CN103103311A - Method for improving high-temperature water vapor oxidation resistance by adding nano rare earth oxide into T91 and P91 steel - Google Patents
Method for improving high-temperature water vapor oxidation resistance by adding nano rare earth oxide into T91 and P91 steel Download PDFInfo
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- CN103103311A CN103103311A CN2013100236467A CN201310023646A CN103103311A CN 103103311 A CN103103311 A CN 103103311A CN 2013100236467 A CN2013100236467 A CN 2013100236467A CN 201310023646 A CN201310023646 A CN 201310023646A CN 103103311 A CN103103311 A CN 103103311A
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Abstract
The invention discloses a method for improving high-temperature water vapor oxidation resistance by adding nano rare earth oxide into T91 and P91 steel. The method is adding rear earth oxide in the smelting process of T91 and P91 steel to prepare T91 and P91 steel containing nano rare earth oxide. The method disclosed by the invention has the technical effects that (1) the T91 and P91 steel has excellent high-temperature water vapor oxidation resistance, and the oxidation speed of the material is reduced; and (2) the nano rare earth oxide modified T91 and P91 steel pipe can obviously promote the formation and growth of chromium oxide on the surface of the material in high-temperature water vapor environment and suppress the reaction between chromium oxide and high-temperature water vapor and consequent formation of volatile substance so as to form a dense oxide film of chromium oxide and reduce the oxidation speed; and iron oxide with relatively bad protection property is quickly formed on the surface of the material not modified by the rare earth oxide.
Description
Technical field
The present invention relates to a kind of method of high temperature resistance steam oxidation, relate in particular to and add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 and P91 steel.
Background technology
Along with the continuous growth of electricity needs, the supercritical unit of elevated steam conditions, high efficiency and ultra supercritical unit are the inexorable trends of thermoelectricity development.Due to heat power plant boiler plant capacity and steam parameter increase, more and more boiler pipe explosion accidents occur thereupon.Statistics shows, bad 2/3 left and right that accounts for boiler breakdowns of quick-fried leakage loss of heating surface tube in the station boiler accident (water wall tube, superheater tube, reheater tube, economizer tube claim again " four pipes ") is the principal element that affects generating set safety, economical operation.Wherein, serious as superheater, reheater inside pipe wall oxidation in the high-temperature water vapor environment of high temperature, high pressure pressure-containing member, oxide film comes off and causes the tube wall effective thickness to reduce; The tube wall oxide film thickens and causes the heat conductivility variation simultaneously, and the average operating temperature of tube wall improves, and pipeline is in the overtemperature service state for a long time, causes the most at last the quick-fried leakage of boiler tube.In addition, the oxide skin that comes off forms the more serious damage of washing away to last stage vane of steam turbine, and main inlet throttle-stop valve also has the phenomenon that causes bite because of the oxide skin that comes off.
metallic substance is significantly different again in oxidation behavior behavior and mechanism and oxygen and air in high-temperature vapor, usually high-temperature water vapor meeting accelerated material oxidation, the T91 steel in water vapor than more serious T. Sundararajan [the T. Sundararajan of oxidation in air, S. Kuroda, J. Kawakita and S. Seal:Surface and Coatings Technology, 2006, 201, 2124.], oxidation mechanism relevant with hydrogen defect and from [Li Tiefan different in air or oxygen, metallic high temperature oxidation and thermal etching [M], Beijing: Chemical Industry Press, 2003.].The people such as Shen Jianian [Li Tiefan, water vapor accelerate the effect of Fe-Cr High Temperature Oxidation for Shen Jianian, Zhou Longjiang, investigation of materials journal, 1998,12(2): 128-132.] think the H of water vapor and the release of Fe-Cr alloy reaction
2Cause the initial Cr that forms
2O
3Destroy and significantly accelerate alloy oxidation.While Cr
2O
3Contact with water vapor and can generate volatile CrO
2(OH)
2And cause its protectiveness to descend or lose.In oxygen, the Fe-Cr alloy forms Cr
2O
3The external oxidation film needs chromium content at 20%(wt.) more than, in water vapor at least 25%, and containing chromium 9%, the T91 steel can not generate the Cr with good protection performance
2O
3Oxide film.
T91 and P91 steel (9Cr-1Mo) have good toughness, creep-resistant property, high temperature oxidation resistance preferably, become the main raw of station boiler supercritical unit main steam line.Because the chrome content of T91 steel and P91 is lower, approximately 9% left and right, so T91 steel and P91 steel raise with temperature under 500 ℃～750 ℃ in steam atmosphere, and oxidation rate is obviously accelerated.Oxidation products is Fe
2O
3, Fe
3O
4(Fe, Cr)
3O
4, because Cr content in this class material is low, can not generate continuous, fine and close Cr in the oxide film that therefore generates under differing temps
2O
3, even do not generate Cr in oxide film
2O
3Phase, normal conditions are with (Fe, Cr)
3O
4The solid solution form exists.Along with the variation of oxidation rate growth and temperature, thicker oxide film is subject to larger growth stress and thermal stresses, and the viscous deformation of oxide film is limited.Therefore, this class material has the phenomenon of obvious spalling of oxide film under arms in process, conversely, and the coming off and further accelerated oxidation rate of oxide film.At present, the approach that realizes that improves T91 steel high temperature resistance corrosion of vapor ability has been summed up two: the one, and adopt the means such as chromium plating, chromising, spraying to apply protective layer or thermodiffusion coating, but it is more difficult that these measures are implemented at inner-walls of duct, and practical application is restricted; The 2nd, adopt suitable surface pre-treating process to promote the T91 steel preferential Cr of formation in surface in oxidising process
2O
3, adopt the shot peening crystal grain thinning as inwall.The people such as Li Xingeng [Li Xingeng, Wang Xuegang, corrosion science and guard technology 2008,20 (3) 157-161.] are at T91 steel surface electrical deposition CeO
2After film, the rate of oxidation in 600 ℃ ~ 770 ℃ water vapour does not obviously reduce, but CeO
2Promoted that the Cr in the oxide film spreads to skin.T. the people such as Sundararajan [T. Sundararajan, S. Kuroda, J. Kawakita and S. Seal:Surface and Coatings Technology, 2006,201,2124.] is at T91 steel surface-coated nano Ce O
2At the about 20～30mm of 650 ℃ of steam oxidation 100h rear oxidation skin thicknesses, reduced by one times than blank T91 steel afterwards.
By adding oxide nano rare earth can improve the heat and corrosion resistant of high chromium steel, anti-airborne oxidation susceptibility performance, the State of Lu is flourish, and [the State of Lu is flourish; Xu Jihua; He Shuping, rare earth, high chromium content ferrite Heat resisting cast steel, patent of invention, CN1032680] etc. the people by add rare earth or oxide compound in high chromium content ferrite cast steel, improved the performance of the aerial antioxidant property of material and kinds of anti-sulfur corrosion.But related environment is not the high-temperature vapor environment, and chromium content reaches 21-23%, and so high chromium content can form the chromic oxide oxide film in air, has only changed the structure of oxide film after therefore adding rare earth, and has not changed the oxidation constituent of the film.And for the oxidation as this class low-chrome steel of T91 steel, especially being oxidized under the high-temperature vapor environment provides relevant information, and do not find in high chromium steel or relate to the preferential accelerating oxidation chromium growth of rare earth Composition of Oxide Scale is changed.[Zhang Guangcheng improves t91/p91 steel oxidation resistant pretreatment process in high-temperature water vapor, application number: 201010111385.0 to the people such as Zhang Douqing for Zhang Douqing, Liu Guangming; Publication number: CN101775599A] adopt the surface-coated Methods of Rare Earth Element to prepare rich chromium oxide film on T91 steel surface, but the method is because rare earth is extremely low at material surface content, and after consuming, the T91 oxidation rate is obviously accelerated, and can't satisfy the long service requirement.
Summary of the invention
The object of the present invention is to provide and added the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 and P91 steel, the method is cheap, technique is simple and can effectively improve T91 and the method for P91 steel high temperature resistance steam oxidation.
The present invention is achieved like this, and method is: in the smelting process of T91 and P91 steel, by adding wherein oxide nano rare earth, and rare earth is dispersed in the T91 steel, preparation contains T91 and the P91 steel of oxide nano rare earth.
Described rare earth oxide purity 〉=99.00%, granularity≤30 nanometers.
The composition of described oxide nano rare earth forms by weight percentage 1 ~ 1.5%.
The interpolation of described oxide nano rare earth needs to carry out under protection of inert gas or vacuum environment, and rare gas element is the argon gas of purity 〉=99.99% or the helium of purity 〉=99.99%, or vacuum is less than 10
-3Pa.
Described rare earth oxide is Y
2O
3, La
2O
3, CeO
2, Nd
2O
3A kind of or several mixture.
Technique effect of the present invention is: 1. the T91 steel and the P91 steel that adopt the present invention to add have good high temperature resistance steam oxidation performance, can reduce significantly this class material in oxidation rate.The constant temperature oxidation is after 150 hours in 650 ℃ of lower water vapor, and the oxidation weight gain of blank sample reaches 8.53mg/cm
2, and the oxidation weight gain of the sample after the modification of interpolation oxide nano rare earth only has 0.12mg/cm
2Do not find surface crack and spalling of oxide film through the sample surfaces that adds oxide nano rare earth.2. the present invention adds T91 and the P91 steel pipe of oxide nano rare earth modification, and under the high-temperature water vapor environment, namely shape is rich in chromium and a small amount of oxide nano rare earth surface.
Description of drawings
Fig. 1 is that T91 steel of the present invention adds nanometer Y
2O
3Sample is oxidation rear surface shape appearance figure in 650 ℃ of water vapour.
Fig. 2 is that T91 steel of the present invention adds nanometer Y
2O
3Sample EDAX results figure after oxidation in 650 ℃ of water vapour.
Fig. 3 is T91 steel oxidation rear surface shape appearance figure in 650 ℃ of water vapour.
Fig. 4 is T91 steel EDAX results after oxidation in 650 ℃ of water vapour.
Fig. 5 is that T91 steel of the present invention adds nanometer La
2O
3Sample is oxidation rear surface shape appearance figure in 650 ℃ of water vapour.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Embodiment 1: raw material: rare earth: nano yttrium oxide (Y
2O
3) purity 〉=99.00%, mean particle size 15nm; The T91 steel pipe.
Put into induction furnace after required T91 or P91 steel are toasted and smelt in protective atmosphere, add nanometer Y after temperature is elevated to 1600 ℃ under argon shield
2O
3, stir, standing, cast, cooling, acquisition contains T91 and the P91 steel of oxide nano rare earth.The constant temperature oxidation is after 150 hours in 650 ℃ of lower water vapor, the oxidation weight gain of blank sample reaches 8.53mg/cm through modified sample
2, and the oxidation weight gain of the sample after the modification of interpolation oxide nano rare earth only has 0.12mg/cm
2Do not find surface crack and spalling of oxide film through the sample surfaces that adds oxide nano rare earth.Fig. 1, Fig. 2 are for adding nanometer Y
2O
3Rear sample is surface topography map and the EDAX results after oxidation 150h in 650 ℃ of lower water vapour, and in figure, visible surface has generated the oxide compound of rich Cr.Fig. 3, Fig. 4 are T91 steel oxidation rear surface shape appearance figure and the EDAX results at the same temperature of not plus nano rare earth oxide.In figure the T91 steel Surface Creation of visible not plus nano rare earth oxide ferric oxide.
Embodiment 2: raw material: nanometer La
2O
3Purity 〉=95.00%, mean particle size 20nm; The T91 steel pipe.
Put into induction furnace after required T91 or P91 steel are toasted and smelt in protective atmosphere, add nanometer La after temperature is elevated to 1600 ℃ under argon shield
2O
3, stir, standing, cast, cooling, acquisition contains T91 and the P91 steel of rare earth oxide.After 150 hours, add nanometer La in constant temperature oxidation in 650 ℃ of lower water vapor through modified sample
2O
3The oxidation weight gain of the sample after modification only has 0.23mg/cm
2Through adding nanometer La
2O
3Sample surfaces is not found surface crack and spalling of oxide film.Fig. 5 is for adding nanometer La
2O
3Rear sample is the surface topography map after oxidation 150h in 650 ℃ of lower water vapour, and in figure, visible surface has generated the oxide compound of rich Cr.
Claims (5)
1. add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a T91 and P91 steel, it is characterized in that method is: in the smelting process of T91 and P91 steel, by adding wherein oxide nano rare earth, and rare earth oxide is dispersed in steel, preparation contains T91 and the P91 steel of oxide nano rare earth.
2. add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 according to claim 1 and P91 steel, it is characterized in that: described oxide nano rare earth purity 〉=99.00%, granularity≤30 nanometers.
3. add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 according to claim 1 and P91 steel, it is characterized in that: the composition of oxide nano rare earth forms by weight percentage≤1 ~ 1.5%.
4. add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 according to claim 1 and P91 steel; it is characterized in that: adding needs to carry out under protection of inert gas or vacuum environment; rare gas element is the argon gas of purity 〉=99.99% or the helium of purity 〉=99.99%, or vacuum is less than 10
-3Pa.
5. add the method that oxide nano rare earth improves the high temperature resistance steam oxidation in a kind of T91 according to claim 1 and P91 steel, it is characterized in that: described oxide nano rare earth is Y
2O
3, La
2O
3, CeO
2, Nd
2O
3A kind of or several mixture, the oxide compound median size is less than 50 nanometers.
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|---|---|---|---|
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| CN2013100236467A CN103103311A (en) | 2013-01-23 | 2013-01-23 | Method for improving high-temperature water vapor oxidation resistance by adding nano rare earth oxide into T91 and P91 steel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106755728A (en) * | 2016-11-23 | 2017-05-31 | 东北大学 | Improve additional nano reinforcement agent and its preparation and application of steel mechanics performance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775599B (en) * | 2010-02-22 | 2011-04-13 | 山东电力研究院 | Pretreatment method for improving oxidation resistance of T91/P91 steel in high temperature water steam |
| CN102321839A (en) * | 2011-09-06 | 2012-01-18 | 南昌航空大学 | Add the method that rare earth improves resistance to high temperature corrosion in a kind of T91 and the P91 steel |
-
2013
- 2013-01-23 CN CN2013100236467A patent/CN103103311A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775599B (en) * | 2010-02-22 | 2011-04-13 | 山东电力研究院 | Pretreatment method for improving oxidation resistance of T91/P91 steel in high temperature water steam |
| CN102321839A (en) * | 2011-09-06 | 2012-01-18 | 南昌航空大学 | Add the method that rare earth improves resistance to high temperature corrosion in a kind of T91 and the P91 steel |
Non-Patent Citations (3)
| Title |
|---|
| 刘乃勇等: "T91钢表面Ni和Ni/CeO2镀层的氧化行为研究", 《失效分析与预防》 * |
| 李志翔等: "火力发电厂新材料T91/P91钢性能综述", 《云南电力技术》 * |
| 黄伯云等: "《中国材料工程大典 第5卷 有色金属材料工程 （下册）》", 31 August 2005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106755728A (en) * | 2016-11-23 | 2017-05-31 | 东北大学 | Improve additional nano reinforcement agent and its preparation and application of steel mechanics performance |
| CN106755728B (en) * | 2016-11-23 | 2018-08-07 | 东北大学 | Improve additional nano reinforcement agent and its preparation and application of steel mechanics performance |
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Application publication date: 20130515 |