WO2019168172A1

WO2019168172A1 - HIGH Mn STEEL AND METHOD FOR PRODUCING SAME

Info

Publication number: WO2019168172A1
Application number: PCT/JP2019/008176
Authority: WO
Inventors: 孝一中島; 植田　圭治; 大地泉; 聡伊木; 知宏小野
Original assignee: Ｊｆｅスチール株式会社
Priority date: 2018-03-02
Filing date: 2019-03-01
Publication date: 2019-09-06
Also published as: KR102387364B1; KR20200123831A

Abstract

Provided is a high Mn steel which has high strength, while exhibiting excellent fatigue resistance characteristics and excellent toughness at low temperatures. This high Mn steel is configured to have a component composition that contains 0.10-0.70% of C, 0.05-1.0% of Si, 20-30% of Mn, 0.030% or less of P, 0.0070% or less of S, 0.01-0.07% of Al, 0.5-7.0% of Cr, 0.040-0.10% of N, 0.0050% or less of O, 0.005% or less of Ti, 0.005% or less of Nb, less than 0.0010% of Mg and less than 0.0010% of REM, while satisfying Ti/N ≤ 0.10, with the balance made up of Fe and unavoidable impurities.

Description

High Mn steel and manufacturing method thereof

The present invention relates to a high Mn steel excellent in fatigue resistance and toughness particularly at low temperatures, and a method for producing the same, which is suitable for use in structural steels used in cryogenic environments such as liquefied gas storage tanks.

Attempts have been made to use hot-rolled steel sheets for structures such as tanks for liquefied gas storage tanks. Since such a structure is used in an extremely low temperature environment, the hot-rolled steel sheet applied to the structure is required to have excellent toughness at an extremely low temperature in addition to high strength. For example, when a hot-rolled steel sheet is used in a liquefied natural gas storage tank, it is necessary to ensure excellent toughness at a boiling point of liquefied natural gas: −164 ° C. or lower. If the low-temperature toughness of the steel material is inferior, the safety as a structure for cryogenic storage tanks may not be maintained. Therefore, there is a strong demand for improving the low-temperature toughness of the applied steel material.

In response to this requirement, conventionally, austenitic stainless steel, 9% Ni steel, or 5000 series aluminum alloy having a structure of austenite that does not show brittleness at extremely low temperatures has been used. However, since alloy costs and manufacturing costs are high, there is a demand for steel materials that are inexpensive and have excellent low-temperature toughness.

Therefore, as a new steel material to replace the conventional cryogenic steel, it is possible to apply high Mn steel, which is a relatively inexpensive austenite stabilizing element Mn, to a structure in a cryogenic environment. 1 and Patent Document 2.
Patent Document 1 proposes regulating the carbide coverage of austenite grain boundaries. Patent Document 2 proposes to control the ratio of the Mn enriched part and the diluted part.

Japanese Unexamined Patent Publication No. 2016-84529 Japanese Unexamined Patent Publication No. 2017-71817

By the way, in Patent Document 1 and Patent Document 2, low temperature toughness by Charpy impact test is evaluated. However, in a liquefied gas storage tank or the like, a load is applied at the time of replacement, operation and transportation of liquefied gas, etc. It is necessary to ensure the structural safety of the structure against repeated loads. Therefore, the hot-rolled steel sheet used for the structure is required to have excellent fatigue characteristics against repeated loads.

Accordingly, an object of the present invention is to provide a high Mn steel having high strength and excellent toughness and fatigue resistance at low temperatures. Here, “excellent toughness at low temperature” means that the absorbed energy vE ₋₁₉₆ of Charpy impact test at −196 ° C. is 100 J or more, and “excellent fatigue property at low temperature” means −165 ° C. It means that the fatigue strength at is 700 MPa or more.

In order to achieve the above-mentioned problems, the present inventors have conducted intensive studies on various factors that determine the component composition of a steel sheet, and obtained the following knowledge.
First, an austenite structure is obtained by setting a high Mn composition. With this austenite structure, a brittle fracture does not occur even at an extremely low temperature, and a steel sheet having excellent low temperature toughness can be obtained. Next, in order to improve fatigue resistance, it is effective to increase the yield stress at extremely low temperatures, and appropriately control the addition amount of C, Mn, Ti and N, and further perform hot working according to appropriate manufacturing conditions. It was found that rolling and cooling are important.

The present invention has been made by further studying the above knowledge, and the gist thereof is as follows.
1. % By mass
C: 0.10 to 0.70%,
Si: 0.05 to 1.0%,
Mn: 20-30%,
P: 0.030% or less,
S: 0.0070% or less,
Al: 0.01 to 0.07%,
Cr: 0.5 to 7.0%,
N: 0.040 to 0.10%,
O: 0.0050% or less,
Ti: 0.005% or less,
Nb: 0.005% or less,
High-Mn steel containing Mg: less than 0.0010% and REM: less than 0.0010%, the balance having a component composition of Fe and inevitable impurities and satisfying the following formula (1).
Ti / N ≦ 0.10 (1)

2. 2. The high Mn steel according to 1, wherein the component composition further satisfies the following formula (2).
(Mn × O) / S <27 (2)

3. The component composition is further mass%,
Cu: 1.0% or less,
Ni: less than 0.1%,
Mo: 2.0% or less,
V: 2.0% or less,
W: 2.0% or less,
3. The high Mn steel according to 1 or 2 above, containing one or more selected from Ca: 0.0005 to 0.0050% and B: 0.0050% or less.

4). After the steel material having the component composition described in the above 1, 2 or 3 is heated to a temperature range of 1100 ° C. or more and 1300 ° C. or less, the finish rolling finish temperature is 750 ° C. or more and less than 950 ° C. and less than 950 ° C. The average cooling rate from a temperature of (finishing finish temperature -100 ° C) or higher to a temperature range of 300 ° C or higher and 650 ° C or lower is 1.0 ° C / s or higher. A method for producing high-Mn steel that performs a cooling treatment.

According to the present invention, it is possible to provide a high Mn steel particularly excellent in low temperature toughness. Therefore, the high Mn steel of the present invention greatly contributes to the improvement of safety and life of a steel structure used in a cryogenic environment such as a liquefied gas storage tank, and has a remarkable industrial effect.

Hereinafter, the high Mn steel of the present invention will be described in detail.
[Ingredient composition]
First, the component composition of the high Mn steel of the present invention and the reason for limitation will be described. The “%” in the component composition means “% by mass” unless otherwise specified.
C: 0.10 to 0.70%
C is an inexpensive austenite stabilizing element and an important element for obtaining austenite. In order to acquire the effect, C needs to contain 0.10% or more. On the other hand, if the content exceeds 0.70%, Cr carbide is excessively generated and low temperature toughness is lowered. Therefore, the C content is 0.10 to 0.70%. Preferably, the content is 0.20% or more and 0.60% or less.

Si: 0.05 to 1.00%
Si acts as a deoxidizer and is not only necessary for steelmaking, but also has the effect of increasing the strength of the steel sheet by solid solution and solid solution strengthening. In order to acquire such an effect, Si needs to contain 0.05% or more. On the other hand, when it contains exceeding 1.00%, weldability will deteriorate. Therefore, the Si content is set to 0.05 to 1.00%. Preferably, the content is 0.07% or more and 0.50% or less.

Mn: 20-30%
Mn is a relatively inexpensive austenite stabilizing element. In the present invention, it is an important element for achieving both strength and cryogenic toughness. In order to acquire the effect, Mn needs to contain 20% or more. On the other hand, even if the content exceeds 30%, the effect of improving the low temperature toughness is saturated, leading to an increase in alloy cost. In addition, weldability and cutability are deteriorated. Furthermore, segregation is promoted and stress corrosion cracking is promoted. Therefore, the Mn content is 20-30%. Preferably, it is 23% or more and 28% or less.

P: 0.030% or less When P exceeds 0.030%, it segregates at the grain boundary and becomes the starting point of stress corrosion cracking. For this reason, it is desirable to make 0.030% an upper limit and to reduce as much as possible. Therefore, P is 0.030% or less. In addition, since excessive P reduction raises refining cost and becomes economically disadvantageous, it is desirable to set it as 0.002% or more from a viewpoint of economical efficiency. Preferably, it is 0.028% or less, more preferably 0.024% or less.

S: 0.0070% or less Since S deteriorates the low-temperature toughness and ductility of the base material, 0.0070% is the upper limit and it is desirable to reduce it as much as possible. Therefore, S is made 0.0070% or less. In addition, since excessive reduction of S raises refining cost and becomes economically disadvantageous, it is desirable to set it as 0.001% or more from an economical viewpoint. Preferably it is 0.0060% or less.

Al: 0.01 to 0.07%
Al acts as a deoxidizer and is most commonly used in the molten steel deoxidation process for steel sheets. In order to acquire such an effect, Al needs to contain 0.01% or more. On the other hand, if the content exceeds 0.07%, it is mixed in the weld metal part during welding and deteriorates the toughness of the weld metal, so the content is made 0.07% or less. For this reason, Al is made 0.01 to 0.07%. Preferably, the content is 0.02% or more and 0.06% or less.

Cr: 0.5 to 7.0%
Cr is an element that stabilizes austenite by addition of an appropriate amount and is effective in improving low-temperature toughness and base material strength. In order to acquire such an effect, Cr needs to contain 0.5% or more. On the other hand, if the content exceeds 7.0%, the low temperature toughness and stress corrosion cracking resistance decrease due to the formation of Cr carbide. Therefore, Cr is 0.5 to 7.0%. Preferably they are 1.0% or more and 6.7% or less, More preferably, they are 1.2% or more and 6.5% or less. Moreover, in order to further improve the stress corrosion cracking resistance, 2.0% to 6.0% is more preferable.

N: 0.0400 to 0.1000%
N is one of the most important elements in this material. It is an austenite stabilizing element and an element effective for improving low-temperature toughness. It also yields at room temperature and extremely low temperature by dissolving in the austenite matrix. It is effective in improving It is known that the effect of increasing the strength by the solid solution element is greatly influenced by interstitial elements such as carbon and nitrogen, but in the austenitic steel, the effect of solid solution nitrogen is particularly large. In order to acquire such an effect, 0.0400% or more of N content is required. On the other hand, if the content exceeds 0.1000%, the effect is saturated, so N is 0.0400 to 0.1000%. Preferably, it is 0.0450 to 0.0950%.

O: 0.0050% or less O deteriorates low-temperature toughness due to the formation of oxides. For this reason, O is made into 0.0050% or less of range. Preferably, it is 0.0045% or less. In addition, since excessive reduction of O raises refining cost and becomes economically disadvantageous, it is desirable to set it as 0.0005% or more from a viewpoint of economical efficiency.

The content of Ti and Nb is suppressed to 0.005% or less respectively The content of Mg and REM is suppressed to less than 0.0010% Ti, Nb, Mg, and REM are high-melting carbonitrides in steel and / or Oxysulfide is formed to suppress the coarsening of crystal grains, and as a result, it becomes a starting point of fracture and a path of crack propagation. In particular, in high Mn steel, the structure control for improving low temperature toughness and improving ductility is hindered, so it is necessary to intentionally suppress it. That is, by suppressing the content of Ti and Nb to 0.005% or less and suppressing the content of Mg and REM to less than 0.0010% respectively, the above-described adverse effects of carbonitride and oxysulfide are reduced. It can be eliminated and excellent low temperature toughness and ductility can be secured. Preferably, each content of Ti and Nb is 0.003% or less.

In the above component composition, it is necessary to satisfy the following formula (1).
Ti / N ≦ 0.10 (1)
As described above, N effectively acts to improve the yield stress at room temperature and extremely low temperature by being dissolved in the austenite matrix. At that time, when Ti / N increases, N is fixed to Ti, and the above-described effects are limited. Therefore, it is important to satisfy Ti / N ≦ 0.10.

In the above component composition, it is preferable that the following formula (2) is further satisfied.
(Mn × O) / S <27 (2)
In an austenitic material with a high Mn composition, the low temperature toughness is improved and stabilized by increasing the crystal grain size without excessively acting the grain growth suppression effect due to the dispersion of oxides and sulfides. ) / S <27.

The balance other than the above components is iron and inevitable impurities. Inevitable impurities here include H and the like, and a total of 0.01% or less is acceptable.
By adjusting to the basic component described above, a steel having a microstructure with austenite as a base phase can be obtained.

[Microstructure based on austenite]
When the crystal structure of the steel material is a body-centered cubic structure (bcc), the steel material may cause brittle fracture in a low temperature environment, and thus is not suitable for use in a low temperature environment. Here, when assumed to be used in a low temperature environment, the base phase in the steel structure is austenite whose crystal structure is a face-centered cubic structure (fcc). The phrase “having austenite as a base phase” indicates that the austenite phase is 90% or more in area ratio, and may be 100%. On the other hand, the remainder other than the austenite phase is composed of the ferrite or martensite phase of BCC structure, inclusions and precipitates, and the ratio of these is preferably 5% or less. The austenite fraction can be determined by observation by EBSD, analysis by XRD, magnetic permeability, and the like.

In the present invention, for the purpose of further improving the strength and the low temperature toughness, the following elements can be contained as required in addition to the above essential elements.
Cu: 1.0% or less, Ni: less than 0.1%, Mo: 2.0% or less, V: 2.0% or less, W: 2.0% or less, Ca: 0.0005 to 0.0050% , B: 1 type or 2 types or more of 0.0050% or less

Cu: 1.0% or less, Ni: less than 0.1% Mo, V, W: 2.0% or less each Cu, Ni, Mo, V, and W contribute to stabilization of austenite and have a base material strength. Contributes to improvement. In order to obtain such an effect, Cu, Ni, Mo, V and W are preferably contained at 0.01% or more.
On the other hand, even if Cu is added in excess of 1.0%, the effect is saturated.

Ni has the effect of improving low-temperature toughness, but it is an important viewpoint in the component design of the present invention to minimize to the minimum necessary from the viewpoint of alloy cost. From this viewpoint, the Ni amount is less than 0.1%. . Here, there are stainless steels such as SUS304 and SUS316 as austenitic steels that are excellent in low temperature toughness. These steels have a large amount from the viewpoint of alloy design for obtaining an austenitic structure, for example, optimization of Ni equivalent-Cr equivalent. Ni is added and the alloy cost is high. For these steels, the present invention is an austenitic material that is reduced in cost by minimizing Ni. A preferable amount of Ni is 0.01% or more and 0.07% or less.

When Mo, V, and W are contained in excess of 2.0%, coarse carbonitrides are generated, which may become a starting point of destruction, and also press production costs. For this reason, when it contains these alloy elements, it is preferable that the content shall be 2.0% or less. More preferably, it is 0.003% or more and 1.7% or less.

Ca: 0.0005 to 0.0050%
Ca is an element useful for controlling the form of inclusions, and can be contained as necessary. Here, the form control of inclusions means that the expanded sulfide inclusions are made into granular inclusions. Ductility, toughness, and resistance to sulfide stress corrosion cracking are improved through shape control of the inclusions. In order to acquire such an effect, it is preferable to contain 0.0005% or more. On the other hand, when it is added in a large amount, the amount of non-metallic inclusions increases, and the ductility, toughness, and resistance to sulfide stress corrosion cracking may decrease. Moreover, it may become economically disadvantageous. Therefore, when Ca is contained, the content is preferably 0.0005 to 0.0050%. More preferably, the Ca content is 0.0005% or more and 0.0040% or less.

The high Mn steel according to the present invention can be obtained by melting a molten steel having the above-described composition by a known melting method such as a converter or an electric furnace. Further, secondary refining may be performed in a vacuum degassing furnace. Then, it is preferable to use a steel material such as a slab having a predetermined size by a known casting method such as a continuous casting method or an ingot-making method. Then, according to the conditions shown below, it cools after hot rolling.

[Hot rolling]
The above steel material is heated to a temperature range of 1100 ° C. or higher and 1300 ° C. or lower. If this heating temperature is less than 1100 ° C., the deformation resistance during hot rolling is large, and an excessive load is applied to the rolling mill. On the other hand, if heating is performed at a temperature exceeding 1300 ° C., the yield may be lowered due to surface oxidation.

After the steel material (steel ingot or steel slab) is heated as described above, hot rolling is performed. In order to create coarse crystal grains, it is preferable to increase the cumulative rolling reduction at high temperatures. That is, when hot rolling is performed at a low temperature, the microstructure becomes fine and excessive processing strain is introduced, resulting in a decrease in low temperature toughness. Therefore, the lower limit of the finish rolling finish temperature is 750 ° C. On the other hand, when finished in a temperature range of 950 ° C. or higher, the crystal grain size becomes excessively coarse and the desired yield strength cannot be obtained. In order to obtain the appropriate microstructure described above, hot rolling is performed in which the finish rolling finish temperature is 750 ° C. or more and less than 950 ° C. and the reduction ratio of less than 950 ° C. is 15% or more.

Next, the average cooling rate in the range from (finishing finish temperature -100 ° C) to 300 ° C to 650 ° C is set to 1.0 ° C / s or more. That is, the cooling is performed promptly after the hot rolling is completed. When the steel sheet after hot rolling is slowly cooled, the formation of precipitates is promoted and the low temperature toughness is deteriorated. Formation of these precipitates can be suppressed by cooling at a cooling rate of 1.0 ° C./s or more. For the above reasons, the cooling after hot rolling is performed at an average cooling rate on the steel sheet surface of 1.0 ° C./s from a temperature of (finishing finish temperature −100 ° C.) or higher to a temperature range of 300 ° C. or higher and 650 ° C. or lower. That's it.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to the following examples.
Steel slabs having the composition shown in Table 1 were produced by a converter-ladder refining-continuous casting method. Next, the obtained steel slab was hot-rolled according to the conditions shown in Table 2, and then cooled to obtain a steel plate having a thickness of 6 to 30 mm. The steel sheet was subjected to tensile properties, toughness, and structure evaluation in the following manner.

(1) Tensile test characteristics JIS No. 5 tensile test specimens were collected from each of the obtained steel sheets, and subjected to a tensile test in accordance with the provisions of JIS Z 2241 (1998) to investigate the tensile test characteristics. In the present invention, the yield strength at room temperature of 450 MPa or more and the tensile strength of 800 MPa or more were determined to be excellent in tensile properties. Furthermore, the elongation of 40% or more was determined to be excellent in ductility.

(2) Low temperature toughness JIS Z 2202 (1998) from the direction parallel to the rolling direction of the plate thickness 1/4 position of each steel plate exceeding 20 mm thickness or the plate thickness 1/2 position of each steel plate thickness 20 mm or less. ) Charpy V-notch specimens were collected in accordance with the provisions of), and three Charpy impact tests were performed on each steel sheet in accordance with the provisions of JIS Z 2242 (1998), and the absorbed energy at -196 ° C was measured. The base metal toughness was evaluated. In the present invention, the average value of three absorbed energy _{(vE -196)} is more than 100J was excellent in base metal toughness.

(3) Evaluation of fatigue characteristics Fatigue strength was evaluated by using a round bar tensile test piece having a diameter of 4 mm x a distance between gauges of 8 mm, at a value when stress was repeatedly applied 2 million times. Test specimens were taken from a direction parallel to the rolling direction at a position of 1/2 the thickness of the steel sheet and tested at -165 ° C. In the present invention, a fatigue strength of 700 MPa or more is excellent in fatigue resistance.
Table 3 shows the evaluation results obtained as described above.

As shown in Table 3, high Mn steel according to the invention, the aforementioned target performance (yield strength of the base material is more than 450 MPa, 100 J or more in the average value of the low-temperature toughness absorbed energy _{(vE -196),} fatigue strength 700 MPa or more) was confirmed. On the other hand, in a comparative example that is out of the scope of the present invention, any one or more of yield strength, low temperature toughness, and fatigue characteristics does not satisfy the above-mentioned target performance.

Claims

% By mass
C: 0.10 to 0.70%,
Si: 0.05 to 1.00%,
Mn: 20-30%,
P: 0.030% or less,
S: 0.0070% or less,
Al: 0.01 to 0.07%,
Cr: 0.5 to 7.0%,
N: 0.0400 to 0.1000,
O: 0.0050% or less,
Ti: 0.005% or less,
Nb: 0.005% or less,
High-Mn steel containing Mg: less than 0.0010% and REM: less than 0.0010%, the balance having a component composition of Fe and inevitable impurities and satisfying the following formula (1).
Ti / N ≦ 0.10 (1)
The high-Mn steel according to claim 1, wherein the component composition further satisfies the following formula (2).
(Mn × O) / S <27 (2)
The component composition is further mass%,
Cu: 1.0% or less,
Ni: less than 0.1%,
Mo: 2.0% or less,
V: 2.0% or less,
W: 2.0% or less,
The high Mn steel according to claim 1 or 2, comprising one or more selected from Ca: 0.0005 to 0.0050% and B: 0.0050% or less.
After the steel material having the component composition according to claim 1, 2 or 3 is heated to a temperature range of 1100 ° C to 1300 ° C, the finish rolling finish temperature is 750 ° C to less than 950 ° C and less than 950 ° C. An average cooling rate from a temperature of (finishing finish temperature -100 ° C) or higher to a temperature range of 300 ° C to 650 ° C is 1.0 ° C / s. The manufacturing method of the high Mn steel which performs the above cooling process.