CN110373628A - Spontaneous High temperature diffusion barrier of a kind of refractory metal surfaces reaction in-situ and preparation method thereof - Google Patents
Spontaneous High temperature diffusion barrier of a kind of refractory metal surfaces reaction in-situ and preparation method thereof Download PDFInfo
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- CN110373628A CN110373628A CN201910790625.5A CN201910790625A CN110373628A CN 110373628 A CN110373628 A CN 110373628A CN 201910790625 A CN201910790625 A CN 201910790625A CN 110373628 A CN110373628 A CN 110373628A
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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
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
Abstract
The invention discloses a kind of spontaneous High temperature diffusion barrier of refractory metal surfaces reaction in-situ, the spontaneous High temperature diffusion barrier of the reaction in-situ is located at refractory metal and fusing between silicide high-temp protective coating coated in refractory metal surfaces, using SiC as main phase；The invention also discloses a kind of preparation methods of the spontaneous High temperature diffusion barrier of refractory metal surfaces reaction in-situ, graphene slurry or graphene oxide slurry, silicide composite suspension slurry are successively preset at the surface of refractory metal basal body after pretreatment by this method, are fused to obtain the spontaneous High temperature diffusion barrier of reaction in-situ.High temperature diffusion barrier of the invention reduces the high temperature counterdiffusion rate between high-temperature protection coating and refractory metal basal body, ensure that the high-temperature oxidation resistance of high-temperature protection coating and extends its high-temperature service service life；The present invention improves interface compatibility, refractory metal-diffusion barrier-high-temperature protection coating is made to have good heat resistanceheat resistant circulation and thermal shock resistance by the spontaneous preparation High temperature diffusion barrier of reaction in-situ.
Description
Technical field
The invention belongs to refractory metal high temperature protection technical fields, and in particular to a kind of refractory metal surfaces reaction in-situ from
Raw High temperature diffusion barrier and preparation method thereof.
Background technique
Refractory metal has excellent elevated temperature strength and toughness and good processing performance, in aerospace and atom
It can be widely used in industry.However, refractory alloy is in superhigh temperature oxidation environment using there are anti-oxidant problems.?
Refractory metal surfaces apply superhigh temperature protective coating, can significantly improve its high-temperature oxidation resistance, extend the height of refractory metal
Warm service life.The most widely used high-temperature protection coating of refractory metal surfaces is silicide coating, coat of aluminide and expensive
Metal coating.
However, there are significant difference, coating and each constituent elements in matrix for the chemical component of above-mentioned coating and refractory metal basal body
Chemical activity it is different, counterdiffusion unavoidably occurs between military service process floating coat and matrix.On the one hand, counterdiffusion causes to apply
A large amount of consumption of the effective constituent element of resistance to high temperature oxidation (Si, Al, Ir etc.), substantially reduce coating life, moreover, matrix element in layer
Coating is diffused into, the chemical composition change of coating is caused, to reduce the high-temperature oxidation resistance of coating；On the other hand, it applies
Interface diffusion and reaction can occur between layer and the intracorporal some constituent elements of base and generate weld metal zone brittle intermetallic thing phase or topological closs packing
Phase causes to form harmful phase region between coating/matrix, and the solid solution that the generation of these precipitated phases not only consumes refractory metal basal body is strong
Change element, weakens the solid solution strengthening effect of solid solution element, and precipitated phase is often that the cradle of crackle and crackle expand rapidly
The channel of exhibition significantly reduces the life-span of creep rupture of refractory metal basal body.
Therefore, counterdiffusion and high-temperature interface between coating and refractory metal basal body is inhibited to be reacted to extend refractory metal
The key in high-temperature service service life.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of refractory metal table
The spontaneous High temperature diffusion barrier of face reaction in-situ.The spontaneous High temperature diffusion barrier of the reaction in-situ significantly reduces high-temperature protection coating and infusibility
High temperature counterdiffusion rate between metal, avoids the consumption of the effective constituent element of resistance to high temperature oxidation in high-temperature protection coating, Yi Jinan
Element in molten metal enters coating, ensure that the high-temperature oxidation resistance of high-temperature protection coating, significantly extends high temperature protection
The high-temperature service service life of coating.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of refractory metal surfaces reaction in-situ from
Raw High temperature diffusion barrier, which is characterized in that the spontaneous High temperature diffusion barrier of the reaction in-situ is located at refractory metal and is coated in refractory metal
Between the high-temperature protection coating on surface, based on the SiC of high-temperature chemical reaction generation between Si and graphene or graphene oxide
Phase, the reaction in-situ spontaneous High temperature diffusion barrier with a thickness of 0.5 μm~10 μm；The high-temperature protection coating is to fuse silicide painting
Layer, High temperature diffusion barrier can inhibit or slow down under the conditions of 2000 DEG C of temperature below refractory metal and high-temperature protection coating it
Between interdiffusion at interface reaction.
The present invention using most common high-temperature protection coating-fuse Si element in silicide coating and graphene oxide or
High-temperature interface reaction between person's graphene is applied in refractory metal basal body with the high temperature protection for being coated in refractory metal basal body surface
It introduces between layer and hinders by the spontaneous High temperature diffusion of the reaction in-situ of main phase of SiC, since the fusing point of SiC is up to 2700 DEG C, crystal knot
Structure (β-SiC) is fine and close, has excellent thermal structure and chemical stability, and SiC is ol cpds, crystal structure midpoint
Battle array defect density is low, this makes diffusion coefficient of the Si element in SiC extremely low, in addition, the thermal expansion coefficient and refractory metal of SiC
And high-temperature protection coating is close, the knot under cold cycling military service operating condition, with refractory metal basal body and high-temperature protection coating
The condition good, satisfaction is used as diffusion barrier coating material is closed, therefore the insertion of SiC diffusion barrier significantly reduces high temperature and prevents
The high temperature counterdiffusion rate between coating and refractory metal basal body is protected, the effective constituent element of resistance to high temperature oxidation in high-temperature protection coating is avoided
Consumption and refractory metal basal body in element (such as Nb, Ta, W) enter high-temperature protection coating, ensure that high temperature protection apply
The high-temperature oxidation resistance of layer, significantly extends the high-temperature service service life of high-temperature protection coating.
A kind of spontaneous High temperature diffusion barrier of above-mentioned refractory metal surfaces reaction in-situ, which is characterized in that the refractory metal
For Nb alloy, Mo or Mo alloy, W or W alloy or Ta alloy.Above-mentioned refractory metal mechanical behavior under high temperature is excellent, room temperature processability
Can be good, after applying high-temperature protection coating, it can be on active service for a long time as high-temperature structural material.
In addition, the present invention also provides a kind of preparation method of the spontaneous High temperature diffusion barrier of refractory metal surfaces reaction in-situ,
It is characterized in that, method includes the following steps:
Step 1: successively being polished the surface of refractory metal, sandblasting, pickling and ungrease treatment, after obtaining pretreatment
Refractory metal；
Step 2: graphene or graphene oxide and dispersant are placed on progress ball milling mixing in ball mill, obtain
To graphene slurry or graphene oxide slurry；The volume of the dispersing agent is the 10~30 of graphene or graphene oxide quality
Times, wherein the unit of volume is mL, and the unit of quality is g；
Step 3: using pneumatic spray application method that graphene slurry obtained in step 2 or graphene oxide slurry is preset
The surface of refractory metal after pretreatment, is then dried, it is preset to obtain slurry in refractory metal surfaces in step 1
Layer；The temperature of the drying is 40 DEG C~80 DEG C, and the time is 30min~120min；
Step 4: by fuse silicide coating to prepare raw material powder uniform with dispersant, it is compound to obtain silicide
Suspended nitride；
Step 5: silicide composite suspension slurry obtained in step 4 to be preset to the obtained infusibility gold in step 3
The surface of the slurry initialization layer of category obtains silicide initialization layer in refractory metal surfaces after drying, is then placed into vacuum burning
It is 7 × 10 in vacuum degree in freezing of a furnace-3Pa~2.0 × 10-2High-temperature melting is carried out under conditions of Pa, in infusibility gold after furnace cooling
Metal surface obtains high-temperature protection coating and the spontaneous High temperature diffusion of reaction in-situ between refractory metal and high-temperature protection coating
Barrier；The detailed process of the high-temperature melting are as follows: 700 DEG C~900 DEG C heat preservations are first warming up to 10 DEG C/min~30 DEG C/min rate
30min~120min, then with 10 DEG C/min~15 DEG C/min rate be warming up to 1450 DEG C~1550 DEG C heat preservation 30min~
90min。
The present invention is anti-in refractory metal and outer layer high temperature by the chemical reaction between graphene or graphene oxide and Si
Spontaneous the is formationed SiC High temperature diffusion of reaction in-situ between coating is protected to hinder, compared with the existing technology in directly in refractory metal and outer layer
The metal/ceramic human interface that ceramic diffusion barrier is formed is prepared between high-temperature protection coating, method of the invention is in refractory metal
The interface formed between matrix, SiC High temperature diffusion barrier and outer layer high-temperature protection coating is the spontaneous interface of reaction in-situ, is avoided
Since matrix and high-temperature protection coating material category, constituent structure difference form diffusion barrier/matrix and diffusion barrier/coating interface,
To have better interface compatibility, refractory metal basal body under coating preparation and cold and hot military service operating condition/SiC diffusion is reduced
Barrier/silicide coating interface stress level makes refractory metal-diffusion barrier-high-temperature protection coating system have good heat resistanceheat resistant
Circulation and thermal shock resistance.
Above-mentioned method, which is characterized in that the sand grains that sandblasting described in step 1 uses is emergy, bead or oxidation
Zircon sand, the pressure of the sandblasting are 0.2MPa~0.8MPa, and blast time is 2min~8min；The acid solution that the pickling uses by
Hydrofluoric acid solution and concentrated nitric acid solution are according to (6~7): the volume ratio of (3~4) mixes, the quality of the hydrofluoric acid solution
Concentration is 40%~60%, and the mass concentration of concentrated nitric acid solution is 65%~68%, and the time of the pickling is 1min~5min.
Due to the affinity of refractory metal and oxygen height, easily generation oxygen uptake, therefore be conducive to further go using above-mentioned pre-treating technology
Except the oxygen absorption layer of refractory metal surfaces, while enhancing refractory metal surfaces roughness, to be more advantageous to diffusion barrier and Metal Substrate
Body forms good interface cohesion.
Above-mentioned method, which is characterized in that the dispersing agent mixed in step 2 with graphene oxide is distilled water or anhydrous
Ethyl alcohol, the dispersing agent mixed with graphene is by varnish and ethyl acetate according to (1~2): the volume ratio of (3~4) mixes.Oxygen
Graphite alkene is dissolved in water, and making solvent with water or dehydrated alcohol can smoothly dissolve, and graphene is not soluble in water, and selection uses varnish
Disperse with the mixed liquor of ethyl acetate as the dissolution that dispersing agent promotes graphene.
Above-mentioned method, which is characterized in that graphene slurry described in step 2 or graphene oxide slurry contain Si powder,
The partial size of the Si powder is not more than 1 μm, the graphite oxide in graphene or graphene oxide slurry in the graphene slurry
The atomic percent of alkene and Si are 1:(0~1).The silicon powder of above-mentioned fine particle size is conducive to spontaneous quick and abundant of reaction in-situ
Carry out, above-mentioned atomic percent be conducive to graphene or graphene oxide and Si it is abundant it is complete react, while being applied with silicide
Layer forms good interface cohesion.
Above-mentioned method, which is characterized in that the drying temperature that silicide slurry initialization layer is obtained described in step 5 is 40
DEG C~200 DEG C, drying time is 0.5h~8h.Above-mentioned drying condition is conducive to obtain the low silicide slurry of water content preset
Layer, is conducive to subsequent high temperature and fuses going on smoothly for process.
Compared with the prior art, the present invention has the following advantages:
1, the present invention introduces between refractory metal basal body and high-temperature protection coating coated in refractory metal basal body surface
The spontaneous High temperature diffusion barrier of reaction in-situ significantly reduces the high temperature counterdiffusion speed between high-temperature protection coating and refractory metal basal body
Rate, avoids the consumption of the effective constituent element of resistance to high temperature oxidation in high-temperature protection coating and the element in refractory metal basal body enters
Coating ensure that the high-temperature oxidation resistance of high-temperature protection coating, significantly extend the high-temperature service service life of high-temperature protection coating.
2, the fusing point of the spontaneous diffusion barrier main phase SiC of reaction in-situ of the present invention is up to 2700 DEG C, and the service temperature of diffusion barrier is high,
And due to the crystal structure of SiC (β-SiC) densification, there is excellent thermal structure and chemical stability, meanwhile, SiC is line
Property compound, dot matrix defect density is low in crystal structure, this makes high-temperature protection coating fuse Si element in silicide coating
Diffusion coefficient in SiC is extremely low, improves the resistance diffusivity for fusing silicide coating, improves and fuse silicide coating
High-temperature oxidation resistance.
3, compared with the existing technology, the present invention passes through the change between graphene or graphene oxide and high-temperature protection coating Si
Learn reaction, spontaneous the is formationed SiC High temperature diffusion of reaction in-situ hinders between refractory metal and outer layer high-temperature protection coating, avoid by
Diffusion barrier/matrix and diffusion barrier/coating interface are formed in matrix and high-temperature protection coating material category, constituent structure difference, from
And have better interface compatibility, reduce high-temperature protection coating preparation and cold and hot military service operating condition under refractory metal basal body/
SiC diffusion barrier/silicide coating interface stress level has refractory metal-diffusion barrier-high-temperature protection coating system good
Heat resistanceheat resistant circulation and thermal shock resistance.
4, the thermal expansion coefficient of in-situ authigenic SiC High temperature diffusion of the invention barrier and refractory metal and high temperature protection apply
Layer-fuses silicide coating and approaches, and under cold cycling military service operating condition, high-temperature protection coating/diffusion barrier/basal body interface heat is answered
Power is small, is conducive to the antistrip performance for enhancing high-temperature protection coating.
Technical solution of the present invention is described in further detail below by embodiment.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the refractory metal that surface of the present invention is provided with slurry initialization layer and silicide initialization layer.
Fig. 2 is the knot for the refractory metal that surface of the present invention forms the spontaneous High temperature diffusion barrier of reaction in-situ and high-temperature protection coating
Structure schematic diagram.
Specific embodiment
As shown in Figure 1, surface is provided with slurry initialization layer and silicide initialization layer in 1~embodiment of the embodiment of the present invention 4
Refractory metal structure are as follows: slurry initialization layer is provided on the surface of refractory metal, the surface of slurry initialization layer is provided with silicon
Compound initialization layer；After high-temperature melting, which forms the spontaneous High temperature diffusion barrier of reaction in-situ and height at the surface in Fig. 2
The structure of the refractory metal of warm protective coating are as follows: the formation of silicide initialization layer fuses silicide coating, and refractory metal is pre- with slurry
Graphene oxide or graphene the generation pyroreaction set in layer generate a small amount of metal carbides, fuse in silicide coating
Si element in slurry initialization layer graphene oxide or graphene occur high-temperature interface react, formation using SiC as main phase
Reaction in-situ spontaneous High temperature diffusion barrier.
Embodiment 1
The spontaneous High temperature diffusion barrier of the Ta12W alloy surface reaction in-situ of the present embodiment is located at Ta12W alloy and is coated in
It is raw with high-temperature chemical reaction between Si and graphene oxide between the Si-Cr-Ti-Zr high-temperature protection coating of Ta12W alloy surface
At SiC be main phase, the reaction in-situ spontaneous High temperature diffusion barrier with a thickness of 10 μm.
The preparation method of the Ta12W alloy surface reaction in-situ of the present embodiment spontaneous High temperature diffusion barrier the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of Ta12W alloy, then carries out sandblasting and pickling, then
It immerses in acetone and carries out ungrease treatment, obtain pretreated Ta12W alloy；The sand grains that the sandblasting uses is emergy, institute
The pressure for stating sandblasting is 0.8MPa, blast time 8min；The acid solution that the pickling uses is molten by hydrofluoric acid solution and concentrated nitric acid
Liquid is mixed according to the volume ratio of 7:3, and the mass concentration of the hydrofluoric acid solution is 40%, the mass concentration of concentrated nitric acid solution
It is 65%, the time of the pickling is 5min；
It is placed in ball mill Step 2: graphene oxide is mixed with distilled water, the condition for being 320 revs/min in revolving speed
Lower ball milling mixes 120min, obtains graphene oxide slurry；The volume of the distilled water is 30 times of graphene oxide quality,
The unit of middle volume is mL, and the unit of quality is g；
It is passed through Step 3: graphene oxide slurry obtained in step 2 is preset in step 1 using pneumatic spray application method
The surface of pretreated Ta12W alloy, is then dried, and obtains slurry initialization layer in Ta12W alloy surface；The drying
Temperature be 80 DEG C, time 120min；
Step 4: by Si-Cr-Ti-Zr fuse silicide coating to prepare raw material powder uniform with dispersant, obtain
Silicide composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
It is closed Step 5: silicide composite suspension slurry obtained in step 4 is preset at Ta12W obtained in step 3
The surface of the slurry initialization layer of gold obtains silicide initialization layer in Ta12W alloy surface, is then placed into 40 DEG C of drying 8h
It is 2.0 × 10 in vacuum degree in vacuum sintering furnace-2High-temperature melting is carried out under conditions of Pa, in refractory metal table after furnace cooling
Face obtains the Si-Cr-Ti-Zr high-temperature protection coating with a thickness of 125 μm and to be located at Ta12W alloy and Si-Cr-Ti-Zr high temperature anti-
Protect hindering between coating with a thickness of 10 μm of the spontaneous High temperature diffusion of reaction in-situ；The detailed process of the high-temperature melting are as follows: first with
10 DEG C/min rate is warming up to 700 DEG C of heat preservation 120min, is then warming up to 1550 DEG C of heat preservation 90min with 15 DEG C/min rate.
Through detecting, relative to the Si-Cr-Ti-Zr high-temperature protection coating for not applying the High temperature diffusion barrier that SiC is main phase, originally
The spontaneous High temperature diffusion barrier of the reaction in-situ of embodiment can significantly slow the Si-Cr- of Ta12W alloy and outer layer at 2000 DEG C or less
Interface diffusion and reaction between Ti-Zr high-temperature protection coating, and Si-Cr-Ti-Zr high-temperature protection coating is anti-in 2000 DEG C of constant temperature
Oxidation life significantly improves.
Embodiment 2
The spontaneous High temperature diffusion barrier of the Nb521 alloy surface reaction in-situ of the present embodiment is located at Nb521 alloy and is coated in
Between the Si-Mo-Zr high-temperature protection coating of Nb521 alloy surface, with the SiC of high-temperature chemical reaction generation between Si and graphene
For main phase, the spontaneous High temperature diffusion barrier of the reaction in-situ with a thickness of 6 μm.
The preparation method of the Nb521 alloy surface reaction in-situ of the present embodiment spontaneous High temperature diffusion barrier the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of Nb521 alloy, then carries out sandblasting and pickling, then
It immerses in acetone and carries out ungrease treatment, obtain pretreated Nb521 alloy；The sand grains that the sandblasting uses for aoxidize zircon sand,
The pressure of the sandblasting is 0.6MPa, blast time 4min；The acid solution that the pickling uses is by hydrofluoric acid solution and concentrated nitric acid
Solution is mixed according to the volume ratio of 6:4, and the mass concentration of the hydrofluoric acid solution is 60%, and the quality of concentrated nitric acid solution is dense
Degree is 68%, and the time of the pickling is 3min；
Step 2: graphene and dispersant are placed in ball mill, ball under conditions of revolving speed is 350 revs/min
Mill mixes 240min, obtains graphene slurry；The dispersing agent by varnish and ethyl acetate according to the volume ratio mixing of 1:4 and
At the volume of dispersing agent is 10 times of graphene quality, and wherein the unit of volume is mL, and the unit of quality is g；
Located in advance Step 3: graphene slurry obtained in step 2 is preset in step 1 using pneumatic spray application method
The surface of Nb521 alloy after reason, is then dried, and obtains slurry initialization layer in Nb521 alloy surface；The temperature of the drying
Degree is 40 DEG C, time 90min；
Step 4: by Si-Mo-Zr fuse silicide coating to prepare raw material powder uniform with dispersant, obtain silicon
Compound composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
It is closed Step 5: silicide composite suspension slurry obtained in step 4 is preset at Nb521 obtained in step 3
The surface of the slurry initialization layer of gold obtains silicide initialization layer in Nb521 alloy surface, then places in 200 DEG C of drying 0.5h
It is 7.0 × 10 in vacuum degree in vacuum sintering furnace-3High-temperature melting is carried out under the conditions of Pa, in Nb521 alloy table after furnace cooling
Face obtains the Si-Mo-Zr high-temperature protection coating with a thickness of 125 μm and is located at Nb521 alloy and Si-Mo-Zr high-temperature protection coating
Between with a thickness of the spontaneous High temperature diffusion barrier of 6 μm of reaction in-situ；The detailed process of the high-temperature melting are as follows: first with 30 DEG C/min
Rate is warming up to 900 DEG C of heat preservation 30min, is then warming up to 1450 DEG C of heat preservation 60min with 10 DEG C/min rate.
Through detecting, relative to the Si-Mo-Zr high-temperature protection coating for not applying the High temperature diffusion barrier that SiC is main phase, this implementation
The spontaneous High temperature diffusion barrier of the reaction in-situ of example can significantly slow the Si-Mo-Zr high temperature of Nb521 alloy and outer layer at 1600 DEG C or less
Interface diffusion and reaction between protective coating, and Si-Mo-Zr high-temperature protection coating is significant 1600 DEG C of constant temperature anti-oxidant service life
It improves.
Embodiment 3
The Mo1 surface in situ self-formed from reaction High temperature diffusion barrier of the present embodiment is located at Mo1 and is coated in the Si-Cr- on the surface Mo1
Between Ti high-temperature protection coating, the SiC generated using high-temperature chemical reaction between Si and graphene oxide is main phase, the reaction in-situ
Spontaneous High temperature diffusion barrier with a thickness of 0.5 μm.
The present embodiment Mo1 surface in situ self-formed from reaction High temperature diffusion barrier preparation method the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of Mo1, then carries out sandblasting and pickling, then immerse third
Ungrease treatment is carried out in ketone, obtains pretreated Mo1；The sand grains that the sandblasting uses is bead, the pressure of the sandblasting
For 0.2MPa, blast time 8min；The acid solution that the pickling uses is by hydrofluoric acid solution and concentrated nitric acid solution according to the body of 7:4
Product ratio mixes, and the mass concentration of the hydrofluoric acid solution is 50%, and the mass concentration of concentrated nitric acid solution is 67%, the acid
The time washed is 1min；
It is 350 revs/min in revolving speed Step 2: graphene oxide, Si powder are mixed and be placed in ball mill with dehydrated alcohol
Under conditions of ball milling mix 180min, obtain the graphene oxide slurry of the powder containing Si；The volume of the dehydrated alcohol is oxidation stone
20 times of black alkene quality, wherein the unit of volume is mL, and the unit of quality is g；The partial size of the Si powder is described no more than 1 μm
The atomic percent of graphene oxide and Si in the graphene oxide slurry of the powder containing Si is 1:1；
Step 3: the graphene oxide slurry of the powder containing Si obtained in step 2 is preset at step using pneumatic spray application method
The surface of Mo1 after pretreatment, is then dried, obtains slurry initialization layer on the surface Mo1 in rapid one；The temperature of the drying
Degree is 60 DEG C, time 30min；
Step 4: by Si-Cr-Ti fuse silicide coating to prepare raw material powder uniform with dispersant, obtain silicon
Compound composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
Step 5: silicide composite suspension slurry obtained in step 4 to be preset to the slurry of Mo1 obtained in step 3
The surface of material initialization layer obtains silicide initialization layer on the surface Mo1, is then placed into vacuum sintering furnace in 120 DEG C of drying 4h
In, it is 1.0 × 10 in vacuum degree-2High-temperature melting is carried out under conditions of Pa, is obtained after furnace cooling on the surface Mo1 with a thickness of 110 μ
The Si-Cr-Ti high-temperature protection coating of m and between Mo1 and Si-Cr-Ti high-temperature protection coating with a thickness of 0.5 μm of original position
Self-formed from reaction High temperature diffusion barrier；The detailed process of the high-temperature melting are as follows: 800 DEG C of heat preservations are first warming up to 20 DEG C/min rate
Then 90min is warming up to 1450 DEG C of heat preservation 30min with 12 DEG C/min rate.
Through detecting, relative to the Si-Cr-Ti coating for not applying the High temperature diffusion barrier that SiC is main phase, the original position of the present embodiment
Self-formed from reaction High temperature diffusion barrier can significantly slow between Mo1 and the Si-Cr-Ti high-temperature protection coating of outer layer at 1400 DEG C or less
Interface diffusion and reaction.
Refractory metal in the present embodiment can also be Mo alloy.
Embodiment 4
The spontaneous High temperature diffusion barrier of the refractory metal surfaces reaction in-situ of the present embodiment is located at W and is coated in the Si- of W surface
Between Mo-Zr high-temperature protection coating, the SiC generated using high-temperature chemical reaction between Si and graphene is main phase, the reaction in-situ
Spontaneous High temperature diffusion barrier with a thickness of 3 μm.
The preparation method of the refractory metal surfaces reaction in-situ of the present embodiment spontaneous High temperature diffusion barrier the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of W, then carries out sandblasting and pickling, then immerse acetone
Middle carry out ungrease treatment, obtains pretreated W；For emergy, the pressure of the sandblasting is the sand grains that the sandblasting uses
0.4MPa, blast time 4min；The acid solution that the pickling uses is by hydrofluoric acid solution and concentrated nitric acid solution according to the volume of 6:3
Than mixing, the mass concentration of the hydrofluoric acid solution is 48%, and the mass concentration of concentrated nitric acid solution is 65%, the pickling
Time be 3min；
Step 2: graphene, Si powder and dispersant are placed in ball mill, the condition for being 350 revs/min in revolving speed
Lower ball milling mixes 120min, obtains the graphene slurry of the powder containing Si；The dispersing agent is by varnish and ethyl acetate according to the body of 2:3
Product ratio mixes, and the volume of the dispersing agent is 25 times of graphene quality, and wherein the unit of volume is mL, the unit of quality
For g；The partial size of the Si powder is not more than 1 μm, the atomic percent of graphene and Si in the graphene slurry of the powder containing Si
For 1:1；
Located in advance Step 3: graphene slurry obtained in step 2 is preset in step 1 using pneumatic spray application method
The surface of W after reason, is then dried, and obtains slurry initialization layer in W surface；The temperature of the drying is 70 DEG C, and the time is
100min；
Step 4: by Si-Mo-Zr fuse silicide coating to prepare raw material powder uniform with dispersant, obtain silicon
Compound composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
Step 5: silicide composite suspension slurry obtained in step 4 to be preset to the slurry of W obtained in step 3
The surface of initialization layer obtains silicide initialization layer in W surface, is then placed into vacuum sintering furnace in 180 DEG C of drying 2h,
Vacuum degree is 8.0 × 10-3High-temperature melting is carried out under conditions of Pa, obtains the Si- with a thickness of 140 μm in W surface after furnace cooling
Mo-Zr high-temperature protection coating and between W and Si-Mo-Zr high-temperature protection coating with a thickness of 3 μm of the spontaneous height of reaction in-situ
Warm diffusion barrier；The detailed process of the high-temperature melting are as follows: 850 DEG C of heat preservation 60min are first warming up to 25 DEG C/min rate, then with
15 DEG C/min rate is warming up to 1500 DEG C of heat preservation 80min.
Through detecting, relative to the Si-Mo-Zr coating for not applying the High temperature diffusion barrier that SiC is main phase, the original position of the present embodiment
Self-formed from reaction High temperature diffusion barrier can significantly slow the boundary between W and the Si-Mo-Zr high-temperature protection coating of outer layer at 1500 DEG C or less
Face diffusion reaction.
Embodiment 5
The spontaneous High temperature diffusion barrier of the refractory metal surfaces reaction in-situ of the present embodiment is located at Ta10W and is coated in Ta10W table
Between the Si-Cr-Ti-Zr high-temperature protection coating in face, using the SiC of high-temperature chemical reaction generation between Si and graphene as main phase,
The reaction in-situ spontaneous High temperature diffusion barrier with a thickness of 5 μm.
The preparation method of the refractory metal surfaces reaction in-situ of the present embodiment spontaneous High temperature diffusion barrier the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of Ta10W, then carries out sandblasting and pickling, then immerse
Ungrease treatment is carried out in acetone, obtains pretreated Ta10W；The sand grains that the sandblasting uses for emergy, the sandblasting
Pressure is 0.6MPa, blast time 3min；The acid solution that the pickling uses is by hydrofluoric acid solution and concentrated nitric acid solution according to 6:3
Volume ratio mix, the mass concentration of the hydrofluoric acid solution is 48%, and the mass concentration of concentrated nitric acid solution is 65%, institute
The time for stating pickling is 3min；
Step 2: graphene, Si powder and dispersant are placed in ball mill, the condition for being 350 revs/min in revolving speed
Lower ball milling mixes 120min, obtains the graphene slurry of the powder containing Si；The dispersing agent is by varnish and ethyl acetate according to 1:3.5's
Volume ratio mixes, and the volume of the dispersing agent is 25 times of graphene quality, and wherein the unit of volume is mL, the list of quality
Position is g；The partial size of the Si powder is not more than 1 μm, the atomic percent of graphene and Si in the graphene slurry of the powder containing Si
Than for 1:0.4；
Located in advance Step 3: graphene slurry obtained in step 2 is preset in step 1 using pneumatic spray application method
The surface of Ta10W after reason, is then dried, and obtains slurry initialization layer on the surface Ta10W；The temperature of the drying is 70
DEG C, time 100min；
Step 4: by Si-Cr-Ti-Zr fuse silicide coating to prepare raw material powder uniform with dispersant, obtain
Silicide composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
Step 5: silicide composite suspension slurry obtained in step 4 is preset at Ta10W obtained in step 3
The surface of slurry initialization layer obtains silicide initialization layer on the surface Ta10W, is then placed into vacuum-sintering in 180 DEG C of drying 2h
It is 1.0 × 10 in vacuum degree in furnace-2High-temperature melting is carried out under conditions of Pa, after furnace cooling the surface Ta10W obtain with a thickness of
150 μm of Si-Cr-Ti-Zr high-temperature protection coating and the thickness between Ta10W and Si-Cr-Ti-Zr high-temperature protection coating
For the spontaneous High temperature diffusion barrier of 5 μm of reaction in-situs；The detailed process of the high-temperature melting are as follows: be first warming up to 20 DEG C/min rate
Then 800 DEG C of heat preservation 60min are warming up to 1500 DEG C of heat preservation 90min with 15 DEG C/min rate.
Through detecting, relative to do not apply SiC be main phase High temperature diffusion hinder Si-Cr-Ti-Zr coating, the present embodiment
The spontaneous High temperature diffusion barrier of reaction in-situ can significantly slow the Si-Cr-Ti-Zr high temperature protection of Ta10W and outer layer at 1600 DEG C or less
Interface diffusion and reaction between coating.
Embodiment 6
The C103 niobium alloy surface in situ self-formed from reaction High temperature diffusion barrier of the present embodiment is located at C103 niobium alloy and is coated in
Between the Si-Cr-Ti high-temperature protection coating on C103 niobium alloy surface, generated with high-temperature chemical reaction between Si and graphene oxide
SiC be main phase, the reaction in-situ spontaneous High temperature diffusion barrier with a thickness of 4 μm.
The present embodiment C103 niobium alloy surface in situ self-formed from reaction High temperature diffusion barrier preparation method the following steps are included:
Step 1: using 600#SiC sand paper polishes to the surface of C103 niobium alloy, then carries out sandblasting and pickling,
It immerses again and carries out ungrease treatment in acetone, obtain pretreated C103 niobium alloy；The sand grains that the sandblasting uses is husky for corundum,
The pressure of the sandblasting is 0.4MPa, blast time 2min；The acid solution that the pickling uses is by hydrofluoric acid solution and concentrated nitric acid
Solution is mixed according to the volume ratio of 7:4, and the mass concentration of the hydrofluoric acid solution is 50%, and the quality of concentrated nitric acid solution is dense
Degree is 67%, and the time of the pickling is 1min；
It is 350 revs/min in revolving speed Step 2: graphene oxide, Si powder are mixed and be placed in ball mill with dehydrated alcohol
Under conditions of ball milling mix 180min, obtain the graphene oxide slurry of the powder containing Si；The volume of the dehydrated alcohol is oxidation stone
20 times of black alkene quality, wherein the unit of volume is mL, and the unit of quality is g；The partial size of the Si powder is described no more than 1 μm
The atomic percent of graphene oxide and Si in the graphene oxide slurry of the powder containing Si is 1:0.6；
Step 3: the graphene oxide slurry of the powder containing Si obtained in step 2 is preset at step using pneumatic spray application method
The surface of C103 niobium alloy after pretreatment, is then dried, it is preset to obtain slurry on C103 niobium alloy surface in rapid one
Layer；The temperature of the drying is 60 DEG C, time 30min；
Step 4: by Si-Cr-Ti fuse silicide coating to prepare raw material powder uniform with dispersant, obtain silicon
Compound composite suspension slurry；The dispersing agent is the ethyl acetate solution of varnish；
It is closed Step 5: silicide composite suspension slurry obtained in step 4 is preset at C103 niobium obtained in step 3
The surface of the slurry initialization layer of gold obtains silicide initialization layer in C103 niobium alloy alloy surface, then in 120 DEG C of drying 4h
It is placed in vacuum sintering furnace, is 9.0 × 10 in vacuum degree-3High-temperature melting is carried out under conditions of Pa, in C103 after furnace cooling
Niobium alloy surface obtains the Si-Cr-Ti high-temperature protection coating with a thickness of 110 μm and is located at C103 niobium alloy and Si-Cr-Ti high temperature
Hindering between protective coating with a thickness of 3 μm of the spontaneous High temperature diffusion of reaction in-situ；The detailed process of the high-temperature melting are as follows: first with
20 DEG C/min rate is warming up to 800 DEG C of heat preservation 90min, is then warming up to 1450 DEG C of heat preservation 60min with 12 DEG C/min rate.
Through detecting, relative to the Si-Cr-Ti coating for not applying the High temperature diffusion barrier that SiC is main phase, the original position of the present embodiment
Self-formed from reaction High temperature diffusion barrier can significantly slow C103 niobium alloy at 1400 DEG C or less and the Si-Cr-Ti high temperature protection of outer layer applies
Interface diffusion and reaction between layer.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (7)
1. a kind of spontaneous High temperature diffusion barrier of refractory metal surfaces reaction in-situ, which is characterized in that the spontaneous high temperature of the reaction in-situ expands
Barrier is dissipated to be located between refractory metal and high-temperature protection coating coated in refractory metal surfaces, with graphene or graphene oxide with
The SiC that high-temperature chemical reaction generates between Si is main phase, the reaction in-situ spontaneous High temperature diffusion barrier with a thickness of 0.5 μm~10 μ
m；The high-temperature protection coating is to fuse silicide coating, and the High temperature diffusion barrier can press down under the conditions of 2000 DEG C of temperature below
The interdiffusion at interface made or slowed down between refractory metal and high-temperature protection coating reacts.
2. the spontaneous High temperature diffusion barrier of a kind of refractory metal surfaces reaction in-situ according to claim 1, which is characterized in that institute
Stating refractory metal is Nb alloy, Mo or Mo alloy, W or W alloy or Ta alloy.
3. a kind of method for preparing the spontaneous High temperature diffusion barrier of the refractory metal surfaces reaction in-situ as described in claims 1 or 2,
It is characterized in that, method includes the following steps:
Step 1: successively being polished the surface of refractory metal, sandblasting, pickling and ungrease treatment, pretreated difficulty is obtained
Molten metal；
Step 2: graphene or graphene oxide and dispersant are placed on progress ball milling mixing in ball mill, stone is obtained
Black alkene slurry or graphene oxide slurry；The volume of the dispersing agent is 10~30 times of graphene or graphene oxide quality,
Wherein the unit of volume is mL, and the unit of quality is g；
Step 3: graphene slurry obtained in step 2 or graphene oxide slurry are preset at step using pneumatic spray application method
The surface of refractory metal after pretreatment, is then dried, obtains slurry initialization layer in refractory metal surfaces in rapid one；Institute
The temperature for stating drying is 40 DEG C~80 DEG C, and the time is 30min~120min；
Step 4: by fuse silicide coating to prepare raw material powder uniform with dispersant, obtain silicide composite suspension
Slurry；
Step 5: obtained refractory metal silicide composite suspension slurry obtained in step 4 being preset in step 3
The surface of slurry initialization layer obtains silicide initialization layer in refractory metal surfaces after drying, is then placed into vacuum sintering furnace
In, it is 7 × 10 in vacuum degree-3Pa~2.0 × 10-2High-temperature melting is carried out under conditions of Pa, in refractory metal table after furnace cooling
Face obtains high-temperature protection coating and the spontaneous High temperature diffusion barrier of reaction in-situ between refractory metal and high-temperature protection coating；Institute
State the detailed process of high-temperature melting are as follows: 700 DEG C~900 DEG C heat preservation 30min are first warming up to 10 DEG C/min~30 DEG C/min rate
Then~120min is warming up to 1450 DEG C~1550 DEG C heat preservation 30min~90min with 10 DEG C/min~15 DEG C/min rate.
4. according to the method described in claim 3, it is characterized in that, the sand grains that uses of sandblasting described in step 1 for emergy,
Bead or oxidation zircon sand, the pressure of the sandblasting are 0.2MPa~0.8MPa, and blast time is 2min~8min；The pickling
The acid solution of use is by hydrofluoric acid solution and concentrated nitric acid solution according to (6~7): the volume ratio of (3~4) mixes, the hydrogen fluorine
The mass concentration of acid solution is 40%~60%, and the mass concentration of concentrated nitric acid solution is 65%~68%, the time of the pickling
For 1min~5min.
5. according to the method described in claim 3, it is characterized in that, the dispersing agent mixed in step 2 with graphene oxide is to steam
Distilled water or dehydrated alcohol, the dispersing agent mixed with graphene is by varnish and ethyl acetate according to (1~2): the volume ratio of (3~4)
It mixes.
6. according to the method described in claim 3, it is characterized in that, graphene slurry described in step 2 or graphene oxide slurry
Material contains Si powder, and the partial size of the Si powder is no more than 1 μm, in the graphene or graphene oxide slurry in the graphene slurry
Graphene oxide and Si atomic percent be 1:(0~1).
7. according to the method described in claim 3, it is characterized in that, obtaining the baking of silicide slurry initialization layer described in step 5
Dry temperature is 40 DEG C~200 DEG C, and drying time is 0.5h~8h.
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| CN115821262A (en) * | 2022-12-06 | 2023-03-21 | 西北有色金属研究院 | High-temperature diffusion barrier for carbide on surface of refractory metal and preparation method thereof |
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