CN105525273B - A kind of stainless steel carborundum hydrogen permeation preventing coating and preparation method thereof - Google Patents
A kind of stainless steel carborundum hydrogen permeation preventing coating and preparation method thereof Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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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
- C23C28/30—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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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
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Abstract
The present invention provides a kind of stainless steel carborundum hydrogen permeation preventing coating, including transition zone, storage H cushions, the resistance hydrogen layer successively arranged upwards from stainless steel base；The transition zone is made up of layer of titanium metal and TiN layer, and the storage H cushions are amorphous SixC1‑xGraded bedding, 1 ＞ x >=0.5, the resistance hydrogen layer is SiC.The present invention also proposes the preparation method of the carborundum hydrogen permeation preventing coating.The present invention proposes to be combined with storage H cushions with resistance H coatings, prepares the anti-hydrogen permeability coating of matrix/transition zone/storage H cushions/SiC composite constructions.On the resistance H coating SiC Membranous Foundations of Flouride-resistani acid phesphatase, storage H cushions Si is prepared using gas phase deposition technologyxC1‑xGraded bedding, utilize SixC1‑xThe very competent C and Si dangling bonds of hydrogen are largely caught present in graded bedding, optimize the anti-hydrogen penetrating quality of matrix/transition zone/storage H cushions/SiC composite constructions.
Description
Technical field
The invention belongs to the plating field to metal material, and in particular to it is a kind of sputter have resistance hydrogen layer metal material and
Its preparation method.
Background technology
In recent years, develop hydrogen permeation barrier coating for various matrix materials and also known as hinder H coatings, it is intended to prevent hydrogen and its same
The infiltration leakage of position element, has carried out numerous studies both at home and abroad, mainly develops various resistance composite for hydrogen and coating technology.Mesh
Preceding conventional resistance H coatings are broadly divided into following a few classes.
Oxide coating:Have the advantages that fusing point is high, chemical property is stable, preparation technology is simple and resistance H is functional, be
The earliest anti-hydrogen permeation coating of research.It can be generated by substrate surface direct oxidation or coating oxidation, including Al2O3,
Cr2O3, Y2O3, SiO2, Er2O3Deng.Usual single layer oxide resistance H coatings are mostly Cr2O3, Al2O3, and SiO2Often answered with other coatings
Close and use.Y2O3The permeability of coating tritium can decline two orders of magnitude, and be used in combination more with other coatings.Japan Atomic can be ground
Study carefully used chemical densification coating technology (CDC) and prepare Cr in 316 stainless steel surfaces2O3-SiO2Ceramic hydrogen resistance coating, tritium ooze
Stop that the factor (PRF) is more than 100 (Takayuki Terai, Toshiaki Yoneoka, Himhisa Tanaka, Tritium thoroughly
permeation through austenitic stainless steel with chemically densified
coating as a tritium permeation barrier,Journal of Nuclear Materials,1994:
212/215:976；).It is micron-sized a-Al that Levchuk etc. obtains thickness using PVD method in Eurofer stainless steel surfaces2O3
Coating result show the PRF of the coating at 700~800 DEG C for 1000 (Serra E, Calza Bini A, Cosoli G,
Hydrogen permeation measurements on alumina,Journal of the American Ceramic
Society,2005,88(1):15).Beijing Non-Ferrous Metal Research General Academy Li Shuai etc. is divided using mocvd method on 316L stainless steels
Al is not prepared for it2O3、Y2O3And Cr2O3Hinder H coating (Journal of Inorganic Materials, 7 phases Li Shuai in 2013, He Di, Liu Xiaopeng, Zhang Chao, king
Tree cyclopentadienyl, Yu Qinghe, Qiu Haochen, Jiang Lijun, the hydrogen penetrating quality of 316L stainless steel base aluminum oxide coating layers, Journal of Inorganic Materials,
2013,28(7)775；), NdFeB permanent magnets are excellent.Wherein Al2O3Coating permeates resistance at 600~700 DEG C to the hydrogen of 316L stainless steels
It is 59~119 to keep off the factor (PRF).Y2O3Coating PRF at 550~700 DEG C is 240-410.Cr2O3Coating is at 550~600 DEG C
When PRF be 24~117.
Ti base ceramic coatings have good corrosion resistance and higher resistance H effects.This type coating mainly includes titanium nitride, carbon
Change titanium and both compound or mixed coatings, various titanium-base ceramics coatings can be prepared using CVD or PVD method, research
As a result show, Ti base ceramic coatings have resistance H performances well at low temperature.Often rise etc. using PVD method in 316L stainless steels on mountain
TiC+TiN coatings (C.Q.Shang, A.J.Wu, Y.J.Li, the The behaviour that thickness is 2~5 microns is prepared in substrate
of diffusion and permeation of tritium through 316L stainless steel with
coating of TiC and TiN+TiC,Journal of Nuclear Materials,1992,191-194:221；), connect
And one layer of CH4 hydrogen permeation preventing coating is prepared on TiC surfaces using thermo-chemical treatment.Test result shows hydrogen oozing in the coating
Saturating rate reduces the 4-6 order of magnitude.But oxidation occurs more than 450 DEG C of temperature and is difficult to overcome by TiC, TiN and TiC/TiN.Yao Zhen
Space etc. adds one layer of higher coating of inoxidizability (SiO2 or TiN) on TiN+TiC gradient coatings surface to prevent TiN+TiC
Gradient coating fails in use, and (Yao Zhenyu, the anti-tritium diffusion performance study of fusion reactor blanket material different coating are Chinese
Atomic Energy Research Establishment's master's thesis, 2001).Prepared with PVD method in the stainless steel bases of 316L TiN+TiC+TiN and
TiN+TiC+SiO2Coating.Coating layer thickness is respectively 2 microns and 3 microns.Two kinds of coating penetration rates are distinguished relative to base material
Reduce 4~5 and 4~6 orders of magnitude.
Silicide coating focuses primarily upon SiC coatings.SiC is the silicide resistance H permeation coatings of current most study, and
Industrially it has been applied, reason is that it has high hardness and anti-wear performance, can be used as superhard coating.SiC is high
Generate one layer very thin of fine and close SiO when warm with oxygen reaction first2Passivating film, make SiC that there is good high temperature oxidation resistance,
SiC can be prevented to continue to aoxidize.Prepare SiC coating generally use CVD and PVD method.Wang Peixuan etc. utilizes ion beam assisted depositing
Method and ion implantation deposited the SiC coatings that thickness is 2 microns on 316L stainless steels, and (Wang Peixuan, Wang Yu, history is valuable, no
Researchs of the rust depositing on surface of steel SiC as hydrogen penetration barrier layer, Acta Metallurgica Sinica, 1999,35 (6):654；).Coating makes stainless steel
Nearly 5 orders of magnitude of the hydrogen permeability reduction of substrate.Chikada et al. is stainless in 316 and F82H with radio-frequency magnetron sputter method
SiC resistance H coatings (Chikada T, Suzuki A, Terai T, Deuterium permeation and are prepared in steel base
thermal behaviors of amorphous silicon carbide coatings on steels,Fu-sion
Engineering and Design,2011,86(9):2192) the resistance H performances and heat endurance of SiC coatings, be have studied.Research
As a result show, the SiC films of preparation are amorphous state.In the range of 450~550 DEG C, PRF is 1000 or so.When temperature is more than 600
DEG C when, resistance H effects can decline, and reason is to produce micro-crack inside the too high SiC of temperature to cause H infiltration aggravations.Chinese engineering
Physical study institute improves the anti-H permeance properties of 316L stainless steels using Er2O3/SiC composite coatings, and thickness is 300nm film layer energy
Enough PRF under the conditions of 500 DEG C reach 500 and (Yao Zhenyu, Yan Hui, Tan Liwen, Han Hua, make Tritium Permeation Barrier with SiC films
Research, Nuclear Fusion andPlasma Physics, 2002,22:65；).
Aluminide composite coating mainly includes A1/Fe+Al2O3With AlN coatings, by being caused in substrate metal near surface
One concentration gradient containing aluminium, an aluminum based metal compound layer is formed, by the aluminium content of parent metal to surface aluminium content
Can be using graded as 30%-80%Al.Due to the difference of thermal coefficient of expansion between matrix and coating material, aluminide is caused to apply
Layer easily comes off, and this is the technical barrier faced at present.In cold and hot change procedure, difference of thermal expansion coefficients is bigger, caused
Stress is also bigger.This cold and hot process iterative cycles, the effect of stress will be accumulated and constantly strengthen, it is possible to produce crackle,
Until coating shedding.Prepare A1/Fe+Al2O3Resistance H coatings method have hot-dip, flame-spraying, vacuum plasma spray, from
Sub- injection, chemical vapor deposition, magnetron sputtering, high temperature insostatic pressing (HIP) and pack cementation aluminizing etc..Kalin etc. by Crl8Nil0Ti austenites not
Rust steel, which is put into 10%Al+90%Li melts 5~100h of aluminising, resulting coating in 600~800 DEG C of temperature ranges, to be had
Complicated intermetallic compound heterogeneous structure, such as FeAl3, FeAl, Fe3Al and NiAl, AlCr2 and a-Fe etc., thickness is because of temperature
It is different and different with the time.Result of study shows that the blocking effect of two sides aluminising is best, and PRF is respectively 2000 and 2700
(B.A.Kalin,V.L.Yakushin,E.P.Fomina,Tritium barrier development for austenitie
stainless steel byits aluminizing in a lithium melt,Fusion Engineering and
Design 1998,41:119；).Fazio etc. is prepared for Fe-Cr-Al coatings using air plasma spraying method, and substrate is selected respectively
With MANETII and F82H2Mod steel.Coating possesses certain resistance H penetrating powers, but exists between coating and substrate larger
Residual stress so that coating in use easily occur peel off (Fazio C, Stein-Fechner K, Serra E,
Investigation on the suitability of plasma sprayed Fe-Cr-Al coatings as
tritium permeation barrier,J Nuclear Material 1999,273:233).Chen Yin etc. utilizes PECVD skills
Art (silver old, Chen Changan, Zhang Pengcheng, PECVD prepare the research of the compound hydrogen resistance coatings of Al-Al2O3, sufacing, and 2008,37
(3):41；) uniform, fine and close, stable Al-Al can be obtained after vacuum thermal oxidation2O3Laminated film, but exist a small amount of
Carbide impurity.It is obvious that film hinders deuterium performance below 450 DEG C, and the resistance H factors can reach 244.
New resistance H materials：In recent years, graphene and BN resistance H performances attract wide attention, emerged in large numbers largely with BN and
Resistance H material systems based on graphene.The magnetically enhanced plasma-ion-plating such as Tamura
BN coatings are obtained in the stainless steel bases of 316L, coating layer thickness is 1.5 microns, after 316L stainless steel surfaces are coated with BN coatings,
Can effectively reduce the H infiltration rates of stainless steel, including 300~500 DEG C of scopes, BN PRF values for 100 (M.Tamuraa,
M.Nomab,M.Yamashitac,Characteristic change of hydrogen permeation in
stainless steel plate by BN coating,Surface and Coatings Technology,2014,260:
148；).
Although the research of resistance H coatings has obtained many progress in material system design, performance optimization and mechanism etc., and
Engineering has actually also been applied.However, current research is found, for the hydrogen atom of " fine ", the painting of H excellent performances is hindered
Layer --- atom gap is so big in corundum so that hydrogen atom can casual wherein " migration ", and in metallic matrix side
Form many small holes.With continuous " the growing up " in hole, hydrogen atom has enough spaces and recombines to form hydrogen molecule simultaneously
Pressure is produced to oxide-film.When the diameter in hole arrives a certain critical dimension greatly, oxide-film will be supportted and must be plastically deformed, and
Bulge to form bubble, destroy resistance H coatings effect (D.G.Xie, Z.J.Wang, J.Sun, J.Li, E.Ma, Z.W.Shan,
In situ study of the initiation of hydrogen bubbles at the aluminium metal/
oxide interface,Nature Materials,2015,10.1038:4336).In addition, current research is also shown that hydrogen can
Relatively easily to pass through the two-dimensional materials such as graphene and BN, and heating and addition catalyst can substantially speed up this process, this
Mean hydrogen that traditional view is thought can not penetrate the two-dimensional materials such as the graphene without defect resistance H thinkings it is also unworkable.
(Algara-Siller,G.O.Lehtinen,F.C.Wang,R.R.Nair,U.Kaiser,H.A.Wu,
A.K.Geim,I.V.Grigorieva,Square ice in graphene nanocapillaries,Nature,2015,
519(7544):443)
Meanwhile in recent years, Hydrogen Technology exploitation and research as cleaning, high efficient energy sources have made great progress, for solution
Certainly anti-hydrogen infiltration problem provides important references.In a word, these new cognitions and find to much to relate to hydrogen application it is related not
The mystery of solution provides important reference.Therefore, carry out performance regulation and control and the study mechanism of anti-hydrogen infiltration composite coating, instruct anti-hydrogen
Penetration material System Design is developed with correlation technique, the performance of optimization resistance H coatings, the controllability for improving resistance H coatings, it has also become relate to
The study hotspot of hydrogen application field.
The content of the invention
To overcome the drawbacks described above of prior art, buffered it is an object of the invention to provide one kind by matrix/transition zone/storage H
The hydrogen permeation preventing coating that layer/SiC composite constructions are formed.
It is another object of the present invention to propose the preparation method of the hydrogen permeation preventing coating.
The technical scheme for realizing the object of the invention is：
A kind of stainless steel carborundum hydrogen permeation preventing coating, including successively arranged upwards from stainless steel base transition zone,
Store up H cushions, resistance hydrogen layer；The transition zone is made up of layer of titanium metal and TiN layer, and the graded bedding is amorphous SixC1-x, 1
＞ x >=0.5, the resistance hydrogen layer is SiC.
Wherein, the transition zone is made up of Ti layers and TiN layer, and wherein 100~300nm of Ti thickness, TiN layer thickness 200~
500nm, the storage H cushions are amorphous SixC1-xGraded bedding, 1 ＞ x >=0.5,1~4 μm of thickness, the resistance hydrogen thickness degree
For 500nm~1 μm.
Wherein, the material of the stainless steel base is one kind in 316L, 304 and 321.
The preparation method of stainless steel of the present invention carborundum hydrogen permeation preventing coating, it is characterised in that including following step
Suddenly：
S1 prepares transition zone Ti/TiN using the method for magnetron sputtering, first using Ti targets as sputtering target material deposited metal Ti
Layer, first forvacuum to 10-5~10-3Pa, be passed through argon gas and carry out d.c. sputtering, electric current be 5~8A, working vacuum for 0.3Pa~
0.6Pa, heating-up temperature are 150~300 DEG C, and target-substrate distance is 80~100mm；Then sputtered using intermediate frequency power supply or radio-frequency power supply
TiN layer；
S2 prepares storage H cushions on transition zone using vapour deposition process, and the vapour deposition process sinks for physical vapor
Area method or chemical vapour deposition technique；
S3 prepares SiC resistance hydrogen layers on storage H cushions using vapour deposition process, and the vapour deposition process sinks for physical vapor
Area method or chemical vapour deposition technique.
Wherein, the preparation method of TiN layer is in transition zone described in S1：
The depositing TiN on metal Ti layers, first forvacuum to 10-5~10-3Pa, it is passed through argon gas and nitrogen, Ar/N2Flow
Than for 2-8, using medium frequency magnetron sputtering (using intermediate frequency power supply), electric current is 5~8A, and working vacuum is 0.3Pa~0.6Pa, is added
Hot temperature is 150~300 DEG C, and target-substrate distance is 80~100mm.
Or, the preparation method of TiN layer is in S1：First forvacuum is to 10-5~10-3Pa, it is passed through argon gas and nitrogen, Ar/N2
Flow-rate ratio is 2-8, and sputtering power is 100~200W (using radio-frequency power supply), and working vacuum is 0.3Pa~2Pa, and heating-up temperature is
150~300 DEG C, target-substrate distance is 80~100mm, and thickness is 200~500nm.
Wherein, the preparation method of storage H cushions is in S2：
Using pure silicon target, first forvacuum to 10-5~10-3Pa, then pass to Ar and C2H2Mixed gas carries out intermediate frequency
Magnetron sputtering, Ar/C2H2Flow-rate ratio is 2~20, and sputtering current is 4~10A, and sputtering pressure is 0.3Pa~0.6Pa, heating-up temperature
For 150~300 DEG C, target-substrate distance 80-100mm.
Preferably, during graded bedding is coated with, the Ar flows being passed through are constant, gradient increase sputtering current from 4A to
10A, or gradient reduce C2H2Gas flow, make Ar/C2H2Flow-rate ratio sets 2~5 gradients, each gradient altogether from 2 to 20
Sputtering current keeps 10~20min, obtains an individual layer and controls gross thickness at 1~4 μm.
Or, the preparation method of storage H cushions described in S2 is：
Precursor raw material is methyl trichlorosilane, carrier gas H2, diluent gas is argon gas, depositing temperature 1100~1300
DEG C, MTS+H2Flow rises to 0.8L/min, carrier gas Ar flow 160L/h, carrier gas H from 0.35L/min gradients2Flow from
1L/min gradients rise to 4L/min, set 2~5 gradients, each gradient MTS+H altogether2Flow keeps 10~20min.
Diluent gas is the working gas in CVD, is not involved in reacting.It is carrier gas with the hydrogen of MTS together, the effect of carrier gas
It is that vacuum chamber is entered with certain flow velocity carrier band gaseous sample or the sample gas after gasification together, so serving as the hydrogen of carrier gas
Gas is that same MTS enters together, and the hydrogen for serving as diluent gas is entered from another air inlet.
Wherein, the preparation method of the resistances of SiC described in S3 hydrogen layer is：
Using pure silicon target, first forvacuum to 10-5~10-3Pa；Then pass to Ar and C2H2Mixed gas carries out intermediate frequency
Magnetron sputtering, Ar/C2H2Flow-rate ratio is 2~20, and sputtering current is 4~10A, and sputtering pressure is 0.3Pa~0.6Pa, heating-up temperature
For 150~300 DEG C, 80~100mm of target-substrate distance.
Or, the preparation method of the resistance hydrogen layers of SiC described in S3 is：
Using SiC target material, first forvacuum to 10-5~10-3Pa；Ar is then passed to, sputtering power is 120~160W, is splashed
Pressure of emanating is 0.3Pa~0.6Pa, and heating-up temperature is 300~600 DEG C, 80~100mm of target-substrate distance.
The beneficial effects of the present invention are：
SiC is the silicide resistance H permeation coatings of current most study, and has industrially been applied, and reason is it
There are high hardness and anti-wear performance, can be used as superhard coating.One layer is generated during SiC high temperature very with oxygen reaction first
Thin fine and close SiO2Passivating film, make SiC that there is good high temperature oxidation resistance, SiC can be prevented to continue to aoxidize.It is in addition, non-
Crystalline state SixC1-xContain substantial amounts of C- and Si- dangling bonds in film, can play a part of storing up H.The two is combined, and not only acts as resistance
The effect of H infiltrations, more the part H that H layers are hindered through SiC can be further fixed, and be the combination of chemical bond, such combination
It is stronger, the effect of anti-hydrogen infiltration can be played.
The series of challenges faced in actual applications based on resistance H coatings, we targetedly enter in previous work
Pre- exploration is gone.Not only from the theoretical side research low-temperature epitaxy mechanism of SiC films, the delay of structure and tritium, diffusion and infiltration
Relation and its mechanism.Meanwhile the surface treatment with reference to matrix and cushion, in the temperature well below 316L stainless steels
Under, complex-shaped matrix surface obtained thickness uniformly, the SiC films that are firmly combined with, structured testing shows that SiC films have
There are excellent Flouride-resistani acid phesphatase, anti-tritium diffusion performance.
The present invention proposes to be combined with storage H cushions with resistance H coatings, and it is multiple to prepare matrix/transition zone/storage H cushions/SiC
Close the anti-hydrogen permeability coating of structure.On the resistance H coating SiC Membranous Foundations of Flouride-resistani acid phesphatase, storage H is prepared using gas phase deposition technology
Cushion SixC1-xGraded bedding, utilize SixC1-xThe very competent C- and Si- dangling bonds of hydrogen are largely caught present in graded bedding, it is excellent
Change the anti-hydrogen penetrating quality of matrix/transition zone/storage H cushions/SiC composite constructions, improve its controllability.
Brief description of the drawings
Fig. 1 is the coating structure figure of the present invention.
Embodiment
Detailed description below is used to illustrate the present invention, but should not be construed as limiting the invention.
The equipment of magnetron sputtering is TRX-750 vacuum magnetic-control sputtering equipment, and Beijing Tianrui starlight thermal technology develops limited public affairs
Department's system.The unit type of chemical vapor deposition is NEE-4000 (M) electron beam evaporation system, and that Nuo Zhong Co., Ltd produces.
In embodiment, unless otherwise instructed, technological means used is this area conventional technology.
Embodiment 1：
Selection is coated with transition zone Ti/TiN on the matrix of austenitic stainless steel 316 L, using the method for medium frequency magnetron sputtering
Prepare, be coated with metal Ti first, base vacuum 1 × 10 is set-3Pa, operating air pressure 0.6Pa, argon flow amount 120sccm, Ti target electricity
8A, voltage 550V, target-substrate distance 80mm, time 10min are flowed, it is obtained that titanium layer thickness is 200nm or so.On the basis of metal Ti
Depositing TiN, base vacuum 1 × 10-3Pa, operating air pressure 0.6Pa, argon flow amount 120sccm, nitrogen flow 15sccm, Ti target electricity
8A, voltage 530V, target-substrate distance 80mm, time 20min are flowed, thickness is 350nm or so.
Storage H cushions are prepared using CVD, design parameter is as follows：
Precursor raw material is MTS, carrier gas H2(its purity 99.8%), diluent gas are argon gas, 1100 DEG C of depositing temperature,
MTS+H2Flow is from first gradient 0.35L/min, the second gradient 0.45L/min, 3rd gradient 0.6L/min, 4th gradient
0.8L/min, rises to 0.8L/min, and each gradient stops 15min, Ar (dilution) flows 160L/h, H2(dilution) flow from
1L/min gradients rise to 4L/min, control 1.5 μm obtained of graded layer thickness.
SiC resistance hydrogen layers are prepared using chemical vapour deposition technique：Trichloromethyl silane (MTS) is used as raw material, process conditions
For:1100 DEG C of temperature, MTS+H2Flow 0.3L/min, H2(dilution) flow 0.5L/min, Ar flow 0.8L/min；Furnace pressure 3kPa,
1 μm of SiC resistance hydrogen thickness degree is made.
Hydrogen permeation preventing coating structure such as Fig. 1 made from the present embodiment, the transition zone successively arranged upwards from stainless steel base,
H cushions, resistance hydrogen layer are stored up, by test, this composite coating PRF in the range of 500~600 DEG C is 1500.
Embodiment 2：
Selection is coated with transition zone Ti/TiN on the matrix of austenitic stainless steel 316 L, using the method for medium frequency magnetron sputtering
Prepare, be coated with metal Ti, 1 × 10-3Pa of base vacuum, operating air pressure 0.3Pa, argon flow amount 90sccm, Ti target current first
8A, voltage 560V, target-substrate distance 80mm, time 10min, thickness are about 200nm.Depositing TiN on the basis of metal Ti, background are true
Sky 1 × 10-3Pa, operating air pressure 0.3Pa, argon flow amount 90sccm, nitrogen flow 15sccm, Ti target current 8A, voltage 540V,
Target-substrate distance is 80mm, time 20min, thickness 350nm.
Storage H cushions are prepared using PVD method, design parameter is as follows：
Using pure silicon target, first forvacuum to 1 × 10-3Pa；Then pass to Ar and C2H2Mixed gas carries out intermediate frequency magnetic
Control sputtering, Ar/C2H2Flow-rate ratio is 5, during graded bedding is coated with, the Ar and C that are passed through2H2Mixed gas flow is constant, point
Five gradients, each gradient increase 1A, the electric current of Si targets increase to 8A from 4A, and each gradient current obtains an individual layer, sputtering
Air pressure is 0.6Pa, and heating-up temperature is 250 DEG C, target-substrate distance 80mm, and control graded layer thickness is at 1.2 μm.
SiC resistance hydrogen layers are prepared using radio-frequency magnetron sputter method：
Using SiC target material, first forvacuum to 1 × 10-3Pa；Ar, sputtering power 120W are then passed to, sputtering pressure is
0.3Pa, heating-up temperature are 300 DEG C, target-substrate distance 80mm, and gross thickness is controlled in 800nm.
Composite coating is by test, and in the range of 500~600 DEG C, PRF is 1500 or so.
Embodiment 3：
Transition zone Ti/TiN is coated with the matrix of 304 stainless steels：Using the method for medium frequency magnetron sputtering：Gold is coated with first
Belong to Ti, base vacuum 1 × 10 is set-3Pa, operating air pressure 0.3Pa, argon flow amount 90sccm, Ti target current 8A, voltage 560V, target
Cardinal distance is 80mm, and time 10min, Ti thickness degree is 200nm.Then sunk on the basis of metal Ti with radio-frequency power supply magnetron sputtering
Product TiN layer：Base vacuum 1 × 10-3Pa, operating air pressure 0.3Pa, argon flow amount 90sccm, nitrogen flow 15sccm, sputtering power
For 100~200W, target-substrate distance 80mm, time 25min, TiN layer thickness is 450nm.
Storage H cushions are prepared using PVD method, design parameter is as follows：
Precursor raw material is MTS, carrier gas H2(its purity 99.8%), diluent gas are argon gas, 1150 DEG C of depositing temperature,
MTS+H2Flow is from first gradient 0.4L/min, the second gradient 0.5L/min, 3rd gradient 0.6L/min, 4th gradient 0.7L/
Min, each gradient stop 10min, Ar (dilution) flows 160L/h, H2(dilution) flow rises to 4L/ from 1L/min gradients
Min, control 1.1 μm obtained of graded layer thickness.
SiC resistance hydrogen layers are prepared using radio-frequency magnetron sputter method：
Using SiC target material, first forvacuum to 1 × 10-3Pa；Ar, sputtering power 120W are then passed to, sputtering pressure is
0.3Pa, heating-up temperature are 300 DEG C, target-substrate distance 80mm, gross thickness 700nm.
Other operations are the same as embodiment 2.
Composite coating is by test, and in the range of 500~600 DEG C, PRF is 1500 or so.
Embodiment 4：
Storage H cushions are prepared using PVD method, design parameter is as follows：
Using pure silicon target, first forvacuum to 10-4Pa, then pass to Ar and C2H2Mixed gas carries out intermediate frequency magnetic control and splashed
Penetrate, Ar/C2H2Flow-rate ratio is 5 (first gradient), and sputtering current 10A, sputtering pressure 0.5Pa, heating-up temperature is 300 DEG C,
Target-substrate distance 80mm.Ar flows are constant, and gradient reduces C2H2Gas flow, make Ar/C2H2Flow-rate ratio fades to 10 from 5, sets 4 altogether
Individual gradient, the Ar/C of each gradient2H2Flow-rate ratio is 5,6,8,10, each gradient C2H2Gas flow keeps 20min, obtains 4 lists
Layer, graded layer thickness are 1.6 μm.
Other operations are the same as embodiment 2.
Composite coating is by test, and in the range of 500~600 DEG C, PRF is 1400 or so.
Embodiment above is only that the embodiment of the present invention is described, and not the scope of the present invention is entered
Row limits, and those skilled in the art can also do numerous modifications and variations, be set not departing from the present invention on the basis of existing technology
On the premise of meter spirit, all variations and modifications that this area ordinary skill technical staff makes to technical scheme,
It all should fall into the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of stainless steel carborundum hydrogen permeation preventing coating, it is characterised in that including successively being arranged upwards from stainless steel base
Transition zone, storage H cushions, resistance hydrogen layer；The transition zone is made up of layer of titanium metal and TiN layer, and the storage H cushions are amorphous
The Si of statexC1-x, 1 ＞ x >=0.5, the resistance hydrogen layer is SiC；
Wherein, the transition zone is made up of Ti layers and TiN layer, wherein 100~300nm of Ti thickness, TiN layer 200~500nm of thickness,
The storage H cushions are amorphous SixC1-xGraded bedding, 1 ＞ x >=0.5,1~4 μm of thickness, the resistance hydrogen thickness degree are
500nm~1 μm.
2. stainless steel according to claim 1 carborundum hydrogen permeation preventing coating, it is characterised in that the stainless steel base
Material be 316L, 304 and 321 in one kind.
3. the preparation method of the stainless steel carborundum hydrogen permeation preventing coating of claim 1 or 2, it is characterised in that including with
Lower step：
S1 prepares transition zone Ti/TiN using the method for magnetron sputtering, first using Ti targets as sputtering target material deposited metal Ti layers, first
Forvacuum is to 10-5~10-3Pa, be passed through argon gas and carry out d.c. sputtering, electric current be 5~8A, working vacuum for 0.3Pa~
0.6Pa, heating-up temperature are 150~300 DEG C, and target-substrate distance is 80~100mm；Then sputtered using intermediate frequency power supply or radio-frequency power supply
TiN layer；
S2 prepares storage H cushions on transition zone using vapour deposition process, and the vapour deposition process is physical vaporous deposition
Or chemical vapour deposition technique；
S3 prepares SiC resistance hydrogen layers on storage H cushions using vapour deposition process, and the vapour deposition process is physical vaporous deposition
Or chemical vapour deposition technique.
4. preparation method according to claim 3, it is characterised in that the preparation method of TiN layer is in the transition zone：
The depositing TiN on metal Ti layers, first forvacuum to 10-5~10-3Pa, it is passed through argon gas and nitrogen, Ar/N2Flow-rate ratio is
2~8, using medium frequency magnetron sputtering, electric current is 5~8A, and working vacuum is 0.3Pa~0.6Pa, and heating-up temperature is 150~300
DEG C, target-substrate distance is 80~100mm；
Or, in the preparation method of the transition zone, the preparation method of TiN layer is：First forvacuum is to 10-5~10-3Pa, it is passed through argon
Gas and nitrogen, Ar/N2Flow-rate ratio is 2~8, and sputtering power is 100~200W, and working vacuum is 0.3Pa~2Pa, heating-up temperature
For 150~300 DEG C, target-substrate distance is 80~100mm, and thickness is 200~500nm.
5. the preparation method according to claim 3 or 4, it is characterised in that the preparation method of the storage H cushions is：
Using pure silicon target, first forvacuum to 10-5~10-3Pa, then pass to Ar and C2H2Mixed gas carries out intermediate frequency magnetic control
Sputtering, Ar/C2H2Flow-rate ratio is 2~20, and sputtering current is 4~10A, and sputtering pressure is 0.3Pa~0.6Pa, and heating-up temperature is
150~300 DEG C, 80~100mm of target-substrate distance.
6. preparation method according to claim 5, it is characterised in that during storage H cushions are coated with, the Ar that is passed through
Flow is constant, and sputtering current increases to 10A from 4A gradients；Or gradient reduces C2H2Gas flow, make Ar/C2H2Flow-rate ratio is from 2
To 20,2~5 gradients, the sputtering current or C of each gradient are set altogether2H2Gas flow keeps 10~20min, obtains 2~5 lists
Layer.
7. the preparation method according to claim 3 or 4, it is characterised in that the preparation method of the storage H cushions is：
Precursor raw material is methyl trichlorosilane, carrier gas H2, diluent gas is argon gas, 1100~1300 DEG C of depositing temperature, MTS+
H2Flow rises to 0.8L/min from 0.35L/min gradients, sets 2~5 gradients, each gradient MTS+H altogether2Flow holding 10~
20min, carrier gas Ar flow 160L/h, carrier gas H2Flow rises to 4L/min from 1L/min gradients.
8. the preparation method according to claim 3 or 4, it is characterised in that the preparation method of SiC resistance hydrogen layer is：
Using pure silicon target, first forvacuum to 10-5~10-3Pa；Then pass to Ar and C2H2Mixed gas carries out intermediate frequency magnetic control
Sputtering, Ar/C2H2Flow-rate ratio is 2~20, and sputtering current is 4~10A, and sputtering pressure is 0.3Pa~0.6Pa, and heating-up temperature is
150~300 DEG C, 80~100mm of target-substrate distance.
9. the preparation method according to claim 3 or 4, it is characterised in that the preparation method of SiC resistance hydrogen layer is：
Using SiC target material, first forvacuum to 10-5~10-3Pa, Ar is then passed to, sputtering power is 120~160W, sputters gas
It is 300~600 DEG C to press as 0.3Pa~0.6Pa, heating-up temperature, 80~100mm of target-substrate distance.
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