Patent Grant
11286546
This is a national stage application filed under 35 USC 371 based on International Application No. PCT/FI2011/050345 filed Apr. 18, 2011, and claims priority under 35 USC 119 of Finnish Patent Application No. 20100178 filed Apr. 29, 2010.
The present invention relates to a method for manufacturing and utilizing a lean ferritic-austenitic stainless steel manufactured mainly in the form of coils with high strength, excellent formability and good corrosion resistance. The formability is achieved by a controlled martensite transformation of the austenite phase resulting in a so called transformation-induced plasticity (TRIP).
Numerous lean ferritic-austenitic or duplex alloys have been proposed to combat the high costs of raw materials such as nickel and molybdenum with the main goal to accomplish adequate strength and corrosion performance. When referring to the following publications, the element contents are in weight %, if not anything else mentioned.
U.S. Pat. No. 3,736,131 describes an austenitic-ferritic stainless steel with 4-11% Mn, 19-24% Cr, up to 3.0% Ni and 0.12-0.26% N containing 10 to 50% austenite, which is stable and exhibits high toughness. The high toughness is obtained by avoiding austenite transformation to martensite.
U.S. Pat. No. 4,828,630 discloses duplex stainless steels with 17-21.5% Cr, 1 to less than 4% Ni, 4-8% Mn and 0.05-0.15% N that are thermally stable against transformation to martensite. The ferrite content has to be maintained below 60% to achieve good ductility.
Swedish patent SE 517449 describes a lean duplex alloy with high strength, good ductility and high structural stability with 20-23% Cr, 3-8% Mn, 1.1-1.7% Ni and 0.15-0.30% N.
WO patent application 2006/071027 describes a low nickel duplex steel with 19.5-22.5% Cr, 0.5-2.5% Mo, 1.0-3.0% Ni, 1.5-4.5% Mn and 0.15-0.25% N having improved hot ductility compared to similar steels.
EP patent 1352982 disclosed a means of avoiding delayed cracking in austenitic Cr—Mn steels by introducing certain amounts of ferrite phase.
In recent years lean duplex steels have been used to a great extent and steels according to U.S. Pat. No. 4,848,630, SE patent 517.449, EP patent application 1867748 and U.S. Pat. No. 6,623,569 have been used commercially in a large number of applications. Outokumpu LDX 2101® duplex steel according to SE 517.449 has been widely used in storage tanks, transport vehicles, etc. These lean duplex steels have the same problem as other duplex steels, a limited formability which makes them less applicable for use in highly formed parts than austenitic stainless steels. Duplex steels have therefore a limited application in components such as plate heat exchangers. However, lean duplex steels have a unique potential to improved ductility as the austenite phase can be made sufficiently low in the alloy content to be metastable giving increased plasticity by a mechanism as described below.
There are a few references that are utilizing a metastable austenitic phase in duplex steels for improved strength and ductility. U.S. Pat. No. 6,096,441 relates austenitic-ferritic steels with high tensile elongation containing essentially 18-22% Cr, 2-4% Mn, less than 1% Ni and 0.1-0.3% N. A parameter related to the stability in terms of martensite formation shall be within a certain range resulting in improved tensile elongation. US patent application 2007/0163679 describes a very wide range of austenitic-ferritic alloys with high formability mainly by controlling the content of C+N in the austenite phase.
Transformation induced plasticity (TRIP) is a known effect for metastable austenitic steels. For example, local necking in a tensile test sample is hampered by the strain induced transformation of soft austenite to hard martensite conveying the deformation to another location of the sample and resulting in a higher uniform deformation. TRIP can also be used for ferritic-austenitic (duplex) steels if the austenite phase is designed correctly. The classical way to design the austenite phase for a certain TRIP effect is to use established or modified empirical expressions for the austenite stability based on its chemical composition, one of which is the Md30-temperature. The Md30-temperature is defined as the temperature at which 0.3 true strain yields 50% transformation of the austenite to martensite. However, the empirical expressions are established with austenitic steels and there is a risk to apply them on duplex stainless steels.
It is more complex to design the austenite stability of duplex steels since the composition of the austenite phase depends on both the steel chemistry and on the thermal history. Furthermore, the phase morphology and size influence the transformation behaviour. U.S. Pat. No. 6,096,441 has used an expression for the bulk composition and claims a certain range (40-115) which is required to obtain the desired effect. However, this information is only valid for the thermal history used for the steels in this particular investigation, as the austenite composition will vary with the annealing temperature. In US patent application 2007/0163679 the composition of the austenite was measured and a general Md formula for the austenite phase was specified to range from −30 to 90 for steels to show the desired properties.
Empirical formulas for the austenite stability are based on investigations of standard austenitic steels and can have a limited usability for the austenite phase in duplex steel as the conditions for stability are not restricted to the composition only but also to residual stresses and phase or grain parameters. As disclosed in US patent application 2007/0163679, a more direct way is to assess the stability of the martensite by measuring the composition of the austenite phase and then calculate the amount of martensite formation upon cold work. However, this is a very tedious and costly procedure and requires a high class metallurgical laboratory. Another way is to use thermodynamic databases to predict the equilibrium phase balance and compositions of each phase. However, such databases cannot describe the non-equilibrium conditions that prevail after thermo-mechanical treatments in most practical cases. An extensive work with different duplex compositions having a partly metastable austenite phase showed that the annealing temperatures and the cooling rates had a very large influence on the austenite content and the composition making predictions of the martensite formation based on the empirical expressions difficult. To be able to fully control the martensite formation in duplex steels, knowledge of the austenite composition together with micro-structural parameters seemed necessary but not sufficient.
In view of the prior art problems a proper way of the invention is instead to measure the Md30 temperature for different steels and to use this information to design optimum compositions and manufacturing steps for high ductility duplex steels. Additional information obtained from measuring the Md30 temperature is the temperature dependence for different steels. As forming processes occur at various temperatures it is of importance to know this dependence and to use it for modelling the forming behaviour.
The principal object of the present invention is to provide a controlled manufacturing method of strain induced martensite transformation in a lean duplex stainless steel to obtain excellent formability and good corrosion resistance. Desired effects can be accomplished with the alloy mainly comprising (in weight %): less than 0.05% C, 0.2-0.7% Si, 2-5% Mn, 19-20.5% Cr, 0.8-1.35% Ni, less than 0.6% Mo, less than 1% Cu, 0.16-0.22% N, the balance Fe and inevitable impurities occurring in stainless steels. Optionally the alloy can further contain one or more deliberately added elements; 0-0.5% tungsten (W), 0-0.2% niobium (Nb), 0-0.1% titanium (Ti), 0-0.2% vanadium (V), 0-0.5% cobalt (Co), 0-50 ppm boron (B), and 0-0.04% aluminium (Al). The steel can contain inevitable trace elements as impurities such as 0-50 ppm oxygen (O), 0-50 ppm sulphur (S) and 0-0.04% phosphorus (P). The duplex steel according to the invention shall contain from 45 to 75% austenite in the heat-treated condition, the remaining phase being ferrite and no thermal martensite. The heat treatment can be carried out using different heat treatment methods, such as solution annealing, high-frequency induction annealing or local annealing, in the temperature range from 900 to 1200° C., advantageously from 1000 to 1150° C. To obtain the desired ductility improvement the measured Md30 temperature shall be between zero and +50° C. Empirical formulas describing the correlation between the steel compositions and the thermo-mechanical treatments are to be used to design the optimum formability for said steels. The essential features of the present invention are enlisted in the appended claims.
An important feature of the present invention is the behaviour of the austenite phase in the duplex microstructure. Work with the different alloys showed that the desired properties are only obtained within a narrow compositional range. However, the main idea with the present invention is to disclose a procedure to obtain the optimum ductility of certain duplex alloys where the proposed steels represent examples with this effect. Nevertheless, the balance between the alloying elements is crucial since all the elements affect the austenite content, add to the austenite stability and influence strength and corrosion resistance. In addition, the size and morphology of the microstructure will affect the phase stability as well as strength of the material and have to be restricted for a controlled process.
Due to failures in predicting the formability behaviour of metastable ferritic-austenitic steels, a new concept or model is presented. This model is based on the measured metallurgical and mechanical values coupled with the empirical descriptions to select proper thermal-mechanical treatments for products with tailor-made properties.
Effects of different elements in the microstructure are described in the following, the element contents being described in weight %:
Carbon (C) partitions to the austenite phase and has a strong effect on austenite stability. Carbon can be added up to 0.05% but higher levels have detrimental influence on corrosion resistance. Preferably the carbon content shall be 0.01-0.04%.
Nitrogen (N) is an important austenite stabilizer in duplex alloys and like carbon it increases the stability against martensite. Nitrogen also increases strength, strain hardening and corrosion resistance. Published general empirical expressions on Md30 indicate that nitrogen and carbon have the same strong influence on austenite stability but the present work shows a weaker influence of nitrogen in duplex alloys. As nitrogen can be added to stainless steels in larger extent than carbon without adverse effects on corrosion resistance contents from 0.16 up to 0.24% are effective in actual alloys. For the optimum property profile 0.18-0.22% is preferable.
Silicon (Si) is normally added to stainless steels for deoxidizing purposes in the melt shop and should not be below 0.2%. Silicon stabilizes the ferrite phase in duplex steels but has a stronger stabilizing effect on austenite stability against martensite formation than shown in current expressions. For this reason silicon is maximized to 0.7%, preferably 0.6%, most preferably 0.4%.
Manganese (Mn) is an important addition to stabilize the austenite phase and to increase the solubility of nitrogen in the steel. By this manganese can partly replace the expensive nickel and bring the steel to the right phase balance. Too high levels will reduce the corrosion resistance. Manganese has a stronger effect on austenite stability against deformation martensite than indicated in published literature and the manganese content must be carefully addressed. The range of manganese shall be from 2.0 to 5.0%.
Chromium (Cr) is the main addition to make the steel resistant to corrosion. Being ferrite stabilizer chromium is also the main addition to create a proper phase balance between austenite and ferrite. To bring about these functions the chromium level should be at least 19% and to restrict the ferrite phase to appropriate levels for the actual purpose the maximum content should be 20.5%.
Nickel (Ni) is an essential alloying element for stabilizing the austenite phase and for good ductility and at least 0.8% must be added to the steel. Having a large influence on austenite stability against martensite formation nickel has to be present in a narrow range. Because of nickel's high cost and price fluctuation nickel should be maximized in actual steels to 1.35%, and preferably 1.25%. Ideally, the nickel composition should be 1.0-1.25%.
Copper (Cu) is normally present as a residual of 0.1-0.5% in most stainless steels, as the raw materials to a great deal is in the form of stainless scrap containing this element. Copper is a weak stabilizer of the austenite phase but has a strong effect on the resistance to martensite formation and must be considered in evaluation of formability of the actual alloys. An intentional addition up to 1.0% can be made.
Molybdenum (Mo) is a ferrite stabilizer that can be added to increase the corrosion resistance. Molybdenum increases the resistance to martensite formation, and together with other additions molybdenum cannot be added to more than 0.6%.
The present invention is described in more details referring to the drawings, where
Detailed studies of the martensite formation were performed for some lean duplex alloys. Particular attention was paid on the effect of martensite formation and Md30 temperature on mechanical properties. This knowledge, crucial in designing a steel grade of optimum properties, is lacking from the prior art patents. Tests were done for some selected alloys according to Table 1.
The alloys A, B and C are examples of the present invention. The alloy D is according to US patent application 2007/0163679, while LDX 2101 is a commercially manufactured example of SE 517449, a lean duplex steel with an austenite phase that has good stability to deformation martensite formation.
The steels were manufactured in a vacuum induction furnace in 60 kg scale to small slabs that were hot rolled and cold rolled down to 1.5 mm thickness. The alloy 2101 was commercially produced in 100 ton scale, hot rolled and cold rolled in coil form. A heat treatment using solution annealing was done at different temperatures from 1000 to 1150° C., followed by rapid air cooling or water quenching.
The chemical composition of the austenite phase was measured using scanning electron microscope (SEM) with energy dispersive and wavelength dispersive spectroscopy analysis and the contents are listed in Table 2. The proportion of the austenite phase (% γ) was measured on etched samples using image analysis in light optical microscope.
The actual Md30 temperatures (Md30 test temp) were established by straining the tensile samples to 0.30 true strain at different temperatures and by measuring the fraction of the transformed martensite (Martensite %) with Satmagan equipment. Satmagan is a magnetic balance in which the fraction of ferromagnetic phase is determined by placing a sample in a saturating magnetic field and by comparing the magnetic and gravitational forces induced by the sample. The measured martensite contents and the resulting actual Md30 temperatures (Md30 measured) along with the predicted temperatures using Nohara expression Md30=551−462(C+N)−9.2Si−8.1Mn−13.7Cr−29(Ni+Cu)−18.5Mo−68Nb (Md30 Nohara) for the austenite composition are listed in Table 3. The measured proportion of austenite transformed to martensite at true stain 0.3 versus testing temperature is illustrated in
Measurements of the ferrite and austenite contents were made using light optical image analysis after etching in Beraha's etchant and the results are reported in Table 4. The microstructures were also assessed regarding the structure fineness expressed as austenite width (γ-width) and austenite spacing (γ-spacing). These data are included in Table 4 as well as the uniform elongation (Ag) and elongation to fracture (A50/A80) results in longitudinal (long) and transversal (trans) directions.
Examples of the resulting microstructures are shown in
1)Strain rate 0.00075 s−1/0.005 s−1
2)A80
To investigate the resistance to corrosion, the pitting potentials of the alloys were measured on samples, which were wet-ground to 320 mesh surface finish, in 1M NaCl solution at 25° C. using Standard Calomel electrode with a voltage scan of 10 mV/min. Three individual measurements were made for each grade. The results are shown in Table 6.
Table 2 reveals that the phase balance and composition of the austenite phase vary with the solution annealing temperature. The austenite content decreases with increasing temperature. The compositional change in substitutive elements is small while the interstitial elements carbon and nitrogen show greater variation. As the carbon and nitrogen elements according to available formulas have a strong effect on the austenite stability against martensite formation, it appears to be crucial to control their level in the austenite. As shown in Table 3, the calculated Md30 temperatures are clearly lower for the heat treatments at higher temperature, indicating a greater stability. However, the measured Md30 temperatures do not display such dependence. For the alloys A, B and C the Md30 temperature is slightly reduced with just 3-4° C. when increasing the solution temperature with 100° C. This difference can be attributed to several effects. For example, the higher annealing temperature results in a coarser microstructure, which is known to affect the martensite formation. The tested examples have an austenite width or an austenite spacing in the order of about 2 to 6 μm. The products with the coarser microstructure show different stability and deviating description. The results show that the prediction of the martensite formation using current established expressions is not functional, even if advanced metallographic methods are employed.
In
The Md30-temperatures and the martensite contents at uniform elongation of the tested steels are also shown in
Apparently, based on the present experimental results, the range of optimum Md30-temperature is substantially narrower than indicated by the prior art patents. A too high Md30-temperature causes rapid peaking of the strain-hardening rate. After peaking the strain-hardening rate drops rapidly, resulting in early onset of necking and low uniform elongation. According to the experimental results, the Md30-temperature of the steel C appears to be close to the upper limit. If the Md30-temperature was much higher, the uniform elongation would be substantially decreased.
On the other hand, if the Md30-temperature is too low, not enough martensite is formed during deformation. Therefore, the strain-hardening rate remains low, and consequently, the onset of necking occurs at a low strain level. In
Based on the experiments, the chemical composition and the thermo-mechanical treatments shall be designed so that the resulting Md30-temperature of the steel ranges is between 0 and +50° C., preferably between 10° C. and 45° C., and more preferably 20-35° C.
The tensile test data in Table 5 illustrates that the elongation at fracture is high for all steels according to the invention while the commercial lean duplex steel (LDX 2101) with a more stable austenite exhibits lower elongation values typical for standard duplex steels.
Both the diagrams,
The control of the Md30 temperature is crucial to attain high deformation elongation. It is also important to take the material temperature during deformation into consideration as it largely influences the amount of martensite that can form. Data in Table 5 and in
The results show that the alloy A with lower Md30 temperature exhibits a reduction in elongation at elevated temperature, while the alloy C with the higher Md30 temperature demonstrates an increased elongation when the temperature is raised.
Table 6 shows that the pitting corrosion resistance, expressed as pitting potential in 1M NaCl, is at least as good as that of the austenitic standard steel 304L.
Prior art has not disclosed sufficient capability to design duplex steels with TRIP-effect properly as the predictions of the steel behaviour using established formulas are unsecure giving too wide ranges in the compositions and in other specifications. According to the present invention lean duplex steels can be more safely designed and manufactured with optimum ductility by selecting certain composition ranges and by using a special procedure involving measurement of the actual Md30 temperature and by employing special empirical knowledge to control the manufacturing processes. This new innovative approach is necessary to be able to utilize the real TRIP effect in the design of highly formable products. As illustrated in
| Number | Date | Country | Kind |
|---|---|---|---|
| 20100178 | Apr 2010 | FI | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FI2011/050345 | 4/18/2011 | WO | 00 | 10/19/2012 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2011/135170 | 11/3/2011 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3736131 | Espy | May 1973 | A |
| 3871925 | Nunes | Mar 1975 | A |
| 4828630 | Daniels et al. | May 1989 | A |
| 6096441 | Hauser et al. | Aug 2000 | A |
| 6623569 | Bergstrom et al. | Sep 2003 | B2 |
| 20070163679 | Fujisawa et al. | Jul 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| 1352982 | Oct 2003 | EP |
| 1867748 | Dec 2007 | EP |
| 2172574 | Apr 2010 | EP |
| 2258885 | Dec 2010 | EP |
| 2006291294 | Oct 2006 | JP |
| 517449 | Jun 2002 | SE |
| 2006071027 | Jul 2006 | WO |
| Entry |
|---|
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| International Search Report PCT/FI2011/050345, completed Jul. 15, 2011, dated Jul. 19, 2011, 3 pages. |
| Finnish Search Report, FI20100178, completed Feb. 18, 2011, 7 pages. |
| Australian Examination Report prepared by IP Australia for related AU Application No. 2011247272, dated Nov. 6, 2015, 3 pages. |
| Notification prepared by the Eurasian Patent Office for related EA application 9-10448/EA, dated Feb. 29, 2016, 2 pages. |
| Written Opinion for related PCT/FI2011/050345, completed Jul. 15, 2011, 2 pages. |
| Extended European Search Report prepared by the European Patent Office for EP11774473.0, dated Nov. 8, 2016, 10 pages. |
| Andersson, Roger, “Deformation Characteristics of Stainless Steels,” Doctoral Thesis, Lulea University of Technology, 2005, pp. 1-133 pages. |
| Talonen, J. et al., “Comparison of Different Methods for Measuring Strain Induced α'-martensite Content in Austenitic Steels,” Materials Science and Technology, Dec. 2004, vol. 20, No. 12, pp. 1506-1512. |
| Number | Date | Country | |
|---|---|---|---|
| 20130032256 A1 | Feb 2013 | US |
