CN116043066B - Low-diffusivity activation auxiliary agent, application thereof, repairing agent and preparation method and alloy repairing method thereof - Google Patents
Low-diffusivity activation auxiliary agent, application thereof, repairing agent and preparation method and alloy repairing method thereof Download PDFInfo
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- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000004913 activation Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 230000008439 repair process Effects 0.000 claims description 74
- 239000002671 adjuvant Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
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- 238000009792 diffusion process Methods 0.000 abstract description 5
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- 239000010410 layer Substances 0.000 description 22
- 229910000601 superalloy Inorganic materials 0.000 description 17
- 239000012071 phase Substances 0.000 description 16
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- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005728 strengthening Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
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- 230000002829 reductive effect Effects 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
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- 229910052727 yttrium Inorganic materials 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
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- 229910019918 CrB2 Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
- B22F2007/068—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts repairing articles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a low-diffusivity activation auxiliary agent and application thereof, a repairing agent and preparation and alloy repairing methods thereof, wherein the element ：Cr(13.70％-18.30％),Co(7.70％-14.70％),Al(1.30％-2.20％),Ti(10.00％-12.00％),Nb(2.0％-3.5％),W(1.50-3.00％),Ta(1.00％-2.00％),Mo(7.00％-9.00％),Si(0.10％-0.50％),Hf(0.10％-0.20％),Zr(0.05-0.20％),Y(0.005％-0.02％),La(0.005％-0.02％),Sc(0.005％-0.02％); repairing agent prepared by the auxiliary agent comprises high-melting-point plastic powder and a binder, and the mass ratio of the auxiliary agent to the high-melting-point plastic powder is 1:1; the mass of the binder is 5% of the total mass of the auxiliary agent and the high melting point plastic powder. The invention does not use high-concentration B as a melting-reducing element, fundamentally eliminates the damage of B to the bonding layer, relieves the mutual diffusion of elements of the bonding layer and the repairing area, thereby enhancing the structural stability of the bonding layer on the repairing area and prolonging the service life of the repaired workpiece.
Description
Technical Field
The invention relates to the field of alloy repair auxiliary agents, in particular to a low-diffusivity activation auxiliary agent and application thereof, a repair agent and a preparation method thereof, and an alloy repair method.
Background
In order to be able to operate stably under severe operating conditions, nickel-based superalloy thermal components such as turbine blades, guide blades and the like of industrial gas turbines are generally made of high-strength, high-temperature-resistant and expensive nickel-based superalloys. During operation of industrial gas turbines, nickel-base superalloy hot components such as turbine blades, guide blades, and the like are subject to various forms of damage, including thermo-mechanical fatigue cracking, oxidation, surface wear, foreign object impingement, and the like, which often cause simultaneous damage to the coating and substrate at the damaged site. For the nickel-based superalloy thermal component with high manufacturing cost, the operation and maintenance cost of the unit can be greatly reduced by repairing the service damaged part of the component by a reasonable and effective method, and the repairing process mainly comprises component substrate repairing and component surface repainting.
Powder metallurgy additive manufacturing is one of several repairing technologies widely applied to the field of repairing of hot end component base materials of industrial gas turbines, and is particularly suitable for repairing and remanufacturing of cast high-temperature alloy hot end components with high aluminum and titanium contents. The repairing material is prepared by mixing a low-melting-point activating auxiliary agent with a connecting function and a high-melting-point plastic powder with a filling function, and the low-melting-point activating auxiliary agent is one of the most widely used low-melting-point activating auxiliary agents at present by adding excessive melting-reduction element B (boron). The repair joint with high density and high strength can be obtained by the repair technology, but for the repair joint with high B content, B with high diffusivity can diffuse into the bonding layer during high-temperature service and Cr in the bonding layer is combined to generate Cr-rich phases such as CrB2, crB and the like, so that the high-temperature oxidation resistance of the bonding layer is deteriorated, and the service life of the coating is greatly shortened.
Disclosure of Invention
The invention aims at: aiming at the problems, the low-diffusivity activation auxiliary agent, the application thereof, the repairing agent, the preparation thereof and the alloy repairing method are provided, the B with high concentration is not used as a melting-reducing element, the damage of the B to the bonding layer is fundamentally eliminated, the mutual diffusion of the bonding layer and the elements of the repairing area is relieved, the structural stability of the bonding layer on the repairing area is enhanced, and the service life of the repaired workpiece is prolonged.
The technical scheme adopted by the invention is as follows: a low diffusivity activation adjuvant, which is prepared from at least the following elements in mass percent:
Cr(13.70％-18.30％),Co(7.70％-14.70％),Al(1.30％-2.20％),Ti(10.00％-12.00％),Nb(2.0％-3.5％),W(1.50-3.00％),Ta(1.00％-2.00％),Mo(7.00％-9.00％),Si(0.10％-0.50％),Hf(0.10％-0.20％),Zr(0.05-0.20％),Y(0.005％-0.02％),La(0.005％-0.02％),Sc(0.005％-0.02％).
Further, the balance is Ni or/and unavoidable impurity elements.
Further, the melting temperature of the auxiliary agent ranges from 1090 ℃ to 1150 ℃.
Further, the particle size of the adjuvant is 30 μm to 106. Mu.m.
The application of the auxiliary agent in alloy repair.
An alloy repairing agent comprises the auxiliary agent, high-melting-point plastic powder and a binder, wherein the mass ratio of the auxiliary agent to the high-melting-point plastic powder is 1:1; the mass of the binder was 5% of the total mass of the adjuvant and the high melting point plastic powder.
Further, the components of the high-melting-point plastic powder comprise the following elements in percentage by mass:
C(0.13％-0.16％),Cr(13.70％-18.30％),Co(7.70％-14.70％),Al(3.70％-6.00％),Nb(0.05％-0.09％),W(0.05-1.50％),Ta(3.50％-5.00％),Mo(0.00％-0.50％), The balance of Ni and unavoidable impurity elements.
The preparation method of the alloy repairing agent comprises the steps of uniformly mixing high-melting-point plastic powder and auxiliary agents according to a proportion, and adding a binder to prepare a paste.
The alloy repairing method using the repairing agent comprises the following steps:
s1: pretreatment of the repair area, so that the surface of the repair area is clean;
S2: preparing a repairing agent, and coating the repairing agent on a repairing area;
S3: heating, and heating the repaired workpiece to 1180-1200 ℃;
S4: preserving heat for enough time;
S5: and cooling, namely cooling the repaired workpiece to room temperature.
Further, the heating speed should be lower than 16.8 ℃/min; the heat preservation time is 120min-180min; the cooling rate should be higher than 40 deg.c/min.
Further, after step S5, the repair area is surface-sprayed.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. The auxiliary agent provided by the invention is different from the traditional high-diffusion type activation auxiliary agent, the high-concentration B is not used as a melting-reducing element, but the melting point of the activation auxiliary agent is reduced through the high-temperature alloy strengthening element Cr, co, ti, mo, so that the damage of the B to the bonding layer is fundamentally eliminated, the element interdiffusion of the bonding layer and the repairing area is relieved, the structural stability of the bonding layer on the repairing area is enhanced, and the service life of the repaired workpiece is prolonged;
2. The auxiliary agent provided by the invention is added with a small amount of Si, hf, zr, Y, la, sc, and the elements are mutually matched, so that the service life of the coating on the repair area is effectively prolonged by three beneficial effects of enhancing the oxidation resistance of the repair area, inhibiting the interdiffusion between interface elements of the bonding layer and the repair area and improving the bonding strength between the bonding layer and the repair area;
3. The auxiliary agent provided by the invention is different from an activation auxiliary agent added with high concentration Hf, si and Zr as melting point inhibitors, and a small amount of Hf, si and Zr added in the low-diffusivity activation auxiliary agent can not separate out harmful heterogeneous eutectic phases, so that the repair area is high-temperature resistant and high in strength.
Drawings
The invention will now be described by way of example and with reference to the accompanying drawings in which:
FIG. 1 is a microscopic morphology of the disclosed adjuvant;
FIG. 2 is a diagram showing the tissue morphology of a repair agent disclosed by the invention to a Mar-M247 superalloy additive repair region;
FIG. 3 shows the morphology of the Mar-M247 superalloy repair region after thermal shock test and long-time oxidation test.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
Example 1
A low diffusivity activation adjuvant, which is prepared from at least the following elements in mass percent:
Cr(13.70％-18.30％),Co(7.70％-14.70％),Al(1.30％-2.20％),Ti(10.00％-12.00％),Nb(2.0％-3.5％),W(1.50-3.00％),Ta(1.00％-2.00％),Mo(7.00％-9.00％),Si(0.10％-0.50％),Hf(0.10％-0.20％),Zr(0.05-0.20％),Y(0.005％-0.02％),La(0.005％-0.02％),Sc(0.005％-0.02％).
In the embodiment, the auxiliary disclosed in the embodiment is different from the traditional activation auxiliary, the auxiliary does not use high-concentration high-diffusivity boron as a melting point inhibitor, a repairing area obtained after repairing the alloy does not damage a thermal barrier coating bonding layer, the service life of the coating is long, and the auxiliary is suitable for powder metallurgy repairing of a high-temperature alloy component substrate with the thermal barrier coating.
A small amount of Si, hf, zr, Y, la, sc is added into the auxiliary agent, so that the oxidation resistance of the repair area is enhanced, the mutual diffusion between interface elements of the bonding layer and the repair area is inhibited, the bonding strength between the bonding layer and the repair area is improved, and the service life of a coating on the repair area is effectively prolonged. And unlike the activation auxiliary agent with high concentration of Hf, si and Zr as melting point inhibitor, small amount of Hf, si and Zr added into the auxiliary agent can not separate out harmful heterogeneous eutectic phase, and the obtained repair area has high temperature resistance and high strength. The auxiliary agent has the following effects on the repair of the nickel-based superalloy:
The main elements used in the auxiliary agent of this embodiment include Cr, co, al, ti, nb, W, ta, mo, which are all strengthening elements in the superalloy, and the beneficial effects are shown in:
Cr is an indispensable alloying element in the nickel-based superalloy, and most of Cr is dissolved in gamma phase, so that the high-temperature oxidation resistance and hot corrosion resistance of a repair area can be remarkably improved, in addition, the effect of solid solution strengthening is also achieved, the stacking fault energy of a solid solution is reduced, and the lasting strength of the solid solution is improved. Co can be infinitely and mutually dissolved with the matrix element nickel in the nickel-based superalloy to form a continuous substitution solid solution, thereby playing the role of solid solution strengthening and improving the creep property of the alloy. In order to make the Cr and Co contents of the repair region at the same level as the repaired substrate, the Cr content is limited to a range of 13.70wt% to 18.30wt% and the Co content is limited to a range of 7.70wt% to 14.70wt% in the alloy composition of the present invention.
Al and Ti are main generating elements of a precipitation strengthening phase gamma 'in the nickel-based superalloy, and the quantity of gamma' phases in unit volume in the alloy is proportional to the creep resistance of the alloy to a certain extent. The Ti content is limited to a range of 10.00wt% to 12.00wt% in the alloy composition of the present invention, which is far higher than that in conventional commercial nickel-based superalloys, and another beneficial effect of high-concentration Ti addition is represented by lowering the melting point of the alloy of the present invention. Since Ti is added in a high concentration, the content of Al is limited to a range of 1.30wt% to 2.20wt% in the alloy composition of the present invention.
Nb and Ta are main strengthening elements of gamma 'phase, can improve the reverse domain boundary energy of gamma', and the yield strength and the lasting creep property of the alloy, and in addition, ta can also improve the stability of gamma 'phase, so that the gamma' phase is not easy to grow up during long-term aging. However, excessive Nb addition causes the repair zone to generate a large amount of TCP phase detrimental to joint performance in long-term high-temperature service, and Ta is very expensive, so that the content of Nb is limited to a range of 2.00 to 3.50wt% and the content of Ta is limited to a range of 1.00 to 2.00wt% in the alloy composition of the present invention.
W, mo is a strengthening element of a matrix gamma phase, plays a solid solution strengthening role, W and Mo have large atomic radius relative to Ni, and can cause obvious lattice expansion when being dissolved in the matrix, and increase a long Cheng Danxing stress field, so that dislocation movement is blocked, the elastic stress field is reduced, and various mechanical properties of a repair area can be obviously improved; since the addition of a large amount of W increases the melting point of the alloy to fail to meet the process requirements, the content of W in the alloy composition of the present invention is limited to a range of 1.50wt% to 3.00 wt%; another beneficial effect of Mo in the present invention is represented by lowering the melting point of the alloy of the present invention, and thus the content of Mo is limited to a range of 7.00wt% to 9.00wt% in the alloy composition of the present invention.
The small addition of Si, hf, zr, Y, la, sc elements, which are added in small amounts within a certain range, can improve some important properties of the alloy powder and the repair area obtained by using the alloy powder. The beneficial effects are as follows:
Si and Zr can improve the fluidity of a liquid phase generated after the auxiliary agent is melted, and improve the wettability of the liquid phase on the surface of the high-melting-point powder, thereby improving the density of a repair area and ensuring the manufacturability of the alloy powder. In addition, when the repair area is in long-term service, the two elements can fill up the vacancy between the repair area and the bonding layer interface, promote the formation of a compact Cr 2O3 oxide layer, effectively inhibit the interdiffusion between the bonding layer and the repair area interface elements, improve the high-temperature oxidation resistance of the repair area and avoid the peeling of the coating on the bonding layer and the repair area interface caused by the thickening of the oxide layer. However, excessive addition can cause the formation of a large amount of harmful low-melting eutectic phases rich in Si and Zr, and the mechanical properties of the repair area are reduced. Therefore, the content of Si is limited to the range of 0.10wt% to 0.50wt% and the content of Zr is limited to the range of 0.05wt% to 0.20wt% in the alloy composition of the present invention.
Hf. Y, la and Sc are rare earth elements, have high affinity with O, can be combined with free O in a repair area, improve the oxidation resistance of the repair area, and the generated dispersion oxide is biased to a grain boundary, so that the strength of the grain boundary can be improved, and the plasticity of the grain boundary can be improved. Another beneficial effect of Hf is that it is soluble in the gamma prime phase, which is enhanced. Another beneficial effect of Y is that it can improve the bond strength of the repair area to the adhesive layer and inhibit cracking of the adhesive layer-repair area interface. When Hf is excessively added, the O content of the powder surface produced by the alloy of the present invention increases and the powder quality decreases, so that the content of Hf in the alloy composition of the present invention is limited to the range of 0.10wt% to 0.20 wt%. When the elements Y, la and Sc are excessively added, rare earth compounds are generated in the repair region to weaken the grain boundary, so that the contents of Y, la and Sc are all limited to the range of 0.005 to 0.02wt% in the alloy composition of the present invention.
In order to further clearly illustrate and describe the technical solution of the present invention, the following non-limiting embodiments are provided, table 1 is an embodiment of the adjuvant, and the following element content data are all mass percent data.
Table 1 embodiment of adjuvant and comparative example
| 1 | 2 | 3 | 4 | Control 1 | Control 2 | Control 3 | Control 4 | |
| Cr | 13.7 | 18.3 | 15.2 | 18.3 | 20.0 | 20.0 | 15.0 | 14.0 |
| Co | 14.7 | 8.2 | 10.1 | 7.7 | 20.0 | 14.0 | 9.0 | |
| Al | 2.2 | 1.3 | 1.5 | 1.3 | \ | 3.5 | 4.0 | |
| Ti | 12.0 | 11.5 | 11.1 | 10.0 | \ | |||
| Nb | 2.5 | 2.3 | 2.5 | 3.5 | \ | |||
| W | 3.0 | 3.5 | 1.5 | 1.5 | \ | |||
| Ta | 1.0 | 2.6 | 1.5 | 2.0 | 3.0 | 2.5 | ||
| Mo | 7.0 | 7.1 | 8.3 | 9.0 | \ | |||
| Si | 0.5 | 0.1 | 0.2 | 0.1 | \ | |||
| Hf | 0.2 | 0.1 | 0.1 | 0.1 | \ | |||
| Zr | 0.2 | 0.2 | 0.1 | 0.05 | \ | |||
| Y | 0.02 | 0.01 | 0.02 | 0.005 | \ | 0.05 | ||
| La | 0.005 | 0.01 | 0.01 | 0.02 | 0.02 | |||
| Sc | 0.02 | 0.01 | 0.01 | 0.005 | \ | |||
| B | / | / | / | 3.0 | 2.7 | 3.0 | 2.5 | |
| Melting point | 1142℃ | 1113℃ | 1129℃ | 1096℃ | 1050℃ | 1099℃ | 1031℃ | 1050℃ |
After the embodiment modes 1 to 4 in this example are compared with the comparative examples 1 to 4, they have the following advantages:
1. the adjuvants of comparative examples 1-4 were used as melting point inhibitors at high concentrations of highly diffusive B, and when components repaired with such adjuvants were in service at high temperatures after spraying a thermal barrier coating, the rankine effect caused a significant amount of highly diffusive B to diffuse into and bond with Cr in the thermal barrier coating, causing the bond to fail rapidly and peel off, thereby losing the protective effect on the substrate. By combining embodiments 1 to 4 of the present example, the high temperature alloy strengthening element Cr, co, ti, mo in the auxiliary agent reduces the melting point of the activation auxiliary agent, fundamentally eliminates the damage of the high concentration B to the bonding layer, and relieves the inter-diffusion of the elements of the bonding layer and the repair area; the alloy repaired by the auxiliary agent in the embodiments 1-4 does not generate heterogeneous weakened phases in the repair area, has high strength and higher high temperature resistance, thereby enhancing the structural stability of the bonding layer on the repair area and prolonging the service life of the repaired workpiece.
2. The melting temperature of embodiments 1-4 of this example is significantly higher than that of comparative examples 1-4, and the higher the melting temperature of the auxiliary agent filled in the repair area after alloy repair, the stronger the high temperature resistance of the repair area.
As a specific embodiment, the remainder is Ni or/and unavoidable impurity elements.
As a specific embodiment, the melting temperature of the adjuvant ranges from 1090 ℃ to 1150 ℃.
As a specific embodiment, the particle size of the adjuvant is 30 μm to 106 μm; the granularity is prepared by adopting an atomization method; specifically, the high-temperature molten auxiliary agent is formed into powder with target granularity by adopting a high-pressure water flow, air flow atomization or ultrasonic atomization mode, so that the auxiliary agent is more tightly piled up when repairing alloy, and the alloy repairing performance is ensured.
As shown in fig. 1, the adjuvant disclosed in embodiment 1 of this example has a microstructure.
The auxiliary disclosed by the embodiment has wide applicability, can be matched with various autonomously developed or commercial high-melting-point plastic powder to repair various types of damage defects on nickel-based casting superalloy with high aluminum and titanium contents such as Mar-M247, IN738LC, IN939, GTD-111, GTD-222 and the like, can repair a plurality of parts at one time, has high repair efficiency and low repair cost, and has higher industrial application value.
Example 2
An alloy repairing agent comprises the auxiliary agent, high-melting-point plastic powder and a binder, wherein the mass ratio of the auxiliary agent to the high-melting-point plastic powder is 1:1; the mass of the binder is 5% of the total mass of the auxiliary agent and the high-melting-point plastic powder, and the binder plays a role of adhering the auxiliary agent and the high-melting-point plastic powder.
The high-melting-point plastic powder comprises the following elements in percentage by mass:
C(0.13％-0.16％),Cr(13.70％-18.30％),Co(7.70％-14.70％),Al(3.70％-6.00％),Nb(0.05％-0.09％),W(0.05-1.50％),Ta(3.50％-5.00％),Mo(0.00％-0.50％), The balance of Ni and unavoidable impurity elements.
In this embodiment, taking a repairing agent capable of repairing Mar-247 superalloy as an example, the repairing agent has a high melting point plastic powder comprising, by mass, C (0.15%), cr (15.0%), co (10.0%), al (4.2%), nb (0.06%), W (1.50%), ta (3.50%), mo (0.1%), and the balance Ni and unavoidable impurity elements.
The preparation method of the alloy repairing agent comprises the steps of uniformly mixing high-melting-point plastic powder and auxiliary agents according to a proportion, so that equal amounts of the high-melting-point plastic powder and the auxiliary agents exist in a unit volume, adding a binder to prepare a paste, enabling the repairing agent to be sticky, reducing fluidity, enabling the repairing agent to be smeared and filled in a repairing area to be stable, and avoiding the repairing agent from being separated from the repairing area before entering heating and melting; the viscous repairing agent is more convenient to fill the repairing area, and is particularly characterized in that the viscous repairing agent has certain fluidity, when the repairing agent fills the repairing area, the shape of the repairing agent can be automatically changed according to the size of the filling position due to the flowability of the repairing agent, so that the filling of the irregular repairing area is met, even if the size of the repairing area is smaller (the defect that the length and the width are smaller than 30mm and the height are smaller than 4 mm), the filling can be completed, the repairing area can be completely filled under the action of the flowability of the repairing agent, and the defect gaps existing in the repairing area are reduced.
Example 3
In this example, the method of repairing an alloy using the repairing agent proposed in example 2 includes the steps of:
s1: pretreatment of the repair area, so that the surface of the repair area is clean;
S2: preparing a repairing agent, and coating the repairing agent on the repairing area;
S3: heating, namely heating the repaired workpiece to 1180-1200 ℃;
S4: preserving heat for enough time;
S5: and cooling, namely cooling the repaired workpiece to room temperature.
Specifically, the repairing agent prepared by combining the auxiliary agent disclosed in the embodiment 1 of the example 1 with the example 2 is used for repairing defects (repairing areas) with the length, the width and the height of 30mm, 30mm and 4mm in Mar-M247 superalloy; in the step S1, the defects of the repair area are polished clean, so that the influence of impurities on defect repair is avoided; in step S2, the process and method for preparing the restorative agent are described in detail in example 2; in step S3, the melting point of the auxiliary agent is 1142 ℃, and the repaired workpiece is heated to 1200 ℃ to sinter and melt the auxiliary agent, so that the auxiliary agent is in a molten state and has fluidity; in step S4, the temperature is kept at 1200 ℃ for a sufficient time, and the repairing agent completely fills the repairing area and uniformly spreads in the repairing area; in step S5, the repairing agent is quickly solidified and forms a target metallographic structure, and the mechanical property, the interface connection property, the thermal shock property and the long-time oxidation resistance of the repairing area are ensured.
As a specific embodiment, the heating rate should be less than 16.8 ℃/min; the heat preservation time is 120min-180min; the cooling rate should be higher than 40 deg.c/min.
In the embodiment, aiming at the defect in Mar-M247 superalloy repaired by the repairing agent, the heating speed is 10 ℃/min, the heat preservation time is 180 ℃, and the cooling speed is 40 ℃/min; for the heating speed, the heating speed is limited by a heating boiler, and in order to ensure that the workpiece is heated uniformly, the heating speed needs to be controlled below 16.8 ℃/min; the selection of the duration of the incubation period has been described in detail above and will not be described in detail herein; for the cooling speed, the gamma' phase with excellent morphology can be formed in the repair area by rapid cooling at 40 ℃/min, and the tensile property, the durability and the creep property of the repair area are ensured.
In this embodiment, after the step S5 is completed, the extra metal overflowed from the repair area is polished and repaired, and the thermal barrier coating is sprayed to complete the material-increasing repair work of the component.
In this embodiment, after step S5, the repair area is surface-sprayed to further improve the oxidation resistance of the repair area.
In this example, the performance after repairing defects of 30mm, 30mm and 4mm in length, width and height respectively in Mar-M247 superalloy was tested as follows:
The tensile properties of the repaired area were measured, and the results are shown in Table 2.
TABLE 2 tensile Properties of the repair area
As shown in fig. 2, the repair area is compact, the interface connection is good, and no heterogeneous weakened phase is generated.
The repair zone with the thermal barrier coating was subjected to 50 thermal shock tests at 1050 ℃ and then oxidized for 5000 hours in an atmospheric furnace at 1050 ℃ without peeling the coating.
As shown in fig. 3, the repair area and the adhesive layer still maintain good adhesion after thermal shock test and long-term oxidation test.
The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (10)
1. A low diffusivity activation adjuvant characterized by: the preparation at least comprises the following elements in percentage by mass:
Cr（13.70%-18.30%）,Co（7.70%-14.70%）,Al（1.30%-2.20%）,Ti（10.00%-12.00%）,Nb（2.0%-3.5%）,W（1.50-3.00%）,Ta（1.00%-2.00%）,Mo（7.00%-9.00%）,Si（0.10%-0.50%）,Hf（0.10%-0.20%）,Zr（0.05-0.20%）,Y（0.005%-0.02%）,La（0.005%-0.02%）,Sc（0.005%-0.02%）; The balance of Ni and unavoidable impurity elements.
2. The low diffusivity activation adjuvant of claim 1 wherein: the melting temperature of the auxiliary agent ranges from 1090 ℃ to 1150 ℃.
3. The low diffusivity activation adjuvant of claim 1 wherein: the particle size of the auxiliary agent is 30-106 μm.
4. Use of an adjuvant according to any one of claims 1-3 for alloy repair.
5. An alloy repair agent comprising the adjuvant of any one of claims 1 to 3, characterized in that: the plastic powder also comprises high-melting-point plastic powder and a binder, wherein the mass ratio of the auxiliary agent to the high-melting-point plastic powder is 1:1; the mass of the binder is 5% of the total mass of the auxiliary agent and the high melting point plastic powder.
6. The alloy repair agent according to claim 5, wherein: the high-melting-point plastic powder comprises the following elements in percentage by mass:
C（0.13%-0.16%）,Cr（13.70%-18.30%）,Co（7.70%-14.70%）,Al（3.70%-6.00%）,Nb（0.05%-0.09%）,W（0.05-1.50%）,Ta（3.50%-5.00%）,Mo（0.00%-0.50%）, The balance of Ni and unavoidable impurity elements.
7. A method for preparing an alloy repairing agent, which is characterized in that the alloy repairing agent is prepared according to any one of claims 5 to 6, and is characterized in that: the high-melting point plastic powder and the auxiliary agent are uniformly mixed according to the proportion, and the adhesive is added to prepare the paste.
8. Alloy repair method using the repair agent according to any one of claims 5 to 6, characterized in that: the method comprises the following steps:
s1: pretreatment of the repair area, so that the surface of the repair area is clean;
S2: preparing a repairing agent, and coating the repairing agent on a repairing area;
S3: heating, and heating the repaired workpiece to 1180-1200 ℃;
S4: preserving heat for enough time;
S5: and cooling, namely cooling the repaired workpiece to room temperature.
9. The alloy repair method according to claim 8, wherein: the heating speed is lower than 16.8 ℃/min; the heat preservation time is 120min-180min; the cooling rate should be higher than 40 deg.c/min.
10. The alloy repair method according to claim 8, wherein: after step S5, the repair area is surface sprayed.
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