CN108165991B - Chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material and preparation method - Google Patents
Chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material and preparation method Download PDFInfo
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- CN108165991B CN108165991B CN201810030720.0A CN201810030720A CN108165991B CN 108165991 B CN108165991 B CN 108165991B CN 201810030720 A CN201810030720 A CN 201810030720A CN 108165991 B CN108165991 B CN 108165991B
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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
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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
- C23C28/04—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 only coatings of inorganic non-metallic material
- C23C28/042—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 only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- 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
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Abstract
The present invention relates to a kind of chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material and preparation methods, belong to hydrogen infiltration-resistant field of material technology.The coating material of the method for the present invention is chromium oxide disperse chromium carbide and its aluminium oxide composition on stainless steel base.The composite coating forms the Cr-C alloy of even compact by coating by pulse electrochemical deposition on stainless steel substrate, then control oxidation generates a kind of chromium carbide disperse in the composite coating of chromium oxide, the finally atomic layer deposition aluminium oxide on composite coating forms chromium carbide dispersion oxidation chromium/alumina composite coating after annealing.Coating material of the invention has the advantages that preparation technology of coating is simple, chromium carbide therein is mixed in chromium oxide coating, play the role of pinning hydrogen to spread in oxide grain boundary, hydrogen and its isotope can be effectively reduced in the permeability of stainless steel, to achieve the purpose that hydrogen infiltration-resistant.
Description
Technical field
The present invention relates to a kind of chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material and preparation methods, belong to
Hydrogen infiltration-resistant field of material technology.
Background technique
Nuclear energy occupies an important position in new energy development due to having the characteristics that cleaning, efficient and energy density are big.Hydrogen
Gas and its isotope play vital effect in the controllable utilization of nuclear energy.In fission-type reactor, the suction hydrogen behavior of material
The corrosion resistance of material can be seriously affected or even hydrogen embrittlement occurs.It is asked to solve to relate to hydrogen infiltration bring in hydrogen application field
Topic, can be by using the hydrogen infiltration-resistant performance for preparing the method for seeping hydrogen barrier coat raising material or container on the surface of the material.
Hydrogen permeation preventing coating is the coating material that reduction and barrier effect have been permeated to the hydrogen of structure member, the high resistant of coating
The hydrogen factor is attributed to strong ionic bond, and metallic atom and oxygen atom are tightly combined together by it, and the diffusion of hydrogen atom must overcome
The overactivity energy of oxide coating.Ceramic material is due to low, the high-temperature stability with hydrogen permeability, higher hardness and strength,
The advantages that chemical bond is strong plays important role in hydrogen resistance coating research.Ceramic hydrogen resistance coating is divided into oxide coating and non-
Oxide coating.Oxide coating is since preparation method is simple, function admirable, thus become current most study, it is most widely used
Coating.It common are Al2O3,Cr2O3,ZrO2And Er2O3Deng generally by matrix direct oxidation or alloy coat oxidation side
Method obtains.Non-oxidized substance coating mainly includes TiC, TiN, SiC and Si3N4.Metal oxide and carbide are fusion reactors
One of most promising hydrogen permeability barrier coating.Chromium oxide ceramics coating has the preferable ability for reducing hydrogen infiltration, because it
There is very strong ionic bond, hydrogen atom diffusion coefficient 5.03 × 10 in chromium oxide at 500 DEG C-10cm2/s.Aluminum oxide coating layer tool
There are the high resistance hydrogen factor, fine and close oxidation membrane structure and stable chemical property, the bond energy of the combination between aluminium and oxygen is
511kJ/mol greater than the bond energy of 428kJ/mol between hydrogen and oxygen, thus needs very high energy that could destroy aluminium when hydrogen infiltration
Oxygen chemical key forms hydrogen-oxygen chemical bond, so the blocking effect that aluminum oxide coating layer spreads hydrogen is excellent.
Disclosed hydrogen resistance coating is CN1971168 using Cr earliest2O3As resistance hydrogen material, hydrogen can be largely prevented
Infiltration, but due to thermal mismatching, coating is weaker with basal body binding force.Patent CN104647828A and CN105500811A utilize gold
Category-organic chemical vapor deposition is formed by deposition of aluminium oxide and chromium oxide coating simultaneously in stainless steel inner surface with aluminium oxide
For main phase, hydrogen resistance coating of the chromium oxide Dispersed precipitate in main phase.Can get thickness using this method is about 0.1-20 μm
Al2O3/Cr2O3Disperse hydrogen resistance coating.The hydrogen resistance coating and substrate combinating strength are high, and NdFeB permanent magnets improve 100 times or more.Patent
CN105667009A prepares a kind of Y by metal-organic chemical vapor deposition method2O3/Al2O3/Cr2O3Complex gradient hinders hydrogen and applies
Layer obtains about 0.1-20 μm of thickness by successive precipitated chromia, aluminium oxide and yttria coating.The hydrogen resistance coating and matrix
Bond strength is high, and NdFeB permanent magnets improve 300 times or more.Patent CN103895282A is carried out using low pressure plasma spray equipment
The preparation of Ni-Cr-Al transition zone forms the Al that thickness is about 0.1-20 μm by subsequent processing2O3/Cr2O3Hydrogen resistance coating.
Summary of the invention
The object of the present invention is to provide a kind of chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material and preparation sides
Method improves existing preparation process, so that the preparation process of composite coating is simple, chromium carbide is mixed in chromium oxide coating
In, play the role of pinning hydrogen and spread in oxide grain boundary, hydrogen and its isotope is effectively reduced in the permeability of stainless steel, thus
Achieve the purpose that hydrogen infiltration-resistant.
It is proposed by the present invention that there is chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material, using stainless steel as base
Plate is followed successively by stainless steel substrate, chromium carbide dispersion oxidation chromium composite coat and aluminum oxide coating layer, wherein the chromium carbide disperse
Chromium oxide composite coating with a thickness of 0.1-10 μm, aluminum oxide coating layer with a thickness of 0.01-1 μm.
It is proposed by the present invention that there is chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material preparation method, packet
Include following steps:
(1) stainless steel surface is polished to 7000# with sand paper, then be polished to stainless steel surface light with flannelette, by stainless steel
Remaining 5 face is sealed with insulating tape, obtains bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid, is electroplated
The composition of liquid are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3, 1mol/L
The NH of KCl, 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid are 2, plating
Liquid temperature makes the current density 30-50A/dm in electroplate liquid at 15-45 DEG C2, pulse duty factor 50-90%, electroplating time
Be 10-60 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 0.1-10 μm；
(3) the obtained stainless steel substrate of above-mentioned steps (2) is put into pressure is oxygen under 500 DEG C of 100Pa, temperature environment
Change reaction 1-5 hours, chromium carbide dispersion oxidation chromium composite coat is obtained on above-mentioned Cr-C coating, chromium carbide dispersion oxidation chromium is multiple
Close coating with a thickness of 0.1-10 μm, the quality of carbon is very 0.5- in chromium carbide dispersion oxidation chromium composite coat
10%；
(4) Atomic layer deposition method is used, deposits oxygen on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3)
Change aluminium, aluminium oxide is generated by presoma trimethyl aluminium and water reaction, with nitrogen as protection and purge gas, nitrogen in reaction chamber
Flow is 15 standard milliliters/minute, and reaction temperature is 70 DEG C, and in each cycle, trimethylaluminum gas and vapor are alternately logical
Enter in reaction cavity, the flow of trimethylaluminum gas and vapor is respectively 20 standard milliliters/minute, in each circulation, will before
It drives body trimethylaluminum gas and is passed through 20 milliseconds, nitrogen cleans 10 seconds, and vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；By
20-1400 circulation, deposition obtains aluminum oxide coating layer, the thickness of aluminum oxide coating layer on chromium carbide dispersion oxidation chromium composite coat
It is 0.01-1 μm, finally at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa, forms alumina crystal phase after annealing
(Al2O3), it obtains with chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material.
Chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material proposed by the present invention and preparation method, advantage
It is:
1, coating material preparation method of the invention, has the advantages that preparation technology of coating is simple, chromium carbide folder therein
It is miscellaneous in chromium oxide coating, play the role of pinning hydrogen oxide grain boundary spread, hydrogen and its isotope can be effectively reduced not
The permeability of rust steel, to achieve the purpose that hydrogen infiltration-resistant.
2, preparation method materials of the present invention are convenient, and cheap, electroplating effect is good, carry out pre-treatment to substrate, can be true
Protecting the coating obtained when plating has sufficiently large adhesive force.Cr3+Electronics is obtained in electrode surface, reduction reaction occurs, obtain metal
The electronplate of chromium, obtained coating toxicity is low, environmental protection and saving, and coating is bright, firm binding force.Chromium carbide disperse is obtained after oxidation
Chromium oxide composite coating light is smooth.
3, preparation method of the present invention utilizes pulse plating to obtain Cr-C coating on stainless steel and what is then aoxidized arrives carbonization
Chromium dispersion oxidation chromium composite coat.The composite coating and substrate combinating strength are high, and preparation process is simple and low in cost, and materials are easy
It obtains.The composite coating light is smooth, and fine and close, ingredient is evenly distributed in stainless steel base, and NdFeB permanent magnets are excellent.
Detailed description of the invention
Fig. 1 is chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material knot that the method for the present invention is prepared
Structure schematic diagram, in Fig. 1,1 is stainless steel base, and 2 be chromium carbide dispersion oxidation chromium composite coat, and 3 be chromium carbide dispersion oxidation chromium
/ alumina composite coating.
Fig. 2 is chromium carbide dispersion oxidation chromium/alumina composite coating stereoscan photograph.It can be seen that coating surface distribution
The Al of even compact2O3。
Fig. 3 is the elemental map for scheming encircled portion in (2).
Fig. 4 is chromium carbide dispersion oxidation chromium/alumina composite coating XRD spectrum.
Fig. 5 is chromium carbide dispersion oxidation chromium/alumina composite coating pattern and its surface potential.
Fig. 6 is that chromium carbide dispersion oxidation chromium/alumina composite coating seeps (a) Bode figure and (b) Nyquist figure before and after hydrogen.
Specific embodiment
It is proposed by the present invention that there is chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material, using stainless steel as base
Plate is followed successively by stainless steel substrate, chromium carbide dispersion oxidation chromium composite coat and aluminum oxide coating layer, wherein the chromium carbide disperse
Chromium oxide composite coating with a thickness of 0.1-10 μm, aluminum oxide coating layer with a thickness of 0.01-1 μm.Its structure is as shown in Figure 1, Fig. 1
In, 1 is stainless steel substrate, and 2 be chromium carbide dispersion oxidation chromium composite coat, and 3 be aluminum oxide coating layer.Cr thereinxCyIt indicates
Cr23C6And Cr7C3。
It is proposed by the present invention that there is chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material preparation method, packet
Include following steps:
(1) stainless steel surface is polished to 7000# with sand paper, then be polished to stainless steel surface light with flannelette, by stainless steel
Remaining 5 face is sealed with insulating tape, obtains bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid, is electroplated
The composition of liquid are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3, 1mol/L
The NH of KCl, 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid are 2, plating
Liquid temperature makes the current density 30-50A/dm in electroplate liquid at 15-45 DEG C2, pulse duty factor 50-90%, electroplating time
Be 10-60 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 0.1-10 μm；
(3) the obtained stainless steel substrate of above-mentioned steps (2) is put into pressure is oxygen under 500 DEG C of 100Pa, temperature environment
Change reaction 1-5 hours, chromium carbide dispersion oxidation chromium composite coat is obtained on above-mentioned Cr-C coating, chromium carbide dispersion oxidation chromium is multiple
Close coating with a thickness of 0.1-10 μm, the quality of carbon is very 0.5- in chromium carbide dispersion oxidation chromium composite coat
10%；
(4) Atomic layer deposition method is used, deposits oxygen on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3)
Change aluminium, aluminium oxide is generated by presoma trimethyl aluminium and water reaction, with nitrogen as protection and purge gas, nitrogen in reaction chamber
Flow is 15 standard milliliters/minute, and reaction temperature is 70 DEG C, and in each cycle, trimethylaluminum gas and vapor are alternately logical
Enter in reaction cavity, the flow of trimethylaluminum gas and vapor is respectively 20 standard milliliters/minute, in each circulation, will before
It drives body trimethylaluminum gas and is passed through 20 milliseconds, nitrogen cleans 10 seconds, and vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；By
20-1400 circulation, deposition obtains aluminum oxide coating layer, the thickness of aluminum oxide coating layer on chromium carbide dispersion oxidation chromium composite coat
It is 0.01-1 μm, finally at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa, forms alumina crystal phase after annealing
(Al2O3), it obtains with chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material.
The embodiment of the method for the present invention introduced below:
Embodiment 1
(1) stainless steel surface is polished to 7000# with sand paper, then be polished to stainless steel surface light with flannelette, by stainless steel
Remaining 5 face is sealed with insulating tape, obtains bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the wet look of the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid
In, the composition of electroplate liquid are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3、
The NH of KCl, 1mol/L of 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid
It is 2, temperature of electroplating solution makes the current density 30A/dm in electroplate liquid at 15 DEG C2, pulse duty factor 50%, electroplating time
Be 10 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 0.1 μm；
(3) the obtained Cr-C coating of above-mentioned steps (2) is put into pressure is oxidation under 500 DEG C of 100Pa, temperature environment
Reaction 5 hours, obtains chromium carbide dispersion oxidation chromium composite coat, chromium carbide dispersion oxidation chromium composite coat with a thickness of 0.1 μ
M, the mass percent of carbon is 0.5% in chromium carbide dispersion oxidation chromium composite coat；
(4) Atomic layer deposition method is used, deposits oxygen on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3)
Change aluminium, aluminium oxide is generated by presoma (trimethyl aluminium) and water reaction, with nitrogen as protecting and purge gas in reaction chamber,
15 standard milliliters of nitrogen flow/minute, reaction temperature are 70 DEG C, in each cycle, trimethylaluminum gas and vapor alternating
It being passed through in reaction cavity, flow is 20 standard milliliters/minute, and trimethyl aluminium presoma is passed through 20 milliseconds, and nitrogen cleans 10 seconds,
Vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；It recycles by 20 times, is deposited on chromium carbide dispersion oxidation chromium composite coat
To aluminum oxide coating layer, aluminum oxide coating layer with a thickness of 0.01 μm, at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa,
Crystalline phase Al is formed after annealing2O3, chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating is obtained, that is, there is chromium carbide disperse
Chromium oxide/alumina composite hydrogen resistance coating material.
By chromium carbide dispersion oxidation chromium/H of the alumina composite coating at 350 DEG C2Reductase 12 hour, the compound painting in test front and back
The variation of layer finds that the NdFeB permanent magnets of coating improve.
Embodiment 2
(1) stainless steel surface is polished to 7000# with sand paper, then be polished to stainless steel surface light with flannelette, by stainless steel
Remaining 5 face is sealed with insulating tape, obtains bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the wet look of the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid
In, the composition of electroplate liquid are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3、
The NH of KCl, 1mol/L of 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid
It is 2, temperature of electroplating solution makes the current density 45A/dm in electroplate liquid at 30 DEG C2, pulse duty factor 70%, electroplating time
Be 30 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 5 μm；
(3) the obtained Cr-C coating of above-mentioned steps (2) is put into pressure is oxidation under 500 DEG C of 100Pa, temperature environment
Reaction 3 hours, obtains chromium carbide dispersion oxidation chromium composite coat, chromium carbide dispersion oxidation chromium composite coat with a thickness of 5 μm, carbon
The mass percent for changing carbon in chromium dispersion oxidation chromium composite coat is 5%；Fig. 2 manufactured in the present embodiment is chromium carbide disperse
Chromium oxide/alumina composite coating stereoscan photograph.The fine and close Al it can be seen that coating surface is evenly distributed2O3.Fig. 3 is figure
The elemental map of encircled portion in 2.It can be seen that C, O, Al and its Cr element are evenly distributed in coating.
(4) Atomic layer deposition method is used, deposits oxygen on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3)
Change aluminium, aluminium oxide is generated by presoma (trimethyl aluminium) and water reaction, with nitrogen as protecting and purge gas in reaction chamber,
15 standard milliliters of nitrogen flow/minute, reaction temperature are 70 DEG C, in each cycle, trimethylaluminum gas and vapor alternating
It being passed through in reaction cavity, flow is 20 standard milliliters/minute, and trimethyl aluminium presoma is passed through 20 milliseconds, and nitrogen cleans 10 seconds,
Vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；It recycles by 750 times, is deposited on chromium carbide dispersion oxidation chromium composite coat
Obtain aluminum oxide coating layer, aluminum oxide coating layer with a thickness of 0.5 μm, at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa,
Crystalline phase Al is formed after annealing2O3, chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating is obtained, that is, there is chromium carbide disperse
Chromium oxide/alumina composite hydrogen resistance coating material.
Fig. 4 is the XRD spectrum of chromium carbide dispersion oxidation chromium/alumina composite coating manufactured in the present embodiment, it can be seen that
Composite coating is mainly made of chromium carbide, chromium oxide and aluminium oxide.Fig. 5 is chromium carbide dispersion oxidation chromium/alumina composite coating
Pattern and its surface potential, due to chromium carbide electric conductivity be higher than chromium oxide, white dot show chromium carbide Dispersed precipitate
In chromium oxide coating.
By chromium carbide dispersion oxidation chromium/H of the alumina composite coating at 350 DEG C2Reductase 12 hour, the compound painting in test front and back
The variation of layer finds that the NdFeB permanent magnets of coating improve.Fig. 6 is before chromium carbide dispersion oxidation chromium/alumina composite coating seeps hydrogen
Fig. 6 (a) Bode and Fig. 6 (b) Nyquist before and after infiltration hydrogen, as can be seen that Al from Fig. 6 (a) and Fig. 6 (b)2O3By atomic layer
After deposition technique is deposited on chromium carbide dispersion oxidation chromium composite coat surface, the integrality of coating NdFeB permanent magnets and coating has obviously
It improves.
Embodiment 3
(1) stainless steel surface is polished to 7000# with sand paper, then be polished to stainless steel surface light with flannelette, by stainless steel
Remaining 5 face is sealed with insulating tape, obtains bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the wet look of the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid
In, the composition of electroplate liquid are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3、
The NH of KCl, 1mol/L of 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid
It is 2, temperature of electroplating solution makes the current density 50A/dm in electroplate liquid at 45 DEG C2, pulse duty factor 90%, electroplating time
Be 60 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 10 μm；
(3) the obtained Cr-C coating of above-mentioned steps (2) is put into pressure is oxidation under 500 DEG C of 100Pa, temperature environment
Reaction 1 hour, obtains chromium carbide dispersion oxidation chromium composite coat, chromium carbide dispersion oxidation chromium composite coat with a thickness of 10 μm,
The mass percent of carbon is 10% in chromium carbide dispersion oxidation chromium composite coat；
(4) Atomic layer deposition method is used, deposits oxygen on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3)
Change aluminium, aluminium oxide is generated by presoma (trimethyl aluminium) and water reaction, with nitrogen as protecting and purge gas in reaction chamber,
15 standard milliliters of nitrogen flow/minute, reaction temperature are 70 DEG C, in each cycle, trimethylaluminum gas and vapor alternating
It being passed through in reaction cavity, flow is 20 standard milliliters/minute, and trimethyl aluminium presoma is passed through 20 milliseconds, and nitrogen cleans 10 seconds,
Vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；It recycles by 1400 times, is deposited on chromium carbide dispersion oxidation chromium composite coat
Obtain aluminum oxide coating layer, aluminum oxide coating layer with a thickness of 1 μm, at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa, is moved back
Crystalline phase Al is formed after fire2O3, chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating is obtained, that is, there is chromium carbide disperse oxygen
Change chromium/alumina composite hydrogen resistance coating material.
By chromium carbide dispersion oxidation chromium/H of the alumina composite coating at 350 DEG C2Reductase 12 hour, the compound painting in test front and back
The variation of layer finds that the NdFeB permanent magnets of coating improve.
Claims (2)
1. one kind have chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material, it is characterised in that the coating material with
Stainless steel is substrate, is followed successively by stainless steel substrate, chromium carbide dispersion oxidation chromium composite coat and aluminum oxide coating layer, wherein described
Chromium carbide dispersion oxidation chromium composite coat with a thickness of 0.1-10 μm, aluminum oxide coating layer with a thickness of 0.01-1 μm.
2. a kind of have the preparation of chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material as described in claim 1
Method, it is characterised in that method includes the following steps:
(1) the sand paper polishing stainless steel surface for being 7000# with mesh number, then it is polished to stainless steel surface light with flannelette, it will be stainless
Remaining 5 face of steel are sealed with insulating tape, obtain bright stainless steel substrate；
(2) coating by pulse electrochemical deposition method is used, the stainless steel substrate of above-mentioned steps (1) is put into electroplate liquid, electroplate liquid
Composition are as follows: the CrCl of 0.5mol/L3·6H2O, the H of HCOOH, 0.65mol/L of 0.8mol/L3BO3, 1mol/L KCl,
The NH of 1mol/L4The NH of Cl, 10g/L4The lauryl sodium sulfate of Br and 0.2g/L, the pH value of electroplate liquid are 2, electroplate liquid temperature
Degree makes the current density 30-50A/dm in electroplate liquid at 15-45 DEG C2, pulse duty factor 50-90%, electroplating time is
10-60 minutes, obtain Cr-C coating in the glossy surface of stainless steel substrate, coating with a thickness of 0.1-10 μm；
(3) the obtained stainless steel substrate of above-mentioned steps (2) is put into pressure is under 500 DEG C of 100Pa, temperature environment, and oxidation is anti-
It answers 1-5 hours, chromium carbide dispersion oxidation chromium composite coat, the compound painting of chromium carbide dispersion oxidation chromium is obtained on above-mentioned Cr-C coating
Layer with a thickness of 0.1-10 μm, the mass percent of carbon is 0.5-10% in chromium carbide dispersion oxidation chromium composite coat；
(4) Atomic layer deposition method, the deposited oxide on the chromium carbide dispersion oxidation chromium composite coat of above-mentioned steps (3) are used
Aluminium, aluminium oxide is generated by presoma trimethyl aluminium and water reaction, with nitrogen as protection and purge gas, nitrogen stream in reaction chamber
Amount is 15 standard milliliters/minute, and reaction temperature is 70 DEG C, and in each cycle, trimethylaluminum gas and vapor are alternately passed through
In reaction cavity, the flow of trimethylaluminum gas and the flow of vapor are respectively 20 standard milliliters/minute, in each circulation,
Presoma trimethylaluminum gas is passed through 20 milliseconds, nitrogen cleans 10 seconds, and vapor enters 10 milliseconds, and nitrogen cleans 20 seconds；Through
20-1400 circulation is crossed, deposition obtains aluminum oxide coating layer, the thickness of aluminum oxide coating layer on chromium carbide dispersion oxidation chromium composite coat
Degree is 0.01-1 μm, finally at 800 DEG C of temperature, pressure 10-44 hours are kept the temperature under the conditions of Pa, forms alumina crystal phase after annealing
Al2O3, obtain with chromium carbide dispersion oxidation chromium/alumina composite hydrogen resistance coating material.
Priority Applications (1)
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| CN104647828B (en) * | 2013-11-21 | 2017-06-16 | 北京有色金属研究总院 | A kind of Cr2O3And Al2O3Complex gradient hydrogen resistance coating and its preparation method and application |
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