CN105296877A - Martensitic stainless steel for building structure fastener and manufacturing method thereof - Google Patents
Martensitic stainless steel for building structure fastener and manufacturing method thereof Download PDFInfo
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- CN105296877A CN105296877A CN201510621186.7A CN201510621186A CN105296877A CN 105296877 A CN105296877 A CN 105296877A CN 201510621186 A CN201510621186 A CN 201510621186A CN 105296877 A CN105296877 A CN 105296877A
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Abstract
The invention discloses martensitic stainless steel for a building structure fastener and a manufacturing method thereof. The martensitic stainless steel comprises the following chemical components in percentage by weight: 0.10-0.20% of C, 0.05-0.15% of N, Si not more than 1%, Mn not more than 1%, P not more than 0.035%, S not more than 0.010%, 13.0-14.0% of Cr, 1.5-2.5% of Mo, 0.3-0.8% of Cu, 1.5-2.5% of Ni, and the balance of Fe and inevitable impurities; and the following conditions can be synchronously satisfied: the pitting equivalent weight PRE is more than 20%; and PRE=Cr+3.3 Mo+16 N. The prepared martensitic stainless steel has the pitting potential more than 270 mV, has the Rockwell hardness number of 52-54 HRC, has equivalent corrosion resistance to 304 stainless steel, and has high strength, high hardness and excellent hot working performance and cold forming performance.
Description
Technical field
The present invention relates to Martensite Stainless Steel, be specifically related to a kind of building structure fastening piece Martensite Stainless Steel and manufacture method thereof, particularly a kind of fastening piece Martensite Stainless Steel and manufacture method thereof with good corrosion resistance, hot workability and cold formability.
Background technology
When roofing or wall covering be aluminium alloy or stainless steel time, fastening piece material must select stainless steel.For the consideration extending building enclosure system work-ing life to greatest extent, the working life of stainless steel support should match with containment system.This just means that the solidity to corrosion of fastening piece should match with containment system material, and when containment system adopts austenitic stainless steel 304,316 or aluminium alloy, the solidity to corrosion of fastening piece at least should be suitable with austenitic stainless steel 304.Otherwise, if the solidity to corrosion of fastening piece is poor, then causing a series of serious problems, as reduced work-ing life of building enclosure, security and aesthetic property, even causing the destruction of whole building enclosure.
Screw ailhead and packing ring corrode, and roofing and metope can be caused to occur corrosion, and wind resistance load declines, and risk of leakage increases; Screw rod corrodes, and tensile strength declines, and weakens shear strength, weakens the resisting pull out forces of screw in purlin, causes fastening piece to be deviate from; Fastening piece is hidden in the part in building enclosure once corrode, and owing to being not easily found, hazardness is larger, can cause containment system local and all lose efficacy.The construction of certain international pro-ject only after 1 year half fastening piece namely corrode, even rust is disconnected, and cause engineering site fastening piece all to change, direct losses reach 1,000,000.Certain domestic construction project, the overall corrosion of about 3 years fastening pieces, deviates from.
Fastening piece stainless steel, except requiring to possess except good solidity to corrosion, also needs to possess high rigidity to have the ability of boring saturating 6mm stainless steel plate.In addition, fastening piece stainless steel also must have good cold forming capability, to be easy to be processed into bolt and tapping screw.
Austenitic stainless steel has excellent solidity to corrosion as 304 and 316, can be used for the fastening piece of high anti-corrosion containment system.But it is high that the shortcoming of austenitic stainless steel is price, work hardening tendency is large, and hardness is low, and machinability is poor, stress corrosion can occur when long service.And due to hardness low, austenitic stainless steel can not be used as the tapping part of tapping screw.
Ferritic stainless steel price is low, and work hardening tendency is low, easily carry out cold working, but this kind of steel hardness is too low, and solidity to corrosion is not as good as austenitic stainless steel 304, therefore can not be used as building fastening piece.
Geneva stainless steel, if 20Cr13 is after Q-tempering, has high rigidity and high strength, general tensile strength >=1500MPa, Rockwell hardness >=48HRC, can be used as fastening piece, but due to chromium content low, there is huge spread in solidity to corrosion and austenitic stainless steel 304, easy origination point corrosion in use procedure.For tapping screw, for improve austenitic stainless steel 304 cannot tapping shortcoming and play the high advantage of geneva stainless steel 410S hardness, generally available 304 and 410S welding, screw head and screw portion adopt austenitic stainless steel 304, and screw tapping part adopts geneva stainless steel 410S.But the shortcoming of this screw is because austenitic stainless steel 304 and geneva stainless steel 410S weld two layers of material exist potential difference and galvanic corrosion easily occurs, and the intensity of geneva stainless steel 410S of tapping part own is high, solidity to corrosion is poor, easily at pitting attack happening part fracture failure.
Based on the problem of conventional mar stainless steel solidity to corrosion difference, technician is studied, but still only has the solidity to corrosion of minority Martensite Stainless Steel to reach 250 ~ 300mV level of austenitic stainless steel 304.Chinese patent CN104278199 improves solidity to corrosion by adding Mo, Cu and N, pitting potential can reach 270 ~ 300mV, reach the level of austenitic stainless steel 304, but this steel grade carbon content is very high, be 0.28 ~ 0.35%, cold forming capability is poor, and owing to containing 2.5 ~ 3.5%Cu, during hot rolling, low melting point rich Cu phase in surface very easily causes surface imperfection.
Same, Chinese patent CN101233254A have employed approximate alloy designs, there is carbon content equally high, the problem that copper content is high, even if with the addition of Ni, but due to Ni content very low, be also difficult to the problem avoiding hot-work surface imperfection.
As mentioned above, need exploitation one badly and be easy to hot-work and cold working, and there is the geneva stainless steel of high anti-corrosion, high rigidity, for building fastener areas.
Summary of the invention
The object of the present invention is to provide a kind of building structure fastening piece Martensite Stainless Steel and manufacture method thereof, this Martensite Stainless Steel has the solidity to corrosion suitable with 304 stainless steels, but also there is high strength, high rigidity, excellent hot workability and cold forming capability, its pitting potential > 270mV, when the microstructure of this steel is tempered martensite, its Rockwell hardness number is 52 ~ 54HRC, the microstructure of this steel is tempering troostite when organizing, and its Rockwell hardness number is 35 ~ 36HRC.
For achieving the above object, technical scheme of the present invention is:
A kind of building structure fastening piece Martensite Stainless Steel, its chemical component weight per-cent is: C:0.10 ~ 0.20%, N:0.05 ~ 0.15%, Si≤1%, Mn≤1%, P≤0.035%, S≤0.010, Cr:13.0 ~ 14.0%, Mo:1.5 ~ 2.5%, Cu:0.3 ~ 0.8%, Ni:1.5 ~ 2.5%, all the other are Fe and inevitable impurity; And above-mentioned element needs satisfied following relation simultaneously: spot corrosion equivalent PRE > 20%, PRE=Cr+3.3Mo+16N.
Further, the microstructure tempered martensite of building structure fastening piece Martensite Stainless Steel of the present invention or tempering troostite.
The pitting potential > 270mV of described building structure fastening piece Martensite Stainless Steel, when microstructure is tempered martensite, its Rockwell hardness number is 52 ~ 54HRC; Microstructure is tempering troostite when organizing, and its Rockwell hardness number is 35 ~ 36HRC.
In the Composition Design of steel of the present invention:
C:C, for expanding austenite phase field element, is solid-solution in matrix with interstitial atom, forms martensitic stucture after Martensite Stainless Steel quenching, significantly improve intensity and hardness, tempering rear portion C is with Carbide Precipitation, and a part of C is still solid-solution in matrix, and hardness decreases.C content is higher than 0.2%, and carbide volume fraction increases, and significantly worsens the corrosion resistance nature of steel, and cold-forming property reduces simultaneously; C content lower than 0.10% time, in steel delta ferrite increase, hot-work difficulty increase.Therefore, in the present invention, C content controls 0.10 ~ 0.20%.
Cr, Mo:Cr and Mo, for reducing austenite phase field element, can improve the corrosion resistance nature of Martensite Stainless Steel, and along with the increase of Cr, Mo content, stainless steel is at Cl
-in solution, anticorrosion stress-resistant, resistance to spot corrosion, slit and corrosion resistant ability are significantly increased.According to spot corrosion equivalent formula PRE=Cr+3.3Mo+16N, adding Mo and N alloying element and can effectively improve stainless solidity to corrosion, this means, by adding Mo, N, the geneva stainless steel solidity to corrosion of such as low Cr content can be made to reach the level of middle Chromium Stainless Steel 304.By ensureing corrosion resistance nature and the austenitic stainless steel 304 of institute's exploitation Martensite Stainless Steel quite, the spot corrosion equivalent of steel of the present invention must be greater than the spot corrosion equivalent of austenitic stainless steel 304.Therefore, the present invention's control PRE > 20%.
Cr:Cr is that stainless steel formation passive film improves the most important element of resistance to pitting attack performance, and Cr content is lower than 13%, and solidity to corrosion is not enough; Cr content higher than 14% time can form delta ferrite again, reduce stainless hot workability.Therefore, in the present invention, Cr content controls 13 ~ 14%.
Mo:Mo significantly improves stainless corrosion resistance nature, but too high Mo also can cause the formation of delta ferrite, reduces hot workability, and oxide skin also can be caused to be difficult to when pickling remove, and therefore in the present invention, Mo content controls 1.5 ~ 2.5%.
N:N, for expanding austenite phase field element, is solid-solution in matrix with interstitial atom, significantly improves intensity and hardness in martensite; As shown in spot corrosion equivalent PRE formula, N significantly improves stainless resistance to pitting attack performance; N can substitute the formation that Ni suppresses delta ferrite.N content lower than 0.05% time, act on not remarkable; N content is more than 0.15%, and strand or ingot casting easily produce bubble or hole defect, and therefore, in the present invention, N content controls 0.05 ~ 0.15%.
Si, Mn:Si and Mn can be used as reductor in Martensite Stainless Steel.Si can improve stainless high-temperature oxidation resistance effectively, but too much Si can cause the plasticity of steel and toughness to decline.Therefore control Si≤1.0%.Mn, for expanding austenitic area element, can affect tissue, control Mn≤1.0%.
P, S:P, S are impurity element in steel, reduce the high-temp plastic of steel, in Martensite Stainless Steel hot procedure, easily and other factors one defect such as work and cause that limit is split.In addition, S also can reduce the pitting resistance of Martensite Stainless Steel.Therefore, P, S content should be reduced as far as possible.
Cu:Cu can improve resistance to pitting attack performance in austenite, ferrite and Martensite Stainless Steel; As expansion austenitic area element, the formation of high temperature delta ferrite can be suppressed; A certain amount of Cu can improve cold-forming property.But too much Cu can cause hot-work problem, easily cause when low-temperature annealing rich Cu phase to be separated out, cause solidity to corrosion to decline.Therefore, in the present invention, Cu add-on is 0.3 ~ 0.8%.
Ni:Ni is for expanding austenite phase field element, and for ensureing to obtain single phase austenite in high-temperature zone, suppress high temperature delta ferrite ferrite to be formed, it is 1.5 ~ 2.5% that Ni content of the present invention controls.
The present invention, in Composition Design, with the addition of Cr, Mo, N alloying element, guarantee spot corrosion equivalent PRE (PRE=Cr+3.3Mo+16N) higher than 304 PRE=18%, to ensure corrosion resistance nature; Avoid adding too much Cu content; Meanwhile, by adding enough N and Ni, eliminate containing the delta ferrite in molybdenum stainless steel, to ensure hot workability; Suitable reduction C content; Add appropriate Cu, to ensure cold-forming property simultaneously; For proof strength and hardness, replace C with N.
The manufacture method of building structure fastening piece Martensite Stainless Steel of the present invention, it comprises the steps:
1) smelt, cast
Smelt by following chemical composition, casting; Described chemical component weight per-cent is: C:0.10 ~ 0.20%, N:0.05 ~ 0.15%, Si≤1%, Mn≤1%, P≤0.035%, S≤0.010, Cr:13.0 ~ 14.0%, Mo:1.5 ~ 2.5%, Cu:0.3 ~ 0.8%, Ni:1.5-2.5%, all the other are Fe and inevitable impurity; And above-mentioned element needs satisfied following relation simultaneously: spot corrosion equivalent PRE > 20%, PRE=Cr+3.3Mo+16N;
2) heat
Heating temperature is 1100 ~ 1200 DEG C;
3) annealing+pickling
Annealing temperature is 780 ~ 860 DEG C, and annealing soaking time is 3 ~ 4 hours;
4) thermal treatment
Quenching: 1000 ~ 1100 DEG C are incubated 1 ~ 2 hour, oil cooling;
Tempering: 200 ~ 500 DEG C are incubated 1 ~ 2 hour, air cooling.
In manufacture method of the present invention:
Billet heating temperature is 1100 ~ 1200 DEG C: at this temperature, as-cast structure homogenizing, and second-phase dissolves, and is organized as single austenite structure; Make the hot strength of steel billet low, plasticity is good, and resistance to deformation is low, is conducive to high temperature rolling.Hot-rolled sheet controls annealing temperature 780 ~ 860 DEG C, annealing soaking time 3 ~ 4 hours: make martensite in hot rolling microstructure be decomposed into ferrite and carbide; Make tissue fully softening, to carry out follow-up cold working.
Steel of the present invention is when quench hot, and carbide is all solid-solution in austenitic matrix, and pitting resistance significantly improves, and by separating out molybdenum carbide during tempering, but not chromium carbide, ensure that pitting resistance after tempering obvious decline does not occur.Specifically: quenching heat treatment: 1000 ~ 1100 DEG C are incubated 1 ~ 2 hour, and obtain single phase austenite tissue, after oil cooling, austenite structure changes lath martensite tissue into; Tempering heat treatment: 200 ~ 500 DEG C are incubated 1 ~ 2 hour, air cooling, lath martensite decomposes in drawing process, tempered martensite is changed into time low temperature (200 ~ 300 DEG C), can be used for self-tapping screw, then change tempering troostite tissue under middle temperature (400 ~ 500 DEG C), be applicable to bolt.
Beneficial effect of the present invention:
1. the present invention is by reducing C content and increasing N content, while guarantee martensite hardness, improves cold-formed property and solidity to corrosion.
2. the present invention is by adding Cr, Mo, N alloying element, make the spot corrosion equivalent (PRE=18%) of spot corrosion equivalent PRE (PRE > 20%) higher than austenitic stainless steel 304 of described Martensite Stainless Steel, thus make the solidity to corrosion of its solidity to corrosion and austenitic stainless steel 304 suitable.
3. the present invention is by adding appropriate Cu and N, inhibits the formation of high temperature delta ferrite, thus improves hot workability.
4. the present invention is by replacing part Ni with N, reduces Ni content, not only reduces cost of alloy, which in turn improve the stainless corrosion resistance nature of geneva.
5. the nitrogen alloy martensite stainless steel of invention preparation has the advantages such as high anti-corrosion, high strength and high rigidity, has again good hot workability and cold-forming property, is suitable for building fastening piece purposes, has wide market outlook.
Accompanying drawing explanation
Fig. 1 is the tempered structure photo after the quenching of the embodiment of the present invention 2 steel at 500 DEG C.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Table 1 is the composition of the embodiment of the present invention and comparative example steel, and table 2 is the processing parameter of the embodiment of the present invention and comparative example, and table 3 is the hot rolling surface quality of the embodiment of the present invention and comparative example, mechanical property and pitting potential.
Build fastening piece Martensite Stainless Steel described in the embodiment of the present invention to smelt through electric furnace+AOD two-step approach by the composition of table 1, after casting square billet, again through heating, hot rolling, annealing+pickling, thermal treatment, wherein, Heating temperature is 1100 ~ 1200 DEG C, annealing temperature 780 ~ 860 DEG C, annealing soaking time 3 ~ 4 hours; Thermal treatment process comprises Quench and temper, and design parameter is see table 2.
Adopt during the tempering of the present embodiment steel low-temperaturetempering process or average tempering process can, after low-temperaturetempering process, the microstructure of steel is tempered martensite; After average tempering process, the microstructure of steel is tempering troostite tissue, and the quenching structure of embodiment 2 is low-carbon lath martensite, is organized as tiny tempered martensite after 200 DEG C of low-temperaturetemperings, it is then tempering troostite tissue that 500 DEG C of average temperings are organized, as shown in Figure 1.
Hardness test is carried out to the sample after thermal treatment, to measure hardness; Adopt the polarization curve of potentiostatic method measure sample, to obtain the pitting potential of sample, concrete outcome is see table 3.
From table 3, the hot rolling surface of high copper content comparative example 1-2 all produces because the rich Cu phase of surperficial low melting point melts the peeling defect caused, and the embodiment 1-5 surface quality that copper content of the present invention is low is intact, shows steel of the present invention and has good hot workability.
From table 3, hardness after the embodiment 1-5 annealing that carbon content is low is starkly lower than the high comparative example 1-3 of carbon content, steel of the present invention is more easily carried out in follow-up cold-drawn, cold-heading molding and screw chasing processing, indicates steel of the present invention and there is good cold forming capability.
From table 3, after embodiment 1-5 low-temperaturetempering, Rockwell hardness number is 52 ~ 54HRC, close with comparative example 1-3, and after average tempering, Rockwell hardness number is 35 ~ 36HRC, which show the present invention by with the effect of N for C, shows the strengthening effect of N.
From table 3, the pitting potential of embodiment of the present invention 1-5 has all exceeded 270mV, far above comparative example 1-3, suitable with austenitic stainless steel 304 pitting potential 290mV.This is attributable to the comprehensive action of low C, Mo, Cu, N.In addition, during quench hot, carbide is all solid-solution in austenitic matrix, and pitting resistance significantly improves, and by separating out molybdenum carbide during tempering, but not chromium carbide, ensure that pitting resistance after tempering obvious decline does not occur.
Claims (6)
1. a building structure fastening piece Martensite Stainless Steel, its chemical component weight per-cent is: C:0.10 ~ 0.20%, N:0.05 ~ 0.15%, Si≤1%, Mn≤1%, P≤0.035%, S≤0.010, Cr:13.0 ~ 14.0%, Mo:1.5 ~ 2.5%, Cu:0.3 ~ 0.8%, Ni:1.5 ~ 2.5%, all the other are Fe and inevitable impurity; And above-mentioned element needs satisfied following relation simultaneously: spot corrosion equivalent PRE > 20%, PRE=Cr+3.3Mo+16N.
2. building structure fastening piece Martensite Stainless Steel according to claim 1, is characterized in that, the microstructure of described building structure fastening piece Martensite Stainless Steel is tempered martensite or tempering troostite.
3. building structure fastening piece Martensite Stainless Steel according to claim 1 and 2, it is characterized in that, the pitting potential > 270mV of described building structure fastening piece Martensite Stainless Steel, when microstructure is tempered martensite, its Rockwell hardness number is 52 ~ 54HRC; Microstructure is tempering troostite when organizing, and its Rockwell hardness number is 35 ~ 36HRC.
4. a manufacture method for building structure fastening piece Martensite Stainless Steel, is characterized in that, it comprises the steps:
1) smelt, cast
Smelt by following chemical composition, casting; Described chemical component weight per-cent is: C:0.10 ~ 0.20%, N:0.05 ~ 0.15%, Si≤1%, Mn≤1%, P≤0.035%, S≤0.010, Cr:13.0 ~ 14.0%, Mo:1.5 ~ 2.5%, Cu:0.3 ~ 0.8%, Ni:1.5-2.5%, all the other are Fe and inevitable impurity; And above-mentioned element needs satisfied following relation simultaneously: spot corrosion equivalent PRE > 20%, PRE=Cr+3.3Mo+16N;
2) heat
Heating temperature is 1100 ~ 1200 DEG C;
3) annealing+pickling
Annealing temperature is 780 ~ 860 DEG C, and annealing soaking time is 3 ~ 4 hours;
4) thermal treatment
Quenching: 1000 ~ 1100 DEG C are incubated 1 ~ 2 hour, oil cooling;
Tempering: 200 ~ 500 DEG C are incubated 1 ~ 2 hour, air cooling.
5. the manufacture method of building structure fastening piece Martensite Stainless Steel according to claim 4, is characterized in that, the microstructure of described building structure fastening piece Martensite Stainless Steel is tempered martensite or tempering troostite.
6. the manufacture method of the building structure fastening piece Martensite Stainless Steel according to claim 4 or 5, it is characterized in that, the pitting potential > 270mV of described building structure fastening piece Martensite Stainless Steel, when microstructure is tempered martensite, its Rockwell hardness number is 52 ~ 54HRC; Microstructure is tempering troostite when organizing, and its Rockwell hardness number is 35 ~ 36HRC.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823362A (en) * | 2018-07-27 | 2018-11-16 | 成都先进金属材料产业技术研究院有限公司 | The heat treatment method of 20Cr13 stainless steel |
| CN109518086A (en) * | 2018-12-12 | 2019-03-26 | 国家电投集团黄河上游水电开发有限责任公司 | Alloy material for carbon strong cooling machine plough share shovel for aluminum |
| CN111304416A (en) * | 2020-03-27 | 2020-06-19 | 包头钢铁（集团）有限责任公司 | Softening annealing heat treatment method for 2Cr13 stainless steel |
-
2015
- 2015-09-25 CN CN201510621186.7A patent/CN105296877A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823362A (en) * | 2018-07-27 | 2018-11-16 | 成都先进金属材料产业技术研究院有限公司 | The heat treatment method of 20Cr13 stainless steel |
| CN109518086A (en) * | 2018-12-12 | 2019-03-26 | 国家电投集团黄河上游水电开发有限责任公司 | Alloy material for carbon strong cooling machine plough share shovel for aluminum |
| CN111304416A (en) * | 2020-03-27 | 2020-06-19 | 包头钢铁（集团）有限责任公司 | Softening annealing heat treatment method for 2Cr13 stainless steel |
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Application publication date: 20160203 |