JP5329632B2 - Duplex stainless steel, duplex stainless steel cast, and duplex stainless steel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an Sn-containing duplex stainless steel, duplex stainless steel cast slab, and duplex stainless steel material which have satisfactory hot productivity and are inexpensive by clarifying the relation between the Sn content and the hot productivity and finding the countermeasures thereof. <P>SOLUTION: The duplex stainless steel, duplex stainless steel cast slab, and duplex stainless steel material each contains, by mass%, 0.03% or less C, 0.05 to 1.0% Si, 0.1 to 7.0% Mn, 0.05% or less P, 0.0001 to 0.0010% S, 0.5 to 5.0% Ni, 18.0 to 25.0% Cr, 0.10 to 0.30% N, 0.05% or less Al, 0.0010 to 0.0040% Ca, 0.01 to 0.2% Sn, with the balance consisting of Fe and inevitable impurities, and has a ratio Ca/O of Ca to O contents being 0.3 to 1.0. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to an inexpensive Sn-containing duplex stainless steel, and includes a duplex stainless steel, duplex stainless steel cast, and duplex stainless steel that can be used as seawater desalination equipment, tanks for transport ships, various containers, and the like. It relates to steel.

  General-purpose duplex stainless steel contains a large amount of Cr, Mo, Ni, and N, and has good corrosion resistance. On the other hand, recently, alloy element-saving duplex stainless steel with reduced Cr, Ni, Mo and the like has been developed. Here, the alloy element-saving duplex stainless steel is a steel whose pitting corrosion resistance is equivalent to SUS304, 316L, and is a pitting corrosion index PI (= Cr + 3.3Mo + 16N) indexed by the content of the alloy element. ) Refers to stainless steel of about 30 to 28 or less. These steels with reduced content of alloying elements useful for pitting corrosion resistance and acid resistance are difficult to obtain the same corrosion resistance as general-purpose duplex stainless steels, but improved steels using cheap alternative elements The development of is considered possible.

  Various proposals have been made regarding duplex stainless steel containing Sn. For example, 0.01 to 0.1% Sn is contained as a selective element in duplex stainless steel containing 25% or more of Cr. Steels (see Patent Documents 1 and 4 below) and steels containing 1% or less or 0.1% Sn (see Patent Documents 3 and 4 below) in alloy element-saving duplex stainless steels. These patent documents aim to improve the corrosion resistance by containing Sn, but the relationship between the steel content and the Sn content has not been specifically studied.

  The present inventors paid attention to the possibility of improving acid resistance and pitting corrosion resistance by Sn, and the relationship between the Sn content, corrosion resistance and hot manufacturability in the alloy element-saving duplex stainless steel targeted by the present invention. As a result of the investigation, although the possibility of improving the corrosion resistance can be found by containing 0.01 to 0.2% of Sn, the hot manufacturability is lowered in these duplex stainless steels containing a large amount of Sn, and the steel material It has been understood that the frequency of decrease in yield increases and a significant cost increase is expected.

  As a result of studying conventional knowledge about manufacturing techniques of conventional Sn-containing duplex stainless steel hot-rolled steel materials including Patent Documents 1 to 4, the present inventors have found that hot brittleness due to Sn contained in duplex stainless steel. It has been found that there is little knowledge about the relationship between the temperature range of generation and the Sn content, and the relationship with the content of other elements.

JP-A-3-158437 JP-A-4-072013 JP 2010-222593 A WO2009-119895 JP 2002-69592 A JP-A-7-118805

  The present invention clarifies the relationship between Sn content and hot manufacturability, and by finding out the countermeasure, Sn-containing duplex stainless steel, duplex stainless steel cast, It is an object to provide a phase stainless steel material. Such alloy element-saving duplex stainless steel is expected to have a good balance between corrosion resistance and cost, and thus is likely to be widely used in various fields.

  In order to solve the above-mentioned problems, the inventors of the present invention are intended to improve the Sn content and hot manufacturability of the alloy element-saving duplex stainless steel, and Ca, B, rare earth elements (REM). The melt | dissolution material which changed content, such as, was created, and the following experiment was conducted.

  Tensile test specimens are collected from cast slabs cast from molten materials, subjected to high-temperature tension at 1200 to 700 ° C., and hot ductility is evaluated by drawing (cross-sectional area reduction rate), and hot forging and hot rolling. Thus, a hot rolled steel sheet having a thickness of 12 mm was obtained, and the ear cracking property was evaluated. For some steels, the hot cracking heating temperature and the rolling temperature were changed to evaluate the ear cracking properties, and the correlation with high temperature ductility was obtained.

  As described in Patent Document 5 and Patent Document 6, when the slab drawing generally evaluated by high-temperature tension in the duplex stainless steel is less than 60%, the heat of the slab is often obtained. It is known that significant ear cracking occurs during hot rolling. For this reason, engineers in this field often refining, casting and hot working steel with the goal of at least 60% or more reduction of the slab at high temperatures. However, when the present inventors evaluated the high temperature ductility of the alloy element-saving duplex stainless steel (base composition 21Cr-2Ni-3Mn-0.18N) slab containing about 0.1% Sn, both of them were evaluated. Several smelting experiments revealed that the aperture value was below 60%. Evaluation of high temperature ductility is performed by heating a parallel part of a round bar of 8 mmφ to 1200 ° C. using a high frequency, then lowering it to a temperature at which a fracture test is performed, pulling and breaking at that temperature at a rate of 20 mm / sec, and shrinking the cross section The rate is obtained. An example of the data is shown in FIG. From this, it was considered that there was little hope to obtain an inexpensive alloy element-saving duplex stainless steel with Sn added.

  The present inventors rarely have ear cracks in observing the length of ear cracks generated by hot rolling a slab of alloy element-saving Sn-containing duplex stainless steel obtained by vacuum melting and casting. It has been found that Sn-containing duplex stainless steel material exists. In the hot rolling experiment, a slab having a thickness of 90 to 44 mm was heated to 1200 ° C. and then reduced to a thickness of 12 to 6 mm through a plurality of rolling passes, and the finish rolling temperature was controlled to about 900 ° C. Ear cracks occurred on the left and right, but the maximum length of each was added to evaluate the ear crack length. Even if the length of the steel ear cracks was arranged with the minimum value of the hot ductility drawing value of the slab (obtained at about 900 ° C. in FIG. 1), a clean correlation could not be obtained, but as shown in FIG. When the aperture value was arranged at 1000 ° C., it was revealed that a good correlation was exhibited regardless of the Sn content. In FIG. 2, ◯ plots correspond to Sn-A and Sn-B in FIG. 1, and ♦ plots are experimental results examined regardless of other Sn contents.

  In order to find out the conditions under which the above-mentioned steel material with few ear cracks can be obtained reliably, the present inventors conducted further melting, casting and rolling experiments with various element contents changed, evaluated the hot ductility of the slab, The steel ear cracks after rolling were evaluated vigorously. Through the above experiments, based on the obtained knowledge, the present invention was clarified with respect to an inexpensive Sn-containing alloy element-saving duplex stainless steel.

That is, the gist of the present invention is as follows.
(1) By mass%, C: 0.03% or less, Si: 0.05 to 1.0%, Mn: 0.1 to 7.0%, P: 0.05% or less, S: 0.0001 To 0.0010%, Ni: 0.5 to 5.0%, Cr: 18.0 to 25.0%, N: 0.10 to 0.30%, Al: 0.05% or less, Ca: 0 .0010 to 0.0040%, Sn: 0.01 to 0.2%, the balance is made of Fe and inevitable impurities, and the Ca / O content ratio Ca / O is 0.3 to 1.0. Is duplex stainless steel.
(2) Furthermore, Mo: 1.5% or less, Cu: 2.0% or less, W: 1.0% or less, Co: 2.0% or less, containing 1 type or 2 types or more selected from (2) The duplex stainless steel according to (1).
(3) Furthermore, it contains one or more selected from V: 0.05 to 0.5%, Nb: 0.01 to 0.20%, and Ti: 0.003 to 0.05%. The duplex stainless steel according to (1) or (2), wherein
(4) Further, it contains one or more selected from B: 0.0050% or less, Mg: 0.0030% or less, REM: 0.10% or less (1) to The duplex stainless steel according to any one of (3).
(5) A duplex stainless steel casting having the composition of the duplex stainless steel according to any one of (1) to (4) and a fracture drawing value at 1000 ° C. of 70% or more. Piece.
(6) A duplex stainless steel material produced by hot working the duplex stainless steel cast according to (5).

  According to the present invention, a duplex stainless steel, a duplex stainless steel slab, having improved corrosion resistance compared to conventional steel as seawater desalination equipment, tanks for transport ships, various containers, etc., and excellent balance with cost, and It is possible to provide a duplex stainless steel material, and the contribution to industrial development is extremely large.

It is a figure which illustrates high temperature ductility of Sn containing and a Sn additive-free duplex stainless steel. It is a figure which shows the relationship between the ear crack length after hot rolling, and the aperture_diaphragm | restriction at 1000 degreeC.

  Below, the limitation reason as described in (1) of this invention is demonstrated first. In addition, content of each component shows the mass%.

  In the present invention, the stainless steel slab means steel in a state after casting and before being subjected to processing such as hot working or forging, and the stainless steel material is after the slab is processed by various methods. Slab, hot rolled steel sheet, cold rolled steel sheet, steel wire, steel pipe and the like. Stainless steel means all forms of steel such as slabs and steel materials. The above processing includes hot and cold processing.

  C limits the content to 0.03% or less in order to ensure the corrosion resistance of the stainless steel. If the content exceeds 0.03%, Cr carbide is generated during hot rolling, and the corrosion resistance and toughness deteriorate.

  Si is added at 0.05% or more for deoxidation. However, if it exceeds 1.0%, the toughness deteriorates. Therefore, the upper limit is limited to 1.0%. A preferable range is 0.2 to 0.7%.

  Mn has the effect of increasing the austenite phase and improving toughness. Moreover, since it has the effect of lowering the nitride precipitation temperature TN, it is preferable to add it positively in this invention steel material. Add 0.1% or more for toughness of base metal and weld. However, if added over 7.0%, corrosion resistance and toughness deteriorate. Therefore, the upper limit is limited to 7.0%. The preferred content is 1.0 to 6.0%, more preferably 2.0 to 5.0%.

  P is an element inevitably mixed from the raw material, and is limited to 0.05% or less in order to deteriorate hot workability and toughness. Preferably, it is 0.03% or less.

  S is an element inevitably mixed from the raw material, and also degrades hot workability, toughness, and corrosion resistance, so is limited to 0.0010% or less. Moreover, reducing to less than 0.0001% increases the cost for desulfurization refining. For this reason, it was determined as 0.0001 to 0.0010%. Preferably, it is 0.0002 to 0.0006%.

  Ni is contained in an amount of 0.5% or more in order to stabilize the austenite structure and improve corrosion resistance to various acids and further toughness. By increasing the Ni content, the nitride precipitation temperature can be lowered. On the other hand, it is an expensive alloy, and in the steel of the present invention intended for alloy-saving duplex stainless steel, the content is limited to 5.0% or less from the viewpoint of cost. The preferred content is 1.0 to 4.0%, more preferably 1.5 to 3%.

  Cr is contained at 18.0% or more in order to ensure basic corrosion resistance. On the other hand, if the content exceeds 25.0%, the ferrite phase fraction increases and the toughness and the corrosion resistance of the welded portion are impaired. Therefore, the Cr content is set to 18.0% or more and 25.0% or less. A preferable content is 19.0 to 23.0%.

  N is an effective element that improves the strength and corrosion resistance by dissolving in the austenite phase. For this purpose, 0.10% or more is contained. On the other hand, the solid solution limit becomes higher depending on the Cr and Mn contents. However, when the content of the steel of the present invention exceeds 0.30%, Cr nitride precipitates and the toughness and corrosion resistance are impaired. In order to inhibit hot manufacturability, the upper limit of the content was set to 0.30%. A preferable content is 0.10 to 0.25%.

  Al is a deoxidizing element of steel, and is contained together with 0.05% or more of Si in order to reduce oxygen in the steel as necessary. In the Sn-containing steel, the reduction of the oxygen amount is essential for securing hot productivity, and for this purpose, the content of 0.003% or more is necessary. On the other hand, Al is an element having a relatively large affinity with N, and if added excessively, AlN is generated and inhibits the toughness of stainless steel. The degree depends on the N content, but when Al exceeds 0.05%, the toughness deteriorates remarkably, so the upper limit of the content is set to 0.05%. Preferably it is 0.04% or less.

  Ca is an important element for hot manufacturability of steel, and it is necessary to contain O and S in the steel as inclusions to improve hot manufacturability. In the steel of the present invention, 0.0010% or more is contained for that purpose. Moreover, excessive addition reduces pitting corrosion resistance. Therefore, the upper limit of the content is set to 0.0040%.

  Sn is contained in order to improve the corrosion resistance of the steel of the present invention. For this purpose, a content of at least 0.01% is necessary. Furthermore, it is preferable to make it contain 0.02% or more. On the other hand, Sn is an element that hinders the hot manufacturability of steel. In the alloying element type saving duplex stainless steel targeted by the present invention, especially at the interface between the ferrite phase and the austenite phase at 900 ° C. or lower. Reduce strength. The degree of the reduction depends on the contents of S, Ca, and O. However, even if other limitations in the present invention are added, if the content exceeds 0.2%, the hot productivity cannot be prevented from being lowered. The upper limit of the content was set to 0.2%.

  The ratio Ca / O of the content of O and Ca is an important component index for improving the hot manufacturability and corrosion resistance of the steel of the present invention. In order to improve the hot manufacturability of the Sn-containing steel, the lower limit of Ca / O is limited. The high temperature ductility of the Sn-containing steel decreases particularly at a temperature of 900 ° C. or less, but if the Ca / O value is less than 0.3, the high temperature ductility at 1000 ° C. also decreases, and hot productivity is greatly impaired. For this reason, Ca / O is limited to 0.3 or more in the steel of the present invention. On the other hand, when Ca is excessively added and Ca / O exceeds 1.0, pitting corrosion resistance is impaired. Moreover, when Ca becomes excessive, the high temperature ductility over 1000-1100 degreeC will also be impaired. For this reason, the upper limit of Ca / O was set to 1.0. Preferably it is 0.4-0.8.

  O is an unavoidable impurity, and its upper limit was not particularly defined. However, O is an important element constituting an oxide that is representative of non-metallic inclusions, and the composition control of the oxide improves hot manufacturability. Very important to. In addition, the formation of coarse clustered oxides causes surface defects. For this reason, the content needs to be limited low. In the present invention, as described above, the O content is limited by setting the ratio of the Ca content and the O content to 0.3 or less. The upper limit of the O content is preferably 0.005% or less.

  In the invention of (2), in order to additionally improve the corrosion resistance, elements to be contained are defined as necessary. The reason for the limitation will be described.

  Mo is a very effective element that additionally increases the corrosion resistance of stainless steel, and can be contained as necessary. In order to improve corrosion resistance, it is preferable to contain 0.2% or more. On the other hand, it is an element that promotes precipitation of intermetallic compounds. In the steel of the present invention, the upper limit is set to a content of 1.5% from the viewpoint of suppressing precipitation during hot rolling.

  Cu is an element that additionally increases the corrosion resistance of stainless steel to acids, and has the effect of improving toughness. Therefore, it is recommended to contain 0.3% or more as necessary. If the content exceeds 2.0%, the solid solubility will be exceeded during hot rolling and εCu will precipitate and embrittlement will occur, so the upper limit was made 2.0%. The preferable content when Cu is contained is 0.3 to 1.5%.

  W, like Mo, is an element that additionally improves the corrosion resistance of stainless steel, and can be added as necessary. For the purpose of enhancing the corrosion resistance in the steel of the present invention, 1.0% is contained at the upper limit. A preferable content is 0.05 to 0.5%.

  Co is an element effective for enhancing the toughness and corrosion resistance of steel, and is selectively added. The content is preferably 0.03% or more. If the content exceeds 2.0%, it is an expensive element, so that an effect commensurate with the cost cannot be exhibited, so the upper limit was set to 2.0%. The preferable content when added is 0.03 to 1.0%.

  Next, the contents defined in (3) will be described for elements that have a greater tendency to form nitrides than Cr. V, Nb, and Ti can be added as necessary, and when contained in a very small amount, the corrosion resistance tends to be improved.

  The nitrides and carbides formed by V are generated during the hot working and cooling of the steel material, and have the effect of increasing the corrosion resistance. Although sufficient confirmation has not been made for this reason, there is a possibility of suppressing the generation rate of chromium nitride at 700 ° C. or lower. In order to improve this corrosion resistance, 0.05% or more is contained. If the content exceeds 0.5%, coarse V-based carbonitrides are produced and the toughness deteriorates. Therefore, the upper limit is limited to 0.5%. The preferable content when added is in the range of 0.1 to 0.3%.

  Nitride and carbide formed by Nb are produced during the hot working and cooling of the steel material, and have the effect of enhancing the corrosion resistance. Although sufficient confirmation has not been made for this reason, there is a possibility of suppressing the generation rate of chromium nitride at 700 ° C. or lower. In order to improve the corrosion resistance, the content is 0.01% or more. On the other hand, excessive addition causes precipitation as an undissolved precipitate during heating before hot rolling and impairs toughness, so the upper limit of its content was set to 0.20%. The preferable content range in the case of adding is 0.03% to 0.10%.

  Ti is an element that forms oxides, nitrides, and sulfides in an extremely small amount, and solidifies the steel and refines the crystal grains of the high-temperature heating structure. Further, like V and Nb, it also has a property of substituting for a part of chromium nitride chromium. A Ti precipitate is formed when the content is 0.003% or more. On the other hand, if it exceeds 0.05% and is contained in the duplex stainless steel, coarse TiN is generated and the toughness of the steel is inhibited. For this reason, the upper limit of the content was set to 0.05%. A suitable content of Ti is 0.005 to 0.020%.

  Furthermore, in order to further improve the hot workability described in (4) of the present invention, B, Mg, and REM to be contained as necessary are limited as follows.

  B, Mg, and REM are all elements that improve the hot workability of steel, and one or more of them are added for that purpose. Since excessive addition of B, Mg, and REM decreases hot workability and toughness, the upper limit of the content is determined as follows. B is 0.0050%, Mg is 0.0030%, and REM is 0.10%. The preferred contents are B: 0.0005 to 0.0030%, Mg: 0.0001 to 0.0015%, and REM: 0.005 to 0.05%, respectively. Here, REM is the total content of lanthanoid rare earth elements such as La and Ce.

  As described above, by having the characteristics described in any of (1) to (4) of the present invention described above, the hot productivity of the alloy-saving duplex stainless steel containing Sn can be remarkably improved. In the slab stage, the fracture drawing value at 1000 ° C. is 70% or more. Moreover, it is possible to obtain a duplex stainless steel material with high yield and few surface defects by subjecting the slab to processing including hot working.

  Examples are described below. Table 1 shows the chemical composition of the test steel. In addition to the components listed in Table 1, the balance is Fe and inevitable impurity elements. Moreover, the part in which content is not described about the component shown in Table 1 shows that it is an impurity level, REM means a lanthanoid type rare earth element, and content shows the sum total of these elements.

  All the steels were cast pieces with a thickness of 100 mm, and the fracture drawing was evaluated first. In the evaluation, the parallel part of the 8 mmφ round bar was heated to 1200 ° C. using a high frequency and then lowered to the temperature at which the fracture test was performed. At that temperature, the specimen was pulled and broken at a rate of 20 mm / sec to obtain the shrinkage ratio of the cross section. It was. Table 2 shows that the drawing at break was 70% or more as ◯, 60 to less than 70% as Δ, and less than 60% as x. The slab was made into a 60 mm thick steel slab by hot forging, and this was used as a hot rolled material. Hot rolling is performed at a predetermined temperature of 1150 to 1250 ° C., and then performed by a two-stage rolling mill in a laboratory. After rolling, the sheet thickness is adjusted at 25 mm, and finish rolling is performed from 1000 ° C. to 900 ° C. The final finish rolling was carried out so that the final plate thickness was 12 mm and the plate width was 120 mm. The maximum value of the ear crack generated in the left and right ears of this hot-rolled steel sheet was measured, and the sum of the left and right maximum values was obtained. Table 2 shows the sum of the ear cracks evaluated as ○ when 5 mm is less than 5 mm, Δ when 10 mm is exceeded, and x.

  Further, this steel sheet was subjected to solution heat treatment. In the solution heat treatment, a steel plate was inserted into a heat treatment furnace set at 1000 ° C., extracted after a soaking time of 5 minutes, and then cooled to room temperature.

The corrosion resistance of the steel sheet was evaluated by the corrosion rate in sulfuric acid. The corrosion rate in sulfuric acid was a 6 mm immersion test in boiling 5% sulfuric acid on a test piece 3 mm thick × 25 mm wide × 25 mm long, and the weight reduction rate was determined by measuring the weight before and after immersion. Shows ○ The corrosion rate 0.3 g / m less than ² · hr in sulfuric acid, △ a 0.3~1g / m ² · hr, the evaluation result of evaluating the × or more 1 g / m ² · hr Table 2 It was.

Impact characteristics were measured with Charpy specimens taken long in the width direction. The test piece was a full size, 2 mm V notch was processed in the rolling direction, two tests were conducted at -20 ° C., and the impact characteristics were evaluated by the average value. Impact value 100 J / cm ² than the ○, the 50~100J / cm ² △, was evaluated as × less than 50 J / cm ^2, as described in Table 2.

  From the examples shown in Table 2, steel Nos. 1-33 satisfying the conditions of the present invention have good hot manufacturability, corrosion resistance and impact properties, while steel Nos. A to A not satisfying the conditions of the present invention. U was inferior in any of hot manufacturability, corrosion resistance and impact properties.

As can be seen from the above examples, according to the present invention, it was clarified that the addition of Sn improves the corrosion resistance, and provides an alloy element-saving duplex stainless steel with good hot productivity and low cost.

  According to the present invention, it is possible to provide an inexpensive alloying element-saving duplex stainless steel material with improved corrosion resistance, which contributes to industries such as seawater desalination equipment, tanks for transport vessels, various containers, etc. Is extremely large.

Claims (6)

% By mass
C: 0.03% or less,
Si: 0.05 to 1.0%,
Mn: 0.1 to 7.0%,
P: 0.05% or less,
S: 0.0001 to 0.0010%,
Ni: 0.5 to 5.0%,
Cr: 18.0 to 25.0%,
N: 0.10 to 0.30%,
Al: 0.05% or less,
Ca: 0.0010 to 0.0040%,
Sn: Duplex stainless steel containing 0.01 to 0.2%, the balance being Fe and inevitable impurities, and the Ca / O content ratio Ca / O being 0.3 to 1.0. Furthermore, Mo: 1.5% or less,
Cu: 2.0% or less,
W: 1.0% or less,
The duplex stainless steel according to claim 1, comprising one or more selected from Co: 2.0% or less. Furthermore,
V: 0.05-0.5%
Nb: 0.01-0.20%,
The duplex stainless steel according to claim 1 or 2, comprising one or more selected from Ti: 0.003 to 0.05%. Furthermore,
B: 0.0050% or less,
Mg: 0.0030% or less,
The duplex stainless steel according to any one of claims 1 to 3, comprising one or more selected from REM: 0.10% or less.   A duplex stainless steel slab having the composition according to any one of claims 1 to 4 and having a fracture drawing value at 1000 ° C of 70% or more. A duplex stainless steel material produced by hot working the duplex stainless steel slab according to claim 5.

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