CN108517548A - A kind of sial composite coating and its preparation process - Google Patents
A kind of sial composite coating and its preparation process Download PDFInfo
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- CN108517548A CN108517548A CN201810301528.0A CN201810301528A CN108517548A CN 108517548 A CN108517548 A CN 108517548A CN 201810301528 A CN201810301528 A CN 201810301528A CN 108517548 A CN108517548 A CN 108517548A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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Abstract
A kind of preparation process of sial composite coating, the preparation process include：1) then the oxide for removing titanium-based alloy matrix surface cleans, is dry；2) absolute ethyl alcohol, water and presoma alkyl silicate are mixed, pH value is adjusted with acid solution, stirs to get precursor solution at room temperature；3) using processed titanium-based alloy matrix as working electrode, using platinized platinum or graphite as to electrode, using precursor solution as the solution system of electro-deposition, electro-deposition is carried out, drying is washed after electro-deposition, and micro-nano oxide coating is obtained on titanium-based alloy matrix surface；4) metal aluminized coating is prepared in the micro-nano oxide-coated surface for being grown on titanium-based alloy matrix surface；5) titanium-base alloy that two layers of coatings is covered with to surface is heat-treated to get to the sial composite coating for being grown in titanium-based alloy matrix surface.
Description
Technical field
The present invention relates to a kind of cermet composite coating field more particularly to it is a kind of it is using titanium-base alloy as matrix,
Sial composite coating and preparation method with outstanding high temperature resistant and good oxidation resistance.
Background technology
Titanium-aluminium alloy has many advantages, such as that density is low, specific strength is high, elasticity modulus is high, high temperature and creep resistance ability is good, is a kind of
The high-temperature material of great application prospect is applied to the high temperature parts such as aero-engine high pressure pressure fan and turbo blade.So
And the actual use temperature of titanium-aluminium alloy is limited in 750 DEG C hereinafter, due at a higher temperature, titanium and aluminium and oxygen it is affine
Ability is similar, and that alloy surface is formed is TiO2And Al2O3Mixed layer, the growth rate of oxidation film quickly, are easy to happen stripping
It falls.
To overcome the above deficiency, domestic and foreign scholars to use alloying, ion implantation, face coat and anodic oxidation etc.
Method is modified to improve the service temperature of titanium-aluminium alloy.Alloy design includes mainly two aspects, first, improving in TiAl alloy
The content of basic element Al, this is no doubt conducive to the improvement of its antioxygenic property, but Al content should not be too high, otherwise once being precipitated
Brittle TiAl3It will influence its mechanical property；Second is that by the way that the third or a variety of alloying elements is added, such as：Nb,Sb,Si,
Cr, Y, although Mo etc. can also be effectively improved the high-temperature oxidation resistance of TiAl alloy, addition is excessively high to normally result in TiAl
Alloy mechanical property declines.Although ion implantation injection rate is controllable, repeatability preferably, the equipment being related to costly, production
It is less efficient, and to TiAl alloy ingredient change depth be limited to the shallower range in surface (<1μm).And protective coating, such as
Metal coating MCrAl (Y), ceramic coating (such as SiO2、Al2O3And ZrO2Deng) and diffusion coating (such as Al, Si) although etc.
It can be used as shielded layer and stop oxygen to matrix permeability, but respectively there are still certain problems.Mutual expansion between metal coating and matrix
More serious, the hard crisp phase of interface easily precipitation is dissipated, while generating Ke Kendaer holes, the combination for seriously reducing coating and matrix is strong
Degree；Ceramic coating internal stress is larger and relatively low with substrate combinating strength；Diffusion coating differs larger with matrix coefficient of thermal expansion.
Patent Office of the People's Republic of China discloses a kind of application for a patent for invention of high temperature resistant titanium alloy plate on January 19th, 2018, application
Publication No. is CN107604210A, and with aluminium and titanium for main matrix composition, with crome metal for main doped chemical, remaining is also main
It is dynamic to be doped with the elements such as Si, V, C, Mn, Mo and Co, and the elements such as Nb, Re, Y and Ce are introduced in inevitable element, i.e., in fact
It is to improve its high-temperature oxidation resistance so that alloying element is added, but it equally also results in the conjunction with titanium aluminium for main composition in matter
Counterdiffusion is serious between gold and coating cross sections, and hard crisp phase is precipitated in interface, in turn results in mechanical property and generates decline, brings unfavorable shadow
It rings.
The preparation that Patent Office of the People's Republic of China disclosed a kind titanium-base alloy resistance to high temperature oxidation composite coating on 2 2nd, 2018
The invention patent mandate of method, Authorization Notice No. CN105714294B, which employs titanium-base alloys containing aluminium as matrix, at it
Matrix surface prepares micro-nano oxide coating, and is coated with the metal aluminized coating of 1~30 μ m thick in coating, and is subject to sky
Gas, which is heat-treated, makes metallic aluminium coating outer surface form fine and close pellumina, and double coating structures are made, and substantially increases its height
Warm oxidation resistance, and avoid the counterdiffusion between metal coating and matrix and lead to asking for the easy hard crisp phase of precipitation occurred
Topic, since wherein interbed is micro-nano-silica coating, that is, be also belong to ceramic coating, although micro-nano-silica with
There are chemical bonding effects between titanium-aluminium alloy matrix, can dramatically reduce ceramic coating institute low with substrate combinating strength
The influence brought, but this is still an inevitable problem, simultaneously because its outermost layer coating is also metal aluminized coating, with
The bond strength of middle layer is equally lower, and the coefficient of thermal expansion differences between its coating and matrix, between coating and coating
Different coating and matrix, coating and the coating of being easy to cause is detached from, i.e., bond strength is low, though therefore its have on high temperature oxidation resistance
It is obviously improved, but the bond strength between coating and matrix and coating and coating is still unsatisfactory.
In addition in Surface and Coatings Technology periodicals in volume 206 in 2012 article《Effect
of a magnetron sputtered(Al2O3-Y2O3)/(Pt-Au)laminated coating on hot corrosion
resistance of 8Nb-TiAl alloy》It describes and high-Nb Ti-Al conjunction is improved for aluminium yttrium oxide and platinum composite coating
The experiment and as a result, its surface platinum coating is resistance to for improving high niobium containing titanium aluminium alloy that the various aspects such as golden heat and corrosion resistant performance carry out
Hot corrosion resistance have remarkable result, but due to platinum be subject under the high temperature conditions a variety of oxidants, highly basic, be easy reduction
Many substance corrosion such as heavy metal element and sulphur, and aluminium yttrium oxide itself is difficult to platinum to generate good protective effect, causes
Keep its applicability extremely limited, is easy in many use environments early to corrosion failure so that performance dramatic decrease.
Invention content
Actual use temperature to solve titanium-aluminium alloy in the prior art is limited in 750 DEG C hereinafter, due at higher temperature
Under degree, titanium and the affinity of aluminium and oxygen are similar, and that alloy surface is formed is TiO2And Al2O3Mixed layer, the growth of oxidation film
Rate quickly, the problems such as being easy to happen peeling, and be that solve the problems, such as that the method therefor exists either large or small in the prior art
The drawbacks of the problem of, the present invention provides it is a kind of it is using titanium-base alloy as matrix, there is outstanding high temperature resistant and good anti-oxidant
The sial composite coating of ability.
It is a further object of the present invention to provide a kind of preparation methods of sial composite coating.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation process of sial composite coating, the preparation process include following preparation process：
1) then the oxide for removing titanium-based alloy matrix surface first cleans, is dry；
2) according to volume ratio (50~100)：(50~100)：Ratio mixing absolute ethyl alcohol, water and the presoma silicic acid of (1~10)
Arrcostab adjusts pH value to 2.0~6.0 with acid solution, stirs 2~48h at room temperature, obtain precursor solution；
3) using the processed titanium-based alloy matrix of step 1) as working electrode, using platinized platinum or graphite as to electrode, with step
2) solution system of the precursor solution as electro-deposition obtained by, is placed in precursor solution simultaneously by working electrode and to electrode
Between the two away from for 1~10cm, control current density is -0.1mAcm for control-2~-5.0mAcm-2, sedimentation time be 30s~
2000s obtains micro-nano oxide coating in 40~150 DEG C of drying after washing on titanium-based alloy matrix surface；
4) the obtained micro-nano oxide-coated surface for being grown on titanium-based alloy matrix surface of step 3) prepare thickness be 1~
30 μm of metal aluminized coating；
5) titanium-base alloy that the obtained surface of step 4) is covered with two layers of coatings is placed in argon gas atmosphere, in 700~1100 DEG C of items
30~120min is heat-treated under part to get to the sial composite coating for being grown in titanium-based alloy matrix surface；
Wherein titanium-based alloy matrix is titanium-base alloy containing aluminium.
Preferably, the titanium-base alloy is Ti3-Al、Ti-Al、Ti-Al3、Ti-6Al-4V、TiAlNb、Ti-47Al-
Any one in 2Cr-2Nb.
Preferably, in step 4), the metal aluminized coating that thickness is 1~30 μm is prepared in the method brushed or sprayed.
Preferably, in step 4), thickness is that 1 μm~30 μm of metal aluminized coating is used according to mass ratio as (1~10)：
(10~100)：(10~100) are by polyvinyl alcohol (model：1788), water and the mixing of fine aluminium aluminium powder, in 70 DEG C~100 DEG C of temperature
Under stir to get mixed uniformly aluminum slurry, and slurry is prepared by the method brushed, sprayed.
Preferably, step 2) the presoma alkyl silicate is any one in ethyl orthosilicate and methyl orthosilicate
Kind.
Preferably, it is -1.0mAcm to control current density in step 3) when electro-deposition-2~-5.0mAcm-2, deposition
Time is 200~600s.
Preferably, heat treatment temperature is 900 DEG C~1100 DEG C in step 5), the time is 60min~90min.
A kind of sial composite coating is made of the micro-nano-silica coating of internal layer and the metal aluminized coating of outer layer.
Preferably, the sial composite coating is used for the cladding of the titanium-based alloy matrix containing aluminium.
Compared with prior art, the invention has the advantages that：
1) the other oxide of micro/nano level is prepared on the surface of titanium-based alloy matrix containing aluminium by the technique of electro-deposition in the present invention
(silica) coating, there are chemical bonding effect between micro-nano-silica coating and the matrix titanium-base alloy containing aluminium, this
Body is more stablized in combination i.e. compared with the combination degree higher between common ceramic coating and titanium-based alloy matrix containing aluminium, and
The other silica dioxide coating surface of micro/nano level has relatively rich pore structure, in its surface system by the way of brushing or spraying
Standby metal aluminized coating, so that the two is even closer in combination under the action of porous structure；
2) argon gas atmosphere protection hot environment (700~1100 DEG C) in, aluminum slurry prepare metal aluminized coating with it is micro-nano
Thermit reaction in situ occurs for silica dioxide coating, and is happened at the interface of metal aluminized coating and micro-nano-silica coating,
In the interface, aluminum metal shows extremely strong reproducibility, by the micro-nano rank reducing silica of interface at smaller
Monocrystalline silicon, and itself be oxidized to aluminium oxide simultaneously, generated between micro-nano oxide coating and metal aluminized coating a large amount of
Reinforced phase particle forms fine and close and continuous monocrystalline silicon layer and pellumina, is played with former micro-nano oxide coating and cooperate with work
With high temperature oxidation resistance is greatly improved；
3) since thermit reaction in situ makes the part of silica at micro-nano-silica coating interface be reduced into monocrystalline silicon,
And at metallic aluminium coating interface and the part metals aluminium of the interface of titanium-based alloy matrix containing aluminium is oxidized to aluminium oxide, lattice structure
It changes, promotes interface, micro-nano oxide coating and the titanium-based containing aluminium of micro-nano oxide coating and metal aluminized coating
The homogenization at alloy substrate interface so that coating is more uniform, and the combination improved between coating and coating, coating and matrix is strong
Degree, and more uniform coating is conducive to improve the coefficient of thermal expansion difference between each coating and matrix；
4) thermit reaction in situ is other than generating fine and close and continuous monocrystalline silicon layer and pellumina and promoting coating uniform dispersion,
Monocrystalline silicon itself is restored from micro-nano-silica coating, restore after still with micro-nano-silica coating knot
It closes closely, aluminium oxide equally keeps very high bond strength while being aoxidized with metal aluminized coating, and due to micro-
There are relatively rich pore structures in interface for nano-oxide coating, are easy during monocrystalline silicon and alumina growth are spread
Mutually doping, therefore also mutually doping forms a combination between the monocrystalline silicon and aluminium oxide formed during thermit reaction in situ
The high reinforced phase layer of intensity so that the combination of original combination degree limited micro-nano-silica coating and metal aluminized coating
Intensity significantly rises to, and interface between the coatings not only occurs for thermit reaction in situ, also occurs at micro-nano oxidation
The interface of object coating and the titanium-based alloy matrix containing aluminium, aluminium in titanium-based alloy matrix containing aluminium the interface also with micro/nano level
Silicon dioxde reaction generates fine and close monocrystalline silicon and aluminium oxide and mutually adulterates, and forms the high reinforced phase layer of bond strength, into
And coating and the bond strength of coating, coating and matrix is made to obtain very big promotion；
5) silica while in micro-nano oxide coating be easy diffusion and with the titanium elements in titanium-based alloy matrix containing aluminium
And aluminium element occurs that immobilization is combined to react, on the surface of titanium-based alloy matrix containing aluminium, formation thickness is minimum and very fine and close and connects
Continuous glassy state protective layer, the protective layer can prevent the metal cation inside titanium-based alloy matrix containing aluminium from being spread to outside,
It avoids since long-term counterdiffusion causes counterdiffusion serious, hard crisp phase is easily precipitated in interface, while generating Ke Kendaer holes, seriously
The problems such as reducing the bond strength of coating and matrix, while the glassy state protective layer equally has and is hindered as aluminum oxide film
Keep off oxygen by characteristic, substantially increase the oxidation-resistance property of the titanium-based alloy matrix containing aluminium；
6) preparation process of the present invention is simple and convenient to operate, is efficient, being easily achieved.
Description of the drawings
Fig. 1 be the kinetic curve that is measured after constant temperature 100h under the conditions of 1000 DEG C of the embodiment of the present invention 4 with through same condition
The kinetic curve comparison diagram that processed naked titanium-aluminium alloy measures；
Fig. 2 is scanning electron microscope diagram of the embodiment of the present invention 4 after 1000 DEG C of constant temperature oxidation 100h；
In figure, 1 is naked titanium-aluminium alloy, and 2 be embodiment 4.
Specific implementation mode
The present invention program is more clearly and completely described below in conjunction with Figure of description and specific embodiment, is shown
Right described embodiment is only a part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiments of the present invention, originally
The every other embodiment that field those of ordinary skill is obtained without making creative work, belongs to the present invention
Protection domain.
Embodiment 1
With sand paper, by titanium-aluminium alloy sample, (titanium al atomic ratio is 1 first:1) polishing removal oxide on surface, then successively third
It is cleaned by ultrasonic 10min in ketone and ethyl alcohol, it is finally for use with hot blast drying.50mL absolute ethyl alcohols, 50mL is added into beaker successively
Water, 1mL ethyl orthosilicates (TEOS), use 0.5molL-1It is for use to stir 2h at room temperature by HAc tune pH to 2.0 or so.It is clear to polish
(titanium al atomic ratio is 1 to washed titanium-aluminium alloy sample:1) it is used as cathode, graphite electrode to be used as to electrode, electrode spacing control exists
1cm, control current density are -0.1mAcm-2Carry out electro-deposition, sedimentation time 2000s, by working electrode after the completion of deposition
In 40 DEG C of drying after being rinsed with deionized water, micro-nano oxide coating is obtained.Thereafter, 1g polyvinyl alcohol is added in beaker
(PVA), 10ml water, stirring and dissolving forms polyvinyl alcohol colloid at 90 DEG C, then polyethylene is added for 10g aluminium powders (Al) in quality
Mixed in alcohol colloid, by way of brushing the titanium-base alloy for being covered with micro-nano oxide coating be matrix on brush, obtain
Obtain metal aluminized coating.12h is then dried in air, is heat-treated 60min in 1100 DEG C under an argon atmosphere, is obtained high temperature resistance
Aoxidize composite coating.Its high temperature oxidation resistance is assessed using the weightening of unit area after 1000 DEG C of constant temperature oxidation 100h, is had
Body result such as table 1.
1 naked TiAl alloy of table and the TiAl alloy sample experiment result for being covered with high temperature coatings
| Sample | Increase weight mg/cm2 |
| Naked TiAl alloy | 46.32 |
| It is covered with the TiAl alloy of high temperature coatings | 0.74 |
Embodiment 2
With sand paper, by titanium-aluminium alloy sample, (titanium al atomic ratio is 3 first:1) polishing removal oxide on surface, then successively third
It is cleaned by ultrasonic 10min in ketone and ethyl alcohol, it is finally for use with hot blast drying.Be added successively into beaker 100mL absolute ethyl alcohols,
100mL water, 10mL methyl orthosilicates (TMOS), use 0.5molL-1It is for use to stir 48h at room temperature by HAc tune pH to 6.0 or so.
With polish cleaned titanium-aluminium alloy sample (titanium al atomic ratio be 1:1) it is used as cathode, graphite electrode is used as to electrode, between electrode
Away from control in 10cm, control current density is -5.0mAcm-2Carry out electro-deposition, sedimentation time 30s, by work after the completion of deposition
Make to obtain micro-nano oxide coating in 150 DEG C of drying after electrode is rinsed with deionized water.Thereafter, it is poly- that 10g is added in beaker
Vinyl alcohol (PVA), 10ml water, stirring and dissolving forms polyvinyl alcohol colloid at 100 DEG C, then quality is added for 10g aluminium powders (Al)
Enter and mixed in polyvinyl alcohol colloid, by way of aerial spraying the titanium-base alloy for being covered with micro-nano oxide coating be base
It is sprayed on body, obtains metal aluminized coating.12h is then dried in air, is heat-treated 30min in 900 DEG C under an argon atmosphere, i.e.,
Resistance to high temperature oxidation composite coating is made.Its high temperature resistance oxygen is assessed using the weightening of unit area after 1000 DEG C of constant temperature oxidation 100h
Change performance.
2 naked TiAl alloy of table and the Ti for being covered with high temperature coatings3Al alloy sample experimental results
| Sample | Increase weight mg/cm2 |
| Naked TiAl alloy | 46.32 |
| It is covered with the Ti of high temperature coatings3Al alloys | 0.98 |
Embodiment 3
With sand paper, by titanium-aluminium alloy sample, (titanium al atomic ratio is 3 first:1) polishing removal oxide on surface, then successively third
It is cleaned by ultrasonic 10min in ketone and ethyl alcohol, it is finally for use with hot blast drying.75mL absolute ethyl alcohols, 75mL is added into beaker successively
Water, 5mL ethyl orthosilicates (TEOS), use 0.5molL-1It is for use to stir 36h at room temperature by HCl tune pH to 4.0 or so.With polishing
(titanium al atomic ratio is 1 to cleaned titanium-aluminium alloy sample:1) it is used as cathode, platinum electrode to be used as to electrode, electrode spacing control exists
5cm, control current density are -1.0mAcm-2Electro-deposition is carried out, sedimentation time 600s uses working electrode after the completion of deposition
Deionized water is dried after rinsing in 90 DEG C, and micro-nano oxide coating is obtained.Thereafter, 1g polyvinyl alcohol is added in beaker
(PVA), 100ml water, stirring and dissolving forms polyvinyl alcohol colloid at 70 DEG C, then poly- second is added for 100g aluminium powders (Al) in quality
It is mixed in enol colloid, in the titanium-base alloy for being covered with micro-nano oxide coating is to brush and obtain on matrix by way of brushing
Obtain metal aluminized coating.12h is then dried in air, is heat-treated 120min in 700 DEG C under an argon atmosphere, is obtained high temperature resistance
Aoxidize composite coating.Its high temperature oxidation resistance is assessed using the weightening of unit area after 1000 DEG C of constant temperature oxidation 100h, it is real
It tests result and is listed in table 3.
3 naked TiAl alloy of table and the Ti for being covered with high temperature coatings3Al alloy sample experimental results
| Sample | Increase weight mg/cm2 |
| Naked TiAl alloy | 46.32 |
| It is covered with the Ti of high temperature coatings3Al alloys | 0.88 |
Embodiment 4
With sand paper, by titanium-aluminium alloy sample, (titanium al atomic ratio is 1 first:1) polishing removal oxide on surface, then successively third
It is cleaned by ultrasonic 10min in ketone and ethyl alcohol, it is finally for use with hot blast drying.50mL absolute ethyl alcohols, 50mL is added into beaker successively
Water, 5mL ethyl orthosilicates (TEOS), use 0.5molL-1HCl tune pH to 4.0 or so is stirred for use for 24 hours at room temperature.With polishing
(titanium al atomic ratio is 1 to cleaned titanium-aluminium alloy sample:1) cathode, graphite electrode is used as to be used as to electrode, electrode spacing control
In 5cm, control current density is -3.0mAcm-2Carry out electro-deposition, sedimentation time 300s, by working electrode after the completion of deposition
In 90 DEG C of drying after being rinsed with deionized water, micro-nano oxide coating is obtained.Thereafter, 10g polyvinyl alcohol is added in beaker
(PVA), 100ml water, stirring and dissolving forms polyvinyl alcohol colloid at 90 DEG C, then poly- second is added for 100g aluminium powders (Al) in quality
Mixed in enol colloid, by way of brushing the titanium-base alloy for being covered with micro-nano oxide coating be matrix on brush,
Obtain metal aluminized coating.12h is then dried in air, is heat-treated 60min in 1100 DEG C under an argon atmosphere, is obtained anti-height
Temperature oxidation composite coating.Its high temperature oxidation resistance is assessed using the weightening of unit area after 1000 DEG C of constant temperature oxidation 100h,
Experimental result is listed in table 4, while measuring under the conditions of 1000 DEG C that embodiment 4 is made during constant temperature oxidation 100h as shown in Figure 1
The kinetic curve comparison diagram of sample and naked TiAl alloy gain in weight is obtained, and 4 sample of the embodiment shooting SEM after oxidized is shone
Piece such as Fig. 2.
4 naked TiAl alloy of table and the TiAl alloy sample experiment result for being covered with high temperature coatings
| Sample | Increase weight mg/cm2 |
| Naked TiAl alloy | 46.32 |
| It is covered with the TiAl alloy of high temperature coatings | 0.29 |
Embodiment 5
Specific steps are with embodiment 4, except that changing the titanium-aluminium alloy matrix used, high temperature oxidation resistance assessment is same
Embodiment 1, experimental result are listed in table 5.
The different titanium-aluminium alloy matrix experimental results of table 5
| Sample | Increase weight mg/cm2 |
| Ti3-Al | 0.91 |
| Ti-Al3 | 0.54 |
| Ti-6Al-4V | 1.01 |
| Ti-47Al-2Cr-2Nb | 0.67 |
| Ti-Al | 0.79 |
| TiAlNb | 0.72 |
Embodiment 6
Specific steps are with embodiment 4, except that changing SiO2Electrodeposition time, respectively 100s, 200s, 300s,
400s、600s.High temperature oxidation resistance is assessed with embodiment 1, and experimental result is listed in table 6.
The different electrodeposition time experimental results of table 6
Embodiment 7
Specific steps are with embodiment 4, except that changing SiO2Electro-deposition current density, respectively -0.1mAcm-2、-
0.5mAcm-2、-1.0mAcm-2、-2.0mAcm-2、-5.0mAcm-2.High temperature oxidation resistance is assessed with embodiment 1, experimental result
It is listed in table 7.
The different electro-deposition current density experimental results of table 7
| Sample | Increase weight mg/cm2 |
| -0.1mA·cm-2 | 19.02 |
| -0.5mA·cm-2 | 15.09 |
| -1.0mA·cm-2 | 0.48 |
| -2.0mA·cm-2 | 0.29 |
| -5.0mA·cm-2 | 1.08 |
Embodiment 8
Specific steps are with embodiment 4, except that changing into platinized platinum to electrode.High temperature oxidation resistance is assessed with embodiment 1,
Experimental result is listed in table 8.
The different experimental results to electrode of table 8
| Sample | Increase weight mg/cm2 |
| Platinized platinum | 0.38 |
| Graphite | 0.29 |
By in the surface system of titanium-based alloy matrix containing aluminium it can be seen from data in the table 1~4 obtained by Examples 1 to 4
Standby sial composite coating of the present invention, can effectively improve the oxidation-resistance property of the titanium-based alloy matrix containing aluminium, with
Absolute advantage is shown in the comparison of naked TiAl alloy.
In addition, by embodiment 5 and embodiment 8, it is apparent that titanium-based alloy matrix containing aluminium and to electrode material to system
Oxidation-resistance property caused by standby sial composite coating coating of the present invention influences smaller, especially to electrode material, selects
Platinized platinum and graphite can generate preferable electrodeposition effect, and titanium-based alloy matrix containing aluminium influences mainly in the crystal of material itself
In structure and ingredient, such as the higher resistance to high temperature oxidation itself having of the volume density of part titanium-based alloy matrix containing aluminium crystal structure
Better performances, and volume density is relatively low then poor, for another example the aluminium in the titanium-based alloy matrix containing aluminium of part and titanium are easier to orient
Diffusion, the glassy state protective layer generated with silica composition is finer and close, more excellent to the protecting effect of body portion.
Again by embodiment 6 and embodiment 7 and its list data this it appears that being applied in the micro-nano oxide of electro-deposition
Electro-deposition current density and electrodeposition time have larger impact, and shadow in turn to micro-nano oxide coating pattern and structure when layer
It rings to high temperature oxidation resistance caused by bulk silicon Aluminium composite coating.This is because when current density is too small, silica
It can not uniformly and securely be deposited on titanium-based alloy matrix containing aluminium, lead to the micro-nano oxide coating growing pullets of matrix surface
It is uneven, relatively rich pore structure can not be formed, high temperature oxidation resistance is caused to decline, and gradually increase in current density-
1.0mA·cm-2This, which is happened, after above substantially change, and micro-nano oxide coating is more uniform and porous structure starts uniformly
And densely occur；And electrodeposition time is also same situation, the micro-nano oxygen of matrix surface when electrodeposition time is too short
Compound coatings growth is extremely uneven, can not form relatively rich pore structure, high temperature oxidation resistance is caused to decline, and in electro-deposition
Time reaches after 200s micro-nano oxide coating more uniformly and porous structure starts uniformly and densely to occur, if electro-deposition
Time is excessive it will cause the blocking of porous structure duct, and high temperature oxidation resistance declines again.
The to sum up power in the data of sial composite coating coating, comparison and Figure of description obtained by Examples 1 to 8
Learn curve comparison figure and SEM figures, it can be seen that sial composite coating coating of the present invention has very to containing aluminium titanium-based alloy matrix
Excellent protecting effect can greatly improve the oxidation-resistance property of matrix.
Claims (9)
1. a kind of preparation process of sial composite coating, which is characterized in that the preparation process includes following preparation process：
1) then the oxide for removing titanium-based alloy matrix surface first cleans, is dry；
2) according to volume ratio (50~100)：(50~100)：Ratio mixing absolute ethyl alcohol, water and the presoma silicic acid of (1~10)
Arrcostab adjusts pH value to 2.0~6.0 with acid solution, stirs 2~48h at room temperature, obtain precursor solution；
3) using the processed titanium-based alloy matrix of step 1) as working electrode, using platinized platinum or graphite as to electrode, with step
2) solution system of the precursor solution as electro-deposition obtained by, is placed in precursor solution simultaneously by working electrode and to electrode
Between the two away from for 1~10cm, control current density is -0.1mAcm for control-2~-5.0mAcm-2, sedimentation time be 30s~
2000s obtains micro-nano oxide coating in 40~150 DEG C of drying after washing on titanium-based alloy matrix surface；
4) the obtained micro-nano oxide-coated surface for being grown on titanium-based alloy matrix surface of step 3) prepare thickness be 1~
30 μm of metal aluminized coating；
5) titanium-base alloy that the obtained surface of step 4) is covered with two layers of coatings is placed in argon gas atmosphere, in 700~1100 DEG C of items
30~120min is heat-treated under part to get to the sial composite coating for being grown in titanium-based alloy matrix surface；
Wherein titanium-based alloy matrix is titanium-base alloy containing aluminium.
2. a kind of preparation process of sial composite coating according to claim 1, which is characterized in that the titanium-base alloy is
Ti3-Al、Ti-Al、Ti-Al3, any one in Ti-6Al-4V, TiAlNb, Ti-47Al-2Cr-2Nb.
3. a kind of preparation process of sial composite coating according to claim 1, which is characterized in that in step 4), thickness
It is prepared in the method brushed or sprayed for 1~30 μm of metal aluminized coating.
4. a kind of preparation process of sial composite coating according to claim 3, which is characterized in that in step 4), thickness
It is used according to mass ratio as (1~10) for 1 μm~30 μm of metal aluminized coatings：(10~100)：(10~100) by polyvinyl alcohol,
Water and the mixing of fine aluminium aluminium powder, stir to get mixed uniformly aluminum slurry, and slurry is passed through brush at a temperature of 70 DEG C~100 DEG C
It applies, prepared by the method for spraying.
5. a kind of preparation process of sial composite coating according to claim 1 or 2 or 3 or 4, which is characterized in that step
2) the presoma alkyl silicate is any one in ethyl orthosilicate and methyl orthosilicate.
6. a kind of preparation process of sial composite coating according to claim 1 or 2 or 3 or 4, which is characterized in that step
3) it is -1.0mAcm to control current density in when electro-deposition-2~-5.0mAcm-2, sedimentation time is 200~600s.
7. a kind of preparation process of sial composite coating according to claim 1 or 2 or 3 or 4, which is characterized in that step
5) heat treatment temperature is 900 DEG C~1100 DEG C in, and the time is 60min~90min.
8. a kind of sial composite coating as claimed in claim 1 or 2 or 3 or 4, which is characterized in that by micro-nano the two of internal layer
The metal aluminized coating of silica coating and outer layer forms.
9. a kind of sial composite coating according to claim 8, which is characterized in that the sial composite coating is used to contain aluminium
The cladding of titanium-based alloy matrix.
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