CN109190311A - Austenite heat-resistant steel oxide film peeling prediction model for ultra-supercritical thermal power generating unit - Google Patents
Austenite heat-resistant steel oxide film peeling prediction model for ultra-supercritical thermal power generating unit Download PDFInfo
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- CN109190311A CN109190311A CN201811269929.9A CN201811269929A CN109190311A CN 109190311 A CN109190311 A CN 109190311A CN 201811269929 A CN201811269929 A CN 201811269929A CN 109190311 A CN109190311 A CN 109190311A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 23
- 239000010959 steel Substances 0.000 title claims abstract description 23
- 229910001566 austenite Inorganic materials 0.000 title claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 230000007547 defect Effects 0.000 claims abstract description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008859 change Effects 0.000 claims abstract description 8
- 230000008646 thermal stress Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000004901 spalling Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000004088 simulation Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 5
- 229910003430 FeCr2O4 Inorganic materials 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000006399 behavior Effects 0.000 description 15
- 230000006872 improvement Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000009659 non-destructive testing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001983 electron spin resonance imaging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F30/00—Computer-aided design [CAD]
- G06F30/20—Design optimisation, verification or simulation
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- General Physics & Mathematics (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
An austenite heat-resistant steel oxide film peeling prediction model for an ultra-supercritical thermal power generating unit is characterized in that a double-layer oxide film is formed on the surface of an alloy in a service process, and an inner layer is FeCr2O4And the outer layer is Fe3O4And the ratio of the interface defect interval l of the double-layer oxide film to the size a meets the following condition: l/a is more than or equal to 0.2 and less than or equal to 6, and the peeling behavior of the oxide film under the action of different thermal stresses is predicted through the change curve of the critical temperature difference along with l/a. The method can predict the peeling behavior of the double-layer oxide film formed on the surface of the alloy by aiming at the size and distribution observation results of the interface defects of the conventional material for the superheater/reheater of the 600-DEG C ultra-supercritical thermal power generating unit in the service process.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of ultra supercritical coal-fired unit austenitic heat-resistance steel oxidation film stripping
Fall prediction model.
Background technique
Ultra supercritical coal-fired unit (USC) has many advantages, such as high efficiency, low energy consumption, low emission, has become at present both at home and abroad
The inexorable trend of thermal power industry development.With the popularization of USC technology, thermal power unit boiler steam parameter is significantly improved, into
And high requirement is proposed to the performance of boiler critical component material.Wherein, Superheater/Reheater is working environment in boiler
Component the most severe, the shadow by factors such as high temperature water vapor oxidation, flue gas corrosion, creeps for a long time in operational process
It rings.Therefore, the ferritic heat-resistant steel with TP91, TP92 etc. for representative has gradually been unable to satisfy Superheater/Reheater pipeline to material
Expect the requirement of performance.Currently, USC Superheater/Reheater more than domestic and international 600 DEG C of grades be widely used TP304H,
The 18-8 series austenite heat resisting steel such as TP347H.Compared with ferritic steel, austenitic heat-resistance steel has more excellent high-temperature and durable
Intensity and antioxygenic property.However, since the thermal expansion coefficient of austenitic steel heat resisting steel is significantly higher compared with oxidation film, because
This will generate biggish compression inside oxidation film in cooling procedure, and leading to it, scale spallation phenomenon is very during service
Seriously.Wherein, scale spallation leads to line clogging, in turn results in pipeline overheating operation even booster phenomenon and has become influence machine
One of the main reason of group safe and stable operation, such as only Guangdong Province 2008-2012 600MW and the above ultra supercritical thermoelectricity
Booster caused by unit is blocked due to scale spallation is as high as 23 times, and causing economic loss is more than 4.6 hundred million yuan.In addition, stripping
Fall oxide skin size it is smaller when will be flowed with steam and Steam-water Quality is caused to deteriorate, while cause turbine blade erosive wear,
The problems such as main inlet throttle-stop valve bite.As it can be seen that studying the peeling behavior of austenitic heat-resistance steel surface scale and improving it on this basis
Antistrip performance has great importance.
Since oxidation film and matrix thermal expansion coefficient mismatch, the behaviors such as boiler varying duty during service or start and stop are equal
It will lead to and generate biggish thermal stress inside oxidation film, in turn result in its cracking and peel off.EPRI is summarizing abundant experimental results
On the basis of establish the relational model of oxide thickness and elastic strain, as a result, it has been found that being lured with the increase of oxide thickness
It sends out it and cracks and peel off required minimum elastic strain and reduce.Due to this model can for boiler superheater or reheater etc. by
Heat pipe material scale spallation behavior predicted, because due to be widely used in safe operation of power plant assessment.According to the prediction mould
Type, oxide thickness is thinner, then elastic strain needed for leading to its cracking is higher, and the anti-strip ability of oxidation film is also better.Cause
This mainly uses novel alloy (TP347HFG, Super304H) and surface for the peeling for inhibiting oxidation film both at home and abroad at present
The methods of processing (cold working, shot-peening), by inhibiting the speed of growth of oxidation film to improve its bond strength with matrix.So
And people have found that Superheater/Reheater tubing reaches after a certain period of time in military service in subsequent research, the oxygen that surface is formed
There are large number of orifices hole defects in change film.Studies have shown that the defect generated inside oxidation film is for its opening under thermal stress effect
Mode is split with significantly affecting, this is because crackle needs to overcome surface needed for generating new surface in germinating and expansion process
Can, and inside oxidation film or the germinating for existing for crackle of itself and defect at basal body interface and extension provide convenient way.Closely
Nian Lai cracks to oxidation film about defect and starts the concern by foreign scholar with the influence of the behavior of peeling.However, at present about
There is not been reported for research in terms of the Fatigue crack initiation mechanism of the oxidation film of multilayer containing defect.For 600 DEG C of grade ultra supercriticals
Unit Superheater/Reheater material, oxidation film has the double-deck knot to most widely used austenitic heat-resistance steel during service now
Structure, and defect has the characteristics that be enriched in double layer oxide film inner boundary, and this has its oxidation film cracking and peeling behavior
Effect prediction proposes new challenge.
Summary of the invention
It is an object of the invention to solve the problems of the prior art, a kind of ultra supercritical coal-fired unit austenite is proposed
Heat resisting steel spalling of oxide film prediction model, the model are normal for current 600 DEG C of grades ultra supercritical coal-fired unit Superheater/Reheater
The size of boundary defect and distribution observation during military service with material (TP304H, TP347H, Super304H, TP347HFG)
It is predicted as a result, it is possible to peel off behavior to the double layer oxide film that alloy surface is formed.
To achieve the above object, the present invention adopts the following technical scheme that:
Ultra supercritical coal-fired unit austenitic heat-resistance steel spalling of oxide film prediction model, alloy surface during military service
Form double layer oxide film, internal layer FeCr2O4And outer layer is Fe3O4, and double layer oxide film boundary defect spacing l and size a it
Than meeting following condition: 0.2≤l/a≤6, then predict that oxidation film is answered in different heat with the change curve of l/a by critical temperature difference
Peeling behavior under power effect.
A further improvement of the present invention lies in that the service temperature of alloy is 600~650 DEG C, steam rates are no more than
2500 ton/hours, dissolved oxygen content is no more than 5ppm.
A further improvement of the present invention lies in that alloying component meets Cr constituent content is no more than 20% by mass percentage,
And alloy substrate is single austenite structure.
A further improvement of the present invention lies in that the thickness of double layer oxide film is not less than 5 microns.
A further improvement of the present invention lies in that double layer oxide film boundary defect size is no more than 200nm.
A further improvement of the present invention lies in that critical temperature difference is calculated with the change curve of l/a by ANSYS simulation softward
It arrives.
Compared with prior art, the invention has the benefit that
Models coupling actual observation of the invention is as a result, mainly investigated when defect is present in double layer oxide film interface to oxygen
Changing caused by skin peels off influences.Oxidation film internal structure is more coincide during this model and the practical oxidation of alloy, can be right
The peeling behavior of oxidation film is effectively predicted.The present invention is directed to current 600 DEG C of grades ultra supercritical coal-fired unit superheater/reheating
The size and distribution of device common used material (TP304H, TP347H, Super304H, TP347HFG) boundary defect during military service
Observation is predicted as a result, it is possible to peel off behavior to the double layer oxide film that alloy surface is formed, and is suitable for ultra supercritical thermal motor
Group superheater, the critical components such as reheater austenitic heat-resistance steel spalling of oxide film behavior prediction during one's term of military service.
Detailed description of the invention
Fig. 1 is figure of changing of the multiple hole double layer oxide film model critical temperature difference VT with l/a.
Fig. 2 is alloy surface Oxide Film Surface Appearance after Super304H alloy oxidation, wherein A FeCr2O4, B Fe3O4。
Specific embodiment
The present invention is suitable for the austenitic heat-resistance steel being on active service under ultra supercritical water vapor conditions for a long time, and surface is being on active service
Double layer oxide film is formed in the process, and there are hole defects at double layer oxide film interface.
It is 600~650 DEG C by service temperature, steam rates are no more than 2500 ton/hours, and dissolved oxygen content is no more than
The alloy of 5ppm, alloy surface during military service form double layer oxide film, internal layer FeCr2O4And outer layer is Fe3O4, double-deck
The thickness of oxidation film is not less than 5 microns, and double layer oxide film boundary defect size is no more than 200nm, defect spacing l and size a
The ratio between meet following condition: 0.2≤l/a≤6, then can by critical temperature difference with l/a change curve predict oxidation film exist
Peeling behavior under different thermal stress (temperature drop) effects.Wherein, Fig. 1 is change curve of the critical temperature difference with l/a, the variation
Curve negotiating ANSYS simulation softward is calculated.
Alloying component meets Cr constituent content and is no more than 20% by mass percentage, and alloy substrate is single austenite group
It knits.
It will appreciate that austenitic heat-resistance steel scale spallation rule, optimization fired power generating unit Maintenance and Repair week through the invention
Phase.It is described in detail with reference to the accompanying drawing by specific embodiment.
Embodiment 1
The present embodiment selects Super304H as test material, and steam oxidation experiment condition is temperature: 620 DEG C, dissolved oxygen
Content: 5ppm, steam flow rate: 0mL/min, steam oxidation time: 600 hours.
1) double layer oxide film thickness and boundary defect observation: alloy surface after oxidation is aoxidized using transmission electron microscope
Film pattern is observed, as shown in Figure 2.As a result, it has been found that by internal layer FeCr after alloy oxidation2O4And outer layer Fe3O4It constitutes, oxidation film
Thickness is respectively 12 microns and 15 microns.Interface void size is about 150~180nm, and alloy l/a value is 3.5 at this time
In~4.5 ranges, from figure 1 it appears that critical-temperature needed for spalling of oxide film is about 390~420 under this condition
℃。
2) double layer oxide film peels off behavior monitoring: being surveyed using sound emission non-destructive testing technology to spalling of oxide film behavior
Fixed, setting threshold value is 30dB.As a result, it has been found that occurring the sound emission letter of spalling of oxide film generation after 2900 seconds after starting cooling
Number, fire box temperature fall off rate is compared, determines that the corresponding temperature range of decrease is 405 DEG C at this time, coincide with model prediction result of the present invention.
Embodiment 2
The present embodiment selects TP347HFG as test material, and steam oxidation experiment condition is temperature: 650 DEG C, dissolved oxygen
Content: 5ppm, steam flow rate: 100mL/min, steam oxidation time: 400 hours.
1) double layer oxide film thickness and boundary defect observation: using scanning and transmission electron microscope to alloy table after oxidation
Surface oxidation film pattern is observed, by internal layer FeCr after discovery alloy oxidation2O4And outer layer Fe3O4It constitutes, oxide thickness difference
For 18 microns and 30 microns.Interface void size is about 140~190nm, and four kinds of alloy l/a values are in 4~5.5 ranges at this time
It is interior.It is compared with ANSYS about the model of spalling of oxide film, is shown critical needed for spalling of oxide film under this condition
Temperature is about 300~350 DEG C.
2) double layer oxide film peels off behavior monitoring: being surveyed using sound emission non-destructive testing technology to spalling of oxide film behavior
Fixed, setting threshold value is 30dB.As a result, it has been found that occurring the sound emission letter of spalling of oxide film generation after 2000 seconds after starting cooling
Number, fire box temperature fall off rate is compared, determines that the corresponding temperature range of decrease is 360 DEG C at this time, with model prediction result base of the invention
This coincide.
Claims (6)
1. ultra supercritical coal-fired unit austenitic heat-resistance steel spalling of oxide film prediction model, it is characterised in that: alloy is being on active service
Surface forms double layer oxide film, internal layer FeCr in the process2O4And outer layer is Fe3O4, and double layer oxide film boundary defect spacing
The ratio between l and size a meet following condition: 0.2≤l/a≤6, then predict oxidation film with the change curve of l/a by critical temperature difference
Peeling behavior under the effect of different thermal stress.
2. ultra supercritical coal-fired unit according to claim 1 austenitic heat-resistance steel spalling of oxide film prediction model,
Be characterized in that: the service temperature of alloy is 600~650oC, and steam rates are no more than 2500 ton/hours, and dissolved oxygen content is not
More than 5ppm.
3. ultra supercritical coal-fired unit according to claim 1 austenitic heat-resistance steel spalling of oxide film prediction model,
Be characterized in that: alloying component meets Cr constituent content and is no more than 20% by mass percentage, and alloy substrate is single austenite
Tissue.
4. ultra supercritical coal-fired unit according to claim 1 austenitic heat-resistance steel spalling of oxide film prediction model,
Be characterized in that: the thickness of double layer oxide film is not less than 5 microns.
5. ultra supercritical coal-fired unit according to claim 1 austenitic heat-resistance steel spalling of oxide film prediction model,
Be characterized in that: double layer oxide film boundary defect size is no more than 200nm.
6. ultra supercritical coal-fired unit according to claim 1 austenitic heat-resistance steel spalling of oxide film prediction model,
Be characterized in that: critical temperature difference is calculated with the change curve of l/a by ANSYS simulation softward.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114169105A (en) * | 2021-12-06 | 2022-03-11 | 天津国华盘山发电有限责任公司 | Method for predicting temperature of outer side pipe wall of 12Cr18Ni12Ti austenitic heat-resistant steel for thermal power plant |
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| US20030231976A1 (en) * | 2002-03-08 | 2003-12-18 | Atsuro Iseda | Austenitic stainless steel tube excellent in steam oxidation resistance and a manufacturing method thereof |
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| CN104372338A (en) * | 2014-11-04 | 2015-02-25 | 西安热工研究院有限公司 | Alloying method of austenitic stainless steel tube surface for boiler superheaters/reheaters |
| CN109237989A (en) * | 2018-08-17 | 2019-01-18 | 西安热工研究院有限公司 | Boiler of power plant heating surface austenic stainless steel inside pipe wall oxide skin accelerates the method peeled off |
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2018
- 2018-10-29 CN CN201811269929.9A patent/CN109190311B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030231976A1 (en) * | 2002-03-08 | 2003-12-18 | Atsuro Iseda | Austenitic stainless steel tube excellent in steam oxidation resistance and a manufacturing method thereof |
| CN102644008A (en) * | 2012-03-22 | 2012-08-22 | 南京理工大学 | High-temperature alloy super-heater pipe material for 700 DEG C ultra-supercritical fossil power generation unit and preparation method thereof |
| CN104372338A (en) * | 2014-11-04 | 2015-02-25 | 西安热工研究院有限公司 | Alloying method of austenitic stainless steel tube surface for boiler superheaters/reheaters |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114169105A (en) * | 2021-12-06 | 2022-03-11 | 天津国华盘山发电有限责任公司 | Method for predicting temperature of outer side pipe wall of 12Cr18Ni12Ti austenitic heat-resistant steel for thermal power plant |
| CN114169105B (en) * | 2021-12-06 | 2024-05-28 | 天津国华盘山发电有限责任公司 | Method for predicting temperature of outer pipe wall of 12Cr18Ni12Ti austenitic heat-resistant steel for thermal power plant |
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