CN103484824B - Compoiste adhering layer material of a kind of anti-1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation and preparation method thereof - Google Patents
Compoiste adhering layer material of a kind of anti-1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses compoiste adhering layer material of a kind of anti-1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation and preparation method thereof.First the present invention adopts plating or electro beam physics vapour deposition method at substrate deposit one deck Ru, then electro beam physics vapour deposition method is adopted to deposit layer of Ni AlHfCrSi layer on Ru layer, after Overheating Treatment, obtain Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat, wherein in Ni (Ru) Al layer, Ru content successively decreases in gradient from matrix skin outer layers direction.This bilayer structure tack coat can stop matrix and the mutual diffusion being coated with interlayer element effectively, suppress the formation of second time reaction zone (SRZ), suppress the formation of spinel-like in During Process of Hot Corrosion, improving the resistance to high temperature oxidation of superalloy and the performance of heat and corrosion resistant, is a kind of novel heat barrier coating bonding layer material.This bonding layer material can reach grade of oxidation resistance at 1200 DEG C, and secondary reaction district does not appear in 1100 DEG C of diffusion in vacuum 100h, and resistance to combustion gas thermal etching ability is also far above common NiAl system metal bonding coating simultaneously.
Description
Technical field
The present invention relates to a kind of novel heat barrier coating bonding layer material and preparation method thereof, refer to the heat barrier coating bonding layer material that a kind of application plating and electro beam physics vapour deposition are prepared bilayer structure and resisted 1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation more specifically.
Background technology
In order to meet the growth requirement of aircraft engine, the material for turbine blade develops into single crystal super alloy from superalloy, directional freeze alloy crystalline, and the use temperature of material improves nearly 300 DEG C, close to the operating limit temperature of metal.And gas turbine engine of new generation requires turbine blade and turning vane long term operation at 1500 DEG C ~ 1600 DEG C, Service Environment is extremely severe, and existing alloy cannot meet the demands.Thermal barrier coating (ThermalBarrierCoatings), as a kind of surface heat guard technology, plays an important role the use temperature improving alloy material further.
Thermal barrier coating (ThermalBarrierCoatings, TBCs) usually by playing the ceramic layer of heat-blocking action and alleviating ceramic layer and do not mate stress with matrix alloy thermal expansion, improve the tack coat of matrix antioxidant anticorrosive performance and form, for reducing aircraft engine hot-end component surface temperature, improve the antioxidant anticorrosive ability of hot-end component, and effectively extend the surface heat guard technology in hot-end component work-ing life, at present, ripe bonding layer material MCrAlY use temperature is generally no more than 1150 DEG C.Along with aircraft engine develops to higher thrust-weight ratio, require that the life-time service temperature of heat barrier coating bonding layer material must reach more than 1150 DEG C.
The NiAl of B2 structure has the advantages such as fusing point is high, high temperature oxidation resistance is excellent, thermal expansivity is lower, meets the prerequisite preparing high temperature coating.But there is very large shortcoming in it simultaneously: one forms a large amount of cavity at metal/interfacial oxide film when being high temperature oxidation, affect the adhesivity of oxide film, oxide film is caused to take off (reference 1:J.A.Haynes, B.A.Pint, K.L.More, Y.Zhang, I.G.Wright.Influenceofsulfur, platinum, andhafniumontheoxidationbehaviorofCVDNiAlbondcoatings.Ox idationofMetals, 58 (2002): 513-544.).Two is mutual diffusion can occur between NiAl tack coat and matrix.In matrix, refractory element is (as W, Mo, Ta, Re etc.) spread to coating, in coating, Al element spreads to matrix, cause second time reaction zone (SecondaryReactionZone, SRZ) formation (reference 2:WalstonW.S., SchaefferJ.C., MurphyW.H..ANewTypeofMicrostructuralInstabilityinSuperal loys-SRZ [J] .Superalloys1996, ed.KissingerR.D., etal.:9-18), seriously reduce the mechanical property of superalloy matrix and the high temperature oxidation resistance of coating.The method of modifying of existing NiAl coating only pays attention to the raising of its antioxidant property usually, have ignored the importance improving its heat and corrosion resistant performance, the especially maritime corrosive environment of turbine engine actual working environment cannot be tackled, the performance in the practical application of NiAl system metal bonding coating is had a greatly reduced quality.And traditional Cr/Si method of oozing prepares coating, its coat-thickness, weave construction and chemical composition all cannot accurately control, and this technical barrier hampers the development of this type coating always.
Summary of the invention
The object of the invention is to propose a kind of novel heat barrier coating bonding layer material, refer to that a kind of application plating and electro beam physics vapour deposition are prepared Ni (Ru) Al/NiAlHfCrSi and resisted 1200 DEG C of high temperature oxidations, resistance to combustion gas thermal etching and suppress diffusion zone to generate the heat barrier coating bonding layer material of triple functions coupling more specifically.This bonding layer material can reach grade of oxidation resistance at 1200 DEG C, and secondary reaction district does not appear in 1100 DEG C of diffusion in vacuum 100h, and resistance to combustion gas thermal etching ability is also far above common NiAl system metal bonding coating simultaneously.
Another object of the present invention proposes a kind of method adopting plating and electro beam physics vapour deposition technology to prepare composite thermal barrier coating tack coat.First this preparation method adopts plating or electro beam physics vapour deposition method at substrate deposit one deck Ru, then electro beam physics vapour deposition method is adopted to deposit layer of Ni AlHfCrSi layer on Ru layer, obtain Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat through simple subsequent disposal, wherein in Ni (Ru) Al layer, Ru content successively decreases in gradient from matrix skin outer layers direction.This bilayer structure tack coat can stop matrix and the mutual diffusion being coated with interlayer element effectively, suppress the formation of second time reaction zone (SRZ), suppress the formation of spinel-like in During Process of Hot Corrosion, improving the resistance to high temperature oxidation of superalloy and the performance of heat and corrosion resistant, is a kind of novel heat barrier coating bonding layer material.
The invention provides a kind of material be suitable for as heat barrier coating bonding layer, this tack coat is Ni (Ru) Al/NiAlHfCrSi bilayer structure, and before thermal treatment, the thickness of Ru is 5 ~ 10 μm, and the thickness of NiAlHfCrSi layer is 40 ~ 60 μm.After thermal treatment, in Ni (Ru) Al layer, Ru content successively decreases in gradient.
Described Ru layer has the effect stoping element mutual diffusion, after vacuum heat treatment, Ru diffuses to form Ni (Ru) Al/NiAlHfCrSi to NiAlHfCrSi layer, thus can stop Al element in coating to refractory element in internal diffusion and matrix if W, Mo, Ta, Re etc. are to external diffusion, restrained the formation in SRZ district.In described NiAlHfCrSi layer, Al content is 40 ~ 55at%, Hf content be 0.05 ~ 0.5at%, Cr content be 0.5 ~ 2at%, Si content is 1 ~ 3at%, and surplus is Ni.
Obtain described Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat, the present invention adopts plating and electro beam physics vapour deposition preparation, and this preparation method includes the following step:
The first step, prepares matrix and evaporation charge bar
(A) with the SiC silicon carbide paper of 150#, 400#, 800#, matrix is polished, make Substrate Surface Roughness Ra < 0.8; The matrix of having polished is cleaned about 10min with acetone and EtOH Sonicate ripple successively, dries, for subsequent use.
(B) use high purity nickel (Ni), raffinal (Al), pure chromium (Cr), pure silicon (Si) and purity 99.7%(mass percent) hafnium (Hf), by designed proportioning components, Al content is 40 ~ 55at%, Hf content is 0.05 ~ 0.5at%, Cr content is 0.5 ~ 2at%, Si content is 1 ~ 3at%, and surplus is Ni.Polish with the existence of security deposit's metal surface No oxided film to nickel block and aluminium block surface, be then about 15min by dehydrated alcohol and acetone ultrasonic cleaning successively, dry, finally the alloy electric arc melting method of preparation is obtained target, for subsequent use.
In the present invention, matrix is Ni based high-temperature alloy or Ni based single-crystal high-temperature alloy;
Second step, plating or electro beam physics vapour deposition Ru layer on matrix
(A) as adopted electrochemical plating to prepare Ru layer:
Matrix after the first step process is put into by NaOH, Na
2cO
3, Na
3pO
4alkaline cleaning fluid (NaOH:10 ~ the 30g/L formulated with deionized water; Na
2cO
3: 10 ~ 30g/L; Na
3pO
4: 10 ~ 30g/L) middle ultrasonic cleaning, wherein alkaline cleaning fluid temperature is 50 ~ 70 DEG C, cleaning 2 ~ 5min.Use washed with de-ionized water again 2 ~ 3 times; Matrix after cleaning being put into thionamic acid concentration is after the sulfamic acid solution activation 50 ~ 100s of 5g/L, with deionized water rinsing 2 ~ 3 times;
Pretreated matrix is put into by RuCl
3, thionamic acid, deionized water composition plating Ru liquid (RuCl
3: 4 ~ 10g/L; Thionamic acid: 40 ~ 100g/L.) middle plating Ru layer; Plating Ru processing parameter: current density is 1.2 ~ 3.0A/dm
2; Bath temperature is 60 ~ 70 DEG C; Anode is Ti-Ru electrode; Negative electrode is matrix to be plated; Electroplating time is 40 ~ 100min; Gained coating Ru layer thickness is 5 ~ 10 μm.
(B) as adopted electro beam physics vapour deposition legal system for Ru layer:
Before deposition Ru layer, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation.EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheated substrate to 650 ~ 750 DEG C; Electron-beam voltage 16 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A.Described depositing time is 20 ~ 40min, and deposition Ru layer thickness is 5 ~ 10 μm.
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer
(A) successively with the sample after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation.
(B) EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Matrix to 600 ~ 750 DEG C after pre-heat deposition Ru layer; Electron-beam voltage 17 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A.Depositing time is 0.5 ~ 1h, and deposit thickness is 40 ~ 60 μm.
4th step, puts into vacuum heat treatment furnace by the matrix through the 3rd step process and carries out vacuum heat treatment; After vacuum heat treatment, Ru diffuses to form Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat to NiAlHfCrSi layer.
Described vacuum heat treatment parameter is: vacuum tightness P:P<2 × 10
-2pa; Temperature: 900 DEG C ~ 1130 DEG C; Time: 2h ~ 5h.
The advantage of heat barrier coating bonding layer of the present invention and preparation technology thereof:
(1) the present invention adopts the NiAl system coating of Hf, Cr, Si modification, improves the bonding force of zone of oxidation and tack coat, reduces high temperature lower substrate surface oxidation layer-growth rate, improves the antioxidant property of tack coat;
(2) the present invention adopts the NiAl system coating of Cr, Si codoped, improves the hot corrosion resistance of resistance to combustion gas of NiAl coating, particularly inhibits the formation of coating spinel-like phase, reduce the erosion rate of coating, thus effectively protect superalloy matrix.
(3) the present invention adopts plating or electro beam physics vapour deposition to prepare Ru layer, Ru layer is typical columnar crystal structure, thickness is about 5 ~ 10 μm, surface is more smooth, be combined with matrix closely good, Al element can be stoped to the diffusion in matrix, and in matrix refractory element W, Mo, Re, Ta etc. to external diffusion, inhibit the formation of second time reaction zone (SRZ), thus the creep strength of raising superalloy matrix, toughness and plasticity.
(4) the present invention adopts electro beam physics vapour deposition legal system for Cr/Si modification NiAlHf coating, can accurately control its coat-thickness, weave construction and chemical composition, compensate for the weak point of oozing Cr/Si method and preparing tack coat.
Accompanying drawing explanation
Fig. 1 is Novel hot barrier coating schematic cross-section;
Fig. 2 is Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat sectional view prepared by the present invention;
Fig. 3 is NiAlHfCrSi and NiAlHf provided by the invention two kinds of different coating resistance to 1200 DEG C of high temperature oxidations weightening finish curve;
Fig. 4 is NiAlHfCrSi and NiAlHf provided by the invention two kinds of different coating resistance to combustion gas thermal etching oxidation weight gain curves;
Fig. 5 is NiAlHfCrSi provided by the invention and common NiAl two kinds of different coating resistance to combustion gas thermal etching surface microscopic topographic figure;
Fig. 6 is cross-section morphology figure after Ni provided by the invention (Ru) Al/NiAlHfCrSi coating tack coat vacuum heat treatment.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Shown in Figure 2, the present invention discloses a kind of material be suitable for as heat barrier coating bonding layer, this tack coat is Ni (Ru) Al/NiAlHfCrSi bilayer structure, as shown in Figure 1, there is outstanding anti-1200 DEG C of high temperature oxidations, resistance to combustion gas thermal etching and suppress diffusion zone to generate triple functions.
Described bilayer structure tack coat realizes by preparing NiAlHfCrSi layer on Ru layer, and Ru layer wherein has the effect stoping element mutual diffusion.After vacuum heat treatment, Ru diffuses to form Ni (Ru) Al/NiAlHfCrSi to NiAlHfCrSi layer, in Ni (Ru) Al layer, Ru content outwards successively decreases in gradient from matrix, thus can stop Al element in coating to refractory element in internal diffusion and matrix as W, Mo, Ta, Re etc., to external diffusion, have restrained the formation in SRZ district.Described NiAlHfCrSi layer, it be 0.05 ~ 0.5at%, Cr content be 0.5 ~ 2at%, Si content is 1 ~ 3at% that preparation to adopt in target that Al content is 40 ~ 55at%, Hf content, and surplus is Ni.
Described Ru layer is by electroplate or electro beam physics vapour deposition obtains, and thickness is 5 ~ 10 μm; NiAlHfCrSi layer is standby by electro beam physics vapour deposition legal system, and thickness is 40 ~ 60 μm.
Obtain described Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat, present invention employs electro beam physics vapour deposition method to prepare, this preparation method includes the following step:
The first step, prepares matrix and evaporation charge bar;
(A) with the SiC silicon carbide paper of 150#, 400#, 800#, matrix is polished, make Substrate Surface Roughness Ra < 0.8; The matrix of having polished is cleaned about 10min with acetone and EtOH Sonicate ripple successively, dries, for subsequent use.
(B) use high purity nickel (Ni), raffinal (Al), pure chromium (Cr), pure silicon (Si) and purity 99.7%(mass percent) hafnium (Hf), by designed proportioning components, Al content is 40 ~ 55at%, Hf content is 0.05 ~ 0.5at%, Cr content is 0.5 ~ 2at%, Si content is 1 ~ 3at%, and surplus is Ni.Polish with the existence of security deposit's metal surface No oxided film to nickel block and aluminium block surface, be then about 15min by dehydrated alcohol and acetone ultrasonic cleaning successively, dry, finally the alloy electric arc melting method of preparation is obtained target, for subsequent use.
In the present invention, matrix is Ni based high-temperature alloy or Ni based single-crystal high-temperature alloy;
Second step, plating or electro beam physics vapour deposition Ru layer on matrix;
(A) as adopted electrochemical plating to prepare Ru layer, concrete grammar is:
Matrix after the first step process is put into by NaOH, Na
2cO
3, Na
3pO
4alkaline cleaning fluid (NaOH:10 ~ the 30g/L formulated with deionized water; Na
2cO
3: 10 ~ 30g/L; Na
3pO
4: 10 ~ 30g/L) middle ultrasonic cleaning, wherein wash temperature is 50 ~ 70 DEG C, cleaning 2 ~ 5min.Use washed with de-ionized water again 2 ~ 3 times; Matrix after cleaning being put into thionamic acid concentration is after the sulfamic acid solution activation 50 ~ 100s of 5g/L, with deionized water rinsing 2 ~ 3 times;
Pretreated matrix is put into by RuCl
3, thionamic acid, deionized water composition plating Ru liquid (RuCl
3: 4 ~ 10g/L; Thionamic acid: 40 ~ 100g/L.) middle plating Ru layer; Plating Ru processing parameter: current density is 1.2 ~ 3.0A/dm
2; Bath temperature is 60 ~ 70 DEG C; Anode is Ti-Ru electrode; Negative electrode is matrix to be plated; Electroplating time is 40 ~ 100min; Gained thickness of coating is 5 ~ 10 μm.
(B) as adopted electro beam physics vapour deposition legal system for Ru layer, concrete grammar is:
Before deposition Ru layer, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation.EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheated substrate to 650 ~ 750 DEG C; Electron-beam voltage 16 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A.Described depositing time is 20 ~ 40min, and deposit thickness is 5 ~ 10 μm.
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer;
(A) successively with the sample after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation.
(B) EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Matrix to 600 ~ 750 DEG C after pre-heat deposition Ru layer; Electron-beam voltage 17 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A.Described depositing time is 0.5 ~ 1h, and deposit thickness is 40 ~ 60 μm.
4th step, puts into vacuum heat treatment furnace and carries out vacuum heat treatment by sample; After vacuum heat treatment, Ru diffuses to form Ni (Ru) Al/NiAlHfCrSi to NiAlHfCrSi layer.
Described vacuum heat treatment parameter is: vacuum tightness P:P<2 × 10
-2pa; Temperature: 900 DEG C ~ 1130 DEG C; Time: 2h ~ 5h.
embodiment 1:
The first step, prepares matrix and evaporation charge bar;
(A) matrix is Ni based single-crystal high-temperature alloy, and the trade mark is N5, is of a size of 10 × 10 × 2mm; With the SiC silicon carbide paper of 150#, 400#, 800#, matrix is polished, make Substrate Surface Roughness Ra < 0.8; Ultrasonic cleaning 10 minutes.
(B) hafnium (Hf) of high purity nickel (Ni), raffinal (Al), pure chromium (Cr), pure silicon (Si) and purity 99.7% is used, by designed proportioning components, Al content is 40at%, Hf content is 0.05at%, Cr content is 0.5at%, Si content is 1at%, and surplus is Ni.Polish with the existence of security deposit's metal surface fresh room oxide film to nickel block and aluminium block surface, be then about 15min by dehydrated alcohol and acetone ultrasonic cleaning successively, dry, finally the alloy electric arc melting method of preparation is obtained target, for subsequent use.
Second step, at substrate deposit Ru layer;
(A) as adopted electrochemical plating to prepare Ru layer:
Matrix after the first step process is put into by NaOH, Na
2cO
3, Na
3pO
4with deionized water (NaOH:10g/L; Na
2cO
3: 10g/L; Na
3pO
4: 10g/L) in formulated alkaline cleaning fluid by ultrasonic cleaning, wherein wash temperature is 50 DEG C, cleaning 2min.Use washed with de-ionized water again 2 times; Matrix after cleaning being put into thionamic acid concentration is after the sulfamic acid solution of 5g/L activates 50s, with deionized water rinsing 2 times;
Pretreated matrix is put into by RuCl
3, thionamic acid, deionized water composition plating Ru liquid (RuCl
3: 4g/L; Thionamic acid: 40g/L) middle plating Ru layer; Plating Ru processing parameter: current density is 1.2A/dm
2; Bath temperature is 60 DEG C; Anode is Ti-Ru electrode; Negative electrode is matrix to be plated; Electroplating time is 40min; Gained thickness of coating is 5 μm.
(B) as adopted electro beam physics vapour deposition legal system for Ru layer:
Before deposited coatings, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation.
EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheating N5 matrix to 650 DEG C; Electron-beam voltage 16kV; Electronic beam current is 1.2A.Described depositing time is 20min, and deposit thickness is 5 μm.
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer;
(A) successively with the sample after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation.
(B) EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; The N5 matrix to 600 DEG C of pre-heat deposition Ru layer; Electron-beam voltage 17kV; Electronic beam current is 1.2A.Described depositing time is 30min, and deposit thickness is 40 μm, as shown in Figure 2.
4th step, puts into vacuum heat treatment furnace by the sample through the 3rd step process and carries out vacuum heat treatment; After vacuum heat treatment, Ru diffuses to form Ru content in Ni (Ru) Al/NiAlHfCrSi, Ni (Ru) Al layer to NiAlHfCrSi layer and outwards successively decreases in gradient from matrix surface.
Described vacuum heat treatment parameter is: vacuum tightness P:P<2 × 10
-2pa; Temperature: 900 DEG C; Time: 2h.
Above-mentioned obtained sample is increased weight as 0.6mg/cm at 1200 DEG C of atmospheric environment high temperature oxidation 100h rear oxidations
2, and the oxidation weight gain of common NiAlHf tack coat is 1.3mg/cm
2(as Fig. 3), illustrates that the antioxidant property of Ni provided by the invention (Ru) Al/NiAlHfCrSi bilayer structure tack coat is better.In addition, the sample prepared with embodiment 1 same material and technique under the Working environment of simulating oceanic atmosphere gas turbine engine (950 DEG C, atomization artificial seawater and standard aviation kerosene mixed gas-artificial seawater concentration: NaCl ~ 0.02mol/L, MgCl
2~ 0.01mol/L, KCl ~ 0.005mol/L, CaCl
2~ 0.002mol/L, standard aviation kerosene: sulphur content 0.2wt.%) carry out combustion gas thermal etching experiment.100h surrosion with Ni (Ru) Al/NiAlHfCrSi tack coat sample is less than common NiAlHf coating sample and does not occur weightlessness, and final weightening finish is about 0.49mg/cm
2, illustrate that the hot corrosion resistance of resistance to combustion gas of Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat is better.After 1100 DEG C of vacuum heat treatment 100h, in alloy substrate, do not form secondary reaction district, illustrate that tack coat of the present invention has the performance of excellent prevention second time reaction zone SRZ formation.
embodiment 2:
The first step, prepares matrix and evaporation charge bar
(A) matrix is Ni based high-temperature alloy, and the trade mark is DZ125, is of a size of 10 × 8 × 3mm; With the SiC silicon carbide paper of 150#, 400#, 800#, matrix is polished, make Substrate Surface Roughness Ra < 0.8; Acetone and dehydrated alcohol ultrasonic cleaning 10 minutes.
(B) hafnium (Hf) of high purity nickel (Ni), raffinal (Al), pure chromium (Cr), pure silicon (Si) and purity 99.7% is used, by designed proportioning components, Al content is 45at%, Hf content is 0.1at%, Cr content is 1at%, Si content is 1at%, and surplus is Ni.Polish with the existence of security deposit's metal surface No oxided film to nickel block and aluminium block surface, be then about 15min by dehydrated alcohol and acetone ultrasonic cleaning successively, dry, finally the alloy electric arc melting method of preparation is obtained target, for subsequent use.
Second step, at substrate deposit Ru layer;
(A) as adopted electrochemical plating to prepare Ru layer, concrete grammar is:
Matrix after the first step process is put into by NaOH, Na
2cO
3, Na
3pO
4with deionized water (NaOH:30g/L; Na
2cO
3: 30g/L; Na
3pO
4: 30g/L) in formulated alkaline cleaning fluid by ultrasonic cleaning, wherein wash temperature is 70 DEG C, cleaning 5min.Use washed with de-ionized water again 3 times; Matrix after cleaning being put into thionamic acid concentration is after the sulfamic acid solution of 5g/L activates 100s, with deionized water rinsing 3 times;
Pretreated matrix is put into by RuCl
3, thionamic acid, deionized water composition plating Ru liquid (RuCl
3: 10g/L; Thionamic acid: 100g/L.) middle plating Ru layer; Plating Ru processing parameter: current density is 3.0A/dm
2; Bath temperature is 70 DEG C; Anode is Ti-Ru electrode; Negative electrode is matrix to be plated; Electroplating time is 100min; Gained thickness of coating is 10 μm.
(B) as adopted electro beam physics vapour deposition legal system for Ru layer, concrete grammar is:
Before deposited coatings, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation.
EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheating DZ125 alloy substrate to 750 DEG C; Electron-beam voltage 19kV; Electronic beam current is 1.5A.Described depositing time is 40min, and deposit thickness is 10 μm.
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer;
(A) successively with the sample after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation.
(B) EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; DZ125 alloy substrate to 750 DEG C after pre-heat deposition Ru layer; Electron-beam voltage 19kV; Electronic beam current is 1.5A.Described depositing time is 1h, and deposit thickness is 60 μm.
4th step, puts into vacuum heat treatment furnace by the sample through the 3rd step process and carries out vacuum heat treatment; After vacuum heat treatment, Ru diffuses to form Ru content in Ni (Ru) Al/NiAlHfCrSi, Ni (Ru) Al layer to NiAlHfCrSi layer and successively decreases in gradient.
Described vacuum heat treatment parameter is: vacuum tightness: P<2 × 10
-2pa; Temperature: 1130 DEG C; Time: 5h.
By above-mentioned obtained sample under the Working environment of simulation oceanic atmosphere gas turbine engine (950 DEG C, atomization artificial seawater and standard aviation kerosene mixed gas---artificial seawater concentration: NaCl ~ 0.02mol/L, MgCl2 ~ 0.01mol/L, KCl ~ 0.005mol/L, CaCl2 ~ 0.002mol/L, standard aviation kerosene: sulphur content 0.2wt.%) carry out combustion gas thermal etching experiment.Experiment loop cycle is 100 times, and each loop cycle is 1 hour, is incubated 50min and pressure-air cooling 10min at being included in 950 DEG C, and every 20 loop tests weightening finish once (as Fig. 4).Surrosion with Ni (Ru) Al/NiAlHfCrSi tack coat sample is less than common NiAlHf coating sample and does not occur weightlessness, and final weightening finish is about 0.52mg/cm
2.This sample is observed surface microscopic topographic through SEM and is found to compare with common NiAl tack coat, tack coat structure provided by the invention generates less spinel-like (see Fig. 5 (a) and (b)) in combustion gas thermal etching rear surface, illustrate that the hot corrosion resistance of resistance to combustion gas of Ni (Ru) the Al/NiAlHfCrSi bilayer structure tack coat that the present invention prepares is better.In addition, increase weight at 1200 DEG C of atmospheric environment high temperature oxidation 100h rear oxidations by sample obtained for the sample prepared with embodiment 2 same material and technique is 0.62mg/cm
2, be obviously better than the oxidation weight gain of common NiAlHf tack coat, illustrate that the antioxidant property of Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat is better.After 1100 DEG C of vacuum heat treatment 100h, in alloy substrate, do not form secondary reaction district, illustrate that coating of the present invention has the performance of excellent prevention second time reaction zone SRZ formation.
embodiment 3:
The first step, prepares matrix and evaporation charge bar
(A) matrix is Ni based single-crystal high-temperature alloy, and the trade mark is N5, is of a size of 10 × 10 × 2mm; With the SiC silicon carbide paper of 150#, 400#, 800#, matrix is polished, make Substrate Surface Roughness Ra < 0.8; The matrix of having polished is cleaned about 10min with acetone and EtOH Sonicate ripple successively, dries, for subsequent use.
(B) hafnium (Hf) of high purity nickel (Ni), raffinal (Al), pure chromium (Cr), pure silicon (Si) and purity 99.7% is used, by designed proportioning components, Al content is 55at%, Hf content is 0.5at%, Cr content is 2at%, Si content is 3at%, and surplus is Ni.Polish with the existence of security deposit's metal surface fresh room oxide film to nickel block and aluminium block surface, be then about 15min by dehydrated alcohol and acetone ultrasonic cleaning successively, dry, finally the alloy electric arc melting method of preparation is obtained target, for subsequent use.
Second step, electro beam physics vapour deposition Ru layer on matrix;
(A) as adopted electrochemical plating to prepare Ru layer, concrete grammar is:
Matrix after the first step process is put into by NaOH, Na
2cO
3, Na
3pO
4with deionized water (NaOH:15g/L; Na
2cO
3: 15g/L; Na
3pO
4: 20g/L) in formulated alkaline cleaning fluid by ultrasonic cleaning, wherein wash temperature is 65 DEG C, cleaning 5min.Use washed with de-ionized water again 3 times; Matrix after cleaning being put into thionamic acid concentration is after the sulfamic acid solution of 5g/L activates 100s, with deionized water rinsing 3 times;
Pretreated matrix is put into by RuCl
3, thionamic acid, deionized water composition plating Ru liquid (RuCl
3: 7g/L; Thionamic acid: 70g/L.) middle plating Ru layer; Plating Ru processing parameter: current density is 3.0A/dm
2; Bath temperature is 65 DEG C; Anode is Ti-Ru electrode; Negative electrode is matrix to be plated; Electroplating time is 70min; Gained thickness of coating is 8 μm.
(B) as adopted electro beam physics vapour deposition legal system for Ru layer, concrete grammar is:
Before deposited coatings, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation.
EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheating Ni based single-crystal high-temperature alloy N5 matrix to 650 DEG C; Electron-beam voltage 17kV; Electronic beam current is 1.5A.Described depositing time is 30min, and deposit thickness is 8 μm.
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer;
(A) successively with the sample after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation.
(B) EB-PVD unit type used is UE205.Sediment chamber is evacuated to 3 × 10
-3pa; Preheating sample to 650 DEG C to be sprayed; Electron-beam voltage 17kV; Electronic beam current is 1.2A.Described depositing time is 30min, and deposit thickness is 40 μm.
4th step, puts into vacuum heat treatment furnace by the sample through the 3rd step process and carries out vacuum heat treatment; After vacuum heat treatment, Ru diffuses to form Ru content in Ni (Ru) Al/NiAlHfCrSi, Ni (Ru) Al layer to NiAlHfCrSi layer and successively decreases in gradient.
Described vacuum heat treatment parameter is: vacuum tightness: P<2 × 10
-2pa; Temperature: 1100 DEG C; Time: 4h.
By above-mentioned obtained sample through after 1100 DEG C of vacuum heat treatment 100h, secondary reaction district is not formed in alloy substrate, this is because Ni (Ru) Al layer inhibits the diffusion of the matrix elements such as Al element and Ni, and this can provide sufficient Al element to form the α-Al of single densification on the one hand
2o
3sull, stops alloy to be oxidized further, significantly improves the anti-cyclic oxidation ability of tack coat; On the other hand, β-NiAl γ '-Ni in opposite directions in tack coat can be suppressed
3the transformation of Al, improves the bonding force of oxide film and tack coat, finally makes tack coat present good resistance of oxidation (as Fig. 6), illustrates that tack coat of the present invention has the performance of excellent prevention second time reaction zone SRZ formation.In addition, the sample prepared with embodiment 3 same material and technique increases weight as 0.61mg/cm at 1200 DEG C of atmospheric environment high temperature oxidation 100h rear oxidations
2, be obviously better than the oxidation weight gain of common NiAlHf tack coat, illustrate that the antioxidant property of Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat is better.Under the Working environment of simulation oceanic atmosphere gas turbine engine, (950 DEG C, be atomized artificial seawater and standard aviation kerosene mixed gas---artificial seawater concentration: NaCl ~ 0.02mol/L, MgCl to this batch sample simultaneously
2~ 0.01mol/L, KCl ~ 0.005mol/L, CaCl
2~ 0.002mol/L, standard aviation kerosene: sulphur content 0.2wt.%) carry out combustion gas thermal etching experiment.The 100h surrosion of Ni (Ru) Al/NiAlHfCrSi coating sample is less than common NiAlHf coating sample and does not occur weightlessness, and final weightening finish is about 0.54mg/cm
2, illustrate that the hot corrosion resistance of resistance to combustion gas of Ni (Ru) Al/NiAlHfCrSi bilayer structure tack coat is better.
Claims (2)
1. a preparation method for the compoiste adhering layer material of anti-1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation, is characterized in that comprising the steps:
The first step, prepares matrix and evaporation charge bar;
(A) matrix polished, clean, dry, for subsequent use; Described matrix is Ni based high-temperature alloy or Ni based single-crystal high-temperature alloy;
(B) NiAlHfCrSi target is prepared, for subsequent use; Part proportioning of described NiAlHfCrSi target is, Al content is 40 ~ 55at%, Hf content be 0.05 ~ 0.5at%, Cr content be 0.5 ~ 2at%, Si content is 1 ~ 3at%, and surplus is Ni;
Second step, electro beam physics vapour deposition Ru layer on matrix, is specially:
Before deposition Ru layer, matrix NiCr silk is fixed on after on fixture, after using dehydrated alcohol and acetone wiping successively, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepare evaporation; Sediment chamber is evacuated to 3 × 10
-3pa; Preheated substrate to 650 ~ 750 DEG C; Electron-beam voltage 16 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A; Depositing time is 20 ~ 40min, and deposition Ru layer thickness is 5 ~ 10 μm;
3rd step, electro beam physics vapour deposition NiAlHfCrSi layer on Ru layer:
(A) successively with the matrix after dehydrated alcohol and acetone wiping deposition Ru layer, the fixture being fixed with matrix is put into electro beam physics vapour deposition equipment, prepares evaporation;
(B) sediment chamber is evacuated to 3 × 10
-3pa; Matrix to 600 ~ 750 DEG C after pre-heat deposition Ru layer; Electron-beam voltage 17 ~ 19kV; Electronic beam current is 1.2 ~ 1.5A; Depositing time is 0.5 ~ 1h, and deposit thickness is 40 ~ 60 μm;
4th step, the matrix through the 3rd step process is put into vacuum heat treatment furnace and carries out vacuum heat treatment, vacuum heat treatment parameter is: vacuum tightness P:P<2 × 10
-2pa; Temperature: 900 DEG C ~ 1130 DEG C; Time: 2h ~ 5h; After vacuum heat treatment, Ru diffuses to form NiRuAl/NiAlHfCrSi bilayer structure tack coat to NiAlHfCrSi layer, described bilayer structure tack coat, one deck near matrix is NiRuAl, and the one deck near coating is that in NiAlHfCrSi, NiRuAl layer, Ru content outwards successively decreases in gradient from matrix.
2. the compoiste adhering layer material of anti-1200 DEG C of resistance to combustion gas thermal etchings of high temperature oxidation, it is characterized in that: adopt preparation method according to claim 1 to prepare, described compoiste adhering layer material is bilayer structure, by vacuum heat treatment, Ru is diffuseed to form to NiAlHfCrSi layer; One deck near matrix is NiRuAl, and the one deck near coating is that in NiAlHfCrSi, NiRuAl layer, Ru content outwards successively decreases in gradient from matrix.
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| CN105369202A (en) * | 2015-11-20 | 2016-03-02 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for preparing thermal barrier coating on heavy gas turbine blade |
| CN114807855A (en) * | 2022-04-19 | 2022-07-29 | 中国航发动力股份有限公司 | Process method for preparing thermal barrier coating containing diffusion-resistant layer by EB-PVD one-step method |
| CN115341176B (en) * | 2022-08-22 | 2024-01-19 | 西安电子科技大学 | Multilayer bonding layer material applied to thermal barrier coating and preparation method thereof |
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| CN1427085A (en) * | 2001-12-17 | 2003-07-02 | 三菱重工业株式会社 | High-temp corrosion-resisting alloy, heat barrier coating material, turbine structural member and gas turbine |
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