CN104818482A - High-temperature-resistant high-bonding-strength low infrared emissivity composite coating, metal alloy material with coating and preparation method of metal alloy material - Google Patents
High-temperature-resistant high-bonding-strength low infrared emissivity composite coating, metal alloy material with coating and preparation method of metal alloy material Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant high-bonding-strength low infrared emissivity composite coating which sequentially comprises a NiCrAlY plasma spraying layer, a ZrO2 plasma spraying layer and ZrO2-Al2O3-SiO2 system containing AgPd alloy glass coating from inside to outside. The surface roughness of a metal alloy material coated with the coating is lower than 2.0 micrometers, the bonding strength of the metal alloy material exceeds 10MPa, the tolerable temperature of the coating is higher than 1000 DEG C, and the average infrared emissivity of the coating in a specified band is less than 0.3. A preparation method of the metal alloy material includes the steps: firstly, performing sand blasting for a base; secondly, sequentially spraying the NiCrAlY layer and the ZrO2 layer on the base by a plasma spraying process; finally, uniformly brushing or printing coatings on the ZrO2 layer, and drying and sintering the coatings to obtain the finished metal alloy material. The metal alloy material can be used in a high-temperature environment, infrared radiation of a high-temperature component is effectively reduced, and the metal alloy material is stable in performance and low in cost.
Description
Technical field
The present invention relates to functional coating and technical field of composite materials thereof, be specifically related to a kind of low infrared emissivity compound coating, metal alloy compositions and preparation method thereof.
Background technology
Infrared eye is collected the infrared signal of target at 3 μm ~ 5 μm (high temperature) and 8 μm ~ 14 μm (normal temperature) wave bands, and the infrared energy difference of recycling object and background identifies target by imaging.According to infrared energy difference calculation formula: △ W=σ ε
ordert
order 4-σ ε
the back of the bodyt
the back of the body 4, in formula, ε
orderfor the infrared emittance of target, ε
the back of the bodyfor the infrared emittance of background, T
orderfor the surface temperature of target, T
the back of the bodyfor ambient temperature.Usually, due to reasons such as heatings, the surface temperature of target higher than the temperature of background, therefore, can reduce target surface temperature, on high-temperature component, prepares low-launch-rate (ε
order) coating reduces the effective means of object and background yield of radiation difference.
Along with the high speed development of aeronautical and space technology, the flight velocity of aircraft is more and more faster, again to supersonic speed even superelevation velocity of sound from subsonic speed to velocity of sound, cause aircraft when flying, the air-flow flowing through aircraft surface is blocked due to reasons such as frictions, kinetic energy is heat energy, produce Aerodynamic Heating phenomenon, aircraft surface temperature is sharply raised, produce strong ir signature, therefore, control the trend that ir radiation that aircraft surface comprises some hot-end components becomes Flight Vehicle Design and preparation, and as controlling the most frequently used low emissivity coatings technology of ir radiation, the resistance to elevated temperatures of its coating becomes researchist's problem in the urgent need to address.
Low emissivity coatings is generally made up of binding agent and low-launch-rate filler, is divided into organic system and inorganic system two class.The low emissivity coatings use temperature of organic system is not high, and use temperature is generally no more than 400 DEG C, is therefore not suitable for using under the environment of high-speed aircraft harshness.The low emissivity coatings of inorganic system uses warm area higher, and its temperature tolerance even can more than 1000 DEG C, but the low emissivity coatings result of use in high temperature environments of current most of inorganic system is unsatisfactory.The major cause of above problem is caused to have: the first, most low-launch-rate fillers unstable properties in high temperature environments, easily transport phenomena occurs; The second, the metal or alloy material of aircraft is at high temperature easily toward the diffusion of surface red external coating (EC), thus causes coating performance to worsen; Three, the thermal expansivity difference between coating and base material (as aviation alloy material) is comparatively large, produces thermal mismatching, thus causes the adhesive power of coating poor, easily come off; 4th, metallic substance such as Au, Pt etc. of existing employing are expensive, and cost is higher; 5th, the preparation technology of some coating existing often needs to carry out under harsher environment (if magnetron sputtering needs are in vacuum environment), and not only equipment requirements is high, and is not suitable for shapingly preparing abnormal complex component.
In sum, along with the high speed development of aeronautical and space technology, day by day urgent to the demand of high temperature resistant, high bond strength, low infrared emissivity coating.Therefore, design and a kind ofly have that use temperature is high, bonding strength is high, emittance is low and the new coating of stable performance, will have important practical significance.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided a kind of to can be used on metal alloy compositions and can use, can effectively reduce the low infrared emissivity compound coating of low high temperature resistant, the high bond strength of high-temperature component ir radiation, stable performance simultaneously, cost in high temperature environments, also correspondingly provide the metal alloy compositions being coated with aforementioned low infrared emissivity compound coating, also correspondingly provide that a kind of technique is simple, the preparation method of the aforementioned metal alloy material of processing ease, excellent product performance.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of low infrared emissivity compound coating of high temperature resistant, high bond strength, described low infrared emissivity compound coating is multiple-layer stacked structure, described multiple-layer stacked structure comprises metal tie coat, ceramic interlayer and low-launch-rate functional layer outward successively by interior, wherein, described metal tie coat is NiCrAlY plasma sprayed coating, and described ceramic interlayer is ZrO
2plasma sprayed coating, described low-launch-rate functional layer is the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2it is glass coating.Each interlayer of described low infrared emissivity compound coating connects with mechanical bond or chemical bonding mode.
In above-mentioned low infrared emissivity compound coating, preferred: the gauge control of described metal tie coat is 50 ~ 150 μm, and the gauge control of described ceramic interlayer is 50 ~ 100 μm.
In above-mentioned low infrared emissivity compound coating, preferred: the described ZrO containing AgPd alloy
2-Al
2o
3-SiO
2be in glass coating, ZrO
2-Al
2o
3-SiO
2be the mass ratio of glassy phase, metal A g and metal Pd for (15 ~ 20): (50 ~ 65): (20 ~ 35).Preferred: described ZrO
2-Al
2o
3-SiO
2be that the mass percent of each component raw material in glassy phase is respectively: ZrO
240% ~ 60%; Al
2o
310% ~ 25%; SiO
215% ~ 25%; CaO 2% ~ 5%; MgO 1% ~ 5%; And B
2o
31% ~ 6%.
As a total technical conceive, the present invention also provides a kind of metal alloy compositions being coated with above-mentioned low infrared emissivity compound coating, comprise alloy base and be coated in the described low infrared emissivity compound coating on alloy base, the surface roughness Ra of described metal alloy compositions is less than 2.0 μm, the bonding strength of low infrared emissivity compound coating is more than 10MPa, the tolerable temperature of described low infrared emissivity compound coating, more than 1000 DEG C, is less than 0.3 (being more preferably less than 0.2) in the average infrared emittance of 3 ~ 5 mu m wavebands.
The low infrared emissivity compound coating of the invention described above and the design of metal alloy compositions thereof are mainly based on following principle: first, the thermal expansivity of this low infrared emissivity compound coating successively decreases from inside to outside successively, this reduces the thermal mismatching of each interlayer, ensure that the high bond strength of low infrared emissivity compound coating; The second, according to Infrared Physics principle, in low infrared emissivity compound coating, control ir radiation and depend on outermost low-launch-rate functional layer; Low-launch-rate functional layer of the present invention adopts ZrO
2-Al
2o
3-SiO
2be glass be binding agent, metal A g and metal Pd are low-launch-rate filler, as the ZrO of binding agent
2-Al
2o
3-SiO
2be glass, its temperature tolerance and oxidation-resistance very well, can ensure that coating is on active service at relatively high temperatures and did not lose efficacy; As metal A g and the metal Pd of filler, continuous solid solution alloy can be formed in sintering process, namely in the coating after sintering, metal A g and metal Pd exist with the form of alloy, alloy structure is very fine and close, there will not be the diffusion mobility phenomenon of pure metal Ag, thus improve the high-temperature stability of coating, the low infrared emissivity of coating under guarantee high temperature; 3rd, the present invention also adopts NiCrAlY plasma sprayed coating directly to bind as metal tie coat and alloy base material, this thermal expansivity mainly due to NiCrAlY material itself is the most close with conventional metal alloy compositions, bonding strength is between the two stronger, simultaneously, the antioxidant property of NiCrAlY material is also better, can stop outside air oxidized metal alloy material; 4th, the present invention also adopts ZrO
2plasma sprayed coating is as ceramic interlayer, to reduce thermal expansivity gradient difference further on the one hand, the problems such as the anchoring strength of coating difference preventing thermal mismatching from bringing, on the other hand, can barrier metal or alloy material at high temperature coating performance be caused to worsen toward the diffusion of low-launch-rate functional layer.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned metal alloy compositions, comprises the following steps:
(1) substrate sandblasting: be placed in sandblast machine by needing the alloy base covering low infrared emissivity compound coating and carry out sandblasting; The preferred processing parameter condition of sandblasting comprises: it is 3 ~ 5MPa that air pressure controls, sandblasting distance 30 ~ 50mm, and sand particle diameter is 50 ~ 100 μm, blast time 20 ~ 60min;
(2) metallize tie coat: adopt on the alloy base of plasma spray coating process after step (1) and spray NiCrAlY plasma sprayed coating;
(3) ceramic coated transition layer: the NiCrAlY plasma sprayed coating adopting plasma spray coating process to obtain after step (2) continues spraying ZrO
2plasma sprayed coating;
(4) low-launch-rate functional layer is prepared: obtained glass powder is mixed obtained coating with metal A g, metal Pd, then adopts spread coating or silk screen print method, evenly brush coating or be printed on the ZrO obtained in step (3)
2on plasma sprayed coating, the thickness of low-launch-rate functional layer can be regulated and controled by brushing (or printing) number of times adjusting coating, after drying (being placed on air apoplexy master stream flat or dry in an oven), sintering (being placed in retort furnace), namely obtain finished product.
Above-mentioned preparation method, preferably, in described step (2) and step (3), the processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 20 ~ 40NL/min, H
2ventilation flow rate be 8 ~ 12NL/min; Powder feeding air-flow Ar is 2.5 ~ 3.2NL/min, powder sending quantity 10% ~ 30%; It is 500 ~ 600A that size of current controls, and power is 30 ~ 50kW; The distance of shower nozzle and substrate is 100 ~ 150mm.
Above-mentioned preparation method, preferably, in described step (4), the preparation of described glass powder specifically comprises the following steps: will comprise ZrO
2, Al
2o
3, SiO
2, CaO, MgO, B
2o
3frit powder mix (load platinum crucible in) in above-mentioned massfraction ratio, be placed in retort furnace again and carry out high melt, glass melt after fusing is poured in deionized water and carries out quenching, the glass obtained is carried out ball milling, dry, sieve (preferably referring to 200 order ~ 400 mesh sieves), obtain glass powder.
In foregoing glass material powder, the massfraction of each oxide components is preferably respectively:
In the preparation of above-mentioned glass powder, the process regulation of described high melt process preferably includes: smelting temperature is 1600 DEG C ~ 1800 DEG C, and melting soaking time is 1h ~ 3h.
In the preparation of above-mentioned glass powder, preferably, described ball milling carries out in zirconia ball grinding jar, take acetone as ball-milling medium, and ratio of grinding media to material is (2 ~ 3): 1, and rotational speed of ball-mill is 380r/min ~ 450r/min, and Ball-milling Time is 6h ~ 12h.
Above-mentioned preparation method, in the preparation of described coating, preferably, described glass powder and metal A g, metal Pd mix in planetary gravity mixer, the processing parameter of described planetary gravity stirrer preferably includes: revolution speed 1280rpm ~ 1500rpm, rotational velocity is 30% ~ 60%, churning time 60 ~ 120min.Further, the preparation of described coating is mixed by three-roll grinder with organic carrier by the compound of glass powder and metal A g, metal Pd again, three-roll grinder rotating speed is preferably 250 ~ 450r/min, grinding mixing time is preferably 3 ~ 6h, wherein the massfraction of compound accounts for 75% ~ 80%, and the massfraction of organic carrier accounts for 25% ~ 20%.Described organic carrier is primarily of tributyl citrate (solvent), nitrocellulose (thickening material) and Yelkin TTS (tensio-active agent) composition, and the mass percent of three in organic carrier is respectively:
Tributyl citrate 70% ~ 80%;
Nitrocellulose 2% ~ 10%;
Yelkin TTS 10% ~ 20%;
The viscosity controller of the coating prepared is 170 ~ 300Pas.
Above-mentioned preparation method, preferably, in described step (4), sintering is generally be placed in retort furnace to carry out, sintering temperature during described sintering is 1000 DEG C ~ 1050 DEG C, heat-up rate is 15 DEG C/and min ~ 20 DEG C/min, sintering time is 10min ~ 60min.
Compared with prior art, the invention has the advantages that:
1, low infrared emissivity compound coating that is high temperature resistant, high bond strength of the present invention adopts multiple-layer stacked structure design, from inside to outside, metal tie coat, ceramic interlayer arrive low-launch-rate functional layer again, the thermal expansivity of each layer realizes gradient and slowly successively decreases, thus reduce the thermal mismatching of each interlayer, make anchoring strength of coating very excellent, the sticking power of coating can reach 25MPa.
2, low infrared emissivity compound coating that is high temperature resistant, high bond strength of the present invention adopts unique metal tie coat and ceramic interlayer design, prevent the High temperature diffusion between base metal material and low-launch-rate functional layer on the one hand, prevent the oxidation behaviors of base metal material on the other hand, more traditional individual layer low-launch-rate functional layer is more stable, ensure that coated material uses under the hot environment of 1000 DEG C.
3, mainly ZrO is comprised in low-launch-rate functional layer of the present invention
2-Al
2o
3-SiO
2be glassy phase and AgPd alloy phase (referring to the thing phase after sintering herein), two-phase all can use under 1000 DEG C of hot environments, infrared emittance when 1000 DEG C can lower than 0.3, organic materials system use temperature conventional comparatively is at present significantly increased, and more current inorganic material coating system high-temperature stability and emittance are significantly improved.
4, the low-launch-rate filler added in low-launch-rate functional layer of the present invention is Ag and Pd, and with other precious metals, such as Au, Pt etc. compare, cost is cheaply a lot, meanwhile, in sintering process, Ag and Pd defines solid solution thereof, overcomes again the simple migration problem adding Ag and cause.
What 5, adopt in preparation method of the present invention is plasma spraying technology, and can carry out in atmosphere, not only cost is low, and processing unit requires low, and is applicable to preparing shaped piece and complex component.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schematic cross-section of the low infrared emissivity compound coating of high temperature resistant in the embodiment of the present invention, high bond strength.
Fig. 2 is the photo in kind on the low infrared emissivity compound coating surface of high temperature resistant in the embodiment of the present invention 1, high bond strength.
Fig. 3 is the average emitted rate of low infrared emissivity compound coating that is high temperature resistant in the embodiment of the present invention 1, high bond strength 3 ~ 5 mu m wavebands at 600 DEG C, 800 DEG C, 1000 DEG C in kind.
Marginal data
1, alloy base; 2, metal tie coat; 3, ceramic interlayer; 4, low-launch-rate functional layer.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
As shown in Figure 1, it is high temperature resistant that one is coated with the present invention, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength, the low infrared emissivity compound coating comprising alloy base 1 (alloy base adopts aerospace K424 alloy) and be coated on alloy base 1, this low infrared emissivity compound coating is multiple-layer stacked structure, multiple-layer stacked structure comprises metal tie coat 2 outward successively by interior, ceramic interlayer 3 and low-launch-rate functional layer 4, wherein, metal tie coat 2 is NiCrAlY plasma sprayed coating, ceramic interlayer 3 is ZrO
2plasma sprayed coating, low-launch-rate functional layer 4 is the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2it is glass coating.The gauge control of metal tie coat 2 is 100 μm, and the gauge control of ceramic interlayer 3 is 50 μm, and the gauge control of low-launch-rate functional layer 4 is 15 μm.At the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2be in glass coating, ZrO
2-Al
2o
3-SiO
2be the mass ratio of glassy phase, metal A g and metal Pd be 20: 60: 20.At ZrO
2-Al
2o
3-SiO
2be that the mass percent of each component in glassy phase is respectively: ZrO
250%; Al
2o
315%; SiO
225%; CaO 3%; MgO 2% and B
2o
35%.
The surface roughness Ra of the metal alloy compositions of the present embodiment is 1.2 μm, the bonding strength of low infrared emissivity compound coating is 17MPa (employing hubbing), the tolerable temperature of low infrared emissivity compound coating can reach 1000 DEG C, is less than 0.3 in the average infrared emittance of 3 ~ 5 mu m wavebands.
The preparation method of the metal alloy compositions of the present embodiment, specifically comprises following preparation process:
1. substrate sandblasting: aerospace are used K424 alloy substrate, carries out sandblasting in sandblast machine, and the processing parameter of sandblasting is respectively: air pressure controls as 3MPa, sandblasting distance 30mm, and sand particle diameter is 50 μm, and blast time is 20min;
2. metallize tie coat: adopt on the K424 alloy substrate of plasma spray coating process after step (1) and spray NiCrAlY plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 20NL/min, H
2ventilation flow rate be 8NL/min; Powder feeding air-flow Ar is 3NL/min, powder sending quantity 10%; Electric current 500A, power 30kW; The distance 100mm of shower nozzle and alloy substrate, sprays 10 times;
3. ceramic coated transition layer: the NiCrAlY plasma sprayed coating adopting plasma spray coating process to obtain after step (2) continues spraying ZrO
2plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 32NL/min, H
2ventilation flow rate be 12NL/min; Powder feeding air-flow Ar is 3.2NL/min, powder sending quantity 15%; Electric current 550A, power 40kW; The distance 130mm of shower nozzle and alloy substrate, sprays 10 times;
4. prepare low-launch-rate functional layer:
4.1 smelting glass: will ZrO be comprised
2, Al
2o
3, SiO
2, CaO, MgO, B
2o
3frit powder mix, load in platinum crucible, then be placed in retort furnace together, be raised to 1600 DEG C with 20 DEG C/min, insulation 3h, subsequently, the glass melt after fusing is poured in deionized water and carries out quenching, namely obtain required glass;
4.2 pulverize glass: the glass above-mentioned melting obtained carries out ball milling, ball milling carries out in zirconia ball grinding jar, take acetone as ball-milling medium, ratio of grinding media to material is 2: 1, rotating speed is 450r/min, Ball-milling Time is 8h, dries 1h, excessively 400 mesh sieves for 100 DEG C, obtain the glass powder of required particle diameter after ball milling completes;
4.3 batch mixing: by the glass powder after above-mentioned pulverizing and sieving, metal A g powder and the metal Pd powder ratio according to mass ratio 20: 60: 20, batch mixing in planetary gravity mixer, the revolution speed of stirrer is 1460rpm, rotational velocity 30%, and the time is 120min;
4.4 prepare coating: first by tributyl citrate, nitrocellulose and Yelkin TTS according to 80: 5: 15 mass ratio be mixed with organic carrier; Subsequently, by compound obtained in above-mentioned steps 4.3 and organic carrier by 75: 25 mass ratio mix, then grind batch mixing in three-roll grinder, rotating speed is 300r/min, grinding mixing time is 3h, obtains the coating of low infrared emissivity compound coating, and the viscosity of coating is 220Pas;
4.5 preparation coatings: adopt the ZrO that spread coating obtains in step 3
2on plasma sprayed coating, the above-mentioned obtained coating of even brushing, brush 1 time, 30min is dried subsequently at 150 DEG C of temperature, sinter after oven dry, heat-up rate is 20 DEG C/min, sintering temperature 1000 DEG C, sintering time 10min, what obtain the present embodiment subsequently is coated with that the present invention is high temperature resistant, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength (see Fig. 2).
The surface roughness Ra of the low infrared emissivity compound coating that the present embodiment obtains is 1.2 μm, anchoring strength of coating is 17MPa, as shown in Figure 3, test the average emitted rate value of its infrared emittance at 600 DEG C, 800 DEG C, 1000 DEG C respectively, test result is respectively 0.137,0.163 and 0.182.
Embodiment 2:
As shown in Figure 1, it is high temperature resistant that one is coated with the present invention, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength, the low infrared emissivity compound coating comprising alloy base 1 (alloy base adopts 1Cr17 stainless steel substrate) and be coated on alloy base 1, this low infrared emissivity compound coating is multiple-layer stacked structure, multiple-layer stacked structure comprises metal tie coat 2 outward successively by interior, ceramic interlayer 3 and low-launch-rate functional layer 4, wherein, metal tie coat 2 is NiCrAlY plasma sprayed coating, ceramic interlayer 3 is ZrO
2plasma sprayed coating, low-launch-rate functional layer 4 is the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2it is glass coating.The gauge control of metal tie coat 2 is 80 μm, and the gauge control of ceramic interlayer 3 is 80 μm, and the gauge control of low-launch-rate functional layer 4 is 28 μm.At the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2be in glass coating, ZrO
2-Al
2o
3-SiO
2be the mass ratio of glassy phase, metal A g and metal Pd be 15: 65: 20.At ZrO
2-Al
2o
3-SiO
2be that the mass percent of each component in glassy phase is respectively: ZrO
245%; Al
2o
325%; SiO
220%; CaO 5%; MgO 2% and B
2o
33%.
The surface roughness Ra of the metal alloy compositions of the present embodiment is 1.0 μm, the bonding strength of low infrared emissivity compound coating is 22MPa, the tolerable temperature of low infrared emissivity compound coating can reach 1000 DEG C, is less than 0.3 in the average infrared emittance of 3 ~ 5 mu m wavebands.
The preparation method of the metal alloy compositions of the present embodiment, specifically comprises following preparation process:
1. substrate sandblasting: by 1Cr17 stainless steel substrate, carries out sandblasting in sandblast machine, and the processing parameter of sandblasting is respectively: air pressure controls as 5MPa, sandblasting distance 50mm, and sand particle diameter is 80 μm, and blast time is 40min;
2. metallize tie coat: adopt on the 1Cr17 stainless steel substrate of plasma spray coating process after step (1) and spray NiCrAlY plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 30NL/min, H
2ventilation flow rate be 10NL/min; Powder feeding air-flow Ar is 2.5NL/min, powder sending quantity 20%; Electric current 600A, power 40kW; The distance 120mm of shower nozzle and stainless steel substrate, sprays 8 times;
3. ceramic coated transition layer: the NiCrAlY plasma sprayed coating adopting plasma spray coating process to obtain after step (2) continues spraying ZrO
2plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 30NL/min, H
2ventilation flow rate be 10NL/min; Powder feeding air-flow Ar is 2.5NL/min, powder sending quantity 20%; Electric current 600A, power 40kW; The distance 120mm of shower nozzle and stainless steel substrate, sprays 8 times;
4. prepare low-launch-rate functional layer:
4.1 smelting glass: will ZrO be comprised
2, Al
2o
3, SiO
2, CaO, MgO, B
2o
3frit powder mix, load in platinum crucible, then be placed in retort furnace together, be raised to 1800 DEG C with 20 DEG C/min, insulation 3h, subsequently, the glass melt after fusing is poured in deionized water and carries out quenching, namely obtain required glass;
4.2 pulverize glass: the glass above-mentioned melting obtained carries out ball milling, ball milling carries out in zirconia ball grinding jar, take acetone as ball-milling medium, ratio of grinding media to material is 3: 1, rotating speed is 400r/min, Ball-milling Time is 12h, dries 1h, excessively 400 mesh sieves for 100 DEG C, obtain the glass powder of required particle diameter after ball milling completes;
4.3 batch mixing: by the glass powder after above-mentioned pulverizing and sieving, metal A g powder and the metal Pd powder ratio according to mass ratio 15: 65: 20, batch mixing in planetary gravity mixer, the revolution speed of stirrer is 1280rpm, rotational velocity 45%, and the time is 120min;
4.4 prepare coating: first by tributyl citrate, nitrocellulose and Yelkin TTS according to 80: 5: 15 mass ratio be mixed with organic carrier; Subsequently, by compound obtained in above-mentioned steps 4.3 and organic carrier by 80: 20 mass ratio mix, then grind batch mixing in three-roll grinder, rotating speed is 300r/min, grinding mixing time is 3h, obtains the coating of low infrared emissivity compound coating, and the viscosity of coating is 250Pas;
4.5 preparation coatings: adopt the ZrO that spread coating obtains in step 3
2on plasma sprayed coating, the above-mentioned obtained coating of even brushing, brush 2 times, 30min is dried subsequently at 150 DEG C of temperature, sinter after oven dry, heat-up rate is 20 DEG C/min, sintering temperature 1000 DEG C, sintering time 15min, what obtain the present embodiment subsequently is coated with that the present invention is high temperature resistant, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength.
The surface roughness Ra of the low infrared emissivity compound coating that the present embodiment obtains is 1.0 μm, and anchoring strength of coating is 22MPa; Test the average emitted rate value of its infrared emittance at 600 DEG C, 800 DEG C, 1000 DEG C respectively, test result is respectively 0.108,0.145,0.170.
Embodiment 3:
As shown in Figure 1, a kind ofly be coated with that the present invention is high temperature resistant, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength, the low infrared emissivity compound coating comprising alloy base 1 (alloy base adopts 304 steel alloys) and be coated on alloy base 1, this low infrared emissivity compound coating is multiple-layer stacked structure, multiple-layer stacked structure comprises metal tie coat 2, ceramic interlayer 3 and low-launch-rate functional layer 4 outward successively by interior, wherein, metal tie coat 2 is NiCrAlY plasma sprayed coating, and ceramic interlayer 3 is ZrO
2plasma sprayed coating, low-launch-rate functional layer 4 is the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2it is glass coating.The gauge control of metal tie coat 2 is 150 μm, and the gauge control of ceramic interlayer 3 is 100 μm, and the gauge control of low-launch-rate functional layer 4 is 15 μm.At the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2be in glass coating, ZrO
2-Al
2o
3-SiO
2be the mass ratio of glassy phase, metal A g and metal Pd be 15: 65: 20.At ZrO
2-Al
2o
3-SiO
2be that the mass percent of each component in glass is respectively: ZrO
255%; Al
2o
325%; SiO
215%; CaO 2%; MgO 2%; And B
2o
31%.
The surface roughness Ra of the metal alloy compositions of the present embodiment is 1.5 μm, the bonding strength of low infrared emissivity compound coating is 25MPa, the tolerable temperature of low infrared emissivity compound coating can reach 1000 DEG C, is less than 0.3 in the average infrared emittance of 3 ~ 5 mu m wavebands.
The preparation method of the metal alloy compositions of the present embodiment, specifically comprises following preparation process:
1. substrate sandblasting: 304 steel alloy substrates are placed in sandblast machine and carry out sandblasting, the processing parameter of sandblasting is respectively: air pressure controls as 3MPa, sandblasting distance 40mm, and sand particle diameter is 50 μm, and blast time is 30min;
2. metallize tie coat: adopt on the 304 steel alloy substrates of plasma spray coating process after step (1) and spray NiCrAlY plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 30NL/min, H
2ventilation flow rate be 10NL/min; Powder feeding air-flow Ar is 3.2NL/min, powder sending quantity 10%; Electric current 600A, power 50kW; The distance 100mm of shower nozzle and stainless steel substrate, sprays 15 times;
3. ceramic coated transition layer: the NiCrAlY plasma sprayed coating adopting plasma spray coating process to obtain after step (2) continues spraying ZrO
2plasma sprayed coating; The processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 32NL/min, H
2ventilation flow rate be 12NL/min; Powder feeding air-flow Ar is 3.2NL/min, powder sending quantity 15%; Electric current 500A, power 40kW; The distance 130mm of shower nozzle and stainless steel substrate, sprays 10 times;
4. prepare low-launch-rate functional layer:
4.1 smelting glass: will ZrO be comprised
2, Al
2o
3, SiO
2, CaO, MgO, B
2o
3frit powder mix according to the above ratio, load in platinum crucible, then be placed in retort furnace together, be raised to 1600 DEG C with 20 DEG C/min, insulation 1h, subsequently, the glass melt after fusing is poured in deionized water and carries out quenching, namely obtain required glass;
4.2 pulverize glass: the glass above-mentioned melting obtained carries out ball milling, ball milling carries out in zirconia ball grinding jar, take acetone as ball-milling medium, ratio of grinding media to material is 2: 1, rotating speed is 400r/min, Ball-milling Time is 12h, dries 1h, excessively 400 mesh sieves for 100 DEG C, obtain the glass powder of required particle diameter after ball milling completes;
4.3 batch mixing: by the glass powder after above-mentioned pulverizing and sieving, metal A g powder and the metal Pd powder ratio according to mass ratio 15: 65: 20, batch mixing in planetary gravity mixer, the revolution speed of stirrer is 1500rpm, rotational velocity 50%, and the time is 120min;
4.4 prepare coating: first by tributyl citrate, nitrocellulose and Yelkin TTS according to 80: 8: 12 mass ratio be mixed with organic carrier; Subsequently, by compound obtained in above-mentioned steps 4.3 and organic carrier by 80: 20 mass ratio mix, then grind batch mixing in three-roll grinder, rotating speed is 300r/min, grinding mixing time is 3h, obtains the coating of low infrared emissivity compound coating, and the viscosity of coating is 280Pas;
4.5 preparation coatings: adopt the ZrO that spread coating obtains in step 3
2on plasma sprayed coating, the above-mentioned obtained coating of even brushing, brush 1 time, 30min is dried subsequently at 150 DEG C of temperature, sinter after oven dry, heat-up rate is 20 DEG C/min, sintering temperature 1000 DEG C, sintering time 30min, what obtain the present embodiment subsequently is coated with that the present invention is high temperature resistant, the metal alloy compositions of the low infrared emissivity compound coating of high bond strength.
The surface roughness Ra of the low infrared emissivity compound coating that the present embodiment obtains is 1.5 μm, and anchoring strength of coating is 25MPa; Test the average emitted rate value of its infrared emittance at 600 DEG C, 800 DEG C, 1000 DEG C respectively, test result is respectively 0.144,0.162,0.187.
Claims (10)
1. the low infrared emissivity compound coating of high temperature resistant a, high bond strength, described low infrared emissivity compound coating is multiple-layer stacked structure, it is characterized in that: described multiple-layer stacked structure comprises metal tie coat, ceramic interlayer and low-launch-rate functional layer outward successively by interior, wherein, described metal tie coat is NiCrAlY plasma sprayed coating, and described ceramic interlayer is ZrO
2plasma sprayed coating, described low-launch-rate functional layer is the ZrO containing AgPd alloy
2-Al
2o
3-SiO
2it is glass coating.
2. low infrared emissivity compound coating according to claim 1, is characterized in that: the gauge control of described metal tie coat is 50 ~ 150 μm, and the gauge control of described ceramic interlayer is 50 ~ 100 μm.
3. low infrared emissivity compound coating according to claim 1 and 2, is characterized in that: the described ZrO containing AgPd alloy
2-Al
2o
3-SiO
2be in glass coating, ZrO
2-Al
2o
3-SiO
2be the mass ratio of glassy phase, metal A g and metal Pd for (15 ~ 20): (50 ~ 65): (20 ~ 35).
4. low infrared emissivity compound coating according to claim 3, is characterized in that: described ZrO
2-Al
2o
3-SiO
2being the mass percent of each component raw material in glassy phase is:
ZrO
240％～60％；
Al
2O
310％～25％；
SiO
215％～25％；
CaO 2％～5％；
MgO 1% ~ 5%; With
B
2O
31％～6％。
5. one kind is coated with the metal alloy compositions of low infrared emissivity compound coating according to any one of Claims 1 to 4, it is characterized in that: comprise alloy base and be coated in the described low infrared emissivity compound coating on alloy base, the surface roughness Ra of described metal alloy compositions is less than 2.0 μm, the bonding strength of low infrared emissivity compound coating is more than 10MPa, the tolerable temperature of described low infrared emissivity compound coating, more than 1000 DEG C, is less than 0.3 in the average infrared emittance of 3 ~ 5 mu m wavebands.
6. a preparation method for metal alloy compositions as claimed in claim 5, comprises the following steps:
(1) substrate sandblasting: be placed in sandblast machine by needing the alloy base covering low infrared emissivity compound coating and carry out sandblasting;
(2) metallize tie coat: adopt on the alloy base of plasma spray coating process after step (1) and spray NiCrAlY plasma sprayed coating;
(3) ceramic coated transition layer: the NiCrAlY plasma sprayed coating adopting plasma spray coating process to obtain after step (2) continues spraying ZrO
2plasma sprayed coating;
(4) low-launch-rate functional layer is prepared: obtained glass powder is mixed obtained coating with metal A g, metal Pd, then adopts spread coating or silk screen print method, evenly brush coating or be printed on the ZrO obtained in step (3)
2on plasma sprayed coating, after drying, sintering, namely obtain finished product.
7. preparation method according to claim 6, is characterized in that, in described step (2) and step (3), the processing parameter condition of plasma spray coating process comprises: the ventilation flow rate of Ar is 20 ~ 40NL/min, H
2ventilation flow rate be 8 ~ 12NL/min; Powder feeding air-flow Ar is 2.5 ~ 3.2NL/min, powder sending quantity 10% ~ 30%; It is 500 ~ 600A that size of current controls, and power is 30 ~ 50kW; The distance of shower nozzle and substrate is 100 ~ 150mm.
8. preparation method according to claim 6, is characterized in that, the preparation of described glass powder specifically comprises the following steps: will comprise ZrO
2, Al
2o
3, SiO
2, CaO, MgO, B
2o
3frit powder mix in massfraction ratio, then be placed in retort furnace and carry out high melt, the glass melt after fusing is poured in deionized water and carries out quenching, the glass obtained is carried out ball milling, dry, sieve, obtain glass powder;
The process regulation of described high melt process comprises: smelting temperature is 1600 DEG C ~ 1800 DEG C, and melting soaking time is 1h ~ 3h; Described ball milling carries out in zirconia ball grinding jar, take acetone as ball-milling medium, and ratio of grinding media to material is (2 ~ 3): 1, and rotational speed of ball-mill is 380r/min ~ 450r/min, and Ball-milling Time is 6h ~ 12h; Described sieving referred to 200 order ~ 400 mesh sieves; Described glass powder and metal A g, metal Pd mix in planetary gravity mixer, and the processing parameter of described planetary gravity stirrer comprises: revolution speed 1280rpm ~ 1500rpm, and rotational velocity is 30% ~ 60%, churning time 60 ~ 120min.
9. the preparation method according to any one of claim 6 ~ 8, it is characterized in that, the preparation of described coating is mixed by three-roll grinder with organic carrier by the compound of glass powder and metal A g, metal Pd again, wherein the massfraction of compound accounts for 75% ~ 80%, and the massfraction of organic carrier accounts for 25% ~ 20%;
Described organic carrier is primarily of tributyl citrate, nitrocellulose and Yelkin TTS composition, and the mass percent of three in organic carrier is respectively:
Tributyl citrate 70% ~ 80%;
Nitrocellulose 2% ~ 10%;
Yelkin TTS 10% ~ 20%;
The viscosity controller of the coating prepared is 170 ~ 300Pas.
10. the preparation method according to any one of claim 6 ~ 8, is characterized in that, sintering temperature during described sintering is 1000 DEG C ~ 1050 DEG C, heat-up rate is 15 DEG C/and min ~ 20 DEG C/min, sintering time is 10min ~ 60min.
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