CN101831592A - Shockproof strip material of nuclear power station steam generator, and preparation method thereof - Google Patents
Shockproof strip material of nuclear power station steam generator, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a shockproof strip material of a nuclear power station steam generator, and a preparation method thereof, in particular to a shockproof strip material of a pressurized water reactor nuclear island CPR 1000 steam generator. The shockproof strip material comprises the components by weight percent: 0.02-0.07% of C, 0.2-1.0% of Si, 0.3-0.8% of Mn, less than or equal to 0.04% of P, less than or equal to 0.03% of S, 11.5-13.5% of Cr, 0.2-0.6% of Ni, less than or equal to 0.05% of N, 0.01-1.0% of Xt as well as balance Fe and unavoidable impurities. The preparation method of the shockproof strip material comprises: preparation of the raw materials, smelting by a vacuum refining furnace, refining the electroslag, forging, hot rolling, normalizing, multi-channel (drawing-annealing-drawing), and thereby obtaining the finished product of the shockproof strip material. The shockproof strip material of the nuclear power station steam generator is reasonable in component design, has excellent corrosion resistance, anti-fatigue property, creep resistance and processing performance, and has important economic significance for improving the production efficiency, prolonging the service life of the nuclear power station steam generator and reducing the production cost.
Description
Technical field
The present invention relates to a kind of Shockproof strip material of new material technology field, particularly a kind of Shockproof strip material of nuclear power station steam generator and preparation method thereof.Be specifically related to a kind of Martensite Stainless Steel X6Cr13 material, be mainly used in pressurized-water reactor nuclear island CPR1000 vapour generator Shockproof strip material.
Background technology
Energy industry is the basis of national economy, be the important step of restriction national economy sustained and rapid development, along with development and national economy, people are more and more higher to standard of living and environmental protection requirement, therefore, greatly develop the dominant direction that the nuclear power cause has become current energy development.It is conspicuous that nuclear power is compared its advantage with thermal power generation and other new forms of energy.Vapour generator is the hinge of pressurized-water reactor nuclear power plant one loop and secondary circuit, is the barrier of cutting apart the medium of a loop and secondary circuit, is one of Nuclear power plants key equipment.A Nuclear power plants need be provided with several vapour generators, includes ten hundreds of heat-transfer pipes, and the high-temperature setting-out flows in tube bank, supplying with water flows with vertical direction along pipe, be heated simultaneously, be vaporized then, steam enters the steam turbine generating, can cause vibrations with these pipe fluid in contact, break because of vibrations can cause damaged tubular, directly cause vapour generator and damage, change a vapour generator and need 200,000,000 dollars of left and right sides expenses, need the shutdown some months, cause great financial loss.For effectively preventing pipe vibrations, be provided with shockproof the nuclear plant safety reliability service played keying action.
Shockproof of vapour generator is to use under high temperature, high pressure, strong corrosive environment, and high temperature strength, erosion resistance, antifatigue, creep resistance and the workability of making Shockproof strip material proposed strict demand.China is used to make still dependence on import of Shockproof strip material at present, therefore research and develop and make Shockproof strip material with superior corrosion resistance, antifatigue, creep resistance and workability, substituting import, the economy and the safe reliability of effective raising Nuclear power plants had crucial meaning.
Summary of the invention
The objective of the invention is to overcome the deficiency in the existing Shockproof strip material technology, a kind of " Shockproof strip material of nuclear power station steam generator and preparation method thereof " is provided.This Shockproof strip material is used to make shockproof of nuclear power station steam generator, and this material price is low, design of components is reasonable, manufacturing process is simple, has superior corrosion resistance, antifatigue, creep resistance and processability.Its tensile strength can reach 590MPa, and yield strength can reach 390MPa, and elongation is greater than 25%, and hardness is less than 160.
To achieve these goals, the present invention is achieved through the following technical solutions: a kind of Shockproof strip material of nuclear power station steam generator, to count by weight percentage, and ingredient is as follows:
C：0.02-0.07％； Si：0.2-1.0％；?Mn：0.3-0.8％；
P：≤0.04％； S：≤0.03％； Cr：11.5-13.5％；
N?i：0.2-0.6％； N：≤0.05％； Xt：0.01-1.0％；
Surplus is Fe and unavoidable impurities.
The purity of described Si, Mn, Cr, Ni, Ti, Fe is greater than 98%, and granularity is 20-50um.
Described rare earth Xt is the mixture of cerium fluoride, lanthanum fluoride, and its purity is greater than 98%, and granularity is 1-10um.
The preparation method of Shockproof strip material of nuclear power station steam generator of the present invention comprises the steps:
1) carry out preparation of raw material by the weight percent meter calculation of Shockproof strip material ingredient:
C：0.02-0.07％； Si：0.2-1.0％；Mn：0.3-0.8％；
P：≤0.04％； S：≤0.03％； Cr：11.5-13.5％；
N?i：0.2-0.6％； N：≤0.05％； Xt：0.01-1.0％；
Surplus is Fe and unavoidable impurities;
2) will pack into by the raw material of aforementioned preparation and smelt in the vacuum refining furnace, refining period, temperature was controlled at 1550 ℃-1600 ℃, refining time 45 minutes;
3) electroslag refining, refining period, temperature was controlled at 1520 ℃-1580 ℃, melting voltage 45-50V,
Melting electric current 2600-3000A;
4) forge, 1160 ℃-950 ℃ of forging temperatures are opened and are forged 1160 ℃ of temperature;
5) hot rolling, 1060 ℃-900 ℃ of hot-rolled temperatures, 1060 ℃ of start rolling temperatures;
6) normalizing, 720 ℃-780 ℃ of normalizing temperatures, 1.5 hours air cooling time;
7) multi-pass carries out (drawing → annealing → drawing), obtains the Shockproof strip material finished product.
Drawing described in the step 7) adopts bicycle to carry out.
Annealing described in the step 7), its annealing temperature are 720 ℃-780 ℃, annealing insulation 1 hour.
The raw material of the preparation step 2) is packed into and smelted in the vacuum refining furnace, and its loading sequence is: carbon C-pure iron Fe-chromium metal Cr-nickel plate Ni-silicon Si-manganese Mn, described rare earth Xt stir coming out of the stove once to add in the molten steel in preceding 5 minutes.
These invention preparation method major technique characteristics are: adopt vacuum refining furnace to smelt, make the degassing fully, again through electroslag refining, make the molten steel cleaning, rare earth Xt adds further raising Shockproof strip material quality and mechanical property in the vacuum metling process, the process annealing of drawing process, drawing adopts bicycle to carry out at a slow speed, the heat accumulation that is produced when reducing friction, finally obtain tensile strength and can reach 690MPa, yield strength can reach 390MPa, and elongation is greater than 25%, and hardness is less than the Shockproof strip material of 180HV.
The principle of the designed composition of Shockproof strip material of nuclear power station steam generator of the present invention is as follows:
C: very effective sclerosis and solution strengthening constituent element, stablize martensitic structure, proof strength.But usually occur as formation of crack, form crisp sclerous tissues easily and cause delayed cracking as too high levels, its composition weight % is limited in 0.02-0.07%;
Mn: deoxidation and desulfidation, guarantee the important element of oxidation-resistance, less than 0.01% can not obtain abundant deoxidation, surpasses 1.5% intensity and reduces, and its composition weight % is limited in 0.3-0.8%;
Si: deoxidation, raising yield strength, high-temperature corrosion resistance, less than 0.01% can not obtain abundant oxidation-resistance, surpasses 0.90% toughness and reduces, and its composition weight % is limited in 0.2-1.0%;
Ni: improve toughness of material, the raising of intensity is also had contribution, its composition weight % is limited in 0.2-0.6%;
Cr: guarantee oxidation-resistance, high-temperature corrosion resistance, improve the indispensable element of hot strength, content is low excessively, can not manifest effect, too high levels, and intensity and toughness significantly reduce, and its composition weight % is limited in 11.5-13.5%;
N: in material, play solid solution, bring into play its fine dispersion-strengthened effect, its composition weight % is limited in≤and 0.05%;
S, P: be inevitable detrimental impurity element in the material, its content is low more good more, its composition weight %, and P :≤0.04%, S :≤0.03%;
Xt: add rare earth in the material, with Cr, has good oxidation-resistance under the compound action of Si, rare earth is the strong reducing property element, rare earth and sulphur have very big avidity, in bath, not only has desoxydatoin, also has the size that obvious desulfurization improves sulfide inclusion, form and distribution effect, reduce the inclusion content in the material, can change the composition of inclusion, form, distribute and character, suppress the segregation of these inclusiones in crystal boundary, thereby the various performances of material have been improved, as toughness, weldability, composition weight % is limited in 0.01-1.0% among the present invention.
Adopt the designed Shockproof strip material of nuclear power station steam generator of the present invention compared with prior art, have following advantage:
1. composition is reasonable in design, cost is low, safe and reliable;
2. its tensile strength of this Shockproof strip material can reach 590MPa, and yield strength can reach 390MPa, and elongation is greater than 25%, and hardness is less than 160, and long term operation has higher-strength and corrosion resistance under 1100 ℃ of high temperature, its high temperature stress intensity stabilization;
3. again because of having added micro-rare earth element and having adopted special preparation technology, guarantee that material has superior corrosion resistance, antifatigue, creep resistance and processability;
4. the safe reliability of shockproof use is guaranteed in the alternative import of this Shockproof strip material, effectively prolongs the work-ing life of nuclear power station steam generator, reduces cost, and significantly improves economic benefit.
Embodiment
Below by non-limiting example, further set forth the present invention, understand the present invention.
Shockproof strip material of nuclear power station steam generator of the present invention has prepared ten stove embodiment, heat (batch) number is: 105-5575,5576,5577,5578,5579,5581,5582,5583,5584,5585, embodiment 1-10 stove Shockproof strip material ingredient and content % by weight calculate, auspicious see as follows:
First stove: C:0.03%, Si:0.4%, Mn:0.5%, P:0.009%, S:0.002%, Cr:13%, Ni:0.4%, N:0.03%, Xt:0.0%,
Second stove: C:0.04%, Si:0.30%, Mn:0.60%, P:0.01%, S:0.015%, Cr:11.50%, Ni:0.5%, N:0.04%, Xt:0.06%,
The 3rd stove: C:0.05%, Si:0.50%, Mn:0.70%, P:0.02%, S:0.01%, Cr:12.50%, Ni:0.55%, N:0.02%, Xt:0.04%,
The 4th stove: C:0.06%, Si:0.60%, Mn:0.40%, P:0.009%, S:0.002%, Cr:13.50%, Ni:0.30%, N:0.03%, Xt:0.06%,
The 5th stove: C:0.067%, Si:0.70%, Mn:0.60%, P:0.01%, S:0.015%, Cr:12.0%, Ni:0.25%, N:0.04%, Xt:0.08%,
The 6th stove: C:0.04%, Si:0.80%, Mn:0.70%, P:0.02%, S:0.01%, Cr:12.50%, Ni:0.40%, N:0.045%, Xt:0.07%,
The 7th stove: C:0.06%, Si:0.40%, Mn:0.40%, P:0.008%, S:0.005%, Cr:11.80%, Ni:0.50%, N:0.003%, Xt:0.09%,
The 8th stove: C:0.05%, Si:0.50%, Mn:0.70%, P:0.03%, S:0.007%, Cr:13.0%, Ni:0.60%, N:0.037%, Xt:0.04%,
The 9th stove: C:0.03%, Si:0.70%, Mn:0.50%, P:0.01%, S:0.008%, Cr:13.50%, Ni:0.40%, N:0.04%, Xt:0.05%,
The tenth stove: C:0.04%, Si:0.30%, Mn:0.60%, P:0.02%, S:0.006%, Cr:12.80%, Ni:0.30%, N:0.02%, Xt:0.07%,
Above-mentioned ten stove embodiment its preparation methods are:
1). select pure iron for use, prepare burden according to the present invention's ten stove embodiment design mix;
2). vacuum refining furnace is smelted, and feeds by its loading sequence: carbon C-pure iron Fe-chromium metal Cr-nickel plate Ni-silicon Si-manganese Mn, described rare earth Xt stir coming out of the stove once to add in the molten steel in preceding 5 minutes.Smelting temperature is controlled at 1550 ℃-1600 ℃, refining time 45 minutes;
3). electroslag refining, temperature are controlled at 1520 ℃-1580 ℃, melting voltage 45-50V, melting electric current 2600A-2800A;
4). forge, 1160 ℃-960 ℃ of forging temperatures are opened and are forged 1160 ℃ of temperature;
5). hot rolling, 1060 ℃-900 ℃ of hot-rolled temperatures, 1060 ℃ of start rolling temperatures
6). normalizing, 720 ℃-780 ℃ of normalizing temperatures, 1.5 hours air cooling time;
7). 720 ℃ of-760 ℃ of annealing are adopted in multi-pass (drawing-annealing-drawing) process annealing, annealing insulation 1 hour, drawing employing bicycle (10 meters/minute of speed) at a slow speed carries out, according to customer need, drawing passes 3 passages
ф16-14.5*14.5-13*11.5-11*8.1。
Above embodiment is designed, the Shockproof strip material of nuclear power station steam generator of preparation relevant department its composition, comprehensive mechanical property have been carried out detection, test, examining report is as follows:
One. mechanical industry quality of materials inspection center
The material classification: shockproof,
Sample title: X6Cr13 (the present invention); Sample characteristic: piece sample
Detect foundation and/judgment basis: ISO 15350:2000 GB/T 11170-2008ASTME1019-2008
Detect data/result
C：0.059％ Cr：12.64％ Mn：0.71％ Si：0.37％
S：0.002％ P：0.009％ N：0.037％
Two. quality physical and chemical measuring room of east electric (Guangzhou) heavy-duty machine company limited
The material classification: shockproof,
Sample title: X6Cr13 (the present invention),
Embodiment 1-10 stove, 2 in every stove, annealing, specification: ф 10mm,
Test basis: DF-SG/PS-011 Rev:A; NPS-DSD-SG022 Rev:A;
Technical qualification: NPS-DSD-SG0ZZ
Test temperature: room temperature,
1. mechanical property test
2. metallographic examination
3. vapour generator is reported with shockproof X6Cr13 (the present invention) test evaluation
1). test specimen state: before shockproof the assembling
2). check type: chemical analysis, mechanical property, UT (Ultrasonic Testing), thermal treatment, visual inspection, dimension inspection.
Assay:
1. visual inspection, dimension inspection, angle and planeness inspection.Result: qualified.
2. heat analysis
1). UT (Ultrasonic Testing) (hot rolling bleaching back).Result: zero defect.
2). thermal treatment.Result: qualified.
3. mechanical property check and analysis (after the thermal treatment pickling).Result: qualified.
4. product analysis.Result: qualified.
Evaluation result: according to shockproof trial-production part evaluation situation analysis, above-mentioned shockproof X6Cr13 (the present invention) satisfies vapour generator with every requirement of shockproof, and manufacturing process and product is stablized.
Detect by above embodiment and mechanical property, the designed Shockproof strip material of nuclear power station steam generator of the present invention has that composition is reasonable in design, cost is low, stable manufacturing process, have superior corrosion resistance, antifatigue, creep resistance and processability, satisfy vapour generator with every service requirements of shockproof, guarantee safe and reliable.To enhancing productivity, effectively prolong the work-ing life of nuclear power station steam generator, reducing production costs has crucial economic implications.
Claims (7)
1. a Shockproof strip material of nuclear power station steam generator is characterized in that, count by weight percentage, ingredient is as follows:
C：0.02-0.07％；Si：0.2-1.0％；Mn：0.3-0.8％；
P：≤0.04％； S：≤0.03％； Cr：11.5-13.5％；
Ni：0.2-0.6％；?N：≤0.05％； Xt：0.01-1.0％；
Surplus is Fe and unavoidable impurities.
2. a kind of Shockproof strip material of nuclear power station steam generator according to claim 1 is characterized in that, the purity of Si, Mn, Cr, Ni, Fe is greater than 98%, and granularity is 20-50um.
3. a kind of Shockproof strip material of nuclear power station steam generator according to claim 1 is characterized in that, described rare earth Xt is the mixture of cerium fluoride, lanthanum fluoride, and its purity is greater than 98%, and granularity is 1-10um.
4. the preparation method of an a kind of Shockproof strip material of nuclear power station steam generator as claimed in claim 1 is characterized in that comprising the steps:
1) carry out preparation of raw material by the weight percent meter calculation of Shockproof strip material ingredient:
C：0.02-0.07％；Si：0.2-1.0％；Mn：0.3-0.8％；
P：≤0.04％； S：≤0.03％； Cr：11.5-13.5％；
Ni：0.2-0.6％；?N：≤0.05％； Xt：0.01-1.0％；
Surplus is Fe and unavoidable impurities;
2) will pack into by the raw material of aforementioned preparation and smelt in the vacuum refining furnace, refining period, temperature was controlled at 1550 ℃-1600 ℃, refining time 45 minutes;
3) electroslag refining, refining period, temperature was controlled at 1520 ℃-1580 ℃, melting voltage 45-50V, melting electric current 2600-3000A;
4) forge, 1160 ℃-950 ℃ of forging temperatures are opened and are forged 1160 ℃ of temperature;
5) hot rolling, 1060 ℃-900 ℃, 1060 ℃ of start rolling temperatures;
6) normalizing, 720 ℃-780 ℃ of normalizing temperatures, 1.5 hours air cooling time;
7) multi-pass carries out drawing → annealing → drawing, obtains the Shockproof strip material finished product.
5. the preparation method of a kind of Shockproof strip material of nuclear power station steam generator according to claim 4 is characterized in that, the drawing described in the step 7) adopts bicycle to carry out.
6. the preparation method of a kind of Shockproof strip material of nuclear power station steam generator according to claim 4 is characterized in that, the annealing described in the step 7), and its annealing temperature is 720 ℃-780 ℃, annealing insulation 1 hour.
7. the preparation method of a kind of Shockproof strip material of nuclear power station steam generator according to claim 4, it is characterized in that, the raw material of the preparation step 2) is packed into and is smelted in the vacuum refining furnace, its loading sequence is: carbon C-pure iron Fe-chromium metal Cr-nickel plate Ni-silicon Si-manganese Mn, described rare earth Xt stir coming out of the stove once to add in the molten steel in preceding 5 minutes.
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| CN102181752A (en) * | 2011-04-21 | 2011-09-14 | 江苏新华合金电器有限公司 | Hand hole sealing cover spring material for steam generator of nuclear power plant and preparation method of hand hole sealing cover spring material |
| CN102553908A (en) * | 2012-01-30 | 2012-07-11 | 江苏新恒基重工有限公司 | Rolling method for puller bolt of steam generator of pressurized-water reactor nuclear power station |
| CN102703828A (en) * | 2012-05-14 | 2012-10-03 | 江苏新华合金电器有限公司 | Novel shockproof strip material of steam generator of nuclear power station and preparation method thereof |
| CN102732801A (en) * | 2012-06-18 | 2012-10-17 | 江苏新华合金电器有限公司 | Pull rod material for nuclear power station steam generator and preparation process thereof |
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| CN103934645A (en) * | 2012-08-20 | 2014-07-23 | 丹阳市龙鑫合金有限公司 | Preparing method for shake-proof strip bar material in shake-proof strip assembly |
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| CN1342781A (en) * | 2001-09-19 | 2002-04-03 | 武汉钢铁(集团)公司 | High-energy welded high-toughness steel for resisting corrosion of molten zinc and its preparing process |
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| CN1342781A (en) * | 2001-09-19 | 2002-04-03 | 武汉钢铁(集团)公司 | High-energy welded high-toughness steel for resisting corrosion of molten zinc and its preparing process |
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| CN102181752A (en) * | 2011-04-21 | 2011-09-14 | 江苏新华合金电器有限公司 | Hand hole sealing cover spring material for steam generator of nuclear power plant and preparation method of hand hole sealing cover spring material |
| CN102553908A (en) * | 2012-01-30 | 2012-07-11 | 江苏新恒基重工有限公司 | Rolling method for puller bolt of steam generator of pressurized-water reactor nuclear power station |
| CN102703828A (en) * | 2012-05-14 | 2012-10-03 | 江苏新华合金电器有限公司 | Novel shockproof strip material of steam generator of nuclear power station and preparation method thereof |
| CN102732801B (en) * | 2012-06-18 | 2014-04-30 | 江苏新华合金电器有限公司 | Pull rod material for nuclear power station steam generator and preparation process thereof |
| CN102732801A (en) * | 2012-06-18 | 2012-10-17 | 江苏新华合金电器有限公司 | Pull rod material for nuclear power station steam generator and preparation process thereof |
| CN103921079A (en) * | 2012-08-20 | 2014-07-16 | 丹阳市龙鑫合金有限公司 | Method for manufacturing anti-vibration strip assembly |
| CN103934646A (en) * | 2012-08-20 | 2014-07-23 | 丹阳市龙鑫合金有限公司 | Method for manufacturing vibration-proof strip assembly of nuclear power unit steam generator |
| CN103934648A (en) * | 2012-08-20 | 2014-07-23 | 丹阳市龙鑫合金有限公司 | Manufacturing method for end caps of vibration-proof strip assembly of nuclear power unit vapor generator |
| CN103934645A (en) * | 2012-08-20 | 2014-07-23 | 丹阳市龙鑫合金有限公司 | Preparing method for shake-proof strip bar material in shake-proof strip assembly |
| CN103934648B (en) * | 2012-08-20 | 2016-05-04 | 丹阳市龙鑫合金有限公司 | The preparation method of the end cap in the antivibration bar assembly of nuclear power generating sets steam generator |
| CN103934645B (en) * | 2012-08-20 | 2016-07-06 | 丹阳市龙鑫合金有限公司 | A kind of preparation method of the anti-vibration bar bar in anti-vibration bar assembly |
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| CN103659169B (en) * | 2012-09-23 | 2016-06-22 | 丹阳市龙鑫合金有限公司 | A kind of method of the anti-vibration bar assembly preparing nuclear power generating sets |
| CN106319344A (en) * | 2016-10-10 | 2017-01-11 | 抚顺圣兴高温合金研究所 | Martensitic stainless steel |
| CN106319344B (en) * | 2016-10-10 | 2018-09-25 | 抚顺圣兴高温合金研究所 | A kind of martensitic stain less steel |
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