CN102899612A - Method for preparing high-temperature protective coating with Cr2AlC as main phase by employing multi-arc ion plating - Google Patents
Method for preparing high-temperature protective coating with Cr2AlC as main phase by employing multi-arc ion plating Download PDFInfo
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Abstract
The invention relates to a preparation technology of high-temperature protective coatings, and specifically provides a method for preparing a high-temperature protective coating with Cr2AlC as a main phase by employing multi-arc ion plating. A block Cr2AlC synthesized by an in situ solid-liquid phase reaction / a hot pressing method is used as a target material; or a compact prepared from hot pressing on an initial raw material comprising three element powders Cr, Al and C in a molar ratio of 2:1.1-1.2:0.9-1.2 is used as the target material. Amorphous Cr-Al-C coatings can be prepared on different substrates under conditions of background vacuum at 2*10 <-3>Pa, Ar gas flow rate of 20-40 SCCM, working pressure of 0.2-0.6Pa and current applied on the target material of 50-70A. The prepared coating is annealed at 620-650 DEG C under protection of Ar gas for 10-20h, so as to obtain the Cr-Al-C coating with Cr2AlC as the main phase. This method has the advantages of low cost, simple preparation process and high deposition rate, and solves problems, such as high cost and inability to realize large-scale production, in existing preparation of the Cr2AlC coating.
Description
Technical field
The present invention relates to the technology of preparing of high-temperature protection coating, provide especially a kind of employing multi-arc ion coating preparation with Cr
2AlC is the method for the new type high temperature protective coating of principal phase.
Background technology
Cr
2AlC is because the thermal expansivity (Cr that has simultaneously good resistance to high temperature oxidation and hot corrosion resistance and mate with alloy phase
2AlC is 13.3 * 10 at the thermal expansivity of 30-1200 ° of C temperature range
-6K
-1), thereby have potential application prospect in the high-temperature protection coating field.Up to the present, adopt magnetron sputtering technique can prepare Cr
2The AlC coating.Cr to the magnetron sputtering preparation
2The AlC coating is carried out the high temperature oxidation experiment and is shown, because continuous, the fine and close Al of outermost layer in the oxidising process
2O
3The generation of oxide film, Cr
2The AlC coating can effectively be improved the antioxidant property of Ti6242 and M38G superalloy.But, there are a large amount of column crystal crystal boundaries owing to utilize in the thinner and coating of the prepared coat-thickness of the method for sputter, at the process floating coat of oxidation serious degeneration can occur, thereby cause the decline of coating antioxidant property.Secondly, in order to obtain the Cr of crystalline state
2AlC coating, depositing temperature must be higher than 450 ° of C.Because the use of high temperature platform, so that magnetron sputtering deposition efficient reduces greatly, cost increases.Therefore, how to improve Cr
2The sedimentation rate of AlC is eliminated the columnar crystal structure in the coating simultaneously, becomes to realize Cr
2An important direction of AlC coatings industry application.Be different from magnetron sputtering, multi-arc ion coating makes target local evaporation and ionization by cathodic arc spot, and this method has the good and sedimentation rate advantages of higher of compactness of incident ionic energy height, coating.But, at present also not about utilizing this method to prepare Cr
2The relevant report of AlC coating.
Summary of the invention
The object of the invention is to propose a kind of multi-arc ion coating that utilizes prepares with Cr
2AlC is the method for the new type high temperature protective coating Cr-Al-C coating of principal phase, solves prior art oxidation in the process floating coat of oxidation can occur along the column crystal crystal boundary, causes the decline of coating antioxidant property, and existing Cr
2AlC coating preparation cost is high and can't realize the problem such as scale operation.
Technical scheme of the present invention is as follows:
A kind of employing multi-arc ion coating preparation is with Cr
2AlC is the method for the Cr-Al-C coating of principal phase, and concrete steps are as follows:
1) selection of target
Adopt the block Cr of sintering
2AlC is as target; Perhaps, take Cr, Al, three kinds of element powder of C according to mol ratio as 2:1.1～1.2:0.9～1.2 powder mixs as initial feed, the compact block of making through hot pressing is as target.
The preparation method of this kind Cr-Al-C target is: select Cr, Al and Graphite Powder 99 as raw material powder; raw material powder process ball milling 20～24 hours; pressure with 5～20MPa is cold-pressed into pie; the time of colding pressing is 5～30 minutes; pack in the graphite jig, in being connected with the hot pressing furnace of rare gas element as protection gas, be warming up to 900～1100 ° of C reaction in－situs 10～60 minutes.Hot pressing is carried out in reaction simultaneously in position, and hot pressing pressure is 20～40MPa, the block body ceramic material of synthesis of densified.
2) preparation technology
In the experimentation, the back end vacuum that adopts is 1 * 10
-3Pa-3 * 10
-3Pa carries out backwash with the body material of anticipating and cleans the preparation that can begin coating behind the 3-10min.In the coating preparation process, selected Ar airshed is 20～40SCCM, and operating air pressure is 0.2～0.6Pa, and depositing temperature is room temperature, and the target electric current is 50～70A.Under this kind processing condition, the coating sedimentation rate reaches 0.3-0.5 μ m/min.Subsequently, the sample that deposition is obtained in Ar gas atmosphere through 620 ° of C～650 ° C anneal 10～20h, can obtain with Cr
2AlC is the Cr-Al-C coating of principal phase.
Principal phase in the Cr-Al-C coating of employing present method preparation is well-crystallized's ternary layered ceramic Cr
2AlC.In addition, also be accompanied by AlCr
2And Cr
7C
3Appearance, principal phase Cr in the coating
2AlC accounts for 60-70wt.%.
Characteristics of the present invention are:
1, technique of the present invention is simple, the coating preparation cost is low, directly adopts the block of single sintering at room temperature to deposit as target.
2, the present invention has prepared with Cr by the method that multi-arc ion coating and follow-up anneal combine
2AlC is the Cr-Al-C coating of principal phase.
3, the Cr-Al-C coating of utilizing the inventive method to prepare is dense and sedimentation rate is high.
4, utilize the Cr-Al-C coating of the inventive method preparation to have good high-temperature oxidation resistance, in 1000 ° of C air, in the process of oxidation, can improve the antioxidant property of M38G superalloy.
Description of drawings
(a) deposited and (b) the XRD result of Cr-Al-C coating after the annealing when Fig. 1 target electric current is 60A.
(a) deposited and (b) the SEM surface topography map of Cr-Al-C coating after the anneal when Fig. 2 target electric current is 60A.
(a) deposited and (b) the SEM Cross Section Morphology figure of Cr-Al-C coating after the anneal when Fig. 3 target electric current is 60A.
The kinetic curve of Cr-Al-C coating after Fig. 4 anneal and M38G superalloy oxidation 20h in 1000 ° of C air.
(a) deposited and (b) the XRD result of Cr-Al-C coating after the annealing when Fig. 5 target electric current is 70A.
Fig. 6 adopts Cr, and Al and graphite element powder as at target, are the XRD result of 70A coating the Cr-Al-C coating through 620 ° Cs annealing 20h after that obtain at electric current at the block of the densification of 1000 ° of C hot pressed sinterings.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Adopt the multi-arc ion coating method, simultaneously to adopt the block Cr of in-situ sintering/solid-liquid reaction preparation
2AlC at room temperature deposits as target and has prepared the Cr-Al-C coating.Total back end vacuum is 2 * 10 in the coating preparation process
-3Pa, Ar airshed are that 40SCCM, operating air pressure are 0.4Pa, the electric current that is applied on the target is that 60A, depositing time are 15min, can prepare the Cr-Al-C coating of amorphous on different matrixes.Prepared coating can obtain with Cr through 620 ℃ of lower annealing 20h of Ar gas protection
2AlC is the Cr-Al-C coating of principal phase, also is accompanied by simultaneously AlCr
2And Cr
7C
3Generation.In the present embodiment, principal phase Cr
2The content of AlC accounts for 69wt.%.
The X-ray diffracting spectrum of the Cr-Al-C coating after deposited and the annealing is listed in accompanying drawing 1, deposits as seen from Figure 1 resulting coating and presents non-crystalline state, and after 620 ° of C annealing, crystallization has occured coating.In the coating that obtains after the crystallization with Cr
2AlC is principal phase.
Fig. 2 is respectively the SEM surface topography map of deposited and the rear Cr-Al-C coating of annealing.Cr-Al-C coatingsurface smoother, densification after deposited and the annealing and do not have the existence of crackle.
Fig. 3 is respectively the SEM Cross Section Morphology figure of the Cr-Al-C coating after deposited and the annealing.Cr-Al-C coating after deposited and the annealing keeps complete densification, and coat-thickness is about 6 μ m.
Fig. 4 is Cr-Al-C coating after the anneal and the kinetic curve of M38G superalloy oxidation 20h in 1000 ° of C air.Behind oxidation 8h, the Cr-Al-C coating after the annealing has less oxidation weight gain (Δ W/A), can improve the antioxidant property of M38G superalloy.
Embodiment 2
Adopt the multi-arc ion coating method, simultaneously to adopt the block Cr of in-situ sintering/solid-liquid reaction preparation
2AlC at room temperature deposits as target and has prepared the Cr-Al-C coating.Total back end vacuum is 2 * 10 in the coating preparation process
-3Pa, Ar airshed are that 40SCCM, operating air pressure are 0.4Pa, the electric current that is applied on the target is that 70A, depositing time are 15min.Can prepare the Cr-Al-C coating of amorphous on different matrixes, prepared coating can obtain with Cr through 620 ℃ of lower annealing 20h of Ar gas protection
2AlC is the Cr-Al-C coating of principal phase, also is accompanied by simultaneously AlCr
2And Cr
7C
3Generation.In the present embodiment, principal phase Cr
2The content of AlC accounts for 67wt.%.The X-ray diffracting spectrum of the Cr-Al-C coating after corresponding deposited and the annealing is listed in accompanying drawing 5, and coat-thickness is about 7.5 μ m.
Embodiment 3
Adopt the multi-arc ion coating method, simultaneously with Cr, Al, three kinds of element powder of C are that 2:1.1～1.2:0.9～1.2 powder mixs are as initial feed according to mol ratio, the compact block of making through hot pressing at room temperature deposits as target and has prepared the Cr-Al-C coating: select Cr, Al and Graphite Powder 99 are as raw material powder, raw material powder process ball milling 20～24 hours, pressure with 10～15MPa is cold-pressed into pie, the time of colding pressing is 15～20 minutes, pack in the graphite jig, in being connected with the hot pressing furnace of rare gas element Ar as protection gas, be warming up to 950～1000 ° of C reaction in－situs 30～40 minutes; Hot pressing is carried out in reaction simultaneously in position, and hot pressing pressure is 25～30MPa, and the block body ceramic material of synthesis of densified is as the Cr-Al-C target.
The back end vacuum is 2 * 10 in the coating preparation process
-3Pa, Ar airshed are that 40SCCM, operating air pressure are 0.4Pa, the electric current that is applied on the target is that 70A, depositing time are 15min.On different matrixes, can prepare the Cr-Al-C coating of amorphous.Prepared coating can obtain with Cr through 620 ℃ of lower annealing 20h of Ar gas protection
2AlC is the Cr-Al-C coating of principal phase, also is accompanied by simultaneously AlCr
2And Cr
7C
3Generation.In the present embodiment, principal phase Cr
2The content of AlC accounts for 61wt.%.The X-ray diffracting spectrum of the Cr-Al-C coating after the annealing is listed in accompanying drawing 6, and coat-thickness is about 7 μ m.
Embodiment result shows that the inventive method is with the Cr of sintering
2The AlC block materials is as target; Perhaps take Cr, Al, three kinds of element powder of C according to mol ratio as 2:1.1～1.2:0.9～1.2 powder mixs as initial feed, the compact block of making through hot pressing is as target.Utilize multi sphere ion plating technology and follow-up anneal, can obtain with Cr
2AlC is the Cr-Al-C coating of principal phase.This method has the advantages such as preparation cost is low, technique is simple, sedimentation rate is fast, for realizing large-scale industrialization deposition Cr
2The AlC coating is laid a good foundation.
Claims (5)
1. one kind is adopted the multi-arc ion coating preparation with Cr
2AlC is the method for the high-temperature protection coating of principal phase, it is characterized in that, concrete steps are as follows:
1) selection of target
Adopt the block Cr of sintering
2AlC is as target; Perhaps, take Cr, Al, three kinds of element powder of C according to mol ratio as 2:1.1～1.2:0.9～1.2 powder mixs as initial feed, the compact block of making through hot pressing is as the Cr-Al-C target;
2) preparation technology
In the coating preparation process, selected Ar airshed is 20～40SCCM, and operating air pressure is 0.2～0.6Pa, and depositing temperature is room temperature, and the target electric current is 50～70A; Subsequently, the sample that deposition is obtained in Ar gas atmosphere through 620 ° of C～650 ° C anneal 10～20h, can obtain with Cr
2AlC is the Cr-Al-C high-temperature protection coating of principal phase.
2. prepare with Cr according to employing multi-arc ion coating claimed in claim 1
2AlC is the method for the high-temperature protection coating of principal phase, it is characterized in that, the principal phase in the Cr-Al-C high-temperature protection coating is well-crystallized's ternary layered ceramic Cr
2AlC also is accompanied by AlCr
2And Cr
7C
3Appearance; Wherein, principal phase Cr
2The content of AlC is 60-70wt.%.
3. prepare with Cr according to employing multi-arc ion coating claimed in claim 1
2AlC is the method for the high-temperature protection coating of principal phase, it is characterized in that, the preparation method of Cr-Al-C target is: select Cr, Al and Graphite Powder 99 as raw material powder, raw material powder process ball milling 20～24 hours, pressure with 5～20MPa is cold-pressed into pie, the time of colding pressing is 5～30 minutes, in the graphite jig of packing into, is warming up to 900～1100 ° of C reaction in－situs 10～60 minutes in being connected with the hot pressing furnace of rare gas element as protection gas; Hot pressing is carried out in reaction simultaneously in position, and hot pressing pressure is 20～40MPa, and the block body ceramic material of synthesis of densified is as the Cr-Al-C target.
4. prepare with Cr according to employing multi-arc ion coating claimed in claim 1
2AlC is the method for the high-temperature protection coating of principal phase, it is characterized in that, in the experimentation, the back end vacuum that adopts is 1 * 10
-3Pa-3 * 10
-3Pa carries out backwash with the body material of anticipating and cleans the preparation that can begin coating behind the 3-10min.
5. prepare with Cr according to employing multi-arc ion coating claimed in claim 1
2AlC is the method for the high-temperature protection coating of principal phase, it is characterized in that, under this kind processing condition, the coating sedimentation rate reaches 0.3-0.5 μ m/min.
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Cited By (7)
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| CN103896592A (en) * | 2013-04-23 | 2014-07-02 | 河南工业大学 | Microwave synthesis method for Cr2AlC ceramic powder |
| CN104894516A (en) * | 2015-05-28 | 2015-09-09 | 中国科学院金属研究所 | Method for efficiently preparing ternary laminar MAX phase ceramic coating layer at low temperature |
| CN108330455A (en) * | 2018-01-26 | 2018-07-27 | 中国科学院宁波材料技术与工程研究所 | A kind of Cr2The regulatable coating production of AlC phase purity |
| CN111519157A (en) * | 2020-06-23 | 2020-08-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of Cr-Al-C series MAX phase coating |
| CN114481048A (en) * | 2022-04-15 | 2022-05-13 | 中国科学院宁波材料技术与工程研究所 | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexistent coating and preparation method and application thereof |
| CN114959569A (en) * | 2022-04-07 | 2022-08-30 | 中国科学院金属研究所 | Cr (chromium) 2 Preparation method of AlC diffusion impervious layer |
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| CN114481048B (en) * | 2022-04-15 | 2022-07-22 | 中国科学院宁波材料技术与工程研究所 | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating and preparation method and application thereof |
| CN115261780A (en) * | 2022-07-25 | 2022-11-01 | 海南大学 | Treatment method for improving wear resistance, corrosion resistance and freezing resistance of surface of metal material |
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