CN110205581A - The method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer - Google Patents

The method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer Download PDF

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Publication number
CN110205581A
CN110205581A CN201910638149.5A CN201910638149A CN110205581A CN 110205581 A CN110205581 A CN 110205581A CN 201910638149 A CN201910638149 A CN 201910638149A CN 110205581 A CN110205581 A CN 110205581A
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powder
infiltration layer
silicide infiltration
modified
crucible
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罗来马
章宇翔
吴玉程
刘东光
谭晓月
昝祥
朱晓勇
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

The invention discloses the methods that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer, Y and Al modified silicide infiltration layer is prepared in W surface by two-step method, on the basis of not changing existing silicide infiltration layer institutional framework, handle to obtain Y and Al modified silicide infiltration layer by subsequent pack cementation aluminizing.The method of the present invention has excellent oxidation-resistance property in Y and Al modified silicide infiltration layer prepared by W surface, and after 1000 DEG C aoxidize 10 hours, the oxidation film of layer surface is compact and complete, and unit area weight gain is 9.27~10.39mg/cm2。

Description

The method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer
Technical field
The invention belongs to high temperature alloy thermal protection technology fields, and in particular to a kind of tungsten surface two-step method preparation Y and Al changes The method of property silicide infiltration layer.
Background technique
W and its alloy are with its high-melting-point, low-density and good high/low temperature mechanical property, it is considered to be Aeronautics and Astronautics With the important candidate material of nuclear industry high temperature structural member.But its high-temperature oxidation resistance as high-temperature structural material away from using It is required that still there is gap, and have become the critical problem for hindering its application.Preparing protective coating on surface is to improve refractory metal The most effective approach of high-temperature oxidation resistance.
Silicide coating is the most widely used high-temperature oxidation resistant coating system of refractory metal surfaces.Although it has been applied to height In the surfacecti proteon of temperature alloy component, but it is more to always exist cumbersome preparation process, coating texture's poor controllability, defect And antioxygenic property it is poor the problems such as.By taking W-Si system as an example, WSi2It is si content highest, antioxygenic property in W-Si bianry alloy Best silicide, but single WSi2The antioxidant effect of infiltration layer is unsatisfactory, needs to add other members and is usually modified.Al The addition of element facilitates the increase of silicide infiltration layer toughness, while the Al generated after Al oxidation2O3It is spread with preferable oxygen With the ability of infiltration, it can be with SiO2In conjunction with generation SiO2-Al2O3Structure makes infiltration layer crackle up, increases SiO2Viscosity so that Oxidation film can keep fine and close, continuous for a long time.And rare earth element y is then a kind of common to improve infiltration layer antioxygenic property Active element, accordingly it is contemplated that being modified simultaneously using Al and Y element to infiltration layer.
Pack cementation method is commonly used one of the method for refractory metal surfaces modified silicide infiltration layer, has required equipment letter It is single, at low cost, limit matrix alloy size small advantage.Metal works are placed in penetration enhancer, certain temperature is heated to, are kept After appropriate time, the active atomic that penetration enhancer thermally decomposes generated metallic element for seep is just adsorbed to workpiece surface, and spreads Into workpiece surface, to change the chemical component of workpiece surface, tissue and performance.Powder pack cementation is due to seeping part by powder bag Enclose, leakage seep seldom, operating procedure is simple, and alloying layer thickness is easy to control, and equipment investment is small, but the temperature of current pack cementation aluminizing compared with Height, it is harmful to the comprehensive performance of alloy, it is not able to satisfy the needs of particular component corrosion-inhibiting coating.
Summary of the invention
The present invention is intended to provide the method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer, mentions for pure tungsten For a kind of resistance to high temperature oxidation protective coating.The present invention silicide coating thickness uniform, controllable modified by Y and Al, coating surface Fine and close flawless.
The method that tungsten surface of the present invention two-step method prepares Y and Al modified silicide infiltration layer, includes the following steps:
Step 1:Si-Y permeation prepares Y modified silicide infiltration layer
1a, matrix alloy surface is polished, is dried up after being cleaned by ultrasonic in alcohol；
1b, will silicon powder, fluorination sodium powder, yttrium powder and alumina powder mix after turned in 200-400 by planetary ball mill/ Ball milling 2-4h under min obtains Si-Y diffusion medium powder；
1c, Si-Y diffusion medium powder is fitted into corundum crucible, pure tungsten is wrapped among Si-Y diffusion medium powder, is covered Crucible cover simultaneously uses Al2O3Powder and the slurry of silica solution allotment seal；Crucible after sealing is placed in high temperature process furnances, in argon gas It is heated to 500-1000 DEG C of heat preservation 5-10h under protection, that is, completes Si-Y permeation processing, obtains Y modified silicide infiltration layer.
In step 1b, each raw material constitutes as follows according to mass percent:
Silicon powder 25~35% is fluorinated sodium powder 3~7%, yttrium powder 3~10%, alumina powder 53~65%.
In step 1c, the Al2O3The proportion of powder and the slurry of silica solution allotment are as follows: in 50-100gAl2O3It is added in powder 20-50ml silica solution.
Step 2: pack cementation aluminizing processing
2a, by step 1 obtain containing Y modified silicide infiltration layer material polishing after in alcohol ultrasonic cleaning 10~ It is dried up after 15min；
2b, by aluminium powder, fluorination sodium powder and Al2O3Pass through planetary ball mill ball milling 2- at 200-400 turns/min after mixing 4h obtains aluminizing medium；
2c, aluminizing medium is fitted into corundum crucible, by Si-Y permeation, treated that material is wrapped in aluminizing medium, covers earthenware Crucible lid simultaneously seals；Crucible after sealing is placed in high temperature process furnances, is heated to 600-1000 DEG C of heat preservation 5- under protection of argon gas 10h completes pack cementation aluminizing processing, obtains Y and Al modified silicide infiltration layer.
In step 2b, each raw material constitutes as follows according to mass percent:
Aluminium powder 5-20% is fluorinated sodium powder 2-8%, surplus Al2O3。
The beneficial effects of the present invention are embodied in:
The present invention prepares Y and Al modified silicide infiltration layer in W surface by two-step method, is not changing existing silicide infiltration layer On the basis of institutional framework, handle to obtain Y and Al modified silicide infiltration layer by subsequent pack cementation aluminizing.The advantages of this method exists In can the silicide infiltration layer with expected structure and thickness be prepared in alloy surface first, the silicide infiltration layer group is not being destroyed It under the premise of knitting structural intergrity, is handled by subsequent aluminising, realizes the addition of appropriate Al and Y, it is furthermore complicated to having The practical work piece of shape also has controllability, thus practicability is stronger.The Y and Al prepared using the above method in W surface is changed Property silicide infiltration layer there is excellent oxidation-resistance property, after 1000 DEG C aoxidize 10 hours, the oxidation film of layer surface is caused Close complete, unit area weight gain is 9.27~10.39mg/cm2。
Detailed description of the invention
Fig. 1 is Technology Roadmap of the invention.
Fig. 2 is the Si-Y co-penetration layer (a) of W surface first step preparation and the surface of two-step method Si-Al-Y compisite seeping layer (b) FE-SEM image.
Fig. 3 is the cross section FE-SEM image that W surface two-step method prepares Si-Al-Y compisite seeping layer.
Fig. 4 is that two-step method prepares oxidizing dynamics curve after Y and Al modified silicide infiltration layer aoxidizes ten hours.It can from Fig. 4 Know, 10 hours oxidation weight gain rates of the modified pure tungsten pack cementation aluminizing antioxidant coating of Y are far below pure tungsten, after 10h rate of body weight gain be 9.27~ 10.39mg/cm2。
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
To verify effect of the invention, selects rolling than being matrix for 50% pure tungsten, use two step packets on pure tungsten surface Method preparation Al, Y modified silicide coating is buried, and carries out the cyclic oxidation test of 10h to it under 1000 DEG C of atmospheric environments.
Embodiment 1:
1, Si-Y permeation prepares Y modified silicide infiltration layer: (a) by alloy sample surface with 80~1200#The polishing of SiC sand paper It is smooth, it is dried up after ultrasonic cleaning 10min in alcohol spare；(b) 30%Si-3%Y-3%NaF-64% by weight percentage Al2O3Penetration enhancer is weighed, configured, the ball milling for carrying out 3h in ball grinder at the 300 turns/min is put into after being then mixed uniformly； (c) metal W after uniformly mixed aluminizing medium and sanding and polishing is sealed in ceramic crucible together；Ceramic crucible is put into again It in tube furnace, vacuumizes at room temperature, then applying argon gas is in furnace chamber to atmospheric pressure；Then be heated to 500 DEG C of heat preservation 10h, i.e., it is complete At the preparation of surface Y modified silicide infiltration layer.
2, pack cementation aluminizing is handled: will (a) be prepared with the specimen surface of the silicide infiltration layer ultrasonic cleaning in alcohol Cooling drying is spare after 10min；(b) according to weight percent 25Al-3NaF-72Al2O3Penetration enhancer is weighed, configures, then by it It is put into the ball milling for carrying out 3h in ball grinder at 300 turns/min after mixing；(c) by after ball milling penetration enhancer and step 1 in Y change The metal W of property silicide infiltration layer is sealed in ceramic crucible together；Ceramic crucible is put into tube furnace again, is taken out at room temperature true Sky, then to atmospheric pressure in applying argon gas and furnace chamber；Then it is heated to 600 DEG C of heat preservation 10h.1000 DEG C of atmosphere are carried out to infiltration layer sample 10h oxidation experiment under environment, the results showed that surface film oxide is compact and complete, no peeling phenomenon, unit area weight gain 9.27mg/ cm2。
Embodiment 2:
1, Si-Y permeation prepares Y modified silicide infiltration layer: (a) by alloy sample surface with 80~1200#The polishing of SiC sand paper It is smooth, it is dried up after ultrasonic cleaning 10min in alcohol spare；(b) 20%Si-10%Y-5%NaF- by weight percentage 65%Al2O3Penetration enhancer is weighed, configured, the ball for carrying out 4h in ball grinder at the 200 turns/min is put into after being then mixed uniformly Mill；(c) metal W after uniformly mixed aluminizing medium and sanding and polishing is sealed in ceramic crucible together；Again by ceramic crucible It is put into tube furnace, vacuumizes at room temperature, then applying argon gas is in furnace chamber to atmospheric pressure；800 DEG C of heat preservation 8h then are heated to, i.e., Complete the preparation of surface Y modified silicide infiltration layer.
2, pack cementation aluminizing is handled: will (a) be prepared with the specimen surface of the silicide infiltration layer ultrasonic cleaning in alcohol Cooling drying is spare after 10min；(b) according to weight percent 30Al-3NaF-67Al2O3Penetration enhancer is weighed, configures, then by it It is put into the ball milling for carrying out 4h in ball grinder at 200 turns/min after mixing；(c) by after ball milling penetration enhancer and step 1 in Y change The metal W of property silicide infiltration layer is sealed in ceramic crucible together；Ceramic crucible is put into tube furnace again, is taken out at room temperature true Sky, then to atmospheric pressure in applying argon gas and furnace chamber；Then it is heated to 800 DEG C of heat preservation 8h.1000 DEG C of atmosphere are carried out to infiltration layer sample 10h oxidation experiment under environment, the results showed that surface film oxide is compact and complete, no peeling phenomenon, unit area weight gain 9.90mg/ cm2。
Embodiment 3:
1, Si-Y permeation prepares Y modified silicide infiltration layer: (a) by alloy sample surface with 80~1200#The polishing of SiC sand paper It is smooth, it is dried up after ultrasonic cleaning 10min in alcohol spare；(b) 25%Si-10%Y-5%NaF- by weight percentage 60%Al2O3Penetration enhancer is weighed, configured, the ball for carrying out 2h in ball grinder at the 400 turns/min is put into after being then mixed uniformly Mill；(c) metal W after uniformly mixed aluminizing medium and sanding and polishing is sealed in ceramic crucible together；Again by ceramic crucible It is put into tube furnace, vacuumizes at room temperature, then applying argon gas is in furnace chamber to atmospheric pressure；1000 DEG C of heat preservation 5h then are heated to, Complete the preparation of surface Y modified silicide infiltration layer.
2, pack cementation aluminizing is handled: will (a) be prepared with the specimen surface of the silicide infiltration layer ultrasonic cleaning in alcohol Cooling drying is spare after 10min；(b) according to weight percent 20Al-3NaF-77Al2O3Penetration enhancer is weighed, configures, then by it It is put into the ball milling for carrying out 2h in ball grinder at 400 turns/min after mixing；(c) by after ball milling penetration enhancer and step 1 in Y change The metal W of property silicide infiltration layer is sealed in ceramic crucible together；Ceramic crucible is put into tube furnace again, is taken out at room temperature true Sky, then to atmospheric pressure in applying argon gas and furnace chamber；Then it is heated to 1000 DEG C of heat preservation 5h.1000 DEG C of atmosphere are carried out to infiltration layer sample 10h oxidation experiment under environment, the results showed that surface film oxide is compact and complete, no peeling phenomenon, unit area weight gain 10.39mg/ cm2。

Claims (4)

1. the method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer, it is characterised in that include the following steps:
Step 1:Si-Y permeation prepares Y modified silicide infiltration layer
1a, matrix alloy surface is polished, is dried up after being cleaned by ultrasonic in alcohol；
1b, pass through planetary ball mill at 200-400 turns/min after mixing silicon powder, fluorination sodium powder, yttrium powder and alumina powder Ball milling 2-4h obtains Si-Y diffusion medium powder；
1c, Si-Y diffusion medium powder is fitted into corundum crucible, pure tungsten is wrapped among Si-Y diffusion medium powder, crucible is covered Gai Bingyong Al2O3Powder and the slurry of silica solution allotment seal；Crucible after sealing is placed in high temperature process furnances, is protected in argon gas Under be heated to 500-1000 DEG C of heat preservation 5-10h, that is, complete Si-Y permeation processing, obtain Y modified silicide infiltration layer；
Step 2: pack cementation aluminizing processing
2a, by step 1 obtain containing Y modified silicide infiltration layer material polishing after in alcohol ultrasonic cleaning 10~ It is dried up after 15min；
2b, by aluminium powder, fluorination sodium powder and Al2O3Pass through planetary ball mill ball milling 2-4h at 200-400 turns/min after mixing, Obtain aluminizing medium；
2c, aluminizing medium is fitted into corundum crucible, by Si-Y permeation, treated that material is wrapped in aluminizing medium, covers crucible cover And it seals；Crucible after sealing is placed in high temperature process furnances, is heated to 600-1000 DEG C of heat preservation 5-10h under protection of argon gas, Pack cementation aluminizing processing is completed, Y and Al modified silicide infiltration layer is obtained.
2. preparation method according to claim 1, it is characterised in that:
In step 1b, each raw material constitutes as follows according to mass percent:
Silicon powder 25~35% is fluorinated sodium powder 3~7%, yttrium powder 3~10%, alumina powder 53~65%.
3. preparation method according to claim 1, it is characterised in that:
In step 1c, the Al2O3The proportion of powder and the slurry of silica solution allotment are as follows: in 50-100gAl2O320- is added in powder 50ml silica solution.
4. preparation method according to claim 1, it is characterised in that:
In step 2b, each raw material constitutes as follows according to mass percent:
Aluminium powder 5-20% is fluorinated sodium powder 2-8%, surplus Al2O3。
CN201910638149.5A 2019-07-16 2019-07-16 The method that a kind of tungsten surface two-step method prepares Y and Al modified silicide infiltration layer Pending CN110205581A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071507A1 (en) * 2004-12-29 2006-07-06 Honeywell International Inc. Low cost inovative diffused mcraly coatings
CN103993259A (en) * 2014-04-25 2014-08-20 西北工业大学 Two-step preparation method for Y and Al modified silicide infiltrated layer on surface of Nb-Si-based alloy
CN107267914A (en) * 2017-06-19 2017-10-20 西北工业大学 A kind of Ti2The method that AlNb alloy surface two-step methods prepare Si Al Y compisite seeping layers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006071507A1 (en) * 2004-12-29 2006-07-06 Honeywell International Inc. Low cost inovative diffused mcraly coatings
CN103993259A (en) * 2014-04-25 2014-08-20 西北工业大学 Two-step preparation method for Y and Al modified silicide infiltrated layer on surface of Nb-Si-based alloy
CN107267914A (en) * 2017-06-19 2017-10-20 西北工业大学 A kind of Ti2The method that AlNb alloy surface two-step methods prepare Si Al Y compisite seeping layers

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