloy surface etc., then in a nitrogen environment Dried.
Step 2, zircaloy is placed in the reaction chamber of microwave plasma CVD equipment, and cavity is taken out Vacuum is to below 1Pa, then is passed through the hydrogen of 50sccm~200sccm, and adjusts microwave power for 1000W~6000W, after by chamber When body air pressure is maintained at 2kPa~9kPa, by hydrogen plasma bombardment zircaloy 10min~180min, then substrate is heated simultaneously Further remove the impurity on surface.
Step 3, be passed through methane and adjust gas ratio start grow graphene film, sedimentation time is 10~120s, sink Accumulated temperature degree is 300~600 DEG C, and gas flow methane/hydrogen is 1/60,1/80,1/100,1/200 or 1/300, cavity air pressure It is 2.7~7.4kPa, microwave power is 1300~6000 W.
After the completion of step 4, deposition, methane gas and microwave power supply are closed, continuing to be passed through hydrogen makes cavity with 2~3 DEG C/s Speed is cooled to less than 100 DEG C, takes out sample.
Step 5, the reaction chamber that the sample of acquisition is placed in atomic layer deposition apparatus, carry out the heavy of carborundum passivation particle Product, treatment is passivated by the defect of metal surface Graphene；Wherein, the deposition of carborundum passivation particle be follow these steps into Capable：
First it is to be passed through argon gas or nitrogen in the reaction chamber to atomic layer deposition apparatus；
Next to that to carbonaceous material is passed through in the reaction chamber of atomic layer deposition apparatus, making it that carbon geochemistry occur with sample surfaces and inhaling It is attached；
It is finally to be passed through silicon-containing material in the reaction chamber to atomic layer deposition apparatus, silicon atom and sample surfaces in silicon-containing material Carbon atom formed carbon silicon bonds, after question response is complete, sample surfaces Graphene fault location is to form silicon-carbide particle.
Based on above-mentioned specific embodiment, the second specific embodiment is that zircaloy is placed in into microwave plasma chemical gas In the reaction chamber of phase depositing device, cavity is evacuated to below 1Pa, selection is passed through the hydrogen of 100sccm, adjusts microwave power To 1300W, cavity air pressure is maintained at 2.6kPa, and zircaloy 30min is bombarded by hydrogen plasma, and substrate is heated and surface is removed Metal oxide and impurity.
Based on above-mentioned specific embodiment, the 3rd specific embodiment is to be passed through methane and adjust gas ratio to start growth Graphene film, selection sedimentation time is 120s, and depositing temperature is 550 DEG C, and gas flow methane/hydrogen is 1/60, cavity gas Pressure is 4.0kPa, and microwave power is 1300W.
Based on above-mentioned specific embodiment, the 4th specific embodiment is contained to being passed through in atomic layer deposition apparatus reaction chamber Carbonizable substance is carbon tetrachloride, and the flow velocity of carbon tetrachloride is 10sccm~400sccm, and inlet period is 0.5s~1s.
Based on above-mentioned specific embodiment, the 5th specific embodiment is contained to being passed through in atomic layer deposition apparatus reaction chamber Silicon matter is silane, and the flow velocity of silane is 10sccm~100sccm, and the inlet period of silane is 0.5s~1s.
Specific embodiment of the invention is further illustrated below by embodiment.
Embodiment 1
By MPCVD method in Zr alloy surface direct growth Graphene, concretely comprise the following steps：By zirconium Alloy is cleaned in acetone, and after immersion in nitric acid and hydrofluoric acid mixed solution, then sonic oscillation 2 times in absolute ethyl alcohol, often Secondary 30min, removes the impurity and greasy dirt on surface, then dries in a nitrogen environment；Then the zircaloy after cleaning is put into micro- In the reaction chamber of ripple apparatus for plasma chemical vapor deposition, cavity is evacuated to below 1Pa, is passed through the hydrogen of 100sccm, To 1300W, cavity air pressure is maintained at 2.6kPa to regulation microwave power, zircaloy 30min is bombarded with hydrogen plasma, so as to by base Piece is heated to suitable temperature and further removes the impurity on surface；After zircaloy is pre-processed, be passed through methane and adjust methane/ Hydrogen is 1/60, and cavity air pressure is 3.0kPa, and microwave power is 1300W, and 120s is reacted at 500 DEG C, grows graphene film； After the completion of deposition, methane gas and microwave power supply are closed, continuing to be passed through hydrogen makes cavity be cooled to 100 DEG C with 2~3 DEG C/s speed Hereinafter, sample is taken out；
The sample that above-mentioned MPCVD method is obtained is put into the reaction chamber of atomic layer deposition apparatus, is carried out The deposition of carborundum passivation particle, treatment is passivated by the defect of Zr alloy surface Graphene.The system of carborundum passivation particle It is standby to comprise the following steps：To being passed through argon gas in atomic layer deposition apparatus reaction chamber；To being passed through in atomic layer deposition apparatus reaction chamber 100sccm carbon tetrachloride, inlet period is 0.5s~1s, makes carbonaceous material that carbon geochemistry occur with sample surfaces and adsorbs；To atom 10sccm silane is passed through in layer depositing device reaction chamber, inlet period is 0.5s~1s.Silicon atom and sample surfaces in silane Carbon atom formed carbon silicon bonds, after question response is complete, sample surfaces Graphene fault location is to form silicon-carbide particle.

Claims (5)

1. a kind of method of Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating, methods described follow these steps to carry out：
（1）Zircaloy is first cleaned in acetone, after being soaked in nitric acid and hydrofluoric acid mixed solution, then the ultrasound in absolute ethyl alcohol Vibration 2 times, each 30min removes surface impurity and greasy dirt, then dries in a nitrogen environment；
（2）Zircaloy is placed in the reaction chamber of microwave plasma CVD equipment, by cavity be evacuated to 1Pa with Under, be passed through the hydrogen of 50sccm~200sccm, regulation microwave power to 1000W~6000W, cavity air pressure be maintained at 2kPa~ 9kPa, by hydrogen plasma bombardment zircaloy 10min~180min, substrate is heated and the impurity on surface is further removed；
（3）It is passed through methane and adjusts gas ratio and start to grow graphene film, sedimentation time is 10~120s, and depositing temperature is 300~600 DEG C, gas flow methane/hydrogen is 1/60,1/80,1/100,1/200 or 1/300, cavity air pressure is 2.7~ 7.4kPa, microwave power is 1300~6000W；
（4）After the completion of deposition, methane gas and microwave power supply are closed, continuing to be passed through hydrogen makes cavity be cooled down with 2~3 DEG C/s speed To less than 100 DEG C, sample is taken out；
（5）The sample of acquisition is placed in the reaction chamber of atomic layer deposition apparatus, the deposition of carborundum passivation particle is carried out, by metal The defect of surface Graphene is passivated treatment；
The deposition of the carborundum passivation particle follow these steps to carry out：
To being passed through argon gas or nitrogen in atomic layer deposition apparatus reaction chamber；
To carbonaceous material is passed through in atomic layer deposition apparatus reaction chamber, makes it that carbon geochemistry occur with sample surfaces and adsorb；
To being passed through silicon-containing material in atomic layer deposition apparatus reaction chamber, the carbon atom of the silicon atom in silicon-containing material and sample surfaces Carbon silicon bonds are formed, after question response is complete, sample surfaces Graphene fault location is to form silicon-carbide particle.
2. the method for Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating according to claim 1, described by zircaloy It is placed in the reaction chamber of microwave plasma CVD equipment, when cavity is evacuated into below 1Pa, is further passed through The hydrogen of 100sccm, to 1300W, cavity air pressure is maintained at 2.6kPa, zircaloy is bombarded by hydrogen plasma regulation microwave power 30min, substrate is heated and the impurity on surface is removed.
3. the method for Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating according to claim 1, described to be passed through methane And adjust gas ratio start grow graphene film, further sedimentation time is 120s, and depositing temperature is 550 DEG C, gas Flow methane/hydrogen is 1/60, and cavity air pressure is 4.0kPa, and microwave power is 1300W.
4. the method for Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating according to claim 1, described to atomic layer It is carbon tetrachloride that carbonaceous material is passed through in depositing device reaction chamber, and the flow velocity of carbon tetrachloride is 10sccm~400sccm, during air inlet Between be 0.5s~1s.
5. the method for Zr alloy surface Graphene Passivation Treatment corrosion-inhibiting coating according to claim 1, described to atomic layer It is silane that silicon-containing material is passed through in depositing device reaction chamber, and the flow velocity of silane is 10sccm~100sccm, the inlet period of silane It is 0.5s~1s.
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CN109797374A (en) * 2019-01-15 2019-05-24 芜湖启迪半导体有限公司 A kind of preparation method and its batch preparation of silicon carbide substrates
CN109852944A (en) * 2019-01-25 2019-06-07 中国科学院半导体研究所 Graphene preparation method based on microwave plasma CVD
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YA-PING HSIEH等: "《Complete Corrosion Inhibition through Graphene Defect Passivation》", 《ACS NANO》 *

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CN109201021A (en) * 2018-11-26 2019-01-15 西安科技大学 A kind of gas adsorption agent and preparation method thereof
CN109797374A (en) * 2019-01-15 2019-05-24 芜湖启迪半导体有限公司 A kind of preparation method and its batch preparation of silicon carbide substrates
CN109852944A (en) * 2019-01-25 2019-06-07 中国科学院半导体研究所 Graphene preparation method based on microwave plasma CVD
CN109852944B (en) * 2019-01-25 2020-08-04 中国科学院半导体研究所 Graphene preparation method based on microwave plasma chemical vapor deposition
CN113076640A (en) * 2021-03-31 2021-07-06 中国核动力研究设计院 Zirconium-based alloy irradiation damage software simulation system and method based on cluster dynamics
CN113076640B (en) * 2021-03-31 2022-06-10 中国核动力研究设计院 Zirconium-based alloy irradiation damage software simulation system and method based on cluster dynamics

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