CN106086997A - A kind of thermally grown Al2o3or Cr2o3membranous type M Cr Al nano-composite plate and preparation and application - Google Patents
A kind of thermally grown Al2o3or Cr2o3membranous type M Cr Al nano-composite plate and preparation and application Download PDFInfo
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- CN106086997A CN106086997A CN201610444096.XA CN201610444096A CN106086997A CN 106086997 A CN106086997 A CN 106086997A CN 201610444096 A CN201610444096 A CN 201610444096A CN 106086997 A CN106086997 A CN 106086997A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Abstract
The present invention relates to electrophoretic deposition technique and electro-deposition techniques, a kind of thermally grown Al2O3Or Cr2O3Membranous type M Cr Al nano-composite plate and preparation and application.Coating is made up of nanocrystalline metal M coating and metal Cr, Al and/or CrAl alloy nanoparticle being dispersed therein, and prepares M Cr Al nano-composite plate by electrophoresis electroplating deposition two-step method；Wherein, M is Ni, Fe or Co, by mass percentage, the content of Cr be Cr be 5～22%, Al content is 3～15%, and surplus is M.In the nano-composite plate that the present invention obtains, nano-particles reinforcement amount is greatly improved, and its antioxygenic property is also greatly improved；The nano-particle amount that preparation process uses is greatly lowered, and the nano composite plating composition of layer of preparation is controlled, compact structure, can thermally grown Al under the conditions of high temperature or heat erosion2O3Or Cr2O3Oxide-film, both can be as resistance to high temperature oxidation, corrosion and heat resistant overcoat, again can be as the tack coat between thermal barrier coating and matrix.
Description
Technical field
The present invention relates to electrophoretic deposition technique and electro-deposition techniques, a kind of electrophoresis-electroplating deposition two-step method
Prepare thermally grown Al2O3Or Cr2O3Membranous type M-Cr-Al (M=Ni, Fe, Co) nano-composite plate and methods and applications.
Background technology
The nano-composite plate of non-oxidizability has been prepared with Nano metal powder or alloyed powder with metal M (common Fe, Co, Ni)
Have been reported that.The ultimate principle of composite plating is to co-deposit with metal M with metal powder or alloyed powder with metal M (common Ni),
While metal reduction metal powder or alloyed powder wrapped up into coating, thus obtain answering of M/ metal powder type or M/ alloyed powder type
Close coating.When ambient temperature is 800～1100 DEG C of high-temperature oxydations, or in the environment of heat erosion, thermally grown Al2O3Or
Cr2O3It is respectively provided with protective value.Therefore, the composite deposite the most often preparing M-Al or M-Cr-Al is desired anti-to obtaining
High-temperature oxydation or hot corrosion resistance.But, the research of current this respect has some difficult problems, predominantly: plate during (1) composite plating
Concentrations of nanoparticles in liquid is the highest, and the utilization rate of granule is low, adds that nano-particle price is the highest, causes this preparation method to become
Ben Taigao and affect the commercial introduction of nano-composite plate；(2) performance of nano compound electroplating technology is mainly by nanometer in coating
The content of granule determines, and a major challenge improving always nano compound electroplating technology of coating endoparticle content, owing to passing
The restriction of system technique, although have a lot of trial to improve the content of nano-particle in coating at present, as added surfactant,
Change electroplating technological parameter such as electric current, change the methods such as solution composition, but effect is the most inconspicuous.
Summary of the invention
For problems of the prior art, it is an object of the invention to provide a kind of electrophoresis-electro-deposition two-step method system
Standby thermally grown Al2O3Or Cr2O3Membranous type M-Cr-Al nano-composite plate and methods and applications, the nano-particle used in preparation
Measuring less, cost is substantially reduced, and in coating, the content of nano-particle is greatly improved, in high temperature or heat compared to conventional composite plating
Can direct growth Al under corrosive environment2O3Or Cr2O3The M-Cr-Al nano-composite plate of membranous type.
Technical scheme is as follows:
A kind of thermally grown Al2O3Or Cr2O3Membranous type M-Cr-Al nano-composite plate, coating is by nanocrystalline metal M coating
Form with metal Cr, Al and/or CrAl alloy nanoparticle being dispersed therein, by electrophoresis-electroplating deposition two-step method system
Standby M-Cr-Al nano-composite plate；Wherein, M is Ni, Fe or Co, by mass percentage, the content of Cr be Cr be 5～22%,
Al content is 3～15%, and surplus is M.
Described thermally grown Al2O3Or Cr2O3Membranous type M-Cr-Al nano-composite plate, by mass percentage, also includes
Accounting for quality of coating 0.5～the rare earth oxide particles of 3%, particle dispersion is distributed in M coating.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, rare earth oxide is
CeO2、Y2O3、La2O3Or Gd2O3。
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, the preparation of coating divides
Electrophoresis-electro-deposition two step is carried out: the first step, with W metal, Fe, Co, carbon steel or low alloy steel as base material, electric in advance on base material
Swimming one layer of uniform, fine and close metal Cr, Al and/or CrAl alloy nanoparticle of deposition, the electrophoresis preparing CrAl nano-particle sinks
Lamination；Second step, puts into the base material of electrophoretic deposition CrAl layer in the electroplating solution of Ni, Fe or Co and electroplates, and makes corresponding
Metal is forming core growth in the hole of nano-particle, prepares M-Cr-Al nano-composite plate, i.e. Ni-Cr-Al, Fe-Cr-
Al or Co-Cr-Al nano-composite plate.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, the first step uses
Electrophoresis solution is: dissolves acetylacetone,2,4-pentanedione solution or the acetone soln of elemental iodine, or dissolves AlCl3·6H2O or MgCl2·6H2O
Ethanol solution；Elemental iodine concentration in acetylacetone,2,4-pentanedione solution or acetone soln is 0.2～3g/L；AlCl3·6H2O or
MgCl2·6H2O concentration in ethanol solution is 0.2～3g/L.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, second step uses
Electroplating solution is: perchloro-plating solution, watt plating solution, low temperature plating solution or sulfamate bath.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, first step electrophoresis sinks
Long-pending CrAl nanoparticle deposition layer thickness is 10 μm～50 μm；Ni-Cr-Al, Fe-Cr-Al or the Co-obtained after second step plating
Cr-Al nano-composite plate, by mass percentage, Cr is 5～22%, and Al content is 3～15%, and surplus is M；Wherein, receive
Rice metal Cr and/or Al granule and/or CrAl alloying pellet size are respectively less than 100 nanometers.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, composite deposite exists
Heat of oxidation growth continuous print protectiveness Al under 800～1100 DEG C of high temperature2O3Or Cr2O3Oxide-film.
Described thermally grown Al2O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, at electrophoretic deposition
Time, add in electrophoresis solution and account for final composite deposite quality 0.5～the rare earth oxide particles of 3%.
Described thermally grown Al2O3Or Cr2O3The application of membranous type M-Cr-Al nano-composite plate, nano-composite plate conduct
The resistance to high temperature oxidation protective coating of aero engine turbine blades, or as peculiar to vessel, warship use, ocean or power industry electromotor whirlpool
The corrosion and heat resistant protective coating of impeller blade, or the tack coat as aero-gas turbine thermal barrier coating Yu matrix.
The design philosophy of the present invention is:
The present invention uses two-step method to prepare M-Cr-Al nano-composite plate, it is possible to use less nano-particle, preparation
The plating of the content of nano-composite plate relatively conventional composite is greatly improved.Its principle is, by the two of traditional composite plating process
Step Adsorption Model separately realizes by electrophoresis and plating two step.First introduce Guglielmi propose composite plating two step Adsorption Model:
The first step, adsorbs hydrated ion in electroplating solution, and the nano-particle of positively charged moves to negative electrode under the effect of electric field force
Surface, thus form reversible physical absorption at cathode surface, for weakly stable；Second step, nanometer with the help of electric field force
Grain migrates to electric double layer and directly contacts with cathode surface, thus forms the Irreversible Adsorption of Electrochemical adsorption, for strong absorption.It
After, along with the metal that nano-particle is reduced that thickens of coating wraps up into coating.
The concrete steps of the present invention and as follows with the relation of two step Adsorption Model: the first step, just adsorb in electrophoresis solution
The nano-particle of electric charge moves to and is deposited on matrix surface under the effect of electric field force, the granule dense uniform of electrophoretic deposition
Distribution, is equivalent to first overlay the skeleton of one layer of nano-particle composition at matrix surface；This step is equivalent to two step Adsorption Model
In the first step, be physical absorption；Second step carries out electroplating deposition, uses small area analysis, makes the Ni can be slowly receiving of overlaying
The forming core growth of rice grain surface, the metal that nano-particle is reduced wraps up the second step being equivalent to two step Adsorption Model into coating.
The nano-composite plate that two-step method prepares is identical with Conventional nano composite plating structure, and nano-particle content is greatly improved.
M-Cr-Al nano-composite plate prepared by the present invention can the protection of thermally grown continuous print under 800～1100 DEG C of high temperature
Property Al2O3Or Cr2O3Film, its principle is as follows: M-Cr-Al nano-composite plate has nanostructured, when Cr, Al unit in coating
Cellulose content meets or exceeds generation Al2O3Or Cr2O3During the marginal value of film, can be controlled by the Cr/Al ratio in regulation coating
The Al of external oxidation is generated during oxidation2O3Or Cr2O3Film, the most only to generate Al2O3As a example by, generate Cr2O3The principle of film is similar to, no
Repeat again.When Cr, Al constituent content in coating meets or exceeds generation Al2O3During the marginal value of film, Cr plays third element effect
Should, at the oxidation initial stage, Cr plays the effect of oxygen absorbent, promotes continuous print Al2O3The generation of film, and then generation Al can be reduced2O3Film
Critical Al content；Protectiveness Al2O3The forming core generating suppression substrate metal oxide MO of film and growth, thus improve antioxidation
Performance.The addition of rare earth oxide further increases the antioxygenic property of coating, is mainly manifested in: 1) reduce Al2O3Or
Cr2O3The speed of growth of film；2) Al is improved2O3Or Cr2O3The film adhesiveness to coating.
Compared with traditional nano compound electroplating technique, advantages of the present invention and good effect are as follows:
1, using cost of the present invention to be substantially reduced, the utilization rate of nano powder improves, and the nano powder concentration used in electrophoresis is
It is only 4g/L, and usually in order to improve the content 200g/L of nano-particle in nano-deposit when electroplating, the use of nano-particle
Amount falls below 1st/50th of nano compound electroplating.
2, in using coating of the present invention, nano-particle content is greatly promoted, and in composite deposite, nano-particle content reaches as high as
37%.
3, present invention process is simple, ripe, low cost, is beneficial to extend to commercial Application.Electrophoretic techniques and electroplating technology are all
It is ripe technique, existing electrophoresis solution has added required nanometer CrAl alloyed powder, in normal plating after drying
Solution is electroplated, it is not necessary to other are too much invested.
4, applied widely.Various nano powders can be carried out electrophoretic deposition by the present invention, and electro-deposition afterwards obtains high-load
Composite deposite, thus solve the difficult problem that composite plating content is low.Further, due to nano-composite plate of the present invention in atmosphere
800～1000 DEG C show good corrosion resistance.Therefore, this composite deposite can be widely applied to prepare aero-engine
Al is grown at said temperature internal heat2O3Or Cr2O3The protective coating of membranous type, it may also be used for the high temperature of carbon steel or low alloy steel is prevented
Protect.
Accompanying drawing explanation
Transmission electron microscope (TEM) pattern of the Fig. 1-1 nanometer CrAl alloyed powder used by one embodiment of the invention, granule
Average-size is 58nm.
Fig. 1-2 is transmission electron microscope (TEM) pattern of the nanometer Cr powder used by one embodiment of the invention, the average chi of granule
Very little for 39nm.
Fig. 2-1 is one embodiment of the invention Cross Section Morphology on pure Ni matrix after electrophoretic deposition nanometer CrAl layer.
When Fig. 2-2 is acetylacetone,2,4-pentanedione solution for one embodiment of the invention electrophoresis solution prepared by electrophoresis-electro-deposition two-step method
The Cross Section Morphology of Ni-8Cr-17Al nano-composite plate.
Fig. 3 is the one embodiment of the invention electrophoresis solution Ni-that prepared by electrophoresis-electro-deposition two-step method when being ethanol solution
The Cross Section Morphology of 10Cr-6Al nano-composite plate.
Fig. 4 is Ni-7.5Al-2.7Cr nano-composite plate prepared by the Conventional nano composite plating with embodiment contrast
Cross Section Morphology.
Fig. 5 be the electrophoresis solvent of one embodiment of the invention when being acetylacetone,2,4-pentanedione solution electrophoresis-electro-deposition two-step method prepare
Nano-composite plate and Conventional nano composite plating prepare the thermogravimetric analysis in 1000 DEG C of air after oxidation 20h of coating
(TGA) curve comparison diagram.Abscissa represents time (h), vertical coordinate representation quality change (mg/cm2)。
The nano-composite plate Ni-that when Fig. 6-1 is acetylacetone,2,4-pentanedione solution for electrophoresis solvent prepared by electrophoresis-electro-deposition two-step method
15Cr-5Al aoxidizes the oxide layer surface topography map after 20h in 1000 DEG C of air, and (growth of oxygen compound is mainly Al2O3)。
Fig. 6-2 prepares nano-composite plate Ni-3Cr-8Al for Conventional nano composite plating and aoxidizes in 1000 DEG C of air
Oxide layer surface topography map (growth of oxygen compound is mainly NiO) after 20h.
The nano-composite plate Ni-that when Fig. 7-1 is acetylacetone,2,4-pentanedione solution for electrophoresis solvent prepared by electrophoresis-electro-deposition two-step method
15Cr-5Al aoxidizes the oxide layer Cross Section Morphology figure after 20h in 1000 DEG C of air, and (growth of oxygen compound is mainly Al2O3, containing a small amount of
NiO and NiAl2O4)。
Fig. 7-2 prepares nano-composite plate Ni-3Cr-8Al for Conventional nano composite plating and aoxidizes in 1000 DEG C of air
Oxide layer Cross Section Morphology figure (growth of oxygen compound is mainly NiO) after 20h.
Fig. 8 is the another embodiment of the present invention electrophoresis solution Ni-that prepared by electrophoresis-electro-deposition two-step method when being ethanol solution
10Cr-6Al nano-composite plate 900 DEG C, 1000 DEG C of air aoxidize thermogravimetric analysis (TGA) the curve comparison diagram of 20h.Horizontal seat
Mark represents time (h), vertical coordinate representation quality change (mg/cm2)。
When Fig. 9-1 is ethanol solution for another embodiment of the present invention electrophoresis solution prepared by electrophoresis-electro-deposition two-step method
Ni-10Cr-6Al nano-composite plate aoxidizes (the predominantly rich Al oxygen of the oxide layer surface topography map after 20h in 900 DEG C of air
Compound).
When Fig. 9-2 is ethanol solution for another embodiment of the present invention electrophoresis solution prepared by electrophoresis-electro-deposition two-step method
Ni-10Cr6Al nano-composite plate aoxidizes (the predominantly rich Al oxygen of the oxide layer surface topography map after 20h in 1000 DEG C of air
Compound).
When Figure 10-1 is ethanol solution for another embodiment of the present invention electrophoresis solution prepared by electrophoresis-electro-deposition two-step method
Ni-10Cr-6Al nano-composite plate aoxidizes (the predominantly rich Al oxygen of the oxide layer Cross Section Morphology figure after 20h in 900 DEG C of air
Compound).
When Figure 10-2 is ethanol solution for another embodiment of the present invention electrophoresis solution prepared by electrophoresis-electro-deposition two-step method
Ni-10Cr-6Al nano-composite plate aoxidizes (the predominantly rich Al oxygen of the oxide layer Cross Section Morphology figure after 20h in 1000 DEG C of air
Compound).
Detailed description of the invention
In specific implementation process, electrophoresis of the present invention-electro-deposition two-step method prepares thermally grown Al2O3Or Cr2O3Membranous type M-
Cr-Al nano-composite plate, its composition be the nanocrystalline metal M of deposition and nano metal Cr, Al of being dispersed therein and/or
CrAl alloy nanoparticle；Wherein, M is Ni, Fe or Co, by mass percentage, the content of Cr be Cr be 5～22%, Al contains
Amount is 3～15%, and surplus is M.
The preparation method of nano-composite plate is undertaken in two steps: (1) is with W metal, Fe, Co, carbon steel or low alloy steel as base
Material, electrophoretic deposition nano metal Cr, Al granule and/or CrAl alloying pellet (particle diameter is respectively less than 100nm) in advance on base material, system
Standby CrAl electrophoretic deposition layer；(2) base material of electrophoretic deposition CrAl layer is put into and the electroplating solution of Ni, Fe or Co carries out electric sinking
Long-pending, make the forming core growth in the hole of nano-particle of corresponding metal, prepare M-Cr-Al type nano-composite plate, i.e. Ni-
Cr-Al, Fe-Cr-Al or Co-Cr-Al nano-composite plate.
Step (1) electrophoresis solution is: has dissolved acetylacetone,2,4-pentanedione solution or the acetone soln of elemental iodine or has dissolved
AlCl3·6H2O or MgCl2·6H2The ethanol solution of O；The concentration of elemental iodine is 0.2～3.0g/L, AlCl3·6H2O or
MgCl2·6H2The concentration of O is 0.2～3.0g/L.During electrophoretic deposition, electrophoresis solution temperature is 20～40 DEG C, and electric field intensity is 15
～200V/cm, electrophoresis time is 5～60s.Before electrophoretic deposition, make Cr, Al and/or CrAl nano-particle by supersonic vibration
Even suspension is in electrophoresis solution.Step (2) use electroplating solution is: watt plating solution, low temperature plating solution or sulfamate plating
Liquid.Not stirring in electroplating process, electric current density is 0.5～1.5A/cm2, electroplating time is 1～6h.
When electrophoretic deposition, electrophoresis solution adds appropriate rare-earth oxide nano particles, afterwards according to step (2)
Carrying out electroplating deposition, final acquisition contains rare earth oxide particles mass percent 0.5～the composite deposite of 3%.This rare-earth oxidation
Composition granule Dispersed precipitate is in M coating, it is expected to improve coating growth Al further2O3Or Cr2O3The antioxygenic property of film；Rare earth oxygen
Chalcogenide particles can be CeO2、Y2O3、La2O3、Gd2O3Deng；In the present invention, the electrophoresis preparing the use of above-mentioned nano-composite plate sinks
Long-pending equipment and electro-deposition devices are conventional equipment.
With embodiment in detail the present invention is described in detail below in conjunction with the accompanying drawings.
Embodiment 1
When the present embodiment provides electrophoresis solution to be acetylacetone,2,4-pentanedione solution, electrophoresis-electro-deposition two-step method prepares nano-composite plate
Preparation and performance, first introduce electrophoresis-galvanoplastic when electrophoresis solution is acetylacetone,2,4-pentanedione solution and prepare the preparation side of nano-deposit
Method, specifically comprises the following steps that
1) taking Ni is base material, is processed into the sample of 15 × 10 × 2mm size, is milled to 800# through silicon carbide paper, in acetone
Dry up standby after ultrasonic cleaning；
2) by CrAl alloy that Cr granule (Fig. 1-2) that 0.3g mean diameter is 39nm, 0.1g mean diameter are 58nm
Grain (Fig. 1-1) is immersed in the electrophoresis solution being made up of 100ml acetylacetone,2,4-pentanedione and 0.03g elemental iodine, in order to granule dispersion is the most equal
Even it is suspended in dispersant.
3) the CrAl coating being made up of nanometer Cr, CrAl granule Ni substrate surface electrophoretic deposition one layer, before each electrophoresis
Making nanometer Cr, CrAl alloying pellet fully be suspended in electrophoresis solution by supersonic vibration, electrophoresis solution temperature is 25 DEG C, uses
Graphite anode, electric field intensity is 250V/cm, each sample electrophoresis 1 time, and each electrophoresis time is 5s.
4) electrophoretic deposition having the coating of nano-particle be placed in watts nickel liquid to electroplate, solution composition is:
NiSO4·7H2O 150g/L、NiCl2 30g/L、H3BO330g/L and water surplus, in electroplating process, bath temperature is 30 DEG C, for
Preventing flow of the electrolyte from the nano-particle of matrix surface, electrophoretic deposition is had percussion, do not stir in electroplating process, electric current is close
Degree is 0.5A/dm2, electroplating time is 2h, and sample thickness is about 10 μm.Energy spectrum analysis shows that electrophoresis solution is acetylacetone,2,4-pentanedione solution
Time the composite deposite prepared by electrophoresis-plating two-step method, in coating, the content of nano-particle is up to 13～37wt.%.
Electrophoresis solution it is described below when being acetylacetone,2,4-pentanedione solution, composite deposite after nano-particle electrophoretic deposition layer and plating
The Nomenclature Composition and Structure of Complexes feature.Fig. 2-1 and 2-2 is respectively electrophoretic deposition nano-particle Cross Section Morphology and electrophoresis-electrocasting/electrodeposition two-step method
The composite deposite Cross Section Morphology of preparation, in Fig. 2-1, Lycoperdon polymorphum Vitt electrophoretic deposition layer is nano-particle CrAl sedimentary, it is seen that granule is uniform
Dispersion, electrophoretic deposition layer cross section is smooth, fine and close and do not have crackle.Fig. 2-2 prepares nano combined for electrophoresis-electrocasting/electrodeposition two-step method
Coating Cross Section Morphology, dark bulbous region is nano-particle, and light color irregular area is the metal in the reduction of nano-particle hole
Nickel, it can be seen that nano-particle is uniformly distributed, plated layer compact and do not have the defect such as hole, crackle.
Below, the simple preparation introducing Conventional nano composite deposite as a comparison and performance.Preparation method is often to use
Rule coelectrodeposition (i.e. composite plating) technology prepares Ni-Cr-Al nano-composite plate, and plating solution is the sulfur with citric acid as chelating agent
Silicate system (note: the coating content prepared compared with watt plating solution because of the content of granule in nano-composite plate prepared by this system
Higher).Solution composition is: NiSO4·7H2O 50g/L、Na3C6H5O7 120g/L、NaCl 15g/L、H3BO3More than 25g/L and water
Amount, adds nanometer Cr granule 140g/L, CrAl alloy nanoparticle 70g/L in plating solution, use plate pump type dress in electrodeposition process
Putting stirring plating solution, to ensure the nanoparticle suspension in plating solution, uniform deposition is on the surface of sample；Temperature of electroplating solution is 30 DEG C,
Electric current density is 2A/dm2, mixing speed is 150r/min, and electroplating time is 1.5h, and sample mean thickness is 10 μm.Coating nickel
Nano-particle is evenly distributed, and in coating knowable to use energy spectrum analysis, the content of nano-particle is 7～11wt.%.Fig. 4 is that tradition is multiple
Closing the Cross Section Morphology figure of the nano-composite plate of plating preparation, in figure, dark spherical position is nano-particle, light color region of disorder
Territory is the W metal of reduction.Conventional composite is electroplated compared with the nano-composite plate that electrophoresis-electro-deposition two-step method prepares, and two
Person's Cross Section Morphology is similar, but the distribution of particles density of the latter is substantially significantly larger than the former, consistent with EDAX results, it is known that electricity
In the nano-composite plate that swimming-electro-deposition two-step method prepares, the content of nano-particle is received far above conventional composite plating preparation
Rice composite deposite endoparticle content.
Embodiment 2
When the present embodiment provides electrophoresis solution to be ethanol solution, electrophoresis-deposition two-step method prepares nano composite plating layer method,
Specifically comprise the following steps that
1) taking Ni is base material, is processed into the sample of 15 × 10 × 2mm size, is milled to 800# through silicon carbide paper, in acetone
Dry up standby after ultrasonic cleaning；
2) by Cr granule that 0.4g mean diameter is 39nm, 0.1g mean diameter be 58nmCrAl alloying pellet be immersed in by
100ml ethanol and 0.4g MgCl2·6H2In the electrophoresis solution of O composition, in order to granule dispersion even suspension are in dispersant.
3) the CrAl coating being made up of Cr, CrAl granule Ni substrate surface electrophoretic deposition one layer.Pass through before electrophoresis every time
Supersonic vibration makes nanometer Cr, CrAl alloying pellet fully be suspended in electrophoresis solution, and electrophoresis solution temperature is 25 DEG C, uses graphite
Anode, electric field intensity is 25V/cm, each sample electrophoresis 2 times, and each electrophoresis time is 15s, with by sample between twice electrophoresis
Take out from electrophoresis solution, dry, and make granule keep dispersion and suspended state by ultrasonic for electrophoresis solution.
4) electrophoretic deposition having the matrix of CrAl layer be placed in watts nickel liquid to electroplate, solution composition is: NiSO4·
7H2O 150g/L、NiCl2 30g/L、H3BO330g/L and water surplus, in electroplating process, bath temperature is 30 DEG C, for preventing plating
Liquid stream is dynamic has percussion to electrophoretic deposition at the nano-particle of matrix surface, does not stirs in electroplating process, and electric current density is
0.5A/dm2, electroplating time is 3h, and sample thickness is about 20 μm.By electrophoresis-electroplate two steps when electrophoresis solution is ethanol solution
Composite deposite prepared by method, in coating, the content of nano-particle is up to 13～23wt.%.
Electrophoresis solution being described below when being ethanol solution, electrophoresis-electro-deposition two-step method prepares nano-composite plate
The Nomenclature Composition and Structure of Complexes feature.Fig. 3 be electrophoresis solution when being ethanol solution electrophoresis-deposition two-step method prepare nano composite plating layer cross section shape
Looks.When the Nomenclature Composition and Structure of Complexes feature of its composite deposite is acetylacetone,2,4-pentanedione solution with electrophoresis solution prepared by electrophoresis-plating two-step method
Composite deposite Cross Section Morphology feature similarity, does not repeats them here, and in the two difference only coating, the content of nano-particle is different.Make
During with ethanol solution electrophoresis, owing in ethanol solution, the electric charge of nano grain surface absorption is H+, add meeting in ethanol solution
Having a small amount of water, have a small amount of hydrogen and separate out in electrophoresis process, gas overflows through electrophoretic deposition layer, therefore after ethanol solution electrophoresis
The porosity obtaining electrophoretic deposition layer nano-particle is slightly above acetylacetone,2,4-pentanedione solution electrophoresis sedimentary, causes the nanometer finally obtained
Composite deposite content is variant.
Embodiment 3
During the present embodiment electrophoresis solution acetylacetone,2,4-pentanedione electrophoresis solution, electrophoresis-electro-deposition two-step method prepares thermally grown Al2O3Membranous type
Ni-Cr-Al nano-deposit oxidation susceptibility after 1000 DEG C of oxidation 20h and shape characteristic (by controlling Cr/Al ratio in coating
Value and then control oxidation product are Al2O3Or Cr2O3Film, so repeating no more generation Cr2O3The embodiment of membranous type), specifically with
As a example by Ni-15Cr-5Al, and prepare with Conventional nano composite plating (in electroplating solution, the concentration of nano powder is 210g/L)
Ni-8Cr-3Al nano-composite plate for contrast.
The TGA instrument that model is TherMax700 that during high-temperature oxydation experiment, employing Thermo Cahn company produces, heats up
Speed is 30 DEG C/min, 1000 DEG C of insulations 20h, then furnace cooling.Fig. 5 is that electrophoresis-electro-deposition two-step method prepares Ni-15Cr-
The Ni-8Cr-3Al nano-composite plate of 5Al nano-composite plate and conventional composite plating preparation aoxidizes in 1000 DEG C of air
Thermogravimetric analysis (TGA) the kinetic curve comparison diagram of 20h.Two-step method prepares Ni-15Cr-5Al nano-composite plate as seen from the figure
The oxidation weight gain of Ni-8Cr-3Al nano-composite plate prepared much smaller than Conventional nano composite plating of oxidation weight gain, the two
Oxidation parabolic rate constant is 1.5 × 10 respectively-12g2/cm4S and 1.1 × 10-10g2/cm4S, the former reduces than the latter
Two orders of magnitude, it can thus be appreciated that nano-composite plate prepared by present invention electrophoresis-plating two-step method is compared to Conventional nano
Nano-composite plate antioxygenic property prepared by composite plating is greatly improved.
Nano-composite plate 1000 prepared by Fig. 6-1 and 6-2 respectively electrophoresis-electro-deposition two-step method and tradition coelectrodeposition
Surface topography after DEG C oxidation, understands in conjunction with XRD analysis and EDAX results, nanometer prepared by electrophoresis-electro-deposition two-step method
Composite deposite oxide is mainly Al2O3, containing a small amount of NiO and NiAl2O4, the tiny densification of surface oxidation composition granule, and tradition is altogether
The oxide of nano-composite plate prepared by electro-deposition is the NiO of coarse grains.In conjunction with corresponding Cross Section Morphology Fig. 7-1 and 7-2
Understand, after nano-composite plate 1000 oxidation prepared by electrophoresis-electro-deposition two-step method, be quickly generated the finest and close Al2O3, thus
Prevent further oxidation；And nano-composite plate oxidation prepared by tradition coelectrodeposition generates the NiO without protectiveness,
Cause matrix oxidation serious.
Embodiment 4
When the present embodiment provides electrophoresis solution to be ethanol solution, electrophoresis-electro-deposition two-step method prepares thermally grown Al2O3Membranous type
Ni-Cr-Al nano-deposit 900 DEG C and 1000 DEG C oxidation 20h after oxidation susceptibility and shape characteristic, specifically with Ni-10Cr-
As a example by 6Al nano-composite plate (preparation method is same as in Example 2, and oxidation experiment is same as in Example 3).
Fig. 8 be electrophoresis solution when being ethanol solution electrophoresis-electro-deposition two-step method prepare Ni-10Cr-6Al nano-composite plate
Thermogravimetric analysis (TGA) the kinetic curve comparison diagram of 20h is aoxidized in 900 DEG C and 1000 DEG C of air.Although aoxidizing when 1000 DEG C
Increase weight accordingly during kinetics weightening finish slightly above 900 DEG C, but the two oxide parabola constant is the most relatively low, when respectively 1000 DEG C
2.7×10-11g2/cm4S and when 900 DEG C 1.6 × 10-12g2/cm4·s.From corresponding oxide layer surface topography map 9-1 and
Fig. 9-2 and energy spectrum analysis understand, and dark color is Al2O3, a small amount of light color position is NiO or NiAl2O4.From corresponding oxide layer cross section
Shape appearance figure 10-1 and 10-2 understands, and 900 DEG C of oxidation rear oxidation film thicknesses are only 0.6 μm, 1 μm after 1000 DEG C of oxidation rear oxidation films.
Thus understand electrophoresis when electrophoresis solution is ethanol solution-electro-deposition two-step method and prepare nano-composite plate at 900 DEG C and 1000 DEG C
The Al of protectiveness all can be generated during oxidation2O3, prevent the further oxidation of matrix, thus improve the antioxygenic property of matrix.
Fe, Co are the main base element of high temperature alloy as Ni, and preparation Fe-Cr-Al, Co-Cr-Al have only to base
Body and corresponding electroplating solution are changed, and its principle is identical with Ni-Cr-Al with preparation method, as long as reaching to generate external oxidation
Al2O3Or Cr2O3Film i.e. can reach the effect of protection group body.Alternatively, it is also possible to only add in electrophoresis solution Al nano-particle or
Cr nano-particle, and then obtain M-Cr or M-Al (M is Ni, Fe, or Co) nano-composite plate, in high-temperature oxydation or heat erosion
Under the conditions of can generate the Al of protectiveness2O3Or Cr2O3Film.Its principle above example uniform with preparation method is identical, at this not
Repeat again.
From the foregoing, it will be observed that the nano-composite plate that present invention preparation is prepared by electrophoresis-electro-deposition two-step method is by nanocrystalline gold
Belong to M (M is Ni, Fe or Co) and Cr, Al and/or CrAl alloy nanoparticle composition.This coating is coated with Conventional nano compound electric
Standby nano-composite plate is identical in structure, but in composite deposite, the content of nano-particle is greatly improved, and in high temperature environments may be used
To generate the Al of protectiveness2O3Or Cr2O3Film.The principle that the present invention prepares the raising of coating nano-deposit granule content is as follows: first
Step electrophoretic deposition prepares CrAl layer, has been equivalent to one layer of fine and close continuous print nano-particle skeleton prefabricated, gold during second step electro-deposition
Belong to Ni forming core growth between the hole of CrAl granule, nano-particle is fixed, thus obtains receiving of high nano-particle content
Rice composite deposite.Owing in nano-composite plate prepared by the present invention, nano-particle content exceedes the Al of generation external oxidation2O3Or
Cr2O3During film marginal value, therefore the Al of the external oxidation with protectiveness can be quickly generated in high-temperature oxidation environment2O3Or Cr2O3
Film.Meanwhile, appropriate rare earth oxide CeO can be added in electrophoresis solution2、Y2O3、La2O3Or Gd2O3Deng granule, it is thus achieved that contain
The nano-composite plate of rare earth oxide, and then improve the antistrip performance of oxide-film.Present invention could apply to 800～1100
Under DEG C high temperature or the Al of heat erosion environment generation protectiveness2O3Or Cr2O3Film, or as gluing between thermal barrier coating and matrix
Knot layer.
Embodiment result shows, in the nano-composite plate that the present invention obtains, nano-particles reinforcement amount is compared to Conventional nano
Composite plating is prepared the compound quantity of coating and is greatly improved, and its antioxygenic property is also greatly improved；The nanometer that preparation process uses
Grain amount is greatly lowered, and has saved that production cost, electrophoretic deposition and electrodeposition technology are simple, ripe, has easily promoted；The nanometer of preparation
Composite deposite composition is controlled, compact structure, can thermally grown Al under the conditions of high temperature or heat erosion2O3Or Cr2O3Oxide-film, both may be used
Using as resistance to high temperature oxidation, corrosion and heat resistant overcoat, again can be as the tack coat between thermal barrier coating and matrix.
Claims (10)
1. a thermally grown Al2O3Or Cr2O3Membranous type M-Cr-Al nano-composite plate, it is characterised in that coating is by nanocrystalline gold
Belong to M coating and metal Cr, Al and/or CrAl alloy nanoparticle composition being dispersed therein, by electrophoresis-electroplating deposition two
Footwork prepares M-Cr-Al nano-composite plate；Wherein, M is Ni, Fe or Co, by mass percentage, the content of Cr be Cr be 5
～22%, Al content is 3～15%, and surplus is M.
2. according to the thermally grown Al described in claim 12O3Or Cr2O3Membranous type M-Cr-Al nano-composite plate, it is characterised in that
By mass percentage, also including accounting for quality of coating 0.5～the rare earth oxide particles of 3%, particle dispersion is distributed in M coating
In.
3. according to the thermally grown Al described in claim 22O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
Being characterised by, rare earth oxide is CeO2、Y2O3、La2O3Or Gd2O3。
4. the thermally grown Al that one of claims 1 to 3 is described2O3Or Cr2O3The preparation of membranous type M-Cr-Al nano-composite plate
Method, it is characterised in that the preparation of coating divides electrophoresis-electro-deposition two step to carry out: the first step, with W metal, Fe, Co, carbon steel or
Low-alloy steel is base material, metal Cr, Al and/or CrAl alloy nano that electrophoretic deposition one layer is uniform, fine and close in advance on base material
Granule, prepares the electrophoretic deposition layer of CrAl nano-particle；Second step, puts into Ni, Fe or Co by the base material of electrophoretic deposition CrAl layer
Electroplating solution in electroplate, make corresponding metal in the hole of nano-particle forming core growth, prepare M-Cr-Al and receive
Rice composite deposite, i.e. Ni-Cr-Al, Fe-Cr-Al or Co-Cr-Al nano-composite plate.
5. according to the thermally grown Al described in claim 42O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
Being characterised by, the electrophoresis solution that the first step uses is: dissolves acetylacetone,2,4-pentanedione solution or the acetone soln of elemental iodine, or dissolves
AlCl3·6H2O or MgCl2·6H2The ethanol solution of O；Elemental iodine concentration in acetylacetone,2,4-pentanedione solution or acetone soln is
0.2～3g/L；AlCl3·6H2O or MgCl2·6H2O concentration in ethanol solution is 0.2～3g/L.
6. according to the thermally grown Al described in claim 42O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
Being characterised by, the electroplating solution that second step uses is: perchloro-plating solution, watt plating solution, low temperature plating solution or sulfamate bath.
7. according to the thermally grown Al described in claim 42O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
Being characterised by, first step electrophoretic deposition CrAl nanoparticle deposition layer thickness is 10 μm～50 μm；Obtain after second step plating
Ni-Cr-Al, Fe-Cr-Al or Co-Cr-Al nano-composite plate, by mass percentage, Cr is 5～22%, and Al content is 3
～15%, surplus is M；Wherein, nano metal Cr and/or Al granule and/or CrAl alloying pellet size are respectively less than 100 nanometers.
8. according to the thermally grown Al described in claim 42O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
Being characterised by, composite deposite is heat of oxidation growth continuous print protectiveness Al under 800～1100 DEG C of high temperature2O3Or Cr2O3Oxide-film.
9. according to the thermally grown Al described in claim 42O3Or Cr2O3The preparation method of membranous type M-Cr-Al nano-composite plate, its
It is characterised by, when electrophoretic deposition, adds in electrophoresis solution and account for final composite deposite quality 0.5～the rare earth oxide of 3%
Granule.
10. the thermally grown Al that one of claims 1 to 3 is described2O3Or Cr2O3Answering of membranous type M-Cr-Al nano-composite plate
With, it is characterised in that described nano-composite plate as the resistance to high temperature oxidation protective coating of aero engine turbine blades, or
As peculiar to vessel, warship use, ocean or the corrosion and heat resistant protective coating of power industry engine turbine blade, or as aircraft gas
Turbine thermal barrier coating and the tack coat of matrix.
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| CN112647108A (en) * | 2021-01-25 | 2021-04-13 | 南昌航空大学 | Method for promoting thermal growth of chromium oxide protective film of low-chromium-content nickel-based alloy |
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