CN1250765C - Thermal barrier coating suitable for nickel-based high-temperature alloy with high Mo content - Google Patents

Thermal barrier coating suitable for nickel-based high-temperature alloy with high Mo content Download PDF

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CN1250765C
CN1250765C CN 200410102701 CN200410102701A CN1250765C CN 1250765 C CN1250765 C CN 1250765C CN 200410102701 CN200410102701 CN 200410102701 CN 200410102701 A CN200410102701 A CN 200410102701A CN 1250765 C CN1250765 C CN 1250765C
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tack coat
charge bar
thermal barrier
barrier coating
ceramic layer
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CN1621557A (en
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徐惠彬
宫声凯
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Beihang University
Beijing University of Aeronautics and Astronautics
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Beihang University
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Abstract

The present invention discloses a thermal barrier coating suitable for nickel-base high temperature alloy with high molybdenum content. A composite double-layer adhesive layer containing an adhesive layer I with silicon (Si) and an adhesive layer II without silicon (Si) is prepared between nickel-base high temperature alloy with high molybdenum content and a ceramic layer by a method of cathode beam physical vapor deposition. The present invention effectively inhibits the diffusion of molybdenum (Mo) in the nickel-base high temperature alloy with high molybdenum (Mo) content so as to extend the service life of thermal barrier coatings with molybdenum-base high temperature alloy as the matrix.

Description

Be applicable to thermal barrier coating of high molybdenum content nickel base superalloy and preparation method thereof
Technical field
The present invention relates to the preparation method of a kind of heat barrier coat material and thermal barrier coating, more particularly, be meant a kind of thermal barrier coating of high molybdenum (Mo) content nickel base superalloy and preparation method of this thermal barrier coating of being applicable to.
Background technology
Utilize the superior prepared superalloy thermal barrier coatings of performance such as high temperature resistant, anticorrosive and low heat conduction of stupalith can make the superalloy hot-end component can bear higher use temperature, prolong hot-end component work-ing life, improve hot-end component high temperature oxidation corrosion resistance ability, improve engine operating temperature.
On the other hand, for ultimate-use temperature and the mechanical behavior under high temperature that improves superalloy self, often in nickel (Ni) base, cobalt (Co) based high-temperature alloy matrix, add a certain amount of high-melting-point molybdenum (Mo).The adding of molybdenum (Mo) element makes the high temperature creep of superalloy and creep rupture strength increase substantially; but; also cause the oxidation-resistance property of superalloy to descend, therefore, the superalloy of high molybdenum (Mo) constituent content must have coating protection in use.
In the thermal barrier coating structure, tack coat is metal alloy coating (nickel, cobalt, chromium, aluminium, yttrium (Ni, Co, the Cr that does not match, also adds between matrix and ceramic coating for the oxidation-resistance that improves matrix simultaneously for the heat of alleviating ceramic coating and matrix, Al, Y)).Because the tack coat composition has decisive action to rate of oxidation, oxide film composition and integrity and with the factors such as bonding force of matrix, and these factors directly influence the life-span of thermal barrier coating; Simultaneously, tack coat also has important effect to the thermal fatigue life that stops vertical crack expansion, raising matrix.Therefore, tack coat composition Design and the Composition Control in coating procedure thereof are most important for the life-span of thermal barrier coating.
General in the world at present tack coat be Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y).This coated component design is rational for the superalloy of common low molybdenum (Mo) content, but, superalloy for high molybdenum (Mo) content, because molybdenum element at high temperature spreads in tack coat, the oxide compound volatilization of the molybdenum under the high temperature causes the tack coat Shen micropore to occur, the compactness of disruptive oxidation layer, make the high temperature oxidation resistance deterioration of tack coat, quicken the oxidation of tack coat, make interface bond strength weaken, the interface bond strength that is weakened can cause thermal barrier coating to peel off and lose efficacy.
Result of study shows, Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al adds a spot of silicon (Si) element in Y), can suppress molybdenum (Mo) elemental diffusion effectively.But at Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) behind middle adding silicon (Si) element, the silicon oxide that oxidation produces under the high temperature has wriggling, easily cause the ceramic layer spalling failure, therefore, Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si) coating is not suitable for independent tack coat use as thermal barrier coating.
Summary of the invention
The purpose of this invention is to provide the composite double layer tack coat that a kind of method that adopts electro beam physics vapour deposition prepares the tack coat I of siliceous (Si) element and do not conform to the tack coat II of silicon (Si) element between high molybdenum (Mo) content nickel base superalloy and ceramic layer, suppress molybdenum (Mo) elemental diffusion in high molybdenum (Mo) the content nickel base superalloy matrix effectively, and not containing silicon (Si) element at the interface at tack coat and ceramic layer, is the service life of the thermal barrier coating of matrix thereby improve with high molybdenum (Mo) content nickel base superalloy.
The present invention is a kind of thermal barrier coating that is applicable to high molybdenum (Mo) content nickel base superalloy, thermal barrier coating comprises tack coat and ceramic layer, described tack coat is made of tack coat I of siliceous (Si) element and the tack coat II of not siliceous (Si) element, be the composite double layer tack coat, tack coat II is located between tack coat I and the ceramic layer;
Described tack coat I material is that (Ni, Co, Cr, Al, Y, Si) alloy material, its weight percent are 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium, 0.07~1.0% silicon and the nickel of surplus to Ni, Co, Cr aluminium yttrium silicon;
Described tack coat II material is that (Ni, Co, Cr, Al, Y) alloy material, its weight percent are 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium and the nickel of surplus to Ni, Co, Cr aluminium yttrium;
Described ceramic layer material is the zirconium white of 6~8wt% stabilized with yttrium oxide;
Molybdenum content is 4~16wt% in the described high molybdenum content nickel base superalloy.
A kind of preparation method who is applicable to the thermal barrier coating of high molybdenum (Mo) content nickel base superalloy of the present invention, be to adopt the electro beam physics vapour deposition method to deposit tack coat I material, tack coat II material and ceramic layer material on high molybdenum (Mo) content nickel base superalloy, step of preparation process is
(A) preparation ceramic layer material charge bar:
Zirconium white (ZrO with stabilized with yttrium oxide 2+ (6-8wt%) Y 2O 3) powder is through sintering 2~6hrs, 1400 ℃~1600 ℃ of sintering temperatures make the ceramic charge bar of electro beam physics vapour deposition;
(B) preparation tack coat I material charge bar:
Take by weighing in proportion Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si) alloying element, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition with tack coat I material metal charge bar through melting;
(C) preparation tack coat II material charge bar:
Take by weighing in proportion Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) alloying element, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition with tack coat II material metal charge bar through melting;
(D) adopt electro beam physics vapour deposition equipment to prepare coating:
1. the above-mentioned charge bar that makes is put into the crucible of electro beam physics vapour deposition equipment respectively, and high molybdenum (Mo) content nickel base superalloy matrix is installed on the substrate;
2. suction to 5 * 10 -3Pa;
3. set the speed of rotation 10~20rpm of rotary plate frame;
Employing electron beam heated substrates to 600~900 ℃, electron-beam voltage 17~19kV;
4. deposit tack coat I: prevapourising tack coat I material charge bar, and regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate, hydatogenesis tack coat I begins, closed baffle plate after deposition is finished;
5. deposit tack coat II:
Regulate the rotary plate frame to second crucible top that tack coat II charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate, hydatogenesis tack coat II begins, and takes out after deposition is finished, and puts into vacuum heat treatment furnace and carry out vacuum heat treatment 2~6hrs, 1000~1100 ℃ of thermal treatment temps;
6. deposited ceramic layer: will be installed on the substrate of electro beam physics vapour deposition equipment through high molybdenum (Mo) the content nickel base superalloy matrix after 5. handling, and regulate the rotary plate frame to the 3rd crucible top that ceramic charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 1.2~1.6mm/min, sedimentation rate 2.0~3.0 μ m/min; Draw back baffle plate, the hydatogenesis ceramic layer begins, and takes out after deposition is finished, i.e. thermal barrier coating preparation is finished.
The preparation method of described thermal barrier coating, during hydatogenesis tack coat I, the top of tack coat I charge bar is added with 80~120g niobium (Nb) element.
The preparation method of described thermal barrier coating, the tack coat I in the hydatogenesis composite double layer tack coat is 1: 1~3 with the ratio of the thickness of tack coat II, the composite double layer tack coat is 1: 1~5 with the ratio of ceramic layer thickness.
Advantage of the present invention: (1) has solved the diffusion of molybdenum (Mo) element in the individual layer tack coat in high molybdenum (Mo) the content nickel base superalloy; (2) do not contain element silicon among the tack coat II in the thermal barrier coating of the present invention, make the thermal barrier coating service life-span increase substantially; (3) adopt electro beam physics vapour deposition technology and equipment, it is easy that its material is equipped with technology, and the layers of material consumption is controlled; (4) thermal barrier coating of the present invention has good resistance to high temperature oxidation and corrosive nature, has improved the service life of thermal barrier coating effectively.
Description of drawings
Fig. 1 is a thermal barrier coating structural representation of the present invention.
Fig. 2 is an electro beam physics vapour deposition equipment synoptic diagram.
Fig. 3 (a) is the profile scanning Electronic Speculum pattern behind the thermal barrier coating process 30h of the tack coat II+ ceramic layer for preparing on IC6 alloy substrate isothermal oxidation.
Fig. 3 (b) is the profile scanning Electronic Speculum pattern behind the thermal barrier coating process 300h of the tack coat II+ ceramic layer for preparing on IC6 alloy substrate isothermal oxidation.
Fig. 4 (a) is the profile scanning Electronic Speculum pattern after the thermal barrier coating process 60h of the tack coat I+ ceramic layer for preparing on IC6 alloy substrate thermal cycling.
Fig. 4 (b) is the profile scanning Electronic Speculum pattern after the thermal barrier coating process 360h of the tack coat I+ ceramic layer for preparing on IC6 alloy substrate thermal cycling.
Fig. 5 is the profile scanning Electronic Speculum pattern after the thermal barrier coating process 600h of the tack coat I+ tack coat II+ ceramic layer for preparing on IC6 alloy substrate thermal cycling.
Among the figure: 1. the vacuum chamber 2a. first crucible 2b. second crucible 2c. the 3rd crucible
3. tack coat II charge bar 4. tack coat I charge bars 5. ceramic layer charge bars 6. baffle plates 7. rotary plate framves
8. electron beam gun 9. electron beam gun 10. substrates 11. tack coat I 12. tack coat II
13. ceramic layer 14. matrixes
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of thermal barrier coating that is applicable to high molybdenum (Mo) content nickel base superalloy, and thermal barrier coating is made of ceramic layer and composite double layer tack coat (tack coat I+ tack coat II), and tack coat II is located between tack coat I and the ceramic layer.Wherein, tack coat I material is that (Ni, Co, Cr, Al, Y, Si) alloy material, its weight percent are 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium, 0.07~1.0% silicon and the nickel of surplus to Ni, Co, Cr aluminium yttrium silicon; Tack coat II material is that (Ni, Co, Cr, Al, Y) alloy material, its weight percent are 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium and the nickel of surplus to Ni, Co, Cr aluminium yttrium; Ceramic layer material is the zirconium white of 6~8wt% stabilized with yttrium oxide.In the present invention, if not refer in particular to tack coat I siliceous (Si) element, tack coat II not siliceous (Si) element.
Design philosophy of the present invention is: earlier double-deck composite double layer tack coat is usually suppressed molybdenum (Mo) elemental diffusion in high molybdenum (Mo) the based high-temperature alloy matrix by add silicon (Si) unit in tack coat I material, simultaneously, also easily generate silicon oxide and cause the ceramic layer spalling failure in order to solve under hot conditions tack coat I and matrix surface, before deposited ceramic layer, the tack coat II that deposits one deck not siliceous (Si) element is again alleviated molybdenum (Mo) element and is spread in thermal barrier coating.
In the present invention, adopt the electro beam physics vapour deposition method to deposit tack coat I material, tack coat II material and ceramic layer material on high molybdenum (Mo) content nickel base superalloy matrix, the processing step of preparation thermal barrier coating is:
(A) preparation ceramic layer material charge bar:
Through sintering 2~6hrs, 1400 ℃~1600 ℃ of sintering temperatures make the ceramic charge bar of electro beam physics vapour deposition with the Zirconium oxide powder of 6~8wt% stabilized with yttrium oxide;
(B) preparation tack coat I material charge bar:
Take by weighing in proportion Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si) alloying element, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition with tack coat I material metal charge bar through melting;
(C) preparation tack coat II material charge bar:
Take by weighing in proportion Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) alloying element, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition with tack coat II material metal charge bar through melting;
(D) adopt electro beam physics vapour deposition equipment to prepare coating:
1. the above-mentioned charge bar that makes is put into 3 crucibles of electro beam physics vapour deposition equipment respectively, in first crucible that tack coat I charge bar is housed, put into 80~120g niobium (Nb) element, and high molybdenum (Mo) content nickel base superalloy matrix is installed on the substrate 10;
2. suction to 5 * 10 -3Pa;
3. set the speed of rotation 10~20rpm of rotary plate frame 7;
Adopt 10 to 600~900 ℃ of electron beam heated substrates, electron-beam voltage 17~19kV;
4. deposit tack coat: prevapourising tack coat I material charge bar, and regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate 6,11 beginnings of hydatogenesis tack coat, closed baffle plate 6 after deposition is finished;
5. deposit tack coat II:
Regulate rotary plate frame 7 to the second crucible 2b top that tack coat II charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate 6, hydatogenesis tack coat II12 begins, and takes out after deposition is finished, and puts into vacuum heat treatment furnace and carry out vacuum heat treatment 2~6hrs, 1000~1100 ℃ of thermal treatment temps;
6. deposited ceramic layer: will be installed on the substrate 10 of electro beam physics vapour deposition equipment through the molybdenum based high-temperature alloy matrix after 5. handling, and regulate rotary plate frame 7 to the 3rd crucible 2c top that ceramic charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 1.2~1.6mm/min, sedimentation rate 2.0~3.0 μ m/min; Draw back baffle plate 6,13 beginnings of hydatogenesis ceramic layer are taken out after deposition is finished, i.e. thermal barrier coating preparation is finished.
The thermal barrier coating that adopts the electro beam physics vapour deposition method to prepare to have tack coat I+ tack coat II+ ceramic layer (structure as shown in Figure 1, surface topography as shown in Figure 5).Concrete preparation technology is as follows:
Tack coat I 11: Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si) alloy material is 20% cobalt, 22% chromium, 8% aluminium, 0.7% yttrium, 0.5% silicon and the nickel of surplus by weight percentage, makes the alloy charge bar of diameter 70mm, long 200mm behind vacuum induction melting;
Tack coat II 12: Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) alloy material by weight percentage component be 20% cobalt, 22% chromium, 8% aluminium, 0.7% yttrium and the nickel of surplus, behind vacuum induction melting, make the alloy charge bar of diameter 70mm, long 200mm;
Ceramic layer 13: the zirconium white of stabilized with yttrium oxide is made diameter 70mm through sintering, the charge bar of long 200mm;
Matrix 14 is molybdenum (Mo) content nickel base superalloy, molybdenum in the alloy (Mo) content 14wt%, i.e. IC6 alloy substrate.
In vacuum tightness is 5 * 10 -3Pa, substrate 10 speed of rotation are 15rpm, 750 ℃ of substrate 10 temperature; Alloy charge bar climbing speed is that 0.8mm/min, electron beam current are the tack coat I 11 that 1.6A evaporation thickness is about 50 μ m; With Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y) alloy charge bar climbing speed is that 0.6mm/min, electron beam current are the tack coat II 12 that 0.7A hydatogenesis thickness is about 10 μ m; With ceramic charge bar climbing speed is that 1.4mm/min, electron beam current are the ceramic layer 13 that 1.5A hydatogenesis thickness is about 150 μ m.
Thermal barrier coating of the present invention can be characterized by the structure formation (as shown in Figure 1) of tack coat I+ tack coat II+ ceramic layer, in adopting electro beam physics vapour deposition method enforcement preparation process, tack coat I charge bar is put into the first crucible 2a, and add niobium (Nb) element of 120g on the top of tack coat I charge bar material, utilize the high-melting-point and the low-steam pressure of niobium (Nb) element, form hot pond on the top of evaporation source, make yttrium (Y), silicon (Si) element to evaporate by required composition; Again tack coat II charge bar is put into the second crucible 2b, again the ceramic layer charge bar is put into the 3rd crucible 2c.After ready, hydatogenesis prepares thermal barrier coating and begins, and the thermal barrier coating of the present invention for preparing through 600 hours scanning electron microscope pattern of thermal cycling as shown in Figure 5.
For the influence in thermal barrier coating in the concrete material component of each layer in the further instruction thermal barrier coating and each layer, below illustrative example is carried out as directed.
(1) matrix+tack coat II+ ceramic layer
Body material is the IC6 alloy substrate, and tack coat II material is NiCrAlY, and the weight percent of component is 23% chromium, 8% aluminium, 0.5% yttrium and the nickel of surplus, and ceramic layer material is the zirconium white of stabilized with yttrium oxide.Deposit thickness: tack coat II60 μ m, ceramic layer 200 μ m.
The chemical ingredients (wt.%) of table 1IC6 alloy substrate
Ni Al Mo B
Equal amount 7~8 14 0.03~0.04
Equipment: Ukraine UE205 electro beam physics vapour deposition equipment (device structure as shown in Figure 2)
Adopt the preparation technology of above-mentioned said electro beam physics vapour deposition method, first deposition tack coat II (Ni, Co, Cr aluminium yttrium (Ni, Co, Cr, Al, Y)), the deposited ceramic layer (zirconium white (ZrO of stabilized with yttrium oxide again on the IC6 alloy substrate 2+ (6~8wt%) Y 2O 3)), behind 1100 ℃ of high temperature, and through behind the isothermal oxidation, its profile scanning Electronic Speculum pattern is shown in Fig. 3 a with the thermal barrier coating for preparing.As we can see from the figure, after the 30h isothermal oxidation, significantly diffusion takes place between tack coat II and the IC6 alloy substrate, tack coat II each point chemical ingredients distributes as shown in table 2, and elements Mo diffuses to from matrix among the tack coat II as can be seen.After the 300h isothermal oxidation, coating begins to peel off, and the interface between tack coat II and matrix is smudgy, shown in Fig. 3 b, tack coat II each point chemical ingredients distributes as shown in table 3, and the content of tack coat II and ceramic layer molybdenum (Mo) element at the interface is up to more than 7%.
This shows that because Mo content is higher in IC6, Mo is diffused among the tack coat II in pyroprocess, easily form (MoO 3, MoO 2) wait oxide compound, make interface bond strength reduction, cause thermal barrier coating to peel off and lost efficacy.In order better to improve the life-span of thermal barrier coating, must be able to suppress the diffusion of Mo.
Chemical ingredients distribution (wt.%) after the table 2 tack coat II+ ceramic layer thermal barrier coating isothermal oxidation 30h.
Al Cr Co Ni Y Mo
1 2 3 4 6.11 6.02 5.87 6.56 15.89 15.56 14.38 13.64 25.98 24.31 23.20 12.60 52.02 52.53 54.58 65.97 -- -- -- -- 1.58 1.97 4.23
Chemical ingredients distribution (wt.%) after the table 3 tack coat II+ ceramic layer thermal barrier coating isothermal oxidation 300h.
Al Cr Co Ni Y Mo
1 2 3 4 6.53 5.25 5.53 6.53 8.26 8.39 7.51 8.26 13.00 11.91 11.20 13.00 65.24 67.99 69.43 65.24 -- -- -- -- 7.29 6.34 6.81 7.29
(2) matrix+tack coat I+ ceramic layer
Body material is the IC6 alloy substrate, and tack coat I material is Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si), the weight percent of component is 23% chromium, 8% aluminium, 0.5% yttrium, 0.5% silicon and the nickel of surplus, and ceramic layer material is the zirconium white of stabilized with yttrium oxide.Deposit thickness: tack coat I 60 μ m, ceramic layer 200 μ m.
Adopt the preparation technology of above-mentioned said electro beam physics vapour deposition method, on the IC6 alloy substrate earlier deposition tack coat I Ni, Co, Cr aluminium yttrium silicon (Ni, Co, Cr, Al, Y, Si), the deposited ceramic layer (zirconium white (ZrO of stabilized with yttrium oxide again 2+ (6~8wt%) Y 2O 3)), behind 1100 ℃ of high temperature, and through after the thermal cycling, its profile scanning Electronic Speculum pattern is shown in Fig. 4 a with the thermal barrier coating for preparing.Find out among the figure, after the 60h thermal cycling, interface between tack coat I and the IC6 alloy substrate broadens, show that mutual diffusion has taken place for element among the tack coat I and the element in the IC6 alloy substrate, its element distributes as shown in table 4, as can be seen, is that the thermal barrier coating of NiCoCrAlY is compared with tack coat II, because the adding of Si, the diffusing capacity of Mo obviously reduces.After the 360h thermal cycling, the interface between tack coat I and the matrix disappears, shown in Fig. 4 b, its chemical ingredients distributes as shown in table 5, as can be seen, though the adding of Si can suppress the diffusion of Mo in tack coat effectively, lost efficacy through thermal barrier coating after the 360h thermal cycling.This mainly be since tack coat I and ceramic layer have a certain amount of silicon (Si) element at the interface, at high temperature easily form silicon oxide (SiO 2), the fragility of oxide film when the wriggling of oxide film and low temperature causes the thermal cycle life of thermal barrier coating to descend when increasing high temperature.
Chemical ingredients distribution (wt.%) after the table 4 tack coat I+ ceramic layer thermal barrier coating thermal cycling 60h.
Al Cr Co Ni Y Mo Si
1 2 3 4 5 6 27.14 7.69 7.33 5.39 9.64 5.66 4.47 6.26 6.74 5.21 0.73 1.44 6.44 9.16 13.12 11.85 3.54 0.44 14.53 75.79 69.55 71.90 76.44 81.54 6.68 -- -- -- -- -- -- 0.55 2.43 4.96 10.81 11.34 -- 0.55 0.51 0.09 -- --
Chemical ingredients distribution (wt.%) after the table 5 tack coat I+ ceramic layer thermal barrier coating thermal cycling 360h.
Al Cr Co Ni Y Mo Si
1 2 3 4 5 6 37.57 15.28 4.83 2.83 5.18 6.93 0.08 0.31 8.31 5.63 5.87 0.38 0.23 0.53 13.62 12.38 10.37 0.06 1.57 2.28 66.54 71.23 73.45 79.68 7.04 -- -- -- -- -- 0.17 0.66 6.25 4.23 4.60 13.63 0.24 0.31 0.35 0.45 0.11 --
(3) matrix+tack coat I+ tack coat II+ ceramic layer
Fig. 5 is a thermal barrier coating structure of the present invention, and this thermal barrier coating is through 600 hours scanning electron microscope pattern of thermal cycling, and corresponding composition distributes as shown in table 6.As can be seen, the thermal barrier coating thermal cycle life of composite double layer tack coat has improved more than 1 times than the thermal barrier coating of above-mentioned two kinds of single tack coats.
Table 6 tack coat I+ tack coat II+ ceramic layer thermal barrier coating thermal cycling 600h chemical ingredients distribution (wt.%).
Al Cr Co Ni Mo Si
1 2 3 4 5 6 5.81 6.58 6.83 7.19 6.78 6.93 14.29 13.49 14.31 14.38 8.87 0.38 15.75 15.37 15.27 15.38 10.37 0.06 63.94 63.66 60.82 58.07 69.00 79.08 0.21 0.75 2.42 4.64 4.84 13.55 -- 0.15 0.35 0.41 0.14 --

Claims (4)

1, a kind of thermal barrier coating that is applicable to high molybdenum content nickel base superalloy, thermal barrier coating comprises tack coat and ceramic layer, it is characterized in that: described tack coat is made of tack coat I that contains element silicon and the tack coat II that do not contain element silicon, and tack coat II is located between tack coat I and the ceramic layer;
Described tack coat I material is a Ni, Co, Cr aluminium yttrium aluminosilicate alloy material, and its weight percent is 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium, 0.07~1.0% silicon and the nickel of surplus;
Described tack coat II material is a Ni, Co, Cr aluminium yittrium alloy material, and its weight percent is 18~22% cobalt, 19~25% chromium, 6~8% aluminium, 0.07~1.0% yttrium and the nickel of surplus;
Described ceramic layer material is the zirconium white of 6~8wt% stabilized with yttrium oxide;
Molybdenum content is 4~16wt% in the described high molybdenum content nickel base superalloy.
2, the preparation method of thermal barrier coating according to claim 1 is characterized in that: adopt the electro beam physics vapour deposition method to deposit tack coat I material, tack coat II material and ceramic layer material on high molybdenum content nickel base superalloy, step of preparation process is
(A) preparation ceramic layer material charge bar:
Through sintering 2~6hrs, 1400 ℃~1600 ℃ of sintering temperatures make the ceramic charge bar of electro beam physics vapour deposition with the Zirconium oxide powder of 6~8wt% stabilized with yttrium oxide;
(B) preparation tack coat I material charge bar:
Take by weighing Ni, Co, Cr aluminium yttrium silicon alloy element in proportion, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition tack coat I material metal charge bar through melting;
(C) preparation tack coat II material charge bar:
Take by weighing Ni, Co, Cr aluminium yittrium alloy element in proportion, 1600 ℃~1800 ℃ of smelting temperatures make electro beam physics vapour deposition tack coat II material metal charge bar through melting;
(D) adopt electro beam physics vapour deposition equipment to prepare coating:
1. the above-mentioned charge bar that makes is put into the crucible of electro beam physics vapour deposition equipment respectively, and high molybdenum content nickel base superalloy matrix is installed on the substrate;
2. suction to 5 * 10 -3Pa;
3. set the speed of rotation 10~20rpm of rotary plate frame;
Employing electron beam heated substrates to 600~900 ℃, electron-beam voltage 17~19kV;
4. deposit tack coat I: prevapourising tack coat I material charge bar, and regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate, hydatogenesis tack coat I begins, closed baffle plate after deposition is finished;
5. deposit tack coat II:
Regulate the rotary plate frame to second crucible top that tack coat II charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 0.8~1.0mm/min, sedimentation rate 1.5~2.0 μ m/min; Draw back baffle plate, hydatogenesis tack coat II begins, and takes out after deposition is finished, and puts into vacuum heat treatment furnace and carry out vacuum heat treatment 2~6hrs, 1000~1100 ℃ of thermal treatment temps;
6. deposited ceramic layer: will be installed on the substrate of electro beam physics vapour deposition equipment through the high molybdenum content nickel base superalloy matrix after 5. handling, and regulate the rotary plate frame to the 3rd crucible top that ceramic charge bar is housed, regulate electronic beam current 1.4~1.8A, charge bar climbing speed 1.2~1.6mm/min, sedimentation rate 2.0~3.0 μ m/min; Draw back baffle plate, the hydatogenesis ceramic layer begins, and takes out after deposition is finished, i.e. thermal barrier coating preparation is finished.
3, the preparation method of thermal barrier coating according to claim 2 is characterized in that: during hydatogenesis tack coat I, the top of tack coat I charge bar is added with 80~120g niobium element.
4, the preparation method of thermal barrier coating according to claim 2 is characterized in that: the tack coat I in the hydatogenesis composite double layer tack coat is 1: 1~3 with the ratio of the thickness of tack coat II, and the composite double layer tack coat is 1: 1~5 with the ratio of ceramic layer thickness.
CN 200410102701 2004-12-28 2004-12-28 Thermal barrier coating suitable for nickel-based high-temperature alloy with high Mo content Expired - Fee Related CN1250765C (en)

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CN100393909C (en) * 2006-05-11 2008-06-11 北京航空航天大学 Method for depositing thermal barrier coating of porous dentrite ceramic layer by electron beam physical vapor deposition process
CN101722308B (en) * 2008-10-11 2012-01-25 四平市北威钼业有限公司 Molybdenum-base rare earth powder metallurgy forming plug and manufacturing method thereof
CN103342016B (en) * 2013-07-05 2016-01-13 中国科学院金属研究所 A kind of high temperature coating and preparation method comprising zirconium oxide active diffusion barrier layer
CN103710661B (en) * 2013-12-23 2016-04-27 西安西航集团莱特航空制造技术有限公司 A kind of anti-oxidant, anticorrosive and wear-resistant coating and spraying method thereof
CN106119760B (en) * 2016-07-28 2018-08-31 西安石油大学 A kind of thermal barrier coating and preparation method thereof with the double-deck adhesive layer
CN111349378A (en) * 2020-05-06 2020-06-30 北京矿冶科技集团有限公司 Long-life high-temperature sealing coating material and preparation method thereof
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