CN105215365A - A kind of metal-cermic coating and preparation method thereof - Google Patents
A kind of metal-cermic coating and preparation method thereof Download PDFInfo
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- CN105215365A CN105215365A CN201410247716.1A CN201410247716A CN105215365A CN 105215365 A CN105215365 A CN 105215365A CN 201410247716 A CN201410247716 A CN 201410247716A CN 105215365 A CN105215365 A CN 105215365A
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Abstract
The present invention relates to a kind of metal-cermic coating and preparation method thereof, comprise cermet skin and the transition zone between described cermet skin and matrix, described cermet skin comprise metal alloy bond phase and Dispersed precipitate described metal alloy bond mutually in as the boride particle of ceramic enhancement phase, described transition zone is made up of self-fusible alloy powder of nickel-base.
Description
Technical field
The present invention relates to a kind of metal-cermic coating and preparation method thereof, be specifically related to a kind of metal-cermic coating with skin and the transition zone between skin and matrix.
Background technology
Along with the development of space flight and aviation cause, more and more higher to the requirement of engine performance, require that engine has very high thrust-weight ratio and large thrust, can at high temperature, at a high speed, the reliable and work that continues under high pressure, oxygen enrichment and the exceedingly odious and harsh environment that washes away containing solid particle.Be commonly used to protect the glass enamel of these parts, glass ceramic coating due to fragility, lowly ablatively do not reached above-mentioned requirement of shelter.
Cermet is a kind of very important composite, it had both maintained the feature such as high strength, high rigidity, wear-resistant, high temperature resistant, anti-oxidant and chemical stability of pottery, there is again obdurability and the plasticity of metal, purposes is extremely extensive, almost relate to the various piece of national economy and the every field of modern technologies, important impetus is played to the raising of industrial expansion and productivity ratio.
At present, the preparation method of metal-cermic coating mainly contains chemical vapour deposition technique and physical vaporous deposition.Wherein chemical vapour deposition technique can realize the deposition of a large amount of parts being carried out simultaneously to coating easily, but due to this technology need carry out under 1000 DEG C of hot conditions, limitation is very large.And physical vaporous deposition comprises vacuum evaporation, sputter coating and ion plating, there is the feature of low temperature, high energy, and the metal-cermic coating of preparation has the excellent properties of high rigidity, high-wearing feature.But adopting physical vaporous deposition to be by evaporating after metallic material, being deposited on the coating that matrix surface is formed, the coating structure that this method is formed is fine and close not, and is combined not tight with matrix.
Therefore, this field, in the urgent need to a kind of new metal-cermic coating, can overcome above-mentioned defect.
Summary of the invention
The present invention is intended to the defect overcoming existing metal-cermic coating, the invention provides a kind of metal-cermic coating with skin and the transition zone between skin and matrix.
The present invention provides a kind of metal-cermic coating, described coating comprises cermet skin and the transition zone between described cermet skin and matrix, described cermet skin comprise metal alloy bond phase and Dispersed precipitate described metal alloy bond mutually in as the boride particle of ceramic enhancement phase, described transition zone is made up of self-fusible alloy powder of nickel-base.
Preferably, described metal alloy bond is made up of the metal dust comprising Ni and Cr.
Preferably, by weight, in described cermet skin, the content of each component is: Ce is 0 ~ 1wt%, Hf be 0 ~ 1wt%, Si be 0.5wt% ~ 3wt%, Cr is 5.0wt% ~ 21wt%, and binary borides particle is 5wt% ~ 25wt%, and surplus is Ni.
Preferably, described boride particle can be selected from TiB
2, ZrB
2, and HfB
2in at least one.
Preferably, described boride particle accounts for the outer field volume fraction of described cermet and can be 5% ~ 50%.
Preferably, by weight, described self-fusible alloy powder of nickel-base can be made up of following component: B is 0.1wt% ~ 4.0wt%, Si is 0.2wt% ~ 5.0wt%, Al be 0.1wt% ~ 5.0wt%, Ti is 0 ~ 2.0wt%, Mo is 0 ~ 1.0wt%, Cr is 5.0wt% ~ 20.0wt%, Fe is 5wt% ~ 10wt%, and surplus is Ni.
Preferably, the thickness of described transition zone can be 20 ~ 60um, and the outer field thickness of described cermet can be 50 ~ 100um.
Preferably, the bond strength of described metal-cermic coating and matrix can be 30 ~ 50MPa.
Present invention also offers a kind of method preparing above-mentioned metal-cermic coating, described method comprises:
1) described self-fusible alloy powder of nickel-base and binding agent is mixed, ball milling 3 ~ 5 hours obtained transition zone slurries;
2) each component is taken, adding additives by the proportioning of each component in described cermet skin, ball milling 3 ~ 5 hours outer slurries of obtained cermet;
3) transition zone slurry described in surface treated matrix dip-coating, at 800 ~ 1000 DEG C, vacuum-sintering is to form transition zone at described matrix surface; And
4) the outer slurry of cermet described in the matrix dip-coating being formed with transition zone, at 800 ~ 1100 DEG C, vacuum-sintering to form cermet skin on described transition zone.
Preferably, step 1) and/or step 2) in, described binding agent can be terpinol and/or polyethylene glycol.
Preferably, step 3) in, the parameter of vacuum-sintering can be: heating rate is 5 ~ 20 DEG C/min, and holding temperature is 800 ~ 1000 DEG C, and temperature retention time is 10 ~ 30 minutes.
Preferably, step 4) in, the parameter of vacuum-sintering can be: heating rate is 5 ~ 15 DEG C/min, and holding temperature is 800 ~ 1100 DEG C, and temperature retention time is 10 ~ 40 minutes.
Preferably, described vacuum-sintering can be carried out in Vacuum graphite oven, and vacuum is greater than 10
-2pa.
Beneficial effect of the present invention:
The invention has the advantages that, adopt vaccum sintering process prepared metal-cermic coating at a lower temperature, and coating uniform, densification, without the defect such as hole and crackle, and can ensure on various complex profile evenly shaping.Compensate for the blank that Present Domestic vaccum sintering process prepares metal-cermic coating.The transition zone applied can define metallurgical binding with nickel alloy base body, and defines diffusion bond layer with cermet skin, and the coating therefore prepared has excellent thermal shock resistance and higher interface bond strength.
Accompanying drawing explanation
Fig. 1 illustrates in an embodiment of the invention the scanning electron microscope (SEM) photograph obtaining transition zone surface topography map, illustrates that the transition zone of preparation is even, fine and close;
Fig. 2 illustrates in an embodiment of the invention the scanning electron microscope (SEM) photograph obtaining the outer pattern of cermet, illustrates to define to be Binder Phase with the metal of solution strengthening, to take ceramic particle as the structure of wild phase, and coating uniform, densification;
Fig. 3 is the scanning electron microscope (SEM) photograph obtaining metal-cermic coating cross section in an embodiment of the invention, illustrates that the transition zone of preparation and matrix define metallurgical binding, defines diffusion bond with cermet coating.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The present invention relates to a kind of metal-cermic coating and preparation method thereof, particularly a kind of with the alloy of solution strengthening for Binder Phase be ceramic enhancement phase with the boride particle of Dispersed precipitate cermet is outer, be particularly that transition zone strengthens the outer method with substrate combinating strength of cermet with nickel-based self-fluxing alloy powder, described coating toughness is high, bond strength is high, and has good thermal shock resistance and non-oxidizability.Described transition zone coating uniform, densification, define metallurgical binding with matrix alloy, defines diffusion bond with cermet skin.This metal-cermic coating has between one deck transition zone and matrix, and object is the bond strength in order to strengthen cermet skin and matrix alloy.The method is vaccum sintering process, and can ensure to prepare even, fine and close coating under the lower temperature be not destroyed in nickel-base alloy performance and intensity, technique be simple, easy to operate, and can be evenly shaping on various complex profile.The metal-cermic coating of preparation is even, fine and close, has good thermal shock resistance, non-oxidizability, obdurability, and high with substrate combinating strength.
Described metallic binding phase is the alloy phase containing solid solution strengthened alloy constituent element.
Described boride wild phase Dispersed precipitate is in metallic binding phase, and volume fraction is 5% ~ 50%.
The raw material that described metallic binding phase is selected mutually are Ni-Cr, and add appropriate rare earth element ce, Hf.
Described boride wild phase comprises TiB
2, ZrB
2, HfB
2in one or more.
Described its size of boride wild phase is across micron, sub-micron and nanoscale.
Described transition zone is nickel-based self-fluxing alloy coating, and this transition is good with nickel alloy matrix wetability layer by layer, and coating preparation temperature is low.The bond strength of metal-cermic coating and nickel alloy matrix is increased by introducing transition zone.
Buffer layer material is self-fusible alloy powder of nickel-base, its constituent content is Ni surplus, B:0.1wt% ~ 4.0wt%, Si:0.2wt% ~ 5.0wt%, Al:0.1wt% ~ 5.0wt%, Ti:0 ~ 2.0wt%, Mo:0 ~ 1.0wt%, Cr:5.0wt% ~ 20.0wt%, Fe:5wt% ~ 10wt%.
Cermet cladding material is for containing binary borides TiB2 (HfB2, ZrB2)/NiCr powder, and wherein each content of material is Ni surplus, Ce:0 ~ 1wt%, Hf:0 ~ 1wt%, Si:0.5wt% ~ 3wt%, Cr:5.0wt% ~ 21wt%, TiB
2(HfB
2, ZrB
2): 5wt% ~ 25wt%.
The invention provides a kind of preparation method of metal-cermic coating, comprise the following steps:
A) substrate pretreatment: routine polishing is carried out to nickel alloy matrix, and carries out blasting treatment;
B) transition zone slip is prepared: the self-fusible alloy powder of nickel-base bought and the binding agent for preparing in advance are put into ball grinder, ball milling 3 ~ 5h in the lump, obtains uniform transition zone slip;
C) dip-coating transition zone slip: the test piece handled well immersed in slip, at the uniform velocity pull out, makes test piece weightening finish 10 ~ 25mg/cm
2, and at room temperature dry;
D) transition zone is sintered: vacuum drying oven is put in the test piece scribbling transition zone and sinters, obtain the transition zone of even compact;
E) the outer slip of cermet is prepared: weigh powder according to formula, and put into ball grinder in the lump, ball milling 3 ~ 5h with the binding agent prepared in advance, obtain uniform cermet coating slip;
F) dip gilding top ceramic layer slip: the test piece handled well immersed in slip, at the uniform velocity pull out, makes test piece weightening finish 20 ~ 40mg/cm
2, and at room temperature dry;
G) sintering metal top ceramic layer: vacuum drying oven is put in the test piece scribbling the outer slurry of cermet and sinters, the cermet obtaining even compact is outer.
In described metal-cermic coating preparation method, the temperature schedule that transition zone prepared by vacuum drying oven is be warming up to 800 ~ 1000 DEG C with the speed of 5 ~ 20 DEG C/min, and insulation 10 ~ 30min, then cools to room temperature with the furnace.
In described metal-cermic coating preparation method, vacuum drying oven is prepared the outer field temperature schedule of cermet and is: be warming up to 800 ~ 1100 DEG C with the speed of 5 ~ 15 DEG C/min, and insulation 10 ~ 40min, then cools to room temperature with the furnace.
In soak district in whole sintering process, the vacuum of Vacuum graphite oven is greater than 10
-2pa.
Transition region thickness is: 20 ~ 60um, and the outer field thickness of cermet is: 50 ~ 100um.
Metal-cermic coating thermal shock resistance prepared by this method is 1100 DEG C ~ 0 DEG C circulation 100 times and does not destroy.
Carry out high-temperature oxidation resistant test to the metal-cermic coating of preparation, prepared metal-cermic coating is oxidized and does not destroy after 50 hours at 1100 DEG C.
The bond strength recording metal-cermic coating and matrix with pulling method is 30 ~ 50MPa.
The metal-cermic coating of preparation is even, fine and close, without the defect such as hole and crackle, transition zone and nickel alloy base body define metallurgical binding, define diffusion bond layer with cermet skin, and the coating therefore prepared has excellent thermal shock resistance and higher interface bond strength.
Vacuum sintering technology refers to and the self-fluxing alloyed powders such as the cobalt-based being coated on surface of the work, Ni-based and iron-based is heated under comparatively low vacuum, make it melting and infiltrate surface of the work, produce metallurgical binding with matrix surface, thus complete the brazing filler metal of composition metal part, the sealing of hole of microdefect and obtain the process with high rigidity, high abrasion, the function of surface coating such as high temperature resistant and anticorrosive.Vacuum sintering technology has the features such as cost is low, easy to operate, processing performance is good, and not by the impact of part geometry shape.Prepare with vaccum sintering process that metal-cermic coating is domestic at present also rarely has report.
The invention has the advantages that, adopt vaccum sintering process prepared metal-cermic coating at a lower temperature, and coating uniform, densification, without the defect such as hole and crackle, and can ensure on various complex profile evenly shaping.Compensate for the blank that Present Domestic vaccum sintering process prepares metal-cermic coating.The transition zone applied and nickel alloy base body define metallurgical binding, and define diffusion bond layer with cermet skin, and the coating therefore prepared has excellent thermal shock resistance and higher interface bond strength.
Fig. 1 obtains transition zone surface topography map in an embodiment of the invention, illustrates that the transition zone of preparation is even, fine and close;
Fig. 2 obtains the outer shape appearance figure of cermet in an embodiment of the invention, illustrate to define to be Binder Phase with the metal of solution strengthening, to take ceramic particle as the structure of wild phase, and coating uniform, densification;
Fig. 3 obtains metal-cermic coating surface topography map in an embodiment of the invention, illustrates that the transition zone of preparation and matrix define metallurgical binding, defines diffusion bond with cermet coating.
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiment; should understand; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
For binary borides TiB
2/ NiCr metal-cermic coating, concrete preparation technology is as follows:
(1) substrate pretreatment: conventional sand papering is first carried out to nickel alloy test piece, then blasting treatment is carried out to strip, finally use alcohol Ultrasonic Cleaning, dry up for subsequent use;
(2) preparation of transition zone: first mixed with the ratio of 50g/20ml with terpinol binding agent by self-fusible alloy powder of nickel-base, puts into ball grinder ball milling 3h, with dip coating at the uniform slip of strip dip-coating one deck, at room temperature dries.Put into vacuum drying oven and be warming up to 900 DEG C with the speed of 15 DEG C/min, insulation 10min, is then cooled to room temperature, obtains the transition zone of even compact;
(3) the outer field preparation of cermet: be Ce:1%, Si:3%, Cr:21%, Ni:50%, TiB according to mass fraction
2: the formula of 25% weighs powder, and is equipped with the terpinol binding agent of 50g/20ml ratio, ball milling 4h in ball grinder, will scribble the uniform slip of test piece dip-coating one deck of transition zone, and at room temperature dry with dip coating.Put into vacuum drying oven and be warming up to 1000 DEG C with the speed of 10 DEG C/min, insulation 15min, cools to room temperature with the furnace, and the cermet obtaining even compact is outer.
As shown in Figure 1, transition zone surface topography map in embodiment 1, illustrates that the transition zone of preparation is even, fine and close;
As shown in Figure 2, the outer shape appearance figure of cermet in embodiment 1, illustrates and defines with the metal of solution strengthening for Binder Phase take ceramic particle as the structure of wild phase, and coating uniform, densification;
As shown in Figure 3, embodiment 1 floating coat surface topography map, illustrates that the transition zone of preparation and matrix define metallurgical binding, defines diffusion bond with cermet coating.
In embodiment 1, the metal-cermic coating thermal shock resistance of preparation is 1100 DEG C ~ 0 DEG C circulation 100 times and does not destroy; Carry out high-temperature oxidation resistant test to the metal-cermic coating of preparation, prepared metal-cermic coating is oxidized and does not destroy after 50 hours at 1100 DEG C; The bond strength recording metal-cermic coating and matrix with pulling method is 30MPa.
Embodiment 2
For binary borides ZrB2/NiCr metal-cermic coating, concrete preparation technology is as follows:
(1) substrate pretreatment is with embodiment 1;
(2) preparation of transition zone is with embodiment 1;
(3) the outer field preparation of cermet is with embodiment 1.
High temperature comprehensive tester is warming up to 1100 DEG C and is incubated the long enough time, burner hearth is put in the test piece preparing coating, insulation 10min, then the mixture of ice and water putting into rapidly 0 DEG C is incubated 5min, after such circulation 100 times, coating is intact, without damaged without cracking.
Claims (13)
1. a metal-cermic coating, it is characterized in that, comprise cermet skin and the transition zone between described cermet skin and matrix, described cermet skin comprise metal alloy bond phase and Dispersed precipitate described metal alloy bond mutually in as the boride particle of ceramic enhancement phase, described transition zone is made up of self-fusible alloy powder of nickel-base.
2. metal-cermic coating according to claim 1, is characterized in that, described metal alloy bond is made up of the metal dust comprising Ni and Cr.
3. metal-cermic coating according to claim 1 and 2, it is characterized in that, by weight, in described cermet skin, the content of each component is: Ce is 0 ~ 1wt%, Hf is 0 ~ 1wt%, Si be 0.5wt% ~ 3wt%, Cr is 5.0wt% ~ 21wt%, binary borides particle is 5wt% ~ 25wt%, and surplus is Ni.
4., according to described metal-cermic coating arbitrary in claim 1-3, it is characterized in that, described boride particle is selected from TiB
2, ZrB
2, and HfB
2in at least one.
5. the metal-cermic coating according to any one of claim 1-4, is characterized in that, it is 5% ~ 50% that described boride particle accounts for the outer field volume fraction of described cermet.
6. the metal-cermic coating according to any one of claim 1-5, it is characterized in that, by weight, described self-fusible alloy powder of nickel-base is made up of following component: B is 0.1wt% ~ 4.0wt%, Si is 0.2wt% ~ 5.0wt%, Al is 0.1wt% ~ 5.0wt%, Ti is 0 ~ 2.0wt%, Mo be 0 ~ 1.0wt%, Cr is 5.0wt% ~ 20.0wt%, Fe is 5wt% ~ 10wt%, and surplus is Ni.
7., according to described metal-cermic coating arbitrary in claim 1-6, it is characterized in that, the thickness of described transition zone is 20 ~ 60um, and the outer field thickness of described cermet is 50 ~ 100um.
8., according to described metal-cermic coating arbitrary in claim 1-7, it is characterized in that, the bond strength of described metal-cermic coating and matrix is 30 ~ 50MPa.
9. prepare a method for arbitrary described metal-cermic coating in claim 1-8, it is characterized in that, described method comprises:
1) described self-fusible alloy powder of nickel-base and binding agent is mixed, ball milling 3 ~ 5 hours obtained transition zone slurries;
2) each component is taken, adding additives by the proportioning of each component in described cermet skin, ball milling 3 ~ 5 hours outer slurries of obtained cermet;
3) transition zone slurry described in surface treated matrix dip-coating, at 800 ~ 1000 DEG C, vacuum-sintering is to form transition zone at described matrix surface; And
4) the outer slurry of cermet described in the matrix dip-coating being formed with transition zone, at 800 ~ 1100 DEG C, vacuum-sintering to form cermet skin on described transition zone.
10. method according to claim 9, is characterized in that, in step 1) and/or step 2, described binding agent is terpinol and/or polyethylene glycol.
11. methods according to claim 9 or 10, it is characterized in that, in step 3), the parameter of vacuum-sintering is: heating rate is 5 ~ 20 DEG C/min, and holding temperature is 800 ~ 1000 DEG C, and temperature retention time is 10 ~ 30 minutes.
12. according to described method arbitrary in claim 9-11, and it is characterized in that, in step 4), the parameter of vacuum-sintering is: heating rate is 5 ~ 15 DEG C/min, and holding temperature is 800 ~ 1100 DEG C, and temperature retention time is 10 ~ 40 minutes.
13. according to described method arbitrary in claim 9-12, and it is characterized in that, described vacuum-sintering is carried out in Vacuum graphite oven, and vacuum is greater than 10
-2pa.
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| CN106637189A (en) * | 2016-11-17 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Metal ceramic coating and preparation method thereof |
| CN110252156A (en) * | 2019-07-09 | 2019-09-20 | 湖南中天元环境工程有限公司 | A kind of metal composite ceramal film and preparation method thereof |
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