CN1266316C - Thermal growth AL2O3 film type M A1 nano composite plating and producing process and application - Google Patents
Thermal growth AL2O3 film type M A1 nano composite plating and producing process and application Download PDFInfo
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- CN1266316C CN1266316C CN 200410069557 CN200410069557A CN1266316C CN 1266316 C CN1266316 C CN 1266316C CN 200410069557 CN200410069557 CN 200410069557 CN 200410069557 A CN200410069557 A CN 200410069557A CN 1266316 C CN1266316 C CN 1266316C
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- 238000007747 plating Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title abstract description 12
- 230000008569 process Effects 0.000 title description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 88
- 230000003647 oxidation Effects 0.000 claims abstract description 84
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910003310 Ni-Al Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 10
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- 239000010962 carbon steel Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 57
- 238000000576 coating method Methods 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 23
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- 238000009792 diffusion process Methods 0.000 claims description 7
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- 239000011253 protective coating Substances 0.000 claims description 5
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- 229910000951 Aluminide Inorganic materials 0.000 claims description 3
- 229910015372 FeAl Inorganic materials 0.000 claims description 3
- 229910010038 TiAl Inorganic materials 0.000 claims description 3
- 229910001566 austenite Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 22
- 239000002131 composite material Substances 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 16
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- 230000001681 protective effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
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- 229910052593 corundum Inorganic materials 0.000 abstract 2
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- 238000012423 maintenance Methods 0.000 abstract 1
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Abstract
The present invention discloses a thermal growth Al2O3 film type M-Al nano composite plating layer, a preparation method and applications. The composite plating layer comprises ingredients of combination of deposited nanocrystal metal M and Al nano particles, wherein the Al nano particles are dispersed and distributed in the deposited nanocrystal metal M; M represents Ni, Fe or Co; the Al content is from 9.8 to 35% measured by the mass percent, and the rest is M. The preparation method comprises the following steps: the metal Ni, Fe or Co, and carbon steel or low alloy steel are used as base materials; the metal M and an Al plating layer are electroplated in a composite way by a coelectrodeposition technique on the base materials; then, a Ni-Al, Fe-Al or Co-Al nano composite plating layer is manufactured. The present invention has the advantages of simple and mature technology, easy popularization, and low production and maintenance cost on economic aspects. Compared with the traditional composite plating layers prepared from metal (namely micrometer metal powder), the nano composite plating layer has the characteristics of high compound quantity, controllable ingredient, compact plating layer, no need for vacuum dispersed treatment of the nano composite plating layer, etc. Protective Al2O3 oxidation films can directly and thermally grow on the nano composite plating layer.
Description
Technical field
The present invention relates to coating technology, specifically a kind of heat growth Al
2O
3Membranous type M-Al (M=Ni, Fe, Co) nano-composite plate and preparation method and application.
Background technology
Report to some extent with metal M (common Ni) and the composite deposite that metal powder or alloyed powder prepare non-oxidizability.Its ultimate principle is by composite electric plating method, with metal powder and M coelectrodeposition, forms M-metal powder type composite deposite.Since under hot environment, the Al of heat growth
2O
3Have protective value, so an Al powder, the alloyed powder that perhaps contains Al once was suggested as powder stock and M coelectrodeposition prepares composite deposite, in the hope of forming Al when the high-temperature oxydation
2O
3Protective oxide film.But; present progress in this respect is little; its key factor is that added powder is micron-sized; the composite deposite of the metal that this usefulness is traditional-micron order metallic particles coelectrodeposition preparation has the following disadvantages: (1) Al distribution of particles is inhomogeneous, and compound quantity does not reach formation protectiveness Al
2O
3The critical value that oxide-film is required, (2) porosity height.Therefore, also must process and the pressurization densification through high-temperature vacuum diffusion homogenising before using with the composite deposite of this preparation, and the oxidation susceptibility after processing to improve be not very big.
Summary of the invention
For these deficiencies, the object of the invention be to provide a kind of have porosity low, can direct heat growth Al in hot environment
2O
3Membranous type M-Al nano-composite plate and preparation method and application.
Technical scheme of the present invention is as follows:
Its preparation method is with metal Ni, Fe, Co, carbon steel, low alloy steel, Ti alloy, stainless steel etc. are base material, realize M and nanometer Al powder (less than, equal 100nm) coelectrodeposition, preparation metal M-Al type nano-composite plate, i.e. Ni-Al, Fe-Al or Co-Al nano-composite plate; Plating bath is sulfate system (MSO
4);
The M-Al nano-composite plate of preparation; its composition is the combination of nanocrystalline metal M and the Al nano particle dispersed therein of deposition; wherein M can be Ni, Fe or Co; in 950～1050 ℃ of temperature ranges; when the Al compound quantity in the nano-composite plate surpassed a critical value, nano-composite plate can the continuous protectiveness Al of heat growth
2O
3Film; The minimum content of Al is 9.8～12.9 parts by mass percentage, and high-load is 35 parts, and surplus is M; In addition, when coelectrodeposition prepares M-Al coating, also can add to plating bath the rare earth oxide particles (CeO for example of 3～6g/L
2, Y
2O
3, La
2O
3Or Gd
2O
3), can make the rare earth oxide particles that the nano-composite plate of preparation can compound trace (0.5～3%).The trace rare earth oxides that adds can to a certain degree improve the Al of heat growth
2O
3The antioxygenic property of film.Keep nano particle to be suspended in the tank liquor during plating; It is conventional equipment that the present invention prepares the used various composite plating equipment of above-mentioned nano-composite plate.
The M-Al nano-composite plate of the present invention's preparation is guaranteed the continuous protectiveness Al of heat growth under 950～1050 ℃ of high temperature
2O
3Oxide-film.Al grows under the high temperature
2O
3The oxide-film basic principle is as follows: because Al Nanoparticles of the present invention is evenly distributed in the nanocrystalline M coating, the metal M that obtains-Al nano-composite plate is compared with the composite deposite of the micron-sized Al that contains same amount, has greatly improved the particle number of Al in the unit are.These particles can be used as Al at the oxidation initial stage
2O
3The nucleating center, thereby greatly improved Al in the unit are
2O
3Number of nuclei; Simultaneously, the nano powder on inferior top layer can be used as " source " of Al, and it dissolves fast and diffuses to the surface, because after the coating nanometer, the Al of coating inside can rapidly along the Grain-Boundary Phase diffusion into the surface, impel established Al
2O
3The continuous Al that examines Fast Growth and form
2O
3Film causes the nucleation and growth of the oxide of coated metal base to be suppressed, thereby prevents from peeling off oxidation, raising oxidation susceptibility.Rare earth oxide further improves the antioxygenic property of oxide-film, is mainly manifested in: 1) reduce Al
2O
3The speed of growth of film; 2) improve Al
2O
3Film is to the adhesiveness of coating matrix.
Compare with traditional composite deposite with metal-micron order metal powder preparation, advantage of the present invention and positively effect are as follows:
1. can form Al
2O
3Protective oxide film.The present invention is by Nano metal powder, and adopts the nano-composite plate of the method preparation of metal-Al nano particle coelectrodeposition, has 1) compounding quantity height and the controllable component of Al; 2) coating densification; 3) nano-composite plate does not need by high-temperature vacuum diffusion and pressure treatment, and coating such as directly can use at characteristics, particularly in air 950～1050 ℃ shown good antioxidant property.Because these characteristics, it at high temperature can form Al
2O
3Protective oxide film.
2. improved coating performance greatly.Compare with metal Ni in the prior art and single Ni coating, the raising of composite deposite performance of the present invention (take metal Ni-Al nano-composite plate as example) is mainly manifested in: 1) compare with metal Ni and single Ni coating, the oxidation weight gain of 950 ℃ of oxidation 20h of Ni-Al nano-composite plate can reduce and reaches 30～50 times; 2) compare with metal Ni and single Ni coating, the oxidation weight gain speed of 1050 ℃ of oxidation 20h of Ni-Al nano-composite plate can reduce respectively and reaches more than 20 times and 85 times.
3. technology is simple, ripe, cost is low: because electronickelling is ripe technology, utilize existing electroplating device, add the Al Nanoparticles of aequum in tank liquor, just can be made into this novel nano composite deposite, do not need other too much investment.
4. applied widely.Nano-composite plate of the present invention in air 950～1050 ℃ shown good antioxygenic property, therefore, adopt the alternative diffusion of the present invention ooze Al coating (coat of aluminide) or other technology of being used for (such as thermal spraying, magnetron sputtering etc.) preparation at said temperature scope internal heat growth Al
2O
3The protective coating of membranous type can also be used for carbon steel, low-alloy steel, austenite or ferritic stainless steel, Ti alloy, TiAl, FeAl base intermetallic compound.
Description of drawings
Fig. 1 is the surface topography of Ni-28Al (mass percent, the as follows) nano-composite plate of one embodiment of the invention.
Fig. 2 is the XRD analysis comparison diagram of nanometer Al powder, Ni coating and the Ni-28Al coating of one embodiment of the invention.
Fig. 3 is the oxidation weight gain comparison diagram that exposes in 950 ℃ of air of one embodiment of the invention behind the 20h.
Fig. 4 is the XRD analysis comparison diagram as a result that exposes the zone of oxidation behind the 20h in 950 ℃ of air of one embodiment of the invention.
Fig. 5-a is the zone of oxidation surface topography map behind the exposure 20h in 950 ℃ of air of base material Ni of a comparative example of the present invention.
Fig. 5-b is the zone of oxidation surface topography map that exposes in 950 ℃ of air of single Ni coating with a comparative example of the present invention behind the 20h.
Fig. 5-c is the zone of oxidation surface topography map that exposes in 950 ℃ of air of one embodiment of the invention Ni-12.9Al nano-composite plate behind the 20h.
Fig. 5-d is the zone of oxidation surface topography map that exposes in 950 ℃ of air with one embodiment of the invention Ni-28Al nano-composite plate behind the 20h.
Fig. 6-a is the zone of oxidation sectional view that exposes in 950 ℃ of air of Ni base material with a comparative example of the present invention behind the 20h.
Fig. 6-b is the zone of oxidation sectional view that exposes in 950 ℃ of air of single Ni coating with a comparative example of the present invention behind the 20h.
Fig. 6-c is oxide layer sectional view (the visible continuous Al that exposes in 950 ℃ of air of one embodiment of the invention Ni-12.9Al nano-composite plate behind the 20h
2O
3Layer forms).
Fig. 6-d is (the visible continuous Al of the oxide layer sectional view behind the exposure 20h in 950 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate
2O
3Layer forms).
Fig. 7 is one embodiment of the invention base material Ni, single Ni coating, the oxidation weight gain comparison diagram in 1050 ℃ of air of Ni-28Al nano-composite plate behind the exposure 20h.
Fig. 8 is one embodiment of the invention base material Ni, single Ni coating, and the XRD analysis of the zone of oxidation in 1050 ℃ of air of Ni-28Al nano-composite plate behind the exposure 20h is comparison diagram as a result.
Fig. 9-a is the zone of oxidation sectional view one embodiment of the invention Ni-28Al nano-composite plate exposes 20h in 1050 ℃ of air after.
Fig. 9-b is the zone of oxidation sectional view the single Ni coating with a comparative example of the present invention exposes 20h in 1050 ℃ of air after.
Fig. 9-c is the zone of oxidation sectional view the base material Ni with a comparative example of the present invention exposes 20h in 1050 ℃ of air after.
Figure 10 adds Rare-Earth Ce O for one embodiment of the invention
2Oxidation weight gain comparison diagram in 1050 ℃ of air behind the exposure 20h.
Figure 11-a is one embodiment of the invention Ni-30Al-0.75CeO
2Nano-composite plate exposes the zone of oxidation cross section comparison diagram behind the 20h in 1050 ℃ of air.
Figure 11-b is the zone of oxidation cross section comparison diagram the intermetallic compound β-NiAl with a comparative example of the present invention exposes 20h in 1050 ℃ of air after.
Figure 12 adds Rare-Earth Ce O for the embodiment of the invention
2The oxidation weight gain comparison diagram of thermal cycling 126h in 1000 ℃ of air (each isothermal 2h, air cooling 15min).
Figure 13-a is the zone of oxidation surface topography map behind the thermal cycling 126h in 1000 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate.
Figure 13-b is the high power intensified image of Figure 13-a regional area.
Figure 14-a is one embodiment of the invention Ni-30Al-0.75CeO
2The zone of oxidation surface topography map of nano-composite plate behind thermal cycling 126h in 1000 ℃ of air.
Figure 14-b is the high power intensified image of Figure 14-a regional area.
Figure 15-a is and the embodiment of the invention zone of oxidation surface topography map of intermetallic compound β-NiAl behind thermal cycling 126h in 1000 ℃ of air relatively.
Figure 15-b is the high power intensified image of Figure 15-a regional area.
Figure 16-a is the low power picture in the zone of oxidation cross section behind the thermal cycling 126h in 1000 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate.
Figure 16-b is the high power picture in the zone of oxidation cross section behind the thermal cycling 126h in 1000 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate.
Figure 17-a is one embodiment of the invention Ni-30Al-0.75CeO
2The low power picture in the zone of oxidation cross section of nano-composite plate behind thermal cycling 126h in 1000 ℃ of air.
Figure 17-b is one embodiment of the invention Ni-30Al-0.75CeO
2The high power picture in the zone of oxidation cross section of nano-composite plate behind thermal cycling 126h in 1000 ℃ of air.
Figure 18 is and the embodiment of the invention zone of oxidation cross section picture of intermetallic compound β-NiAl behind thermal cycling 126h in 1000 ℃ of air relatively.
Embodiment
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
M-Al nano composite plating composition of layer of the present invention is second combination of Al nanoparticle mutually that nanocrystalline M base coating and disperse distribute, i.e. M-Al, and wherein M can be Ni, Fe or Co; Its preparation method is to adopt coelectrodeposition (being composite plating) technology to prepare Ni-Al, Fe-Al or Co-Al nano-composite plate; Plating bath is above-mentioned sulfate system (MSO commonly used
4), the Al powder is a nano-scale.Present embodiment will with the preparation of Ni-Al nano-composite plate and as a result example elaborate, the nanometer Cr powder mean particle size of employing is respectively 40 and 75nm.
Its flow process that present embodiment prepares the Ni-Al nano-composite plate is:
Substrate metal adopts Ni (also can Fe, Co, carbon steel or low alloy steel is a base material)-surface finish to 800# waterproof abrasive paper-surperficial ultrasonic cleaning-carry out in containing the plating Ni tank liquor of nanometer Al powder coelectrodeposition-acquisition Ni-Al nano-composite plate.Keep nano particle to be suspended in the tank liquor when preparation key of nano-deposit of the present invention is plating, present embodiment prepares with traditional composite plating facility.
Specific as follows:
The electrolysis Ni plate of getting purity 99.96% is a base material, is processed into the small sample of 15 * 10 * 2mm size, is milled to 800 through silicon carbide paper
#, ultrasonic cleaning in acetone;
Be averaged granularity and be 40 or the nanometer Al powder of 75nm be immersed in the sodium dodecyl sulfate solution earlier so that the dispersion of nano particle is avoided reuniting;
Electroplate liquid adopts the low temperature modification plating bath, and composition is as follows: NiSO
4.7H
2O 150g/l, NH
4Cl 15g/l, H
3BO
315g/l, C
12H
25NaO
4S 0.1g/l; The solution of preparation is placed 24h through fully stirring after-filtration; The solution pH value can use (present embodiment can be 5.5) in 5.4～6.0 scopes.
Adopt plate pump formula device to stir plating bath in the electrodeposition process, to guarantee the suspension of nano particle in the plating bath, uniform deposition is at specimen surface; Bath temperature is 30 ℃, current density I=2A/dm
2, mixing speed is 110rpm.Electroplating time is 2h, and sample mean thickness is 45～60 μ m.
The compounding quantity of the nanometer Al powder in the coating increases with the increase of Al in the plating bath.Utilize the inventive method, maximum Al compound quantity and Al change in size relation are little, and maximum compound quantity can reach 35% (mass percent meter, lower same) at present.
Introduce below pattern and the architectural feature of Ni-Al nano-composite plate of the present invention.With compound mean sizes is the Al powder of 75nm, and content is that 28 Ni-Al nano-composite plate is an example, and the nano-composite plate of other composition compares therewith, and difference is little.
Generally speaking, the grain fineness number of the Ni coating of Ni-Al nano-composite plate, regularly improve or regularly reduce when content one at size of particles one with size of particles with content, all slightly reduce, this is because the interior institute of unit surface compound population increases and can suppress growing up of existing crystal grain by the forming core that promotes new Ni crystal grain.But, in the size ranges of the nanometer Al that present embodiment adopted (40～75nm), in compounding quantity is between 9.8～35 parts, and the variation of the grain fineness number of the Ni of composite deposite is not very big, and the surface appearance feature of composite deposite is also very similar with the XRD analysis result simultaneously.Fig. 1 is the surface topography of present embodiment Ni-28Al nano-composite plate.Show by energy spectrum analysis: the shape particle that looses is rich Al nano particle, and the Al amount of darker regions is high, is just to have deposited the nano particle that enters coating surface, and the Ni that white portion Al particle has newly been deposited covers.The grain-size of nanometer Al powder, single Ni coating and Ni-28Al composite deposite is by XRD determining, the result as shown in Figure 2, a is the XRD diffractogram of nanometer Al powder, the average grain size that is calculated by Scherrer according to the peak width at half height of the diffraction peak that obtains is 75nm; B is single Ni coating, and average grain size is 40nm; C is a composite deposite, and it is the Ni crystal grain of 38nm and the Al granulometric composition that mean particle size is 75nm by mean sizes.
Embodiment 2 (950 ℃ of oxidation susceptibilities)
Whether nano-composite plate of the present invention has superior high temperature oxidation resistance depends on that can nano-composite plate the continuous protectiveness Al of heat growth
2O
3Oxide-film.
The temperature that present embodiment adopts is in 950～1050 ℃ of scopes, and when the Al compound quantity in the nano-composite plate surpassed a critical value, nano-composite plate can hot growth protecting Al
2O
3Film.Heat growth Al
2O
3The required minimum content (or critical content) of film is relevant with the nano-scale of added Al powder.Particle size is more little, and critical content is more low.For example be respectively 40 and during 75nm in the used mean sizes of embodiment, the minimum content of Al is respectively 9.8 and 12.9% by mass percentage in the time of 950 ℃, and high-content is 35%, and surplus is M; Improve with oxidizing temperature, critical content increases.For example in the time of 1050 ℃, the Al size of particles is respectively 40 and during 75nm, and required critical size is respectively 11.2 and 14.3%.Mean particle size during below with 950 ℃ of oxidations is that the Ni-Al nano-composite plate of 75nm is an example.
Oxidation experiment carries out under laboratory environment, and oxidizing temperature is 950 ℃, and the time is 20h.Fig. 3 is Ni matrix, single Ni coating and Ni-12.9Al and the Ni-28Al nano-composite plate oxidation weight gain situation at 20h, and the oxidation para-curve constant that described sample calculates is respectively 6.3 * 10
-11, 1.1 * 10
-10, 1.0 * 10
-11With 2.1 * 10
-12g
2/ cm
4S.As seen compare at least low order of magnitude of Ni-12.9Al and Ni-28Al oxidation rate with the oxidation rate of single Ni coating.But rear two kinds of nano-composite plates, content are that the coating of 28Al is more much lower than 12.9Al, compare with metal Ni and single Ni coating, and the oxidation weight gain of 950 ℃ of oxidation 20h of Ni-Al nano-composite plate can reduce and reaches 30～50 times. this is because the Al of the former growth
2O
3Film can form fast and be fine and close, and this can be verified from following oxide layer surface and Cross Section Morphology comparative analysis.
XRD analysis is the result show, as shown in Figure 4, and the oxide skin(coating) of the two kinds of Ni-Al nano-composite plates Al that all grows
2O
3, in addition, NiO and NiAl also grow
2O
4Fig. 5-a, 5-b, 5-c, 5-d are that several embodiment grown oxide surface topography under above-mentioned oxidizing condition resembles.As seen: (Fig. 5-a) (Fig. 5-b) upward the oxide on surface size of formation is bigger, is typical NiO crystal grain with single Ni coating at the Ni base material.In contrast to this, ((Fig. 5-d) the oxide on surface crystal grain of nano composite plating layer growth is more tiny for Fig. 5-c) and Ni-28Al at Ni-12.9Al.Wherein: clear zone growth NiO (contains NiAl
2O
4), and dark-coloured district's growth Al
2O
3Comparison diagram 5-c and Fig. 5-d, though Al content raises as can be seen, the growth of surperficial Ni oxide compound is suppressed.Can find out that from corresponding oxide layer sectional view ((Ni-12.9Al all can grow continuous Al on Fig. 6-d) nano-composite plate surface for Fig. 6-c) and Ni-28Al
2O
3Protective layer, but the oxide layer outline of growing at the Ni-28Al nano-composite plate is thin, and the oxidation kinetics curve of its result and Fig. 3 matches.Reason is the raising of Al compound quantity, helps Al
2O
3Quick formation, and the Al that forms
2O
3Layer is finer and close, thus the NiO Fast Growth of establishment non-protective more.And under the same conditions, base material Ni (sees Fig. 6-a) and single Ni coating (all grow thick and porous NiO layer on Fig. 6-b).Therefore, because the Al of the continuous protectiveness of hotly growing
2O
3Oxide layer, the antioxygenic property of Ni-Al nano-composite plate significantly improves.
Embodiment 3 (antioxidant properties under 1050 ℃)
As previously mentioned, as long as compound Al content surpasses critical content, nano-composite plate is with regard to the Al of the continuous protectiveness of growing
2O
3Oxide layer, and Al content is more high, forms continuous Al
2O
3The oxide layer required time is more short, also is that barrier propterty is more good.Present embodiment is mainly introduced the oxidation situation of Ni-28Al nano-composite plate under 1050 ℃ that mean particle size is 75nm.
Oxidation experiment carries out under laboratory environment, and temperature is 1050 ℃, and the time is 20h.Fig. 7 is base material Ni, single Ni coating, and the Ni-28Al nano-composite plate is in the oxidation weight gain situation of 20h.The oxidation para-curve constant of three kinds of sample calculating is respectively 2.5 * 10
-11, 6.4 * 10
-10, 5.5 * 10
-12g
2/ cm
4S.The oxidation rate of Ni-28Al and Al
2O
3Hot growth rate suitable.According to the oxidation parabola constant that calculates, to compare with base material Ni and single Ni coating, the oxidation weight gain rate reduction of 1050 ℃ of oxidation 20h of Ni-Al nano-composite plate reaches more than 20 times and 85 times.
XRD analysis is the result show, as shown in Figure 8, the oxide skin(coating) of Ni-Al coating is mainly by Al
2O
3Form, wherein contain a small amount of NiO and NiAl
2O
4From zone of oxidation sectional view (referring to Fig. 9-a, 9-b, 9-c) as can be seen, wherein: Fig. 9-a is the zone of oxidation sectional view that exposes in 1050 ℃ of air of Ni-28Al nano-composite plate behind the 20h, and Fig. 9-b and Fig. 9-c are respectively the zone of oxidation sectional view single Ni coating of making comparisons and base material Ni expose 20h in 1050 ℃ of air after.Relatively can find out that from figure it is very thin main by continuous Al to have grown at the Ni-28Al nano-composite plate
2O
3The oxide skin(coating) that layer forms, and at base material Ni, what obtain after the oxidation of single Ni coating is thick and the NiO oxide layer of porous.As seen, the Ni base material, the oxidation rule of single Ni coating and Ni-Al nano-composite plate is similar to 950 ℃.
Embodiment 4
Be with embodiment 2 and 3 differences:
When coelectrodeposition, can in coating, add in addition the rare earth oxide CeO of 0.75 (mass percent)
2Particle; This rare earth oxide enters in the coating, can further improve the Al of coating growth
2O
3The antioxygenic property of film.
Antioxidant property under (1) 1050 ℃
Oxidation experiment carries out under laboratory environment, and temperature is 1050 ℃, and the time is 20h.Figure 10 is for containing the CeO of 0.75 (mass percent)
2Ni-30Al-0.75CeO
2The weightening finish curve of the coating of nano-composite plate and Ni-28Al.As a comparison, the superior β-NiAl intermetallic compound oxidation curve under the same conditions of antioxidant property also provides in the drawings.On scheming, can find out adding trace rare-earth CeO
2Obviously do not reduce the oxidation rate of Ni-Al nano-composite plate, this explanation rare earth oxide is to Al under the constant temperature oxidizing condition
2O
3The dynamics situation impact of heat growth is little.Comparison shows that Ni-28Al, Ni-30Al-0.75CeO with β-NiAl
2The antioxidant property of nano-composite plate is near β-NiAl.
Zone of oxidation sectional view in 1050 ℃ of air of Ni-28Al nano-composite plate behind the exposure 20h sees that Fig. 9-a. Figure 11-a is one embodiment of the invention Ni-30Al-0.75CeO
2Expose the zone of oxidation sectional view behind the 20h in 1050 ℃ of air of nano-composite plate, Figure 11-b be the zone of oxidation sectional view the intermetallic compound β-NiAl with embodiment of the invention comparison exposes 20h in 1050 ℃ of air after.From figure, relatively can find out that these sample surfaces all form continuous Al
2O
3Oxide skin(coating).
Anti-cyclic oxidation performance under (2) 1000 ℃
Oxidation experiment carries out under laboratory environment, and temperature is 1000 ℃, and every 2h is a circulation, and air cooling 15min, oxidization time are 126h.Figure 12 is intermetallic compound β-NiAl, Ni-28Al and Ni-32.0Al-0.75CeO
2Nano-composite plate is in the oxidation weight gain situation of 126h.On scheming, can find out adding trace rare-earth CeO
2Improved the anti-cyclic oxidation ability of Ni-Al nano-composite plate, β-NiAl comparison shows that with intermetallic compound, Ni-32Al-0.75CeO
2The anti-cyclic oxidation performance of nano-composite plate is near the anti-cyclic oxidation performance of intermetallic compound β-NiAl.
Figure 13-a is the oxide layer surface topography map behind the thermal cycle 126h in 1000 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate, and wherein the raised areas of white is NiO, the rich Al of the main growth in other zone
2O
3Oxide skin(coating), Figure 13-b is the intensified image of regional area, some of them NiO crystal grain (white light tone) is distributed in therebetween.Figure 14-a is one embodiment of the invention Ni-32Al-0.75CeO
2The zone of oxidation surface topography map of nano-composite plate behind thermal cycling 126h in 1000 ℃ of air compared with Figure 13-a, and the prominent body number of NiO obviously reduces, and from the local high power picture of Figure 14-b as seen, the growth of NiO crystal grain is suppressed.Based on the oxidation experiment result (referring to Figure 10) of front, Ni-32Al-0.75CeO
2Comparing oxidation kinetics with Ni-28Al is more or less the same.Therefore, can infer, add CeO
2Effect mainly make the Al of growth
2O
3Mechanical property is obviously improved, and improves Al
2O
3Cracking resistance and peel off behavior.This is relevant with the intercrystalline bonding force of oxide film with the sticking power that rare earth oxide strengthens between oxide film and the base material.Figure 15-a, 15-b are and embodiment of the invention zone of oxidation surface topography map and the high power picture of intermetallic compound β-NiAl behind thermal cycling 126h in 1000 ℃ of air relatively.There is crackle (Figure 15-a), these crackles and β-metastable Al of NiAl oxidation primary growth to occur in oxide layer surface
2O
3, be generally the Θ phase.It can change the α phase of stable state in oxidising process, it is about 13.5% that the result causes that the oxide compound volume shrinks, and causes crackle to produce.Figure 15-b is the high power picture of regional area, shows the α-Al of the upper growth of β-NiAl
2O
3Crystal grain.With Figure 13-b and 14-b relatively, this crystal grain do not see, this may with nano-composite plate at oxidation initial stage Al
2O
3Growth with to change mutually situation different from β-NiAl oxidizing process, but owing to all form continuous protectiveness Al
2O
3Layer, antioxygenic property is significantly increased.Figure 16-a, 16-b are the low power and the high power picture in the zone of oxidation cross section behind the thermal cycling 126h in 1000 ℃ of air of one embodiment of the invention Ni-28Al nano-composite plate.Can find continuous Al
2O
3The NiO that grows on the oxide layer body of dashing forward, this is consistent with surface topography observation, simultaneously, a large amount of crackles of appearance in the coating.Figure 17-a, 17-b are one embodiment of the invention Ni-30Al-0.75CeO
2The low power and the high power picture in the zone of oxidation cross section of nano-composite plate behind thermal cycling 126h in 1000 ℃ of air.Can see Al
2O
3Oxidated layer thickness is thin and even, does not occur obvious crackle in the coating, and this also confirms CeO
2Can improve the anti-cyclic oxidation performance of coating.Figure 18 is and the embodiment of the invention zone of oxidation cross section picture of intermetallic compound β-NiAl behind thermal cycling 126h in 1000 ℃ of air relatively.As seen, Ni-30Al-0.75CeO
2The quality of oxide layer of growing behind the thermal cycling 126h in 1000 ℃ of air of nano-composite plate can with β-NiAl on quite.
By above experimental result as seen, nano-composite plate adds trace rare-earth CeO
2After, although effect is not obvious under the constant temperature oxidizing condition, can improve the Al of growth
2O
3The anti-cyclic oxidation performance of film.
As from the foregoing, the nano-composite plate of the present invention's preparation is made up of Ni base and the Al nano metal particles dispersed therein of nanometer structure, and it produces significantly " nano effect " in high-temperature oxydation or corrosive environment, can Fast Growth protectiveness Al
2O
3The mechanism that produces " nano effect " can be expressed as follows: on the one hand, the compound Ni of entering base coating and the Al particle that contains dispersed therein can be used as seed, growth Al when oxidation
2O
3When one timing of metallic compound quantity, the particle of composite Nano size can greatly improve the population (compare with micron order, two more than the order of magnitude) that distributes in the unit are, namely increases the density of seed in the unit are, reduces Al
2O
3Internuclear spacing, thus reduce the required time of dinuclear healing, also namely shorten protective oxide film healing required time.On the other hand, have highdensity crystal boundary in the coating of nanometer structure, they can serve as the rapid diffusion passage of Al, further impel the rapid transverse growth of above-mentioned nascent oxide core, form the successive protective oxide layer in very short transient state oxidising process.According to this principle, can infer: when Al nanopowders size one timing of adding, as long as compound quantity reaches a critical value and above value thereof, nano-composite plate of the present invention is the hot continuous protectiveness Al that grows of energy just
2O
3Oxide-film; And when the Al particle size that adds is more little, form continuous Al
2O
3The content of film will reduce (comparable 9.8% is low).This deduction can fully be verified by example of the present invention.
Fe, Co are the same with Ni to be the main matrix element of high temperature metallic material commonly used.Because the basic principle of nano-composite plate Fe-Al, Co-Al is identical with the preparation of Ni-Al, and according to the oxidation behaviors of this composite deposite, protectiveness Al
2O
3Growth only relevant with the structure (crystallite dimension) of size, compound quantity and the matrix element of nano particle, and do not have direct relation with the matrix pivot.Therefore, select the electrolyte of plating Fe or plating Co, adopt the experimental technique identical with preparation Ni-Al nano-composite plate, can prepare respectively heat growth Al
2O
3The Fe-Al of membranous type, Co-Al and nano composite plating coating systems.Because the preparation scheme roughly the same, and anti-oxidation characteristics is similar, does not do at this and repeats.When coelectrodeposition, can also in plating bath, add in addition Y
2O
3, La
2O
3Or Gd
2O
3Deng rare earth oxide particles.Because of they impact and CeO to the nano-composite plate antioxygen property in oxidizing process
2Similar, say so also no longer go to live in the household of one's in-laws on getting married here.
M-Al nano-composite plate of the present invention can be used as the protective coating of resistance to high temperature oxidation, is used under 950 ℃～1050 ℃ envrionment temperatures.Adopt the alternative diffusion of the present invention ooze Al coating (coat of aluminide) or be used for other technology preparation at said temperature scope internal heat growth Al
2O
3The protective coating of membranous type can also be used for carbon steel, low-alloy steel, austenite or ferritic stainless steel, Ti alloy, TiAl, FeAl base intermetallic compound.
Claims (8)
1. heat growth Al
2O
3Membranous type M-Al nano-composite plate is characterized in that: its composition is the combination of nanocrystalline metal M and the Al nano particle dispersed therein of deposition, and wherein M can be Ni, Fe or Co; The content of Al is 9.8～35% by mass percentage, and surplus is M; The continuous protectiveness Al of control heat growth under 950～1050 ℃ of high temperature
2O
3Oxide-film.
2. by the described heat growth of claim 1 Al
2O
3Membranous type M-Al nano-composite plate is characterized in that: the CeO that also can add quality of coating 0.5～3%
2, Y
2O
3, La
2O
3Or Gd
2O
3Rare earth oxide particles.
3. heat growth Al
2O
3The preparation method of membranous type M-Al nano-composite plate, it is characterized in that: with metal Ni, Fe or Co, carbon steel or low alloy steel is base material, adopt the coelectrodeposition technology to prepare nano-composite plate at base material, described nano-composite plate is made up of nanocrystalline metal M primitive and nano particle Al dispersed therein, and wherein: M can be Ni, Fe or Co, by mass percentage, the content of Al is 9.8～35%, and surplus is M;
The continuous protectiveness Al of control heat growth under 950～1050 ℃ of high temperature
2O
3Oxide-film.
4. by the described heat growth of claim 3 Al
2O
3The preparation method of membranous type M-Al nano-composite plate is characterized in that: keep nano particle to be suspended in the tank liquor during plating.
5. by the described heat growth of claim 3 Al
2O
3The preparation method of membranous type M-Al nano-composite plate is characterized in that: when coelectrodeposition, can add in addition the trace rare earth oxides particle in plating bath.
6. by the described heat growth of claim 5 Al
2O
3The preparation method of membranous type M-Al nano-composite plate is characterized in that: rare earth oxide particles is CeO
2, Y
2O
3, La
2O
3Or Gd
2O
3
7. by the described heat growth of claim 5 Al
2O
3The preparation method of membranous type M-Al nano-composite plate is characterized in that: described trace is 0.5～3% of quality of coating.
8. press the described heat growth of claim 1 Al for one kind
2O
3The application of membranous type M-Al nano-composite plate is characterized in that: described Ni-Al nano-composite plate, can be used as the protective coating of resistance to high temperature oxidation, and be used for the continuous protectiveness Al of control heat growth under 950 ℃～1050 ℃ environment temperatures
2O
3Oxide-film; And alternative diffusion ooze the Al coating be coat of aluminide or be used for other technology preparation at said temperature scope internal heat growth Al
2O
3The protective coating of membranous type can also be used for carbon steel, low-alloy steel, austenite or ferritic stainless steel, Ti alloy, TiAl, FeAl base intermetallic compound.
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| CN03133896.8 | 2003-07-11 | ||
| CN 200410069557 CN1266316C (en) | 2003-07-11 | 2004-07-05 | Thermal growth AL2O3 film type M A1 nano composite plating and producing process and application |
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| CN1880513B (en) * | 2005-06-15 | 2010-07-21 | 中国科学院金属研究所 | Thermally-grown Cr2O3 or Al2O3 film type M-Cr-Al nano composite coating and method for preparing same and application thereof |
| CN100519842C (en) * | 2006-06-23 | 2009-07-29 | 中国科学院金属研究所 | Methd of preparing coating layer of gamma'Ni3Al /gamma-Ni |
| CN102776546B (en) * | 2011-05-11 | 2015-03-18 | 中国科学院金属研究所 | High temperature oxidation resistant NiAl-Y2O3 coating, its preparation method and its application |
| CN102441668B (en) * | 2011-11-10 | 2013-10-30 | 华中科技大学 | Method for preparing Fe/Al micro-nano composite powder |
| AU2016316565B2 (en) * | 2015-09-02 | 2022-06-23 | Cirrus Materials Science Limited | A plating or coating method |
| CN107177813B (en) * | 2016-03-09 | 2019-03-29 | 中国科学院金属研究所 | One kind direct thermally grown α-Al on M-Al intermetallic compound2O3Method and application |
| CN105908131B (en) * | 2016-06-15 | 2018-09-04 | 中国科学院金属研究所 | It is a kind of can thermally grown oxide aluminium film TiAl coatings and preparation method thereof |
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