CN108118285A - Improve low temperature aluminizing agent, method and the material of high temperature resistance steam oxidation performance - Google Patents
Improve low temperature aluminizing agent, method and the material of high temperature resistance steam oxidation performance Download PDFInfo
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- CN108118285A CN108118285A CN201711480614.4A CN201711480614A CN108118285A CN 108118285 A CN108118285 A CN 108118285A CN 201711480614 A CN201711480614 A CN 201711480614A CN 108118285 A CN108118285 A CN 108118285A
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- high temperature
- aluminizing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
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Abstract
The invention discloses a kind of low temperature aluminizing agent, method and materials for improving material high temperature resistance steam oxidation performance, are made of iron aluminium powder (FeAl) or aluminium, activator, energizer etc..In the qualified header product of inner surface cleaning, the Paste aluminising agent of this aluminizing medium or brushing being filled, aluminising is carried out at 600 780 DEG C, 2 20h of time need not prepare single FeAl phase aluminized coatings through high temperature diffusion annealing, a step, and without Fe2Al5Etc. other brittlement phases.The aluminising sample of preparation has excellent steam-resistant oxidation susceptibility.The present invention is the hypotonic aluminum technology of temperature under the conditions of base material mechanical property is not influenced using iron aluminium powder (FeAl) or aluminium powder as a kind of technique of main penetration enhancer.Header high-temperature oxidation resistance can be effectively improved, to ensure the safe operation of boiler, is prolonged the service life, is a kind of reasonable in economy, technically feasible technical solution.
Description
Technical field
The present invention relates to field of boilers.
Background technology
At present, the installed capacity of China's super (super-) critical unit and production technology have reached advanced international standard, but such as
Fruit requirement further improves the generating efficiency of super (super-) critical unit, will be more to the material requirements involved by generating equipment
It is harsh.
The raising of generating efficiency, it is meant that higher high-temperature water vapor parameter, inevitable requirement material have more preferably anti-height
Heated steam oxidation susceptibility otherwise when long under the conditions of operation, easily causes material at high temperature creep life to reduce, scale spallation
It the problems such as aggravation or even can therefore lead to problems such as booster, seriously affect the reliability of unit operation, especially high temperature reheating collection
Case and tube socket region.
Based on header material common at present, such as T/P91, T/P92 and G115, in 620 DEG C or more water steam medium rings
Border, the antioxygenic property Shortcomings of material in itself.Common surface oxidation guard technology, such as laser melting coating, thermal spraying, chromising
The service requirement or since header reasons in structure can not be implemented when that can not meet long.
The content of the invention
It is an object of the invention to：It proposes a kind of low temperature aluminizing agent for improving material high temperature resistance steam oxidation performance, oozes
The material of aluminium method and high temperature resistance steam oxidation effectively improves header etc. and is used in high-temperature water vapor media environment material
High-temperature oxidation resistance, to ensure the safe operation of the products such as boiler, prolong the service life, and scheme reasonable in economy, skill
It is feasible in art, especially suitable for super (super-) critical unit header, in 620 DEG C or more water steam medium environment.
The purpose of the present invention is realized by following technical proposals：
A kind of low temperature aluminizing agent for improving material high temperature resistance steam oxidation performance, each component and its weight percent are：
Iron aluminium powder：95%-98% or aluminium+alundum (Al2O3), wherein aluminium：33%-70%, alundum (Al2O3)：23%-
60%；
Activator：1%-5%；
Energizer：0%-2%.
Alternatively, low temperature aluminizing agent each component and its weight percent are：Iron aluminium powder：95%-97% or aluminium+three
Al 2 O, wherein aluminium：40%-70%, alundum (Al2O3)：23%-50%；
Activator：1%-4%；
Energizer：1%-2%.
As further selection, low temperature aluminizing agent each component and its weight percent are：Iron aluminium powder：95%-96% or
Aluminium+alundum (Al2O3), wherein aluminium：50%-70%, alundum (Al2O3)：23%-40%；
Activator：2%-3%；
Energizer：1%-2%.
Alternatively, low temperature aluminizing agent each component and its weight percent are：Iron aluminium powder：95%-98% or aluminium+three
Al 2 O, wherein aluminium：35%-40%, alundum (Al2O3)：55%-60%；
Activator：4%-5%；
Energizer：1%-2%.
Alternatively, iron aluminium powder, aluminium powder, aluminium oxide are 50-300 mesh powder shape particles, and activator is selected from ammonium chloride, fluorine
Change the one or more in ammonium, prodan, potassium fluosilicate, energizer is selected from the oxide or chloride of rare earth.
As further selection, rare earth element is lanthanum, yttrium.
A kind of high temperature resistance steam oxidation material prepared using foregoing low temperature aluminizing agent, including material matrix, Yi Jicai
Expect the aluminized coating of matrix surface, aluminized coating is the non-brittle phases of FeAl, and aluminized coating includes ferroalloy parts and diffusion layer, ferroaluminium
The thickness of layer is 3 μm~80 μm, and the thickness of diffusion layer is 1 μm~30 μm.
Alternatively, high temperature resistance steam oxidation material can be resistant to 660 DEG C or more of steam oxidation corrosion.
Alternatively, basis material is 9Cr steel, TP347 stainless steels or S30432 stainless steels.
As further selection, basis material T/P91, T/P92 or G115 header, aluminized coating is arranged on collection chamber interior wall.
A kind of method that low temperature aluminizing is carried out using foregoing low temperature aluminizing agent, is especially made foregoing high temperature resistance steam oxidation
The aluminizing method of material, comprises the following steps successively：
1) substrate pretreatment：Substrate material surface is cleared up, removes foreign matter；Chemical cleaning, interior boring processing can be used
Or the effective measures such as shot blastinog.
2) aluminising：
A) aluminizing medium is prepared：It is sufficiently mixed uniformly according to composition；
B) aluminizing medium is filled：Uniformly mixed aluminizing medium is filled in the surface or add in viscous that basis material is processed
Agent is tied, the surface being processed after mixing in the form of slurry coated on basis material, and encapsulation process；
C) aluminising is spread：To fill the basis material that finishes of aluminizing medium be placed in 600-780 DEG C (preferably 650-700 DEG C, it is more excellent
Select 660-690 DEG C) under keep the temperature 2-20h (preferably 4-20h, more preferable 6-10h), after heat preservation, cool to room temperature with the furnace, refer to
Shown in Figure 10；
3) post-process：Aluminising DIFFUSION TREATMENT finishes, and removes basis material aluminizing medium.
The foregoing main solution of the present invention and further alternatives thereof can be freely combined to form multiple schemes, be this
Invent the scheme that can be used and be claimed；And the present invention selects it between (each non conflicting selection) selection and with other
Between can also be freely combined.Those skilled in the art can understand after the present invention program is understood according to the prior art and common knowledge
There are many combinations, are the claimed technical solution of the present invention, do not do exhaustion herein.
Beneficial effects of the present invention：By slurry or powder embedding techniques, in substrate material surface (such as table in header
Face) complete, fine and close ferroaluminium aluminized coating is formed, which not only has excellent high-temperature resistant water steam oxidation, heat resistance
Can, at the same have the characteristics that it is not easy to crack, be not easy to peel off.High-temperature water vapor media environment material surface is used in for slowing down
The high temperature water vapor oxidation of (such as header and inner-walls of duct) prolongs the service life, improves generating efficiency aspect with extensive/bright
Aobvious economic benefit and social benefit.
Although in the prior art there are aluminizing technology, low temperature aluminizing method of the present invention can be located at low temperature
Reason, more than 800 DEG C minimum less than the prior art, usual 900 DEG C even 1000 DEG C or more of high-temperature process need not more expand through high temperature
Dissipate annealing, can a step obtain single-phase FeAl infiltration layers, and without other brittlement phases such as Fe2Al5.The aluminising workpiece of preparation has excellent
Steam-resistant oxidation susceptibility.
The low temperature aluminizing technical characterstic of the present invention is：Aluminising temperature is low, does not influence substrate performance, infiltration layer is uniformly and without crisp
Phase constitution because aluminized coating has excellent high temperature resistance steam oxidation performance, resists so as to reach the raising materials such as header and tube socket
Oxidation susceptibility and the purpose to prolong the service life.At the same time, the component of penetration enhancer is simple, material source enriches, good economy performance and
It is easy to get, the cost of aluminising can be reduced.The preparation process of penetration enhancer is simple and practicable, and the materials such as header and tube socket are remarkably improved for one kind
The technique for expecting high temperature resistance steam oxidation.
Description of the drawings
Fig. 1 is the aluminized coating thickness chart of the embodiment of the present invention 1；
Fig. 2 is the object phase composition figure of the aluminized coating of the embodiment of the present invention 1；
Fig. 3 is the high temperature water vapor oxidation power of the non-aluminisings of G115 and aluminising sample of the embodiment of the present invention 1 at 660 DEG C
Learn graph；
Fig. 4 is the aluminized coating thickness chart of the embodiment of the present invention 2；
Fig. 5 is the object phase composition figure of the aluminized coating of the embodiment of the present invention 2；
Fig. 6 is the high temperature water vapor oxidation power of the non-aluminisings of G115 and aluminising sample of the embodiment of the present invention 2 at 660 DEG C
Learn graph；
Fig. 7 is the aluminized coating thickness chart of the embodiment of the present invention 3；
Fig. 8 is the object phase composition figure of the aluminized coating of the embodiment of the present invention 3；
Fig. 9 is the high temperature water vapor oxidation power of the non-aluminisings of G115 and aluminising sample of the embodiment of the present invention 3 at 660 DEG C
Learn graph；
Figure 10 is the low temperature aluminizing thermal diffusion curve of the present invention.
Specific embodiment
With reference to specific embodiments and the drawings, the present invention is further illustrated.
Embodiment 1：
1st, in percentage by weight, aluminizing medium includes following component：Aluminium 35%；Ammonium chloride 4%；Alundum (Al2O3)
60%；Yttrium oxide 1%.
2nd, after aluminizing medium is sufficiently mixed in proportion uniformly, using powder investment, aluminising processing is carried out in atmosphere furnace.
Be heated to 660-690 DEG C heat preservation 6 it is small when, then cool to room temperature with the furnace.
3rd, handling result：It it is about 24 μm through treated G115 headers aluminized coating alloying layer thickness, as shown in Figure 1；It oozes
Aluminium layer is FeAl phases, as shown in Figure 2.
4th, treated that G115 samples are placed in 660 DEG C of high-temperature water vapor rings for aluminising formula and alumetizing process using the present invention
When oxidation 2000 is small in border, sample weightening is very slight, and weightening is significantly lower than 660 DEG C of non-aluminising samples.Infiltration layer uniformly and nothing
Crisp phase constitution, as shown in Figure 2.As shown in figure 3, show that aluminized coating has excellent high temperature resistance steam oxidation performance.
5th, aluminized coating under high temperature, high-pressure water vapor environment can in-situ preparation is fine and close, complete aluminum oxide film, the oxidation
Aluminium film can effectively stop that the corrosive mediums such as water vapour and active oxygen atom are spread to metal base, while also can effectively inhibit gold
The iron atom belonged in base material outwards diffuses to form oxide.Therefore, preparation-aluminized coating have excellent high temperature resistance water vapour oxygen
Change performance.Simultaneously because aluminum oxide film physical state in high-temperature water vapor environment is stablized, aluminized coating is in hot conditions in addition
Under be capable of providing enough silicon sources, ensure that aluminized coating the long-acting service life and it is long when high temperature resistance steam oxidation performance.
Embodiment 2：
1st, in percentage by weight, aluminizing medium includes following component：Aluminium 40%；Ammonium fluoride 4%；Alundum (Al2O3)
55%；Yttrium oxide 1%.
2nd, after aluminizing medium is sufficiently mixed in proportion uniformly, using powder investment, aluminising processing is carried out in atmosphere furnace.
Be heated to 660-690 DEG C heat preservation 6 it is small when, then cool to room temperature with the furnace.
3rd, handling result：It it is about 28 μm through treated G115 headers aluminized coating alloying layer thickness, as shown in Figure 4；It oozes
Aluminium layer is FeAl phases, as shown in Figure 5.
4th, treated that G115 samples are placed in 660 DEG C of high-temperature water vapor rings for aluminising formula and alumetizing process using the present invention
When oxidation 2000 is small in border, sample weightening is very slight, and weightening is significantly lower than 660 DEG C of non-aluminising samples.Infiltration layer uniformly and nothing
Crisp phase constitution, as shown in Figure 5.As shown in fig. 6, show that aluminized coating has excellent high temperature resistance steam oxidation performance.
Embodiment 3：
1st, in percentage by weight, aluminizing medium includes following component：Aluminium 35%；Ammonium chloride 5%；Alundum (Al2O3)
59%；Aoxidize billows 1%.
2nd, after aluminizing medium is sufficiently mixed in proportion uniformly, using powder investment, aluminising processing is carried out in atmosphere furnace.
Be heated to 660-690 DEG C heat preservation 6 it is small when, then cool to room temperature with the furnace.
3rd, handling result：It it is about 36 μm through treated G115 headers aluminized coating alloying layer thickness, as shown in Figure 7；It oozes
Aluminium layer is FeAl phases, as shown in Figure 8.
4th, treated that G115 samples are placed in 660 DEG C of high-temperature water vapor rings for aluminising formula and alumetizing process using the present invention
When oxidation 2000 is small in border, sample weightening is very slight, and weightening is significantly lower than 660 DEG C of non-aluminising samples.Infiltration layer uniformly and nothing
Crisp phase constitution, as shown in Figure 8.As shown in figure 9, show that aluminized coating has excellent high temperature resistance steam oxidation performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of low temperature aluminizing agent for improving material high temperature resistance steam oxidation performance, it is characterised in that each component and its weight hundred
Point ratio is：
Iron aluminium powder：95%-98% or aluminium+alundum (Al2O3), wherein aluminium：33%-70%, alundum (Al2O3)：23%-60%；
Activator：1%-5%；
Energizer：0%-2%.
2. the low temperature aluminizing agent of material high temperature resistance steam oxidation performance is improved as described in claim 1, it is characterised in that each
Component and its weight percent are：
Iron aluminium powder：95%-97% or aluminium+alundum (Al2O3), wherein aluminium：40%-70%, alundum (Al2O3)：23%-50%；
Activator：1%-4%；
Energizer：1%-2%.
3. the low temperature aluminizing agent of material high temperature resistance steam oxidation performance is improved as claimed in claim 2, it is characterised in that each
Component and its weight percent are：
Iron aluminium powder：95%-96% or aluminium+alundum (Al2O3), wherein aluminium：50%-70%, alundum (Al2O3)：23%-40%；
Activator：2%-3%；
Energizer：1%-2%.
4. the low temperature aluminizing agent of the raising material high temperature resistance steam oxidation performance as described in claim 1,2 or 3, feature exist
In：Iron aluminium powder, aluminium powder, aluminium oxide be 50-300 mesh powder shape particles, activator be selected from ammonium chloride, ammonium fluoride, prodan,
One or more in potassium fluosilicate, energizer are selected from the oxide or chloride of rare earth.
5. the low temperature aluminizing agent of material high temperature resistance steam oxidation performance is improved as claimed in claim 4, it is characterised in that：It is dilute
Earth elements are lanthanum, yttrium.
6. a kind of high temperature resistance water vapour prepared by low temperature aluminizing agent using as described in any claim in claim 1-5
Oxidation material, it is characterised in that：Aluminized coating including material matrix and material matrix surface, aluminized coating are non-brittle for FeAl
Phase, aluminized coating include ferroalloy parts and diffusion layer, and the thickness of ferroalloy parts is 3 μm~80 μm, and the thickness of diffusion layer is 1 μm
~30 μm.
7. high temperature resistance steam oxidation material as claimed in claim 6, it is characterised in that：High temperature resistance steam oxidation material energy
Steam oxidation corrosion resistance to 660 DEG C or more enough.
8. high temperature resistance steam oxidation material as claimed in claim 6, it is characterised in that：Basis material is 9Cr steel, TP347
Stainless steel or S30432 stainless steels.
9. high temperature resistance steam oxidation material as claimed in claim 8, it is characterised in that：Basis material is T/P91, T/P92
Or G115 headers, aluminized coating are arranged on collection chamber interior wall.
10. a kind of low temperature aluminizing agent using as described in any claim in claim 1-5 carries out the side of low temperature aluminizing
Method, it is characterised in that comprise the following steps successively：
1) substrate pretreatment：Substrate material surface is cleared up, removes foreign matter；
2) aluminising：
A) aluminizing medium is prepared：It is sufficiently mixed uniformly according to composition；
B) aluminizing medium is filled：Uniformly mixed aluminizing medium is filled in surface or the addition bonding that basis material is processed
Agent, the surface being processed after mixing in the form of slurry coated on basis material, and encapsulation process；
C) aluminising is spread：The basis material that filling aluminizing medium finishes is placed at 600-780 DEG C and keeps the temperature 2-20h, after heat preservation,
Cool to room temperature with the furnace；
3) post-process：Aluminising DIFFUSION TREATMENT finishes, and removes basis material aluminizing medium.
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| CN109023363A (en) * | 2018-07-16 | 2018-12-18 | 北京科技大学 | A kind of ferroaluminium adhesive layer/compound hydrogen resistance coating of zirconium oxide layer and preparation method thereof |
| CN109735798A (en) * | 2019-01-17 | 2019-05-10 | 长沙理工大学 | The excellent modification austenitic stainless steel and preparation method thereof of high temperature creep resistance |
| CN109881196A (en) * | 2019-04-11 | 2019-06-14 | 华能国际电力股份有限公司 | A kind of main steam line and preparation method thereof comprising inner wall antioxidant coating |
| CN109913795A (en) * | 2019-04-17 | 2019-06-21 | 华能国际电力股份有限公司 | The effective austenitic heat-resistance steel of boiler and its surface chemical heat-treatment process |
| CN110218969A (en) * | 2019-07-16 | 2019-09-10 | 合肥工业大学 | A kind of preparation method of 316L stainless steel surface Y2O3 modified aluminide resistance tritium coating |
| CN111926284A (en) * | 2020-07-30 | 2020-11-13 | 西安热工研究院有限公司 | Steam turbine high-medium pressure inner cylinder steam oxidation resistant coating and preparation method thereof |
| CN114622156A (en) * | 2022-03-01 | 2022-06-14 | 中国原子能科学研究院 | Stainless steel surface composite coating and preparation method thereof |
| CN117107192A (en) * | 2023-08-15 | 2023-11-24 | 中国航发贵州黎阳航空动力有限公司 | Preparation method of GH4698 superalloy surface aluminizing protective coating |
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|---|---|---|---|---|
| CN109023363A (en) * | 2018-07-16 | 2018-12-18 | 北京科技大学 | A kind of ferroaluminium adhesive layer/compound hydrogen resistance coating of zirconium oxide layer and preparation method thereof |
| CN109735798B (en) * | 2019-01-17 | 2020-08-07 | 长沙理工大学 | Modified austenitic stainless steel with excellent high-temperature creep resistance and preparation method thereof |
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| CN109881196A (en) * | 2019-04-11 | 2019-06-14 | 华能国际电力股份有限公司 | A kind of main steam line and preparation method thereof comprising inner wall antioxidant coating |
| CN109881196B (en) * | 2019-04-11 | 2021-05-04 | 华能国际电力股份有限公司 | Main steam pipeline with inner wall anti-oxidation coating and preparation method thereof |
| CN109913795A (en) * | 2019-04-17 | 2019-06-21 | 华能国际电力股份有限公司 | The effective austenitic heat-resistance steel of boiler and its surface chemical heat-treatment process |
| CN110218969A (en) * | 2019-07-16 | 2019-09-10 | 合肥工业大学 | A kind of preparation method of 316L stainless steel surface Y2O3 modified aluminide resistance tritium coating |
| CN111926284A (en) * | 2020-07-30 | 2020-11-13 | 西安热工研究院有限公司 | Steam turbine high-medium pressure inner cylinder steam oxidation resistant coating and preparation method thereof |
| CN111926284B (en) * | 2020-07-30 | 2022-09-09 | 西安热工研究院有限公司 | Steam turbine high-medium pressure inner cylinder steam oxidation resistant coating and preparation method thereof |
| CN114622156A (en) * | 2022-03-01 | 2022-06-14 | 中国原子能科学研究院 | Stainless steel surface composite coating and preparation method thereof |
| CN114622156B (en) * | 2022-03-01 | 2023-09-29 | 中国原子能科学研究院 | Stainless steel surface composite coating and preparation method thereof |
| CN117107192A (en) * | 2023-08-15 | 2023-11-24 | 中国航发贵州黎阳航空动力有限公司 | Preparation method of GH4698 superalloy surface aluminizing protective coating |
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Application publication date: 20180605 |