CN104372390A - Novel process for manufacturing MCrAlY thermal barrier coatings - Google Patents
Novel process for manufacturing MCrAlY thermal barrier coatings Download PDFInfo
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- CN104372390A CN104372390A CN201410746542.3A CN201410746542A CN104372390A CN 104372390 A CN104372390 A CN 104372390A CN 201410746542 A CN201410746542 A CN 201410746542A CN 104372390 A CN104372390 A CN 104372390A
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Abstract
The invention discloses a novel process for manufacturing MCrAlY thermal barrier coatings. The novel process includes (1), preparing electroplate liquid, cleaning workpieces to be electroplated, and grinding and polishing the surfaces of the cleaned workpieces to be electroplated; (2), manufacturing CrAlY powder, connecting the workpieces to be electroplated with cathodes of power sources, connecting pure nickel bars with anodes of the power sources, inserting the pure nickel bars and the workpieces to be electroplated into electrolytic tanks, dissolving the CrAlY powder in the electroplate liquid, sufficiently and uniformly stirring the CrAlY powder, then adding the CrAlY powder and the electroplate liquid into the electrolytic tanks, adjusting the temperatures and PH (potential of hydrogen) values of the electrolytic tanks, selecting voltage and current density, turning on the power sources and electroplating the workpieces to obtain electroplated semi-finished products; (3), placing the electroplated semi-finished products into vacuum furnaces, filling the vacuum furnaces with protective gas, heating the vacuum furnaces until diffusion and phase change of the electroplated semi-finished products are completed, and acquiring electroplated finished products. The novel process has the advantages that the novel process is free of constraints of complicated appearance of the workpieces, the coatings are uniform, have smooth and clean surfaces and can be tightly combined with matrixes, the speeds can be controlled, the cost is low, and the novel process can be applied to manufacturing the MCrAlY thermal barrier coatings on a large scale.
Description
Technical field
The present invention relates to a kind of preparation technology of MCrAlY thermal barrier coating, particularly relate to a kind of novel process preparing MCrAlY thermal barrier coating.
Background technology
Industry gas turbine achieves the development of advancing by leaps and bounds in the past few decades, is mainly reflected in temperature of combustion and these two aspects of efficiency of heat engine that industry gas turbine improves constantly.And everything mainly gives the credit to the development of material, the especially development of combustion engine blade material and coated material.
At present, most of combustion engine blade material adopts nickel base superalloy, and nickel has the stable and comprehensive exsertile advantage of higher melt, alloy substrate good toughness, high temperature undertissue.But along with further developing of aviation and industry gas turbine technology, the use temperature of hot-end component requires more and more higher, has has much met or exceeded the fusing point of superalloy and monocrystal material.For the heating part of gas turbine (as nozzle, blade, combustion chamber), the temperatures as high that it bears in routine duties 1100 DEG C, exceed the ultimate temperature 1075 DEG C that high temperature nickel alloy uses, particularly F, H level combustion engine (ultimate temperature is 1200 ~ 1400 DEG C), its temperature of combustion is far above the fusing point of nickelalloy, in this case, the application of thermal barrier coating seems particularly important.
Thermal barrier coating is made up of ceramic plated layer, metal bonding coating and hot grown layer, and thermal barrier coating is deposited on the surface of superalloy, has certain thickness and durability degree.Thermal barrier coating serves heat-blocking action to body material, the temperature of matrix can be reduced, improve resistance to high temperature oxidation, the anticorrosive and wear resistance of matrix, high-temperature alloy blades can be used in the hot environment more than its fusing point, further increase the use temperature of superalloy.Therefore, Thermal Barrier Coating Technologies has become one of most active research topic in international high temperature coating field in the last few years.
MCrAlY/YSZ thermal barrier coating is the industrial combustion engine coating of most widespread use, and it is mainly through air plasma spraying (APS) or electro beam physics vapour deposition (EB-PVD) preparation.Wherein, air plasma spraying uses powder as coating material, utilize between anode (nozzle) and negative electrode (electrode) and light hf electric arc, coated material is dissolved a kind of technique forming coating with plasma gas plume directive target drone body.But the coating structure prepared by APS is sheet, cavity is more, poor performance is shaken in heat resistanceheat resistant, easily causes coating to be peeled off in advance, causes blade failure, affect the normal operation of combustion engine.And EB-PVD is under vacuum conditions, utilize the electron beam of high-energy-density to heat material to be evaporated, make it reach fusion and gasification state, and under magnetic deflection field effect, be evaporated to technique base material condensing into coating.The coating binding force prepared by EB-PVD is strong, and ability of anti-deformation is strong, but its sedimentation rate is low, and dimensional requirement can not be too large, and cost is high, and the further genralrlization hindering this technique is suitable for.
Summary of the invention
The object of the present invention is to provide the novel process of the preparation MCrAlY thermal barrier coating that a kind of technique is simple, preparation efficiency is high, long service life, cost are low, effectively can avoid producing laminated structure, reduce porosity, improve the bonding force of coating and matrix, coating surface is bright and clean, thickness is even and be easy to control, be applied to the workpiece of various size, be applicable to scale operation.
Object of the present invention realizes by the following technical solutions: a kind of novel process preparing MCrAlY thermal barrier coating, it is characterized in that specifically comprising the following steps:
(1) pre-treatment in early stage:
1. electroplate liquid is configured: Ni ion, SO in electroplate liquid
4the mol ratio of ion, Cl ion is 5:4:1, and all the other are additive.Electroplate liquid is (as NiSO based on the ionogen of Ni ion
4or NiCl
2), specifically according to the specific requirement of coated component and thickness, suitable electrolyte prescription can be selected;
2. electroplated workpiece is cleaned to remove impurity and the oxide compound of electroplated workpiece surface;
3. the electroplated workpiece surface after cleaning is carried out polishing, polishing, to increase the bonding force of coating;
(2) electroplate:
1. CrAlY powder is prepared: the mass percent of Cr, Al, Y element is: Cr:50 ~ 70wt%, Al:30 ~ 40wt%, Y:2 ~ 3wt%, wt% is mass percent, Cr, Al, Y element are melted into one, obtain CrAlY particle after solidification, CrAlY particulate abrasive is become CrAlY powder;
The concrete proportioning of Cr, Al, Y element utilizes Theoretical Calculation (according to chemical formula and composition proportion, the content of the various elements required for calculating) and test (whether the proportioning of chemical experiment measurement resultant reaches the requirement of needs, adjusting again, make its composition consistent with expection) method that combines to be to determine the proportioning of the elements such as Cr, Al, Y.
2. electroplated workpiece is connected with the negative pole of power supply, pure nickel rod is connected with the positive pole of power supply, then electroplated workpiece is inserted in electrolyzer together with pure nickel rod;
3. the CrAlY powder (2) 1. obtained by step is dissolved in the electroplate liquid (1) 1. obtained by step, adds in electrolyzer together again after stirring, and make the electroplate liquid submergence electroplated workpiece containing CrAlY powder;
4. adjust temperature and the pH value of electrolyzer, select voltage and current density, opening power is electroplated, and obtains plating work in-process;
According to the specific requirement of plating, as parameters such as thickness of coating, workpiece size, electrodepositing speeds, suitable voltage and electric current (relevant with the size of electroplated workpiece) can be selected.
(3) Post isothermal treatment: plating work in-process are put into vacuum oven, is filled with shielding gas in vacuum oven, and heating is until plating work in-process complete diffusion and phase transformation, obtains plating finished product.
The present invention adopts the method for electrochemical deposition, electroplated workpiece is immersed in electroplate liquid completely, utilizes the codeposition of CrAlY particle and nickel, required coating is plated on electroplated workpiece surface, so not by the restriction of workpiece complex configuration, uniform coating thickness.Because can not produce gas in electroplating process, coatingsurface is bright and clean, and coating is combined closely with matrix.And due to electrochemical co-deposition technological operation simple, electroplate liquid is cheap, can control electroplating velocity by voltage and current, thus the present invention to have preparation speed controlled, cost is low, can apply to the advantages such as scale operation.
The material of electroplate liquid of the present invention is composed as follows: single nickel salt 260 ~ 300g/L, nickelous chloride 35 ~ 45g/L, boric acid 40 ~ 50g/L, brightening agent 0.1 ~ 0.2ml/L, open cylinder agent 8 ~ 10ml/L.
The present invention described step (1) 2. in, described cleaning electroplated workpiece surface is impurity and the oxide compound of being dried removing electroplated workpiece surface by washing, acetone immersion, pickling, washing.
The present invention described step (1) 3. in, use sand papering polishing electroplated workpiece surface to be Ra1.0 ~ 5 μm to smooth finish.
The present invention described step (2) 1. in, utilize high-temperature electric arc to melt Cr, Al, Y element, after being solidified into CrAlY particle, re-using ball mill and CrAlY particulate abrasive is become to be less than the CrAlY powder of 50 μm.
The present invention described step (2) 4. in, the temperature of electrolyzer is 50 ~ 85 DEG C, pH value is 4.0 ~ 5.0, and voltage is 6 ~ 9V, current density is 1 ~ 2A/dm
2.
The present invention described step (3) in, the temperature of heating is 1000 ~ 1200 DEG C and keeps 1 ~ 20 hour, plating work in-process complete diffusion and phase transformation, obtain plating finished product.
Step of the present invention (3) in shielding gas be nitrogen or argon gas.
Compared with prior art, the present invention has following significant effect:
(1) the MCrAlY thermal barrier coating prepared by the present invention is dense, porosity is low, the bonding force of coating and matrix is strong, and long service life, coating surface are bright and clean, and thickness evenly and be easy to control, can be applied to complicated internal combustion turbine machine blade.
(2) the coating surface prepared by the present invention is bright and clean smooth, effectively can reduce the generation probability of fatigue cracking, and improve the anti-deformation tolerance limit of coating, thermal cycle life is good.
(3) the present invention prepares speed soon, and cost is low, can be widely used in scale operation.
(4) the coating prepared by the present invention has high corrosion resistance, wear resistance, the advantage that high rigidity imporosity rate is low.
(5) the present invention is not subject to the restriction of workpiece complex configuration, is not subject to the restriction of workpiece size, and speed is fast, and cost of manufacture is low.
Embodiment
Embodiment 1
A kind of novel process preparing MCrAlY thermal barrier coating of the present invention, specifically comprises the following steps:
(1) pre-treatment in early stage:
1. electroplate liquid is configured: electroplate liquid is (as NiSO based on the ionogen of Ni ion
4or NiCl
2), in the present embodiment, the material of electroplate liquid is composed as follows: single nickel salt 260g/L, nickelous chloride 35g/L, boric acid 40g/L, brightening agent 0.1ml/L, open cylinder agent 8ml/L.Specifically according to the specific requirement of coated component and thickness, suitable electrolyte prescription can be selected;
2. clean electroplated workpiece surface to remove impurity and the oxide compound of electroplated workpiece surface, dry particular by washing, acetone immersion, pickling, washing the impurity and oxide compound of removing electroplated workpiece surface;
3. the electroplated workpiece surface after cleaning is carried out polishing, polishing, specifically use sand papering polishing electroplated workpiece surface to be Ra 1.0 μm to smooth finish.Thus increase the bonding force of coating;
(2) electroplate:
1. CrAlY powder is prepared: the mass percent of Cr, Al, Y element is: Cr:50wt%, Al:30wt%, Y:2wt%, wt% is mass percent, utilize high-temperature electric arc that Cr, Al, Y element are melted into one, obtain CrAlY particle after solidification, re-use the CrAlY powder that CrAlY particulate abrasive is become to be less than 50 μm by ball mill;
The proportioning of Cr, Al, Y element is the composition according to concrete MCrAlY thermal barrier coating, utilizes Theoretical Calculation and test the method combined to determine, Theoretical Calculation refers to according to chemical formula and composition proportion, the content of the various elements required for calculating; Experiment refers to whether the proportioning of chemical experiment measurement resultant reaches the requirement of needs, then adjusts, and makes its composition consistent with expection;
2. electroplated workpiece is connected with the negative pole of power supply, pure nickel rod is connected with the positive pole of power supply, then electroplated workpiece is inserted in electrolyzer together with pure nickel rod; Check whether connection is intact, with or without short circuit, misses.
3. the CrAlY powder (2) 1. obtained by step is dissolved in the electroplate liquid (1) 1. obtained by step, adds in electrolyzer together again after stirring, and make the electroplate liquid submergence electroplated workpiece containing CrAlY powder;
4. the temperature adjusting electrolyzer is 50 DEG C, pH value is 4.0, and voltage is 6V, current density is 1A/dm
2.Opening power is electroplated, and electroplating time is relevant with the thickness of thermal barrier coating, and the thermal barrier coating of plating 200um, needs a hours.Obtain plating work in-process; According to the specific requirement of plating, as parameters such as thickness of coating, workpiece size, electrodepositing speeds, suitable voltage and electric current can be selected;
Following item is should be noted in electroplating process:
1, notice that voltage, electric current and pH value are isoparametric stable, if there is larger fluctuation, corresponding measure should be taked to solve and give problem, or stop plating, ascertain the reason.
2, in electroplating process, as occurred, sedimentation velocity is excessively slow, and coating is coarse, and the phenomenon of coating obfuscation, should stop plating, ascertain the reason.
3, suitably improve temperature and be conducive to electrolytical diffusion, increase the electroconductibility of plating solution, improve the homogeneity of plating solution, but the too high meeting of temperature causes coating coarse, obfuscation.
4, the whipping appts in electrolyzer can select glass stick or magnet rotor, and object improves the homogeneity of plating solution, and make electroplating process steady, plating thickness is even, plated layer compact.
(3) Post isothermal treatment: after electroplated workpiece completes electrochemistry plating, although the composition of coating and thickness reach target call, the microtexture of its coating does not also reach use standard, need carry out Post isothermal treatment.Post isothermal treatment mainly diffusion in vacuum process, object utilizes the diffusion at high temperature of Al, Cr, CO, Ni element, allows coating and matrix composition at high temperature occur to spread and phase transformation, produce the columnar crystal structure of non-lamella, be mainly β phase.Plating work in-process are put into vacuum oven, is filled with shielding gas (nitrogen or argon gas), and is heated to 1000 DEG C in vacuum oven, keep 10 hours, plating work in-process complete diffusion and phase transformation, obtain plating finished product.In practical matter, actual temp and time can be determined according to the parameter such as Coating composition, thickness.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: step (1) 1. in, the material of electroplate liquid is composed as follows: single nickel salt 280g/L, nickelous chloride 40g/L, boric acid 45g/L, brightening agent 0.15ml/L, open cylinder agent 9ml/L; Step (1) 3. in, use sand papering polishing electroplated workpiece surface to be Ra 3 μm to smooth finish; Step (2) 1. in, the mass percent of Cr, Al, Y element is: Cr:60wt%, Al:35wt%, Y:2.5wt%; Step (2) 4. in, the temperature of adjustment electrolyzer is 70 DEG C, pH value is 4.5, and voltage is 8V, current density is 1.5A/dm
2; Step (3) in, the temperature of heating is 1100 DEG C and keeps 15 hours, plating work in-process complete diffusion and phase transformation, obtain plating finished product.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: step (1) 1. in, the material of electroplate liquid is composed as follows: single nickel salt 300g/L, nickelous chloride 45g/L, boric acid 50g/L, brightening agent 0.2ml/L, open cylinder agent 10ml/L; Step (1) 3. in, use sand papering polishing electroplated workpiece surface to be Ra5 μm to smooth finish; Step (2) 1. in, the mass percent of Cr, Al, Y element is: Cr:70wt%, Al:40wt%, Y:3wt%; Step (2) 4. in, the temperature of adjustment electrolyzer is 85 DEG C, pH value is 5.0, and voltage is 9V, current density is 2A/dm
2; Step (3) in, the temperature of heating is 1200 DEG C and keeps 20 hours, plating work in-process complete diffusion and phase transformation, obtain plating finished product.
Embodiments of the present invention are not limited thereto, and according to foregoing of the present invention, according to ordinary technical knowledge and the customary means of this area, are not departing under the present invention's above-mentioned basic fundamental thought prerequisite, Ni ion, SO in electroplate liquid of the present invention
4the mol ratio of ion, Cl ion is 5:4:1, and all the other are additive; The mass percent of Cr, Al, Y element is: Cr:50 ~ 70wt%, Al:30 ~ 40wt%, Y:2 ~ 3wt%; Single nickel salt 260 ~ 300g/L, nickelous chloride 35 ~ 45g/L, boric acid 40 ~ 50g/L, brightening agent 0.1 ~ 0.2ml/L, open cylinder agent 8 ~ 10ml/L; Sand papering polishing electroplated workpiece surface is used to be Ra 1.0 ~ 5 μm to smooth finish; The temperature of electrolyzer is 50 ~ 85 DEG C, pH value is 4.0 ~ 5.0, and voltage is 6 ~ 9V, current density is 1 ~ 2A/dm
2; Step (3) in, the temperature of heating is 1000 ~ 1200 DEG C and keeps 1 ~ 20 hour; Therefore the present invention can also make the amendment of other various ways, replacement or change, all drops within rights protection scope of the present invention.
Claims (8)
1. prepare a novel process for MCrAlY thermal barrier coating, it is characterized in that specifically comprising the following steps:
(1) pre-treatment in early stage:
1. electroplate liquid is configured: Ni ion, SO in electroplate liquid
4the mol ratio of ion, Cl ion is 5:4:1;
2. electroplated workpiece is cleaned to remove impurity and the oxide compound of electroplated workpiece surface;
3. the electroplated workpiece surface after cleaning is carried out polishing, polishing;
(2) electroplate:
1. CrAlY powder is prepared: the mass percent of Cr, Al, Y element is: Cr:50 ~ 70wt%, Al:30 ~ 40wt%, Y:2 ~ 3wt%; Cr, Al, Y element are melted into one, obtain CrAlY particle after solidification, CrAlY particulate abrasive is become CrAlY powder;
2. electroplated workpiece is connected with the negative pole of power supply, pure nickel rod is connected with the positive pole of power supply, then electroplated workpiece is inserted in electrolyzer together with pure nickel rod;
3. the CrAlY powder (2) 1. obtained by step is dissolved in the electroplate liquid (1) 1. obtained by step, adds in electrolyzer together again after stirring, and make the electroplate liquid submergence electroplated workpiece containing CrAlY powder;
4. adjust temperature and the pH value of electrolyzer, select voltage and current density, opening power is electroplated, and obtains plating work in-process;
(3) Post isothermal treatment: plating work in-process are put into vacuum oven, is filled with shielding gas in vacuum oven, and heating is until plating work in-process complete diffusion and phase transformation, obtains plating finished product.
2. the novel process of preparation MCrAlY thermal barrier coating according to claim 1, is characterized in that: the material of described electroplate liquid is composed as follows: single nickel salt 260 ~ 300g/L, nickelous chloride 35 ~ 45g/L, boric acid 40 ~ 50g/L, brightening agent 0.1 ~ 0.2ml/L, open cylinder agent 8 ~ 10ml/L.
3. the novel process of preparation MCrAlY thermal barrier coating according to claim 1 and 2, it is characterized in that: described step (1) 2. in, described cleaning electroplated workpiece surface is impurity and the oxide compound of being dried removing electroplated workpiece surface by washing, acetone immersion, pickling, washing.
4. the novel process of preparation MCrAlY thermal barrier coating according to claim 3, is characterized in that: described step (1) 3. in, use sand papering polishing electroplated workpiece surface to be Ra 1.0 ~ 5 μm to smooth finish.
5. the novel process of preparation MCrAlY thermal barrier coating according to claim 4, it is characterized in that: described step (2) 1. in, utilize high-temperature electric arc to melt Cr, Al, Y element, after being solidified into CrAlY particle, re-use the CrAlY powder that CrAlY particulate abrasive is become to be less than 50 μm by ball mill.
6. the novel process of preparation MCrAlY thermal barrier coating according to claim 5, is characterized in that: described step (2) 4. in, the temperature of electrolyzer is 50 ~ 85 DEG C, pH value is 4.0 ~ 5.0, and voltage is 6 ~ 9V, current density is 1 ~ 2A/dm
2.
7. the novel process of preparation MCrAlY thermal barrier coating according to claim 6, is characterized in that: described step (3) in, the temperature of heating is 1000 ~ 1200 DEG C and keeps 1 ~ 20 hour, and plating work in-process complete diffusion and phase transformation, obtains plating finished product.
8. the novel process of preparation MCrAlY thermal barrier coating according to claim 7, is characterized in that: described step (3) in shielding gas be nitrogen or argon gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5824205A (en) * | 1994-07-22 | 1998-10-20 | Praxair S.T. Technology, Inc. | Protective coating |
| CN101724301A (en) * | 2008-10-15 | 2010-06-09 | 中国科学院金属研究所 | MCrAlY+AlSiY composite coating and preparation technique thereof |
| CN104099657A (en) * | 2014-06-25 | 2014-10-15 | 北京理工大学 | Preparation method of MCrAlY alloy coating layer |
-
2014
- 2014-12-08 CN CN201410746542.3A patent/CN104372390A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5824205A (en) * | 1994-07-22 | 1998-10-20 | Praxair S.T. Technology, Inc. | Protective coating |
| CN101724301A (en) * | 2008-10-15 | 2010-06-09 | 中国科学院金属研究所 | MCrAlY+AlSiY composite coating and preparation technique thereof |
| CN104099657A (en) * | 2014-06-25 | 2014-10-15 | 北京理工大学 | Preparation method of MCrAlY alloy coating layer |
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