CN102560338B - Metal ceramic coating and preparation method thereof - Google Patents
Metal ceramic coating and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 72
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 109
- 239000011248 coating agent Substances 0.000 claims abstract description 100
- 150000004767 nitrides Chemical class 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000006104 solid solution Substances 0.000 claims abstract description 6
- 229910000905 alloy phase Inorganic materials 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 230000008021 deposition Effects 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
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- 238000002844 melting Methods 0.000 claims description 3
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- 238000001816 cooling Methods 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
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- 238000007733 ion plating Methods 0.000 description 12
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a metal ceramic coating, composed of a metal phase matrix and dispersed nanometer crystal nitride phase particles, wherein a metal phase (b) is an alloy phase or pure metal containing solid solution strengthened alloy component; the nitride phases (c) are dispersed in the metal phase (b); the volume percentage of the nitride (c) is 5-60%. A preparation method of the metal ceramic coating specifically adopts a vacuum physical vapor deposition method, comprising three steps: (1), putting parts to a vacuum chamber (3); (2), introducing reaction air (f) into the vacuum chamber (e); (3), enabling substances on the surface of a target (g) to form a gaseous phase (h). The coating of the invention has high fracture toughness, oxidization resistance and corrosion resistance, high viscosity of an oxidation film, and good hardness and wearing resistance. The preparation process of the coating is simple; after being prepared, the coating does not need subsequent treatment such as vacuum annealing and the like, thereby having high production efficiency.
Description
Technical field
The present invention relates to the high temperature protection technology, a kind of metal-ceramic coating and preparation method thereof is provided especially.
Background technology
The MCrAlY coating is comparatively desirable coating.Because it has good high temperature oxidation resistance and hot corrosion resistance, and good toughness and thermal fatigue resistance intensity, be widely used on the turbine blade of aircraft engine, internal combustion turbine etc.The advantage of MCrAlY coating is the diversity that it becomes component selections, can select suitable coated component according to different Working environments and different matrix material, not limited by matrix chemical composition and microtexture.But MCrAlY coating hardness and wear resistance await improving.The main preparation methods of MCrAlY coating has physical vapor deposition and plasma spraying at present.
With the MCrAlY coating, compare, nitride coatings hardness is high, and has excellent wear resistance.But the thermostability of nitride coatings is not high, and heat crack resistance is poor, therefore less in the applied research in high temperature protection field.In recent years, CrN, the CrAlN coating is owing to having very high hardness and wear resistance, good high temperature oxidation resistance and erosion resistance and obtain people's extensive concern.But, the poor toughness of nitride coatings, after oxidation, the oxide compound of coatingsurface at high temperature is subject to thermal cycling and mechanical effect is easily peeled off, and accelerates the inefficacy of coating, so the bonding strength of nitride coatings and matrix and toughness thereof also await raising.Nearest Lin etc. utilizes the method for pulse non-balance magnetically controlled sputter to prepare the CrAlN coating of different al content, and it shows high-temperature behavior preferably, has reduced the AISI304 stainless steel 800
othe rate of oxidation of C.The increase along with Al content is found in research simultaneously, and the oxidation-resistance of CrAlN coating improves gradually, and has effectively suppressed the minimizing of nitrogen content in coating under the hot environment adding of Al, makes coating 800
oc still maintains the hardness value of 25Gpa through the 1h anneal.But; this coating at high temperature follows the formation of oxide compound to decompose; only can provide short-term protection [referring to document J. Lin, et al. A study of the oxidation behavior of CrN and CrAlN thin films in air using DSC and TGA analyses [J]. Surface; Coatings Technology, 202 (2008): 3272-3283.].
At present, the nitride protective coating of superalloy, or because its poor toughness, low with the bonding strength of matrix, structure is not fine and close, or can not play effective corrosion prevention effect to superalloy because of problems such as thermostability are not high, does not far reach the industrial application requirement.Therefore, the novel high-temperature protection coating that development has high antioxidant, high corrosion resistance, high thermal stability, high-wearing feature and high tenacity, be still high temperature alloy protective field problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of metal-ceramic coating and preparation method thereof.This metal-ceramic coating is by metallographic phase parent and the disperse nanocrystalline Nitride Phase granulometric composition that distributes.The microhardness of this metal-ceramic coating, wear resistance, anti-1000 ℃ of high temperature oxidation stabilities all are enhanced about more than once than MCrAlY coating (M=Ni, Co, or NiCo), are applicable to metal works.This preparation method is the physical vacuum vapour deposition type method that target and nitrogen are reactant gases for adopting alloy, includes but not limited to multi-arc ion coating, magnetron sputtering.Can control parameter by adjusting alloy target material composition and vacuum chamber temperature, the gaseous tension passed into, substrate bias etc., with acquisition, meet the different coatings that require such as hardness, wear resistance, oxidation-resistance and corrosion and heat resistant.Preparation technology of coating is simple, after preparation, does not need through subsequent disposal such as vacuum annealings, has higher production efficiency.
A kind of metal-ceramic coating of the present invention is characterized in that: this metal-ceramic coating is by metallographic phase parent and the disperse nanocrystalline Nitride Phase granulometric composition that distributes;
Described metallographic phase (b) is for containing alloy phase or the pure metal of solid solution strengthened alloy constituent element, when for pure metal comprising but be not limited to Ni;
Nitride Phase (c) disperse is distributed in metallographic phase (b), and wherein the volume fraction of nitride (c) is 5～60 %.
Described metal-ceramic coating is characterized in that: Nitride Phase (c) is containing at least one metallic element; Nitride Phase (c) grain-size≤80nm.
The present invention is claimed metal-ceramic coating preparation method also, it is characterized in that:
Finished product after preparation is by metallographic phase parent and the disperse nanocrystalline Nitride Phase granulometric composition that distributes; Described metallographic phase (b) is for containing alloy phase or the pure metal of solid solution strengthened alloy constituent element, when for pure metal comprising but be not limited to Ni; Nitride Phase (c) disperse is distributed in metallographic phase (b), and wherein the volume fraction of nitride (c) is 5～60 %;
The concrete physical vacuum vapour deposition type method that uses, include but not limited to multi-arc ion coating, magnetron sputtering etc.;
Preparation process comprises three steps: (1) part must be placed in vacuum chamber (e), and (2) pass into reactant gases (f) in vacuum chamber (e), and (3) make the material on target (g) surface form gas phase (h).
Described metal-ceramic coating preparation method is characterized in that:
In preparation process, reactant gases (f) must also can lead to other gases such as argon gas containing nitrogen simultaneously, and the amount of reactant gases passed into should make the air pressure >=0.2Pa of vacuum chamber;
The material of target is alloy, quantity >=1; The alloy constituent element of target, containing the alloy constituent element that is difficult for forming or not forming nitride, includes but not limited to Ni etc.;
In preparation process, requirement can pass through to change the chemical composition of target to regulate Nitride Phase (c) volume fraction of metal-ceramic coating (a); In preparation process, requirement can be regulated vacuum chamber temperature, the gaseous tension passed into, substrate bias etc. and control parameter to regulate Nitride Phase (c) volume fraction in metal-ceramic coating (a).
Described metal-ceramic coating preparation method, further preferred the requirement is:
Preparation process is as follows: the preparation of (1) alloy target material: adopt the method for vacuum melting to prepare multicomponent alloy as cathode targets; (2) workpiece pre-treatment: before plated film, sample is carried out to conventional polishing, mirror polish processing, finally use respectively acetone and alcohol ultrasonic cleaning, dry up standby; (3) coating preparation: the preparation method of described metal-ceramic coating adopts multi-arc ion coating;
The coating preparation process is specially:
At first sample is placed on the specimen holder of vacuum film coating chamber, passes into the Ar of purity 99.99% and the N of purity 99.99% after vacuumizing
2, the amount of reactant gases passed into should make the air pressure>=0.2Pa of vacuum chamber; Then utilize and inspire electrode, adopt the method for arc-over, produce the cathodic arc spot of strong luminescence at the solid state cathode target material surface, make the target metal directly evaporate and ionize; Substrate is applied to certain negative bias simultaneously, ionic fluid is accelerated; N
2form plasma body with the Ar ion mixing of the cathode substance of emitting from cathodic arc spot, after negative bias is accelerated, be deposited on substrate and form metal-ceramic coating, design parameter is:
Ion Cleaning: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, Substrate negative bias voltage: 600V, scavenging period: 3min;
Coating deposition: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, arc voltage: 18-22V, Substrate negative bias voltage: 100-500V, substrate temperature: 200-300
oc, the Ar flow is 8-20sccm, N
2flow is 100-400sccm, target and matrix distance: 200mm, depositing time: 1-5h.
The specific requirement that relevant parameters is controlled is as follows:
(1) before the coating deposition, pass into purity 99.99% high-purity Ar and purity 99.99% N
2, substrate is carried out to Ion Cleaning and injection effect, make the nitrogenize of cathode targets top layer simultaneously, effectively reduce the oarse-grained generation of deposition initial stage;
(2) in being coated with layer deposition process, strictly arc current is controlled between 65-72A, the Ar flow is between 8-20sccm, and its numerical value is too high or too low all can cause the coating molten drop to increase severely or the phenomenons such as blow-out.According to the different workpieces material, strictly control the temperature of substrate: 200-300
oc, temperature is too low, and the bonding force of coating and matrix descends, and excess Temperature will cause matrix softening; The speed rotation of specimen holder maintenance 18 rpm/min in the process of Ion Cleaning, coating deposition of workpiece is housed, to guarantee the coating deposition evenly;
(3), in being coated with layer deposition process, adjust N
2flow: modification scope 100-400sccm, substrate bias: modification scope 100-500V, depositing time: 1-5h; To obtain thickness, hardness, wear resistance, coating that oxidation-resistance is different with the corrosion and heat resistant requirement;
(4) after deposition finishes, make the vacuum chamber slow cooling, take out after workpiece is fully cooling, to prevent workpiece, be subject to thermooxidizing.
Metal-ceramic coating of the present invention has following feature:
1. metal-ceramic coating of the present invention is comprised of metallographic phase and nitride, and the volume fraction of nitride is 5～60 %.This metal-ceramic coating is usingd metallographic phase as matrix, usings the nitride of nanoscale as strengthening phase, forms the composite structure that nitride diffusion is distributed in matrix phase.Metallographic phase can be pure metal or contains the alloy phase of solid solution strengthened alloy constituent element, and the nitride grain-size that disperse distributes is less than 80nm.
2. metal-ceramic coating of the present invention is usingd metallographic phase as matrix, make coating there is higher fracture toughness property, antioxidant property and corrosion resistance nature, while is due to the rare earth element of solid solution in metallographic phase, as Y, can effectively improve the adhesivity of oxide film, thereby effectively improve the heat crack resistance of coating; The nitride that disperse is distributed in matrix phase is strengthening phase, makes this metal-ceramic coating have higher hardness and wear resistance.The microhardness of the metal-ceramic coating in the present invention, wear resistance, anti-1000 ℃ of high temperature oxidation stabilities all are enhanced about more than once than MCrAlY coating (M=Ni, Co, or NiCo).
The preparation method of metal-ceramic coating of the present invention, determine physical vacuum vapour deposition type method, include but not limited to multi-arc ion coating, magnetron sputterings etc. are as described ceramic-metallic technology of preparing, described method feature is: (1) adopts single alloys target or a plurality of alloys target, (2) while adopting alloys target, contain the alloy constituent element that is difficult for forming or not forming nitride in alloys target, include but not limited to Ni etc., (3) can be by regulating the chemical composition of physical vacuum vapour deposition parameter and alloys target, acquisition meets thickness, hardness, wear resistance, the different coatings that require such as oxidation-resistance and corrosion and heat resistant.
The preparation method of a kind of metal-ceramic coating of the present invention, can be by adjusting vacuum chamber temperature, nitrogen flow, Substrate negative bias voltage, the processing parameters such as depositing time, to obtain the different coatings that require such as thickness, hardness, wear resistance, oxidation-resistance and corrosion and heat resistant.This metal-ceramic coating is applicable to metal works, is not subject to the structure of material, and effects limit becomes to grade.Preparation technology of coating is simple, after preparation, does not need through subsequent disposal such as vacuum annealings, has higher production efficiency.
Adopt physical vacuum vapour deposition type method in the present invention, include but not limited to that the microhardness, wear resistance, anti-1000 ℃ of high temperature oxidation stabilities of the metal-ceramic coating of the preparation such as multi-arc ion coating, magnetron sputtering are all than MCrAlY coating (M=Ni, Co, or NiCo) be enhanced about more than once.The preparation method of a kind of metal-ceramic coating of the present invention, can be by adjusting nitrogen flow, Substrate negative bias voltage, and the processing parameters such as depositing time, to obtain the different coatings that require such as thickness, hardness, wear resistance, oxidation-resistance and corrosion and heat resistant.Preparation technology of coating is simple, after preparation, does not need through subsequent disposal such as vacuum annealings, has higher production efficiency.
The accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is for adopting multi sphere ion plating technology to prepare the TEM Ming field of this metal-ceramic coating as photo on martensite heat-resistant steel 1Cr16Ni2MoN matrix;
Fig. 2 is for adopting multi sphere ion plating technology to prepare the Photomicrograph of this metal-ceramic coating on nickel base superalloy K417 matrix;
Fig. 3 for the metal-ceramic coating that adopts multi sphere ion plating technology to prepare on nickel base superalloy K417 matrix 1000
othe Photomicrograph of C constant temperature oxidation 100h;
Fig. 4 for the metal-ceramic coating that adopts multi sphere ion plating technology to prepare on nickel K417 matrix 900
oc, NaCl/Na
2sO
4(25:75wt.%) thermal etching 80h Photomicrograph in the environment;
Fig. 5 is for adopting multi sphere ion plating technology to prepare the TEM Ming field of metal-ceramic coating as photo on glass basis.
Embodiment
Embodiment 1
Take martensite heat-resistant steel 1Cr16Ni2MoN as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material (usining the NiCrAlSiY alloys target as example): Ni-Cr-Al-Si-Y multicomponent alloy prepared by the method for employing vacuum melting is as cathode targets, its alloying constituent is: 8～13wt.% Al, 20～26 wt.% Cr, 0.5～1.0 wt.% Si, about 0.5 wt.% Y, surplus is Ni, and the total content of Al and Cr is 31～37 wt.%;
(2) part pre-treatment: before plated film, part is carried out to conventional polishing, mirror polish processing, finally use respectively acetone and alcohol ultrasonic cleaning, dry up standby;
(3) coating preparation: sample is placed on the specimen holder of vacuum film coating chamber, passes into high-purity Ar (purity 99.99%) and N after vacuumizing
2(purity 99.99%), utilize and inspire electrode, adopts the method for arc-over, produces the cathodic arc spot of strong luminescence at NiCrAlSiY solid state cathode target material surface, makes the target metal directly evaporate and ionize.Substrate is applied to certain negative bias simultaneously, ionic fluid is accelerated.N
2form plasma body with the Ar ion mixing of the cathode substance of emitting from cathodic arc spot, after bias voltage accelerates, be deposited on substrate and form metal-ceramic coating, design parameter is:
Ion Cleaning: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, Substrate negative bias voltage: 600V, scavenging period: 3min.
Coating deposition: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, Substrate negative bias voltage: 100V, substrate temperature: 210
oc, the Ar flow is 8sccm, the N2 flow is 225sccm, target and matrix distance: 200mm, depositing time: 3h.
Mutually as shown in Figure 1, the nitride diffusion that grain-size is less than 30nm is distributed in coated substrate phase Ni above in the TEM Ming field of coating, and the volume fraction of nitride is about 35%.Sedimentation rate is 183.3nm/min, and coating is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 19.43at%, and the content of Al and Cr is respectively: 14.40 at.%, 18.60 at.%.The hardness of coating is 889.6 HV
25gf, while loading 10N, the abrasion loss of coating is 11.0 * 10
-3mm
3/ m.
Embodiment 2
Take nickel base superalloy K417 as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material is with embodiment 1;
(2) the part pre-treatment is with embodiment 1;
(3) coating preparation: during the coating deposition, Substrate negative bias voltage is 300V, and other processing parameters are with embodiment 1.
The coating sedimentation rate is 148.9nm/min, and coating is γ-Ni, CrN and AlN phase, and its microtexture is as shown in Figure 2.The nitrogen content of coating is 15.40 at.%, and the content of Al and Cr is respectively 14.88 at.% and 16.87 at.%.The hardness of coating is 970.2 HV
25gf, while loading 10N, the abrasion loss of coating is 6.96 * 10
-3mm
3/ m.Sample is through 1000
oc constant temperature oxidation 100h, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin, sample unit surface oxidation weight gain: 0.34mg/cm
2.
Embodiment 3
Take nickel base superalloy K438 as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, preparation technology is with embodiment 2.
The coating sedimentation rate is 145.4 nm/min, and coating is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 16.35 at.%, and the content of Al and Cr is respectively 14.18 at.% and 16.14 at.%.The hardness of coating is 980.6 HV
25gf, while loading 10N, the abrasion loss of coating is 6.04 * 10
-3mm
3/ m.Sample is through 1000
oc constant temperature oxidation 100h, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin, sample unit surface oxidation weight gain: 0.37mg/cm
2.
Embodiment 4
Take nickel base superalloy K417 as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material is with embodiment 1;
(2) the part pre-treatment is with embodiment 1;
(3) coating preparation: during the coating deposition, Substrate negative bias voltage is 400V, and other processing parameters are with embodiment 1.
The coating sedimentation rate is 112.8 nm/min, and coating is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 14.01 at.%, and the content of Al and Cr is respectively 14.91 at.% and 17.87 at.%.The hardness of coating is 824.7 HV
25gf, while loading 10N, the abrasion loss of coating is 8.46 * 10
-3mm
3/ m.Sample is through 1000
oas shown in Figure 3, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin to C constant temperature oxidation 100h microtexture, and oxide thickness is: 1.25 μ m, 100h sample unit surface oxidation weight gain: 0.33mg/cm
2.
Embodiment 5
Take nickel base superalloy K417 as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material is with embodiment 1;
(2) the part pre-treatment is with embodiment 1;
(3) coating preparation: N during the coating deposition
2flow is 300sccm, and other processing parameters are with embodiment 1.
The coating sedimentation rate is 236.7 nm/min, and coating is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 20.08 at.%, and the content of Al and Cr is respectively 10.97 at.% and 18.64 at.%.The hardness of coating is 787.4 HV
25gf, while loading 10N, the abrasion loss of coating is 8.78 * 10
-3mm
3/ m.Sample is through 1000
oc constant temperature oxidation 100h, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin, sample unit surface oxidation weight gain: 0.45mg/cm
2.
Embodiment 6
Take nickel base superalloy K417 as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material is with embodiment 1;
(2) the part pre-treatment is with embodiment 1;
(3) coating preparation: depositing time is 5h, and other processing parameters are with embodiment 1.
Coat-thickness is 28 μ m.1000
oafter C preoxidation 1h, coating is through being coated with 25%NaCl+75%Na
2sO
4(wt.%) salt, being coated with the salt amount is 1.5-2.5 mg/cm
2, 900
oc thermal etching test 80h rear oxidation film thickness is 3.3 μ m, and as shown in Figure 4, coatingsurface generates single pellumina to microstructure photograph.80h sample unit surface weightening finish: 0.27mg/cm
2.Test 100h rear oxidation film thickness is 4.5 μ m, because the Al in coating consumes in a large number, is not enough to form continuous protectiveness pellumina, and Cr generates chromic oxide to external diffusion, and it is chromic oxide, the bilayer structure that internal layer is aluminum oxide that the oxide film of generation forms outer.100h sample unit surface weightening finish: 1.7mg/cm
2.
Embodiment 7
Take martensite heat-resistant steel 1Cr16Ni2MoN as matrix, adopt the preparation method that multi sphere ion plating technology is this ceramic coating, its preparation technology is with embodiment 2.
CrN coating and prepared metal-ceramic coating are carried out to splitting resistance relatively, by sample 800
oc carries out thermal shock test, after insulation 10min, take out to quench, and thermal shock finds for 14 times, and peeling phenomenon appears in the sample surfaces edge that is coated with the CrN coating, and peeling phenomenon does not appear in the sample that is coated with metal-ceramic coating.By sample 1000
oc carries out thermal shock test, after insulation 10min, takes out and quenches.Every twice test, sample is weighed, by observation by light microscope, find, after a thermal shock, serious peeling phenomenon appears in the CrN coatingsurface, and peeling phenomenon does not appear in the prepared metal-ceramic coating coatingsurface after ten thermal shocks of the present invention.The sample that is coated with the CrN coating changes and is respectively through coating unit area quality after 2 times and 10 thermal shocks: 0.0144mg/cm
2with-0.3515 mg/cm
2.The sample that is coated with this metal-ceramic coating changes and is respectively as 0.0091mg/cm through coating unit area quality after 2 times and 10 thermal shocks
2with 0.0401 mg/cm
2.
Embodiment 8
Take nickel base superalloy K438 as matrix, adopt the preparation method that magnetron sputtering technique is this ceramic coating, its preparation technology is as follows:
(1) preparation of alloy target material is with embodiment 1;
(2) the part pre-treatment is with embodiment 1;
(3) coating preparation: the nitrogen (purity is 99.99%) of take is reactant gases, and the argon gas (purity is 99.99%) of take is sputter gas.Part is put into to the magnetron sputtering reaction chamber, and in chamber, vacuum tightness reaches 6 * 10
-3pa, cavity is heated to 200
oc, to starting deposition after matrix etching 30min.Processing parameter is: sputtering pressure is 0.20Pa, and substrate bias is 300V, and target-substrate distance is from being 150mm, N
2flow is 450 sccm, and sputtering power is 2kw, and depositing time is 4h.
The coating sedimentation rate is 62.5 nm/min, and coating exists with the form of column crystal, is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 14.40 at.%, and the content of Al and Cr is respectively 16.88 at.% and 16.95 at.%.The hardness of coating is 981.2 HV
25gf, while loading 10N, the abrasion loss of coating is 6.67 * 10
-3mm
3/ m.Sample is through 1000
oc constant temperature oxidation 100h, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin, sample unit surface oxidation weight gain: 0.41mg/cm
2.
Embodiment 9
Take nickel base superalloy K417 as matrix, adopt the preparation method that magnetron sputtering technique is this ceramic coating, its preparation technology is with embodiment 8.
The coating sedimentation rate is 59.5 nm/min, and coating exists with the form of column crystal, is γ-Ni, CrN and AlN phase.The nitrogen content of coating is 14.82 at.%, and the content of Al and Cr is respectively 15.97 at.% and 17.05 at.%.The hardness of coating is 984.2 HV
25gf, while loading 10N, the abrasion loss of coating is 6.83 * 10
-3mm
3/ m.Sample is through 1000
oc constant temperature oxidation 100h, coatingsurface has generated the pellumina of the continuous densification that one deck is very thin, sample unit surface oxidation weight gain: 0.43mg/cm
2.
Claims (2)
1. a metal-ceramic coating preparation method is characterized in that:
This metal-ceramic coating is by metallographic phase parent and the disperse nanocrystalline Nitride Phase granulometric composition that distributes;
Described metallographic phase (b) is alloy phase or pure metal containing the solid solution strengthened alloy constituent element;
Nitride Phase (c) disperse is distributed in metallographic phase (b), and wherein the volume fraction of Nitride Phase (c) is 5～60%;
Nitride Phase (c) is containing at least one metallic element; Nitride Phase (c) grain-size≤80nm;
The concrete physical vacuum vapour deposition type method that uses;
Preparation process comprises three steps: (1) part must be placed in vacuum chamber (e), and (2) pass into reactant gases (f) in vacuum chamber (e), and (3) make the material on target (g) surface form gas phase (h);
In preparation process, reactant gases (f) must also can lead to argon gas containing nitrogen simultaneously, and the amount of reactant gases passed into should make the air pressure >=0.2Pa of vacuum chamber;
The material of target is alloy, quantity >=1; The alloy constituent element of target is containing the alloy constituent element that is difficult for forming or not forming nitride;
In preparation process, requirement can pass through to change the chemical composition of target to regulate Nitride Phase (c) volume fraction of metal-ceramic coating (a); In preparation process, requirement can be regulated vacuum chamber temperature, the gaseous tension passed into, substrate bias control parameter to regulate Nitride Phase (c) volume fraction in metal-ceramic coating (a).
2. according to the described metal-ceramic coating preparation method of claim 1, it is characterized in that:
Preparation process is as follows: the preparation of (1) alloy target material: adopt the method for vacuum melting to prepare multicomponent alloy as cathode targets; (2) workpiece pre-treatment: before plated film, sample is carried out to conventional polishing, mirror polish processing, finally use respectively acetone and alcohol ultrasonic cleaning, dry up standby; (3) coating preparation: the preparation method of described metal-ceramic coating adopts multi-arc ion coating;
The coating preparation process is specially:
At first sample is placed on the specimen holder of vacuum film coating chamber, passes into the Ar of purity 99.99% and the N of purity 99.99% after vacuumizing
2, the amount of reactant gases passed into should make the air pressure>=0.2Pa of vacuum chamber; Then utilize and inspire electrode, adopt the method for arc-over, produce the cathodic arc spot of strong luminescence at the solid state cathode target material surface, make the target metal directly evaporate and ionize; Substrate is applied to certain negative bias simultaneously, ionic fluid is accelerated; N
2form plasma body with the Ar ion mixing of the cathode substance of emitting from cathodic arc spot, after negative bias is accelerated, be deposited on substrate and form metal-ceramic coating, design parameter is:
Ion Cleaning: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, Substrate negative bias voltage: 600V, scavenging period: 3min;
Coating deposition: vacuum tightness: P ﹤ 6 * 10
-3pa, flame current: 65-72A, arc voltage: 18-22V, Substrate negative bias voltage: 100-500V, substrate temperature: 200-300 ℃, the Ar flow is 8-20sccm, N
2flow is 100-400sccm, target and matrix distance: 200mm, depositing time: 1-5h;
The specific requirement that relevant parameters is controlled is as follows:
(1) before the coating deposition, pass into purity 99.99% high-purity Ar and purity 99.99%N
2, substrate is carried out to Ion Cleaning and injection effect, make the nitrogenize of cathode targets top layer simultaneously, effectively reduce the oarse-grained generation of deposition initial stage;
(2) in being coated with layer deposition process, strictly arc current is controlled between 65-72A, the Ar flow is between 8-20sccm, and the too high or too low coating molten drop that all can cause of its numerical value increases severely or the blow-out phenomenon;
According to the different workpieces material, strictly control the temperature of substrate: 200-300 ℃; The speed rotation of specimen holder maintenance 18rpm/min in the process of Ion Cleaning, coating deposition of workpiece is housed, to guarantee the coating deposition evenly;
(3), in being coated with layer deposition process, adjust N
2flow: modification scope 100-400sccm, substrate bias: modification scope 100-500V, depositing time: 1-5h; To obtain thickness, hardness, wear resistance, coating that oxidation-resistance is different with the corrosion and heat resistant requirement;
(4) after deposition finishes, make the vacuum chamber slow cooling, take out after workpiece is fully cooling, to prevent workpiece, be subject to thermooxidizing.
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| CN101230448A (en) * | 2008-01-31 | 2008-07-30 | 沈阳大学 | Method for preparing multi-arc ion plating aluminium titanium chrome silicon yttrium nitride multi-component ultra-hard reaction film |
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