JP2019178363A - AUSTENITIC STAINLESS STEEL WITH HIGH CONTENT OF Si, HAVING EXCELLENT MANUFACTURABILITY - Google Patents
AUSTENITIC STAINLESS STEEL WITH HIGH CONTENT OF Si, HAVING EXCELLENT MANUFACTURABILITY Download PDFInfo
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Abstract
【課題】本発明は高Ｓｉ含有のオーステナイト系ステンレス鋼の製造において、鋳片の割れを防止して良好な製造性を提供する。【解決手段】質量％でＣ：≦０．２５％、Ｓｉ：１．５〜４．０％、Ｍｎ：≦２．０％、Ｐ：≦０．０４５％、Ｓ：≦０．００１５％、Ｃｒ：１６〜２６％、Ｎｉ：８．０〜２２．０％、Ｍｏ：≦３．０％、Ｃｕ：≦２．５％、Ａｌ：０．００３〜０．２％、Ｃａ：１〜５０ｐｐｍ、Ｍｇ；１〜５０ｐｐｍ、Ｎ：≦０．１％を満足し、かつ下式で表されるＣｒｅｑ／Ｎｉｅｑ＝（［Ｃｒ］＋１．３７［Ｍｏ］＋１．５［Ｓｉ］）／（［Ｎｉ］＋０．３１［Ｍｎ］＋［Ｃｕ］＋２２［Ｃ］＋１４．２［Ｎ］）＞１．３を満足し、ステンレス鋼中に含まれる非金属介在物がＣａＯ、ＭｇＯ、ＣａＳ、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物の１種または２種以上からなる。【選択図】なしAn object of the present invention is to provide an austenitic stainless steel having a high Si content, which prevents cracks in a slab and provides good manufacturability. SOLUTION: In mass%, C: ≤ 0.25%, Si: 1.5 to 4.0%, Mn: ≤ 2.0%, P: ≤ 0.045%, S: ≤ 0.0015%, Cr: 16 to 26%, Ni: 8.0 to 22.0%, Mo: ≤ 3.0%, Cu: ≤ 2.5%, Al: 0.003 to 0.2%, Ca: 1 to 50 ppm , Mg; 1 to 50 ppm, N: satisfies 0.1% and Creq / Nieq = ([Cr] +1.37 [Mo] +1.5 [Si]) / ([Ni ] +0.31 [Mn] + [Cu] +22 [C] +14.2 [N])> 1.3, and the nonmetallic inclusions contained in the stainless steel are CaO, MgO, CaS, CaO-Al2O3. -One or more of MgO-based oxides. [Selection diagram] None
Description
本発明は、鋳造時の割れを抑制し、製造性に優れた高Ｓｉ含有のオーステナイト系ステンレス鋼に関する。 The present invention relates to an austenitic stainless steel containing a high Si content that suppresses cracking during casting and has excellent manufacturability.
高Ｓｉのオーステナイト系ステンレス鋼は、高温強度や耐酸化性、耐硝酸性や耐硫酸性に優れている事が知られている。 High Si austenitic stainless steels are known to be excellent in high temperature strength, oxidation resistance, nitric acid resistance and sulfuric acid resistance.
耐熱性、耐酸化性に優れた高Ｓｉのオーステナイト系ステンレス鋼として、特許文献１に開示される重量％で１．５〜４．０質量％Ｓｉを含む耐熱鋼が開発されている。しかしながら、高Ｓｉ含有のオーステナイト系ステンレス鋼では鋳造時に割れを生じ易く、製造性に優れたものでは無かった。 As a high-Si austenitic stainless steel excellent in heat resistance and oxidation resistance, a heat-resistant steel containing 1.5 to 4.0 mass% Si disclosed in Patent Document 1 is developed. However, a high Si content austenitic stainless steel is prone to cracking during casting, and is not excellent in manufacturability.
特許文献２には高Ｓｉオーステナイト系ステンレス鋼の熱間加工性を改善するために、１１００℃〜１２５０℃でソーキングして金属間化合物の固溶化を行っているが、鋳片で生じる割れを防止する手法に関しては開示されていない。 In Patent Document 2, in order to improve the hot workability of high-Si austenitic stainless steel, soaking at 1100 ° C. to 1250 ° C. is performed to solidify the intermetallic compound, but cracks that occur in the slab are prevented. It is not disclosed about the technique to do.
特許文献３ではＡｌ２Ｏ３等のＢ１系介在物の面積率を０．０３％以下、ＳｉＯ２等のＡ２系介在物を０．０６％以下に規定する事で、加工性と高温・高濃度硝酸環境中での耐食性向上を図っているが、Ｂ１系介在物の含有量を制限する事によって間接的にＣａＯやＣａＯを含む複合介在物を抑制しているため、鋳造時の割れを十分に抑制出来ない。 In Patent Document 3, by defining the area ratio of B 1 inclusions such as Al 2 O 3 to 0.03% or less and A 2 inclusions such as SiO 2 to 0.06% or less, workability and high temperature are controlled. · while working to improve corrosion resistance at high concentrations of nitric acid in the environment, because it suppresses indirectly compound inclusions containing CaO and CaO by limiting the content of B 1 type inclusions, during casting The crack cannot be suppressed sufficiently.
このように、従来技術は耐食性の向上や耐熱性の向上、熱間圧延時の割れ抑制に関すものはあるが鋳造時の割れを防止する技術は無く、高Ｓｉ含有のオーステナイト系ステンレス鋼の製造性に関しては改善の必要があった。 As described above, there are technologies related to improved corrosion resistance, improved heat resistance, and suppression of cracking during hot rolling, but there is no technology to prevent cracking during casting. There was a need to improve sex.
本発明の目的は、高Ｓｉを含有するオーステナイト系ステンレス鋼の鋳造時の割れを防止し、通常の連続鋳造プロセスによって安価に、しかも安定的に提供する事を目的とする。 An object of the present invention is to prevent cracking during casting of austenitic stainless steel containing high Si, and to provide it inexpensively and stably by a normal continuous casting process.
本発明者らは、高Ｓｉ含有のオーステナイト系ステンレス鋼で鋳造時に割れが生じる理由を検討した結果、以下の知見を得た。 The present inventors have studied the reason why cracking occurs during casting in a high Si content austenitic stainless steel, and have obtained the following knowledge.
鋼中のＳｉ、Ｓ、Ｐが鋳造時に液相に濃縮する事で液相が低融点化し、液相が低温まで残留する事で鋳造時の応力で割れを生じる。そのため、割れの抑制にはＳｉ、Ｓ、Ｐの低減が望ましい。 The Si, S, and P in the steel are concentrated in the liquid phase during casting, thereby lowering the melting point of the liquid phase. Therefore, it is desirable to reduce Si, S, and P in order to suppress cracking.
Ｓｉの低減は耐熱性や耐硝酸性、耐硫酸性など材質特性の観点から添加しているため、低減は望ましく無い。Ｐはステンレス鋼において精錬除去が困難なため、Ｐの低減には［Ｐ］濃度の低い高品位の原料を用いて溶解する必要があり原料コストが上昇する。Ｓの低減は割れ防止に有効であり、可能な範囲で精錬による低Ｓ化することが望ましい。 Since Si is added from the viewpoint of material properties such as heat resistance, nitric acid resistance, and sulfuric acid resistance, reduction is not desirable. Since P is difficult to be refined and removed from stainless steel, it is necessary to dissolve P using a high-quality raw material with a low [P] concentration, and the raw material cost increases. Reduction of S is effective for preventing cracking, and it is desirable to reduce S by refining as much as possible.
上記のＳｉ、Ｓ、Ｐに起因した鋳片の割れはＣｒｅｑ／Ｎｉｅｑ＞１．３とする事で低減する事が出来る。これはＣｒｅｑ／Ｎｉｅｑ＞１．３とする事で凝固末期に微量晶出したフェライト相がＳｉ、Ｐ、Ｓを固定し、液相への濃縮が抑制されたためと考えられる。 The crack of the slab resulting from said Si, S, and P can be reduced by setting it as Creq / Nieq> 1.3. This is considered to be because the ferrite phase that was crystallized at the end of solidification fixed Si, P, and S by setting Creq / Nieq> 1.3, and the concentration to the liquid phase was suppressed.
更に、鋼中に含まれる非金属介在物がＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物やＣａＯ、ＭｇＯ、ＣａＳ、となる場合に鋳片の割れが抑制される。これは割れに有害なＳが介在物中に固定されるため、凝固時の液相へのＳ濃縮が緩和されて液相の低融点化が抑制されたためと考えられる。一方、脱酸不良で生じる非金属介在物のＭｇＯ・Ａｌ２Ｏ３や脱酸元素のＡｌを過剰添加した際に生じるＡｌ２Ｏ３、またＣａＯ−Ａｌ２Ｏ３−ＭｇＯスラグ系介在物でもＳｉＯ２＞１０質量％且つＣａＯ＜１０質量％且つＡｌ２Ｏ３＞７０質量％となる組成の場合には鋳片の割れ抑制効果は発現しない。これは、これらの介在物のＳ固定能が小さいためと考えられる。そのため、鋳片の割れを防止するには鋼中の非金属介在物をＳ固定能を有する組成のＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物、ＣａＯ、ＭｇＯ、ＣａＳに制御する必要がある。 Furthermore, when the nonmetallic inclusions contained in the steel are CaO—Al 2 O 3 —MgO-based oxides, CaO, MgO, and CaS, cracking of the slab is suppressed. This is thought to be because S, which is harmful to cracking, is fixed in the inclusions, so the concentration of S in the liquid phase during solidification is relaxed and the lowering of the melting point of the liquid phase is suppressed. On the other hand, results of Al MgO · Al 2 O 3 and a deoxidizing element of nonmetallic inclusions resulting poor deoxidation upon excessive addition Al 2 O 3, also in CaO-Al 2 O 3 -MgO slag inclusions In the case of a composition satisfying SiO 2 > 10% by mass, CaO <10% by mass and Al 2 O 3 > 70% by mass, the crack suppression effect of the slab is not exhibited. This is presumably because the S fixing ability of these inclusions is small. Therefore, in order to prevent cracking of the slab, it is necessary to control the non-metallic inclusions in the steel to CaO—Al 2 O 3 —MgO-based oxide, CaO, MgO, and CaS having a composition having S fixing ability.
即ち、本発明の高Ｓｉ含有オーステナイト系ステンレス鋼は、下記の構成を要旨とする。
〔１〕質量％で、
Ｃ：≦０．２５％、
Ｓｉ：１．５〜４％、
Ｍｎ：≦２．０％、
Ｐ：≦０．０４５％、
Ｓ：≦０．００１５％、
Ｃｒ：１６〜２６％、
Ｎｉ：８．０〜２２．０％、
Ｍｏ：０．０１〜３．０％、
Ｃｕ：０．０１〜２．５％、
Ａｌ：０．００３〜０．２％、
Ｎ：≦０．１％、
Ｃａ：０．０００１〜０．００５％、
Ｍｇ：０．０００１〜０．００５％、
を満足し、残部Ｆｅおよび不可避的不純物よりなり、かつ下記（１）で表されるＣｒｅｑ／Ｎｉｅｑが１．３以上であり、
前記のステンレス鋼中に含まれる非金属介在物として、ＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系の介在物をいずれも含有せず、
前記の非金属介在物が、ＣａＯ、ＭｇＯ、ＣａＳ、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物の１種または２種以上からなる
ことを特徴とする製造性に優れた高Ｓｉ含有のオーステナイト系ステンレス鋼。
Ｃｒｅｑ／Ｎｉｅｑ＝（［Ｃｒ］＋１．３７×［Ｍｏ］＋１．５×［Ｓｉ］）／（［Ｎｉ］＋０．３１×［Ｍｎ］＋［Ｃｕ］＋２２×［Ｃ］＋１４．２×［Ｎ］）・・・（１）
但し、式中の［元素名］は、当該元素の含有質量％を意味する。
〔２〕前記非金属介在物において、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物の組成がＳｉＯ２≦１０質量％且つＣａＯ≧１０質量％且つＡｌ２Ｏ３≦７０質量％を満たすことを特徴とする〔１〕に記載の製造性に優れた高Ｓｉ含有のオーステナイト系ステンレス鋼。
That is, the high Si content austenitic stainless steel of the present invention is summarized as follows.
[1] By mass%
C: ≦ 0.25%
Si: 1.5-4%,
Mn: ≦ 2.0%,
P: ≦ 0.045%
S: ≦ 0.0015%,
Cr: 16 to 26%,
Ni: 8.0 to 22.0%,
Mo: 0.01 to 3.0%,
Cu: 0.01 to 2.5%,
Al: 0.003 to 0.2%,
N: ≦ 0.1%
Ca: 0.0001 to 0.005%,
Mg: 0.0001 to 0.005%,
Satisfying the above, the balance Fe and inevitable impurities, and Creq / Nieq represented by the following (1) is 1.3 or more,
As the non-metallic inclusions contained in the stainless steel, MgO · Al 2 O 3 -based and Al 2 O 3 -based inclusions are not included,
The non-metallic inclusions are composed of one or more of CaO, MgO, CaS, and CaO—Al 2 O 3 —MgO-based oxides. Stainless steel.
Creq / Nieq = ([Cr] + 1.37 × [Mo] + 1.5 × [Si]) / ([Ni] + 0.31 × [Mn] + [Cu] + 22 × [C] + 14.2 × [N ]) ... (1)
However, [element name] in the formula means the mass% of the element.
[2] In the non-metallic inclusion, the composition of the CaO—Al 2 O 3 —MgO-based oxide satisfies SiO 2 ≦ 10 mass%, CaO ≧ 10 mass%, and Al 2 O 3 ≦ 70 mass%. The high Si content austenitic stainless steel excellent in manufacturability according to [1].
本発明の高Ｓｉオーステナイト系ステンレス鋼では、鋳造時の割れを抑制出来、従来よりも安定して安価に素材を提供する事が可能となる。 In the high Si austenitic stainless steel of the present invention, cracking during casting can be suppressed, and it becomes possible to provide a material more stably and inexpensively than in the past.
以下、本発明の実施形態を説明する。なお、本発明において成分含有量は、特に注記しない限り質量％を意味する。 Embodiments of the present invention will be described below. In the present invention, the component content means mass% unless otherwise noted.
Ｃは鋼中に存在する不可避的な元素であり、その含有量が０．２５％を超えると、Ｃｒと結合し炭化物を形成するため、靭性及び耐食性が劣化する。そのため、Ｃの含有量を０．２５％以下に限定した。望ましくは０．１％以下である。 C is an unavoidable element present in steel, and when its content exceeds 0.25%, it combines with Cr to form carbides, so that toughness and corrosion resistance deteriorate. Therefore, the C content is limited to 0.25% or less. Desirably, it is 0.1% or less.
Ｓｉは耐酸化性や高温強度、硝酸や硫酸に対する耐食性向上に有効で１．５％以上添加する。一方、４％を超えて添加すると熱間加工性が著しく劣化し、製造性が損なわれる。そのため、上限を４．０％とする。 Si is effective in improving oxidation resistance, high temperature strength, and corrosion resistance against nitric acid and sulfuric acid, and is added in an amount of 1.5% or more. On the other hand, when it exceeds 4%, hot workability is remarkably deteriorated, and manufacturability is impaired. Therefore, the upper limit is made 4.0%.
ＭｎはＮｉと同様、γ相の化学的安定性を高める元素であるため、２．０％以下の量で含有させる。一方、２．０％を超えて添加すると耐食性が劣化する。そのため、上限を２．０％とする。好ましくは、０．２％以上、１．５％以下である。 Mn, like Ni, is an element that enhances the chemical stability of the γ phase, so it is contained in an amount of 2.0% or less. On the other hand, if it exceeds 2.0%, the corrosion resistance deteriorates. Therefore, the upper limit is made 2.0%. Preferably, it is 0.2% or more and 1.5% or less.
Ｐは鋼中に不可避的に含有される元素であり、鋳造時の割れ感受性を高め、熱間加工性も劣化させるため、その含有量を０．０４５％以下に限定する。望ましくは０．０３０％以下である。 P is an element inevitably contained in the steel, and the content is limited to 0.045% or less in order to increase cracking susceptibility during casting and deteriorate hot workability. Desirably, it is 0.030% or less.
Ｓは鋼中に不可避的に含有される元素であって、鋳造時の割れ感受性を高め、熱間加工性も劣化させるため、その含有量を０．００１５％以下に限定する。望ましくは０．００１０％以下である。 S is an element inevitably contained in steel, and its content is limited to 0.0015% or less in order to increase cracking susceptibility during casting and deteriorate hot workability. Desirably, it is 0.0010% or less.
Ｃｒは耐食性を確保するために必要な元素であり１６．０％以上含有させる。一方で、Ｃｒを多量に含むとフェライトを含む二相組織となってしまうために熱間加工性や靭性の低下に繋がってしまうため、添加量を２６．０％以下とする。好ましくは、１７．０〜２０．０％である。 Cr is an element necessary for ensuring corrosion resistance and is contained by 16.0% or more. On the other hand, if a large amount of Cr is contained, a two-phase structure containing ferrite is formed, leading to a decrease in hot workability and toughness. Preferably, it is 17.0 to 20.0%.
Ｎｉはγ相を安定化させる元素であり、さらに耐食性および靭性を改善するため、８．０％以上添加することが望ましい。一方高価な元素であり、過剰に添加することはコストアップにつながるため、上限を２２．０％とする。好ましくは、９．０〜１５．０％である。 Ni is an element that stabilizes the γ phase, and is preferably added in an amount of 8.0% or more in order to further improve the corrosion resistance and toughness. On the other hand, since it is an expensive element and excessive addition leads to an increase in cost, the upper limit is made 22.0%. Preferably, it is 9.0 to 15.0%.
Ｍｏは０．０１％以上の含有で耐食性の向上に有効な元素であるが、高価である事と金属間化合物の生成による靭性劣化に繋がる事から、上限を３％以下とする。一方、０．０１質量未満とするにはスクラップの使用に制限が出るためコストアップに繋がる。好ましくは、０．１〜１．６％である。 Mo is an element effective for improving the corrosion resistance when contained in an amount of 0.01% or more. However, since it is expensive and leads to toughness deterioration due to the formation of an intermetallic compound, the upper limit is made 3% or less. On the other hand, if the amount is less than 0.01 mass, the use of scrap is limited, leading to an increase in cost. Preferably, it is 0.1 to 1.6%.
Ｃｕは０．０１％以上の含有で耐食性の向上に有効な元素であり２．５％以下で添加する。２．５％を超えて添加すると、熱間加工性低下するため上限を２．５％以下とする。一方、０．０１質量未満とするにはスクラップの使用に制限が出るためコストアップに繋がる。好ましくは２．０％以下である。 Cu is an element effective in improving corrosion resistance when contained in 0.01% or more, and is added in 2.5% or less. If added over 2.5%, the hot workability deteriorates, so the upper limit is made 2.5% or less. On the other hand, if the amount is less than 0.01 mass, the use of scrap is limited, leading to an increase in cost. Preferably it is 2.0% or less.
Ａｌは脱酸のために重要な元素であり、鋼中の酸素を低減し、脱硫を促進するために０．００３％以上の添加が必要である。一方、０．２％を超えて添加すると靭性を劣化させるため、含有量の上限は０．２％とする。好ましくは０．００５〜０．１％である。 Al is an important element for deoxidation, and 0.003% or more of addition is necessary to reduce oxygen in steel and promote desulfurization. On the other hand, if added over 0.2%, the toughness deteriorates, so the upper limit of the content is 0.2%. Preferably it is 0.005 to 0.1%.
Ｎは耐食性を向上させるとともに、γ相の化学的安定性に有効な元素であるが、０．１％を超えて含有すると靭性を劣化させてしまう。そのため、含有量の上限を０．１％とする。好ましくは０．０１％以上である。 N is an element effective for improving the corrosion resistance and chemical stability of the γ phase, but if it exceeds 0.1%, the toughness is deteriorated. Therefore, the upper limit of the content is 0.1%. Preferably it is 0.01% or more.
Ｃａは熱間加工性を改善する元素であり、０．０００１％以上添加する。一方で、０．００５％超の添加では逆に熱間加工性を低下させるので上限を０．００５％とする。 Ca is an element that improves hot workability, and is added in an amount of 0.0001% or more. On the other hand, if over 0.005% is added, the hot workability is reduced, so the upper limit is made 0.005%.
Ｍｇは熱間加工性を改善させる元素であり、０．０００１％以上添加する。一方で、０．００５％超の添加は逆に熱間加工性を低下させるため、上限０．００５％とする。 Mg is an element that improves hot workability and is added in an amount of 0.0001% or more. On the other hand, addition of over 0.005% conversely decreases hot workability, so the upper limit is made 0.005%.
また、上述してきた鋼の成分含有量は、下記（１）式で表されるＣｒｅｑ／Ｎｉｅｑ値で１．３以上の範囲となるように調整する必要がある。Ｃｒｅｑ／Ｎｉｅｑ値は、鋼中のフェライト相とオーステナイト相の安定度バランスを示す指標であり、Ｃｒｅｑ／Ｎｉｅｑ値が１．３を超えると鋳片での割れを低減出来る。
Ｃｒｅｑ／Ｎｉｅｑ＝（［Ｃｒ］＋１．３７［Ｍｏ］＋１．５［Ｓｉ］）／（［Ｎｉ］＋０．３１［Ｍｎ］＋［Ｃｕ］＋２２［Ｃ］＋１４．２［Ｎ］）・・・（１）
但し、式中の［元素名］は、当該元素の含有質量％を意味する。
Moreover, it is necessary to adjust the component content of the steel described above so that the Creq / Nieq value represented by the following formula (1) is in the range of 1.3 or more. The Creq / Nieq value is an index indicating the stability balance between the ferrite phase and the austenite phase in the steel. If the Creq / Nieq value exceeds 1.3, cracks in the slab can be reduced.
Creq / Nieq = ([Cr] +1.37 [Mo] +1.5 [Si]) / ([Ni] +0.31 [Mn] + [Cu] +22 [C] +14.2 [N])... (1)
However, [element name] in the formula means the mass% of the element.
また、本発明では、凝固割れに有害なＳの固定に有効となるよう、非金属介在物がＣａＯ、ＭｇＯ、ＣａＳ、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物の１種または２種以上から構成されることを必須条件としている。なお、ＣａＯ、ＭｇＯ、ＣａＳとはそれぞれの主要酸化物濃度が８０質量％を超える物のことを意味している。
また、ＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系の介在物をいずれも含有しない。割れに有効な介在物を含む場合であっても、ＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系を含む場合は、生成したＭｇＯ・Ａｌ２Ｏ３やＡｌ２Ｏ３が鋳造時の浸漬ノズルに付着してノズル閉塞を引き起こす。また、ノズル付着物の脱落に起因した表面疵に繋がるため回避する。
ここで、本発明において、「ＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系の介在物をいずれも含有しない」とは、鋳片においては、直径（最大径）１０μｍ以上のＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系の介在物をいずれも含有しないことを意味し、鋼板または線材においては、圧延によって介在物が延伸したり破砕されて小さくなっているため、１μｍ以上の上記介在物が存在しないことを意味する。
鋼板または線材の場合、非金属介在物の組成分析は、鋼板または線材から厚み中心を通る圧延と平行なＬ断面で試験片を切り出して鏡面研磨した後に、１μｍ以上の介在物をランダムに２５個選んで日本電子製の走査型電子顕微鏡ＪＳＭ−６４９０Ａを用いてＥＤＳにより定量分析する。
Further, in the present invention, the non-metallic inclusions are made of one or more of CaO, MgO, CaS, and CaO—Al 2 O 3 —MgO-based oxides so as to be effective for fixing S harmful to solidification cracking. It is a necessary condition to be composed. In addition, CaO, MgO, and CaS mean that each main oxide density | concentration exceeds 80 mass%.
Further, neither MgO · Al 2 O 3 -based or Al 2 O 3 -based inclusions are contained. Even when inclusions effective for cracking are included, when MgO · Al 2 O 3 and Al 2 O 3 are included, the generated MgO · Al 2 O 3 and Al 2 O 3 are immersed during casting. It adheres to the nozzle and causes nozzle clogging. Moreover, since it leads to the surface flaw resulting from omission of a nozzle deposit, it avoids.
Here, in the present invention, “there is no MgO · Al 2 O 3 -based or Al 2 O 3 -based inclusion” means that MgO · Al 2 having a diameter (maximum diameter) of 10 μm or more in a slab. This means that neither O 3 -based or Al 2 O 3 -based inclusions are contained, and in steel plates or wire rods, inclusions of 1 μm or more are included because the inclusions are stretched or crushed by rolling. It means that there is no thing.
In the case of a steel plate or wire, composition analysis of non-metallic inclusions was performed by cutting out a test piece from a steel plate or wire with an L cross section parallel to the rolling through the thickness center and mirror-polishing 25 inclusions of 1 μm or more at random. Selected and quantitatively analyzed by EDS using a scanning electron microscope JSM-6490A manufactured by JEOL.
上記非金属介在物で鋳片の割れを抑制するためには、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物が以下の条件を満たすことが好ましい。 In order to suppress cracking of the slab with the non-metallic inclusions, it is preferable that the CaO—Al 2 O 3 —MgO-based oxide satisfies the following conditions.
ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物中のＣａＯ濃度が１０％を下回る場合、ＳｉＯ２濃度が１０％を超えて高い場合、Ａｌ２Ｏ３濃度が７０質量％を超えて高い場合は、介在物のＳ吸収能が低く、十分な割れ抑制効果を得られない。鋳造時の割れ抑制効果を得るにはＣａＯ≧１０％且つＳｉＯ２≦１０％且つＡｌ２Ｏ３≦７０％とする必要がある。 When the CaO concentration in the CaO—Al 2 O 3 —MgO-based oxide is less than 10%, the SiO 2 concentration is higher than 10%, the Al 2 O 3 concentration is higher than 70% by mass, The S-absorbing ability of inclusions is low, and a sufficient crack suppression effect cannot be obtained. In order to obtain a cracking suppressing effect during casting, it is necessary to satisfy CaO ≧ 10%, SiO 2 ≦ 10%, and Al 2 O 3 ≦ 70%.
［製造方法］
本発明に係る高Ｓｉオーステナイト系ステンレス鋼を確実に製造する事ができる方法を次に説明する。ただし、上記の化学組成および介在物により特定される本発明に係るステンレス鋼が製造する事ができる限り、他の製造方法を採用することも可能である。
[Production method]
Next, a method capable of reliably producing the high Si austenitic stainless steel according to the present invention will be described. However, as long as the stainless steel according to the present invention specified by the above chemical composition and inclusions can be manufactured, other manufacturing methods can be adopted.
鋼中の非金属介在物をＣａＯ、ＭｇＯ、ＣａＳ、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物に制御するには、脱酸により溶鋼中の［Ｏ］を十分に下げた上でＣａ−Ｓｉを添加してＣａＯの富化した介在物組成に制御する。脱酸不良の場合はＭｇＯ・Ａｌ２Ｏ３を生じ、過剰脱酸の場合にはＡｌ２Ｏ３を生じるため、介在物の組成制御にはＶ−ＡＯＤでの脱酸元素のＡｌ添加量により溶鋼［Ａｌ］濃度とスラグ組成を精度良く制御する必要がある。 In order to control non-metallic inclusions in the steel to CaO, MgO, CaS, CaO—Al 2 O 3 —MgO-based oxides, [O] in the molten steel is sufficiently lowered by deoxidation and then Ca—Si Is added to control inclusion composition enriched in CaO. For deoxidation defects occur MgO · Al 2 O 3, to produce the Al 2 O 3 in the case of excessive deoxidation, the composition control of inclusions of Al addition amount of deoxidizing element in V-AOD It is necessary to accurately control the molten steel [Al] concentration and the slag composition.
本発明に係る高Ｓｉオーステナイト系ステンレス鋼を製造する際の精錬における操業上望ましい条件を以下に示す。 Conditions desirable for operation in refining when producing the high-Si austenitic stainless steel according to the present invention are shown below.
電気炉でスクラップおよび合金原料を装入して溶解を行う。Ｐは精錬除去が困難なため、本発明で規定した０．０４５質量％以下となるように原料を選択する。 Scrap and alloy materials are charged and melted in an electric furnace. Since P is difficult to be refined and removed, the raw material is selected so as to be 0.045% by mass or less as defined in the present invention.
精錬工程としてＶ−ＡＯＤ炉で脱炭を行う。脱炭は酸素と希釈ガスのＡｒまたは窒素を吹き込み、溶鋼中のＣをＣＯガスとして除去する。さらに減圧によってＣＯガス分圧を低下させてＣｒ酸化を抑制しながら脱炭を行う。脱炭後、ＣａＯおよびＣａＦ２を添加してスラグを形成し、Ａｌを添加してスラグに移行したＣｒ酸化物の還元回収と溶鋼の脱酸による脱硫を進め、［Ｓ］≦０．００１５質量％に成分調整した。ここで、脱酸不良の場合はＭｇＯ・Ａｌ２Ｏ３を生じるため、出鋼前にＡｌ添加による脱酸を実施するが、Ａｌを過剰添加してしまうとＡｌ２Ｏ３を生じてしまうため、Ｖ−ＡＯＤ出鋼前に溶鋼とスラグ組成分析を行ってＡｌ添加量を決定する。 As a refining process, decarburization is performed in a V-AOD furnace. In the decarburization, oxygen and dilution gas Ar or nitrogen are blown to remove C in the molten steel as CO gas. Further, decarburization is performed while reducing the CO gas partial pressure by reducing pressure and suppressing Cr oxidation. After decarburization, CaO and CaF 2 are added to form slag, and Al is added to reduce recovery of Cr oxide transferred to slag and desulfurization by deoxidation of molten steel, [S] ≦ 0.0015 mass The ingredients were adjusted to%. Here, in the case of poor deoxidation, MgO · Al 2 O 3 is generated. Therefore, deoxidation is performed by adding Al before steel output. However, if Al is excessively added, Al 2 O 3 is generated. The molten steel and slag composition analysis are performed before V-AOD steelmaking, and the amount of Al added is determined.
Ａｌ添加量は、Ａｌ添加後のスラグ（ＳｉＯ２）濃度を５質量％以上１０質量％以下、（Ｃｒ２Ｏ３）濃度が０．３質量％以下に希釈し、溶鋼中の［Ａｌ］濃度が０．１質量％以下となる範囲を狙い、Ａｌ添加量最適範囲の下限Ａｍｉｎ（ｋｇ）と上限Ａｍａｘ（ｋｇ）は下記の式で計算する。 The amount of Al added is that the slag (SiO 2 ) concentration after addition of Al is diluted to 5 mass% or more and 10 mass% or less, and the (Cr 2 O 3 ) concentration is diluted to 0.3 mass% or less, and the [Al] concentration in the molten steel The lower limit A min (kg) and the upper limit A max (kg) of the optimum Al addition amount range are calculated by the following equations.
Ａ１＝（５３．９６／４７．９７）×スラグ重量（ｋｇ）×｛（ＳｉＯ２）−１０｝／１００×（３１．９８／６０．０６）・・・（２）
Ａ２＝（１０３．９８／４７．９７）×スラグ重量（ｋｇ）×｛（Ｃｒ２Ｏ３）−０．３｝／１００×（４７．９７／１５１．９５）・・・（３）
Ａｍｉｎ（ｋｇ）＝Ａ１＋Ａ２・・・（４）
Ａ３＝（５３．９６／４７．９７）×スラグ重量（ｋｇ）×｛（ＳｉＯ２）−５｝／１００×（３１．９８／６０．０６）・・・（５）
Ａ４（ｋｇ）＝｛溶鋼重量（ｋｇ）×（０．１−［Ａｌ］）｝／（１００−０．１）・・・（６）
Ａｍａｘ（ｋｇ）＝Ａ２＋Ａ３＋Ａ４・・・（７）
A 1 = (53.96 / 47.97) × slag weight (kg) × {(SiO 2 ) −10} / 100 × (31.98 / 60.06) (2)
A 2 = (103.98 / 47.97) × slag weight (kg) × {(Cr 2 O 3 ) −0.3} / 100 × (47.97 / 151.95) (3)
A min (kg) = A 1 + A 2 (4)
A 3 = (53.96 / 47.97) × slag weight (kg) × {(SiO 2 ) −5} / 100 × (31.98 / 60.06) (5)
A 4 (kg) = {weight of molten steel (kg) × (0.1− [Al])} / (100−0.1) (6)
A max (kg) = A 2 + A 3 + A 4 (7)
（ＳｉＯ２）はスラグの（ＳｉＯ２）濃度、（Ｃｒ２Ｏ３）はスラグの（Ｃｒ２Ｏ３）濃度、［Ａｌ］は溶鋼の［Ａｌ］濃度で、溶鋼重量はクレーン重量から求めた。スラグ重量はスラグ厚さ測定値を用いて密度から推定できるが、本実施例のスラグ重量に関しては溶鋼重量６０ｔｏｎで操業した際の平均スラグ重量の１５００ｋｇを用いて計算した。 (SiO 2 ) is the (SiO 2 ) concentration of slag, (Cr 2 O 3 ) is the (Cr 2 O 3 ) concentration of slag, [Al] is the [Al] concentration of molten steel, and the molten steel weight is obtained from the crane weight. . Although the slag weight can be estimated from the density using the measured slag thickness, the slag weight in this example was calculated using 1500 kg of the average slag weight when operating at a molten steel weight of 60 tons.
Ａ１はスラグ（ＳｉＯ２）濃度を１０％に希釈するのに必要なＡｌ量、Ａ２はスラグ（Ｃｒ２Ｏ３）濃度を０．３％に希釈するのに必要なＡｌ量で、Ａｍｉｎは正の値となる場合のＡ１、Ａ２を合計したものである。 A 1 is the amount of Al necessary to dilute the slag (SiO 2 ) concentration to 10%, A 2 is the amount of Al necessary to dilute the slag (Cr 2 O 3 ) concentration to 0.3%, min is the sum of A 1 and A 2 in the case of a positive value.
Ａ３はスラグ（ＳｉＯ２）濃度を５％に希釈するのに必要なＡｌ量、Ａ４は溶鋼［Ａｌ］濃度を０．１質量％とするのに必要なＡｌ量で、Ａｍａｘは正の値となる場合のＡ２、Ａ３、Ａ４の値を合計したものである。 A 3 is the amount of Al necessary to dilute the slag (SiO 2 ) concentration to 5%, A 4 is the amount of Al necessary to reduce the molten steel [Al] concentration to 0.1% by mass, and A max is a positive value. Is the sum of the values of A 2 , A 3 , and A 4 .
その後、ＬＦで合金添加による成分調整とＣａ−Ｓｉワイヤ添加によるスラグ系介在物の組成をＣａの富化した組成に制御した後、Ａｒの底吹きで５ｍｉｎ以上撹拌する事で均一化と過剰な介在物の浮上を行った。
一方、ＭｇはＡＯＤでスラグにＭｇＯを添加してスラグ中のＭｇＯ活量を高める事で溶鋼中のＡｌを還元する反応３ＭｇＯ＋２Ａｌ→３Ｍｇ＋Ａｌ２Ｏ３によりＭｇを溶鋼に取り込む。
このようにして溶鋼の成分と非金属介在物の組成を制御し、連続鋳造機にて鋳造する事で、鋳片の凝固割れを抑制し、製造性に優れたγ系高Ｓｉステンレス鋼が提供される。
Then, after adjusting the composition of the slag inclusions by adding an alloy with LF and adding Ca-Si wire to a Ca-enriched composition, the mixture is homogenized and excessively mixed by stirring at the bottom of Ar for 5 min or more. The object was lifted.
On the other hand, Mg takes in Mg into the molten steel by the reaction 3MgO + 2Al → 3Mg + Al 2 O 3 which reduces Al in molten steel by adding MgO to the slag by AOD and increasing the MgO activity in the slag.
In this way, by controlling the composition of the molten steel and the composition of non-metallic inclusions and casting with a continuous casting machine, γ-based high Si stainless steel with excellent manufacturability is provided by suppressing solidification cracking of the slab. Is done.
次に、本発明の実施例を参照しながら本発明を説明する。なお、本実施例は本発明の一実施形態を示すものであり、以下の構成に限定されるものではない。 The present invention will now be described with reference to examples of the present invention. In addition, a present Example shows one Embodiment of this invention, and is not limited to the following structures.
表１に示す組成の溶鋼を電気炉で溶解後、表２に示したＶ−ＡＯＤ出鋼前成分とＡｌ添加条件でＶ−ＡＯＤで精錬し、ＬＦで成分調整後に連続鋳造によりφ＝１８０ｍｍの丸ブルームおよび２００ｍｍ厚のスラブを鋳造した。 The molten steel having the composition shown in Table 1 was melted in an electric furnace, then refined by V-AOD under the conditions before adding V-AOD steel and Al added as shown in Table 2, and after adjusting the components by LF, φ = 180 mm by continuous casting A round bloom and a 200 mm thick slab were cast.
このようにして得られた鋳片とＶ−ＡＯＤで採取した溶鋼とスラグについて以下の評価を行った。 The following evaluation was performed about the molten steel and slag which were extract | collected with the slab obtained in this way, and V-AOD.
スラグ組成分析は、Ｖ−ＡＯＤで採取したスラグを粉末状に砕き、蛍光Ｘ線分析装置を用いて分析を行った。
Ｖ−ＡＯＤで採取した溶鋼および鋳片の組成分析は試験片をベルト研磨後に蛍光Ｘ線分析装置により測定した。またＣ、Ｓは炭素・硫黄分析装置を、Ｎは酸素・窒素分析装置を用いて測定した。
In the slag composition analysis, the slag collected by V-AOD was crushed into a powder and analyzed using a fluorescent X-ray analyzer.
The composition analysis of the molten steel and slab collected by V-AOD was measured by a fluorescent X-ray analyzer after the test piece was belt-polished. C and S were measured using a carbon / sulfur analyzer, and N was measured using an oxygen / nitrogen analyzer.
非金属介在物の組成分析は、鋳片から切り出した試験片を鏡面研磨し、１０μｍ以上の介在物をランダムに１５２５点選んで日本電子製の走査型電子顕微鏡ＪＳＭ−６４９０Ａを用いてＥＤＳにより定量分析した。介在物は単体酸化物の質量％が８５を超えるものについては単体酸化物のＣａＯ、ＣａＳ、ＭｇＯ、Ａｌ２Ｏ３に分類し、２０％＜ＭｇＯ＜３０％且つ６０％＜Ａｌ２Ｏ３＜８０％の場合はＭｇＯ・Ａｌ２Ｏ３に分類し、それ以外をスラグ系のＣａＯ−Ａｌ２Ｏ３−ＭｇＯに分類し、種類毎にＥＤＳで測定した組成の平均値をそれぞれの介在物組成とした。なお、同一介在物中に１μｍ以上の組成の異なる別種の介在物が含まれる複合介在物の場合は、それぞれ別種の介在物として分類して組成の平均値を求めた。 Composition analysis of non-metallic inclusions was performed by mirror polishing a specimen cut from a slab, randomly selecting 1525 inclusions of 10 μm or more, and quantifying by EDS using a scanning electron microscope JSM-6490A manufactured by JEOL. analyzed. Inclusions whose mass% of the single oxide exceeds 85 are classified into single oxides CaO, CaS, MgO and Al 2 O 3 , and 20% <MgO <30% and 60% <Al 2 O 3 < In the case of 80%, it is classified as MgO · Al 2 O 3 , and the others are classified as slag CaO—Al 2 O 3 —MgO, and the average value of the composition measured by EDS for each type is included in each inclusion composition It was. In addition, in the case of the composite inclusions in which different types of inclusions having different compositions of 1 μm or more are included in the same inclusion, the average values of the compositions were obtained by classifying them as different types of inclusions.
鋳片の割れ評価は、鋳片表層を１．５ｍｍ研削した後に、浸透探傷液を用いた簡易ＰＴでチェックした。１．５ｍｍ研削で割れの無いものは○評価とし、追加の１ｍｍ研削で割れが除去出来たものは△評価とし、それよりも割れが深いものは×評価とした。 The crack evaluation of the slab was checked by simple PT using a penetrant flaw detection liquid after grinding the slab surface layer by 1.5 mm. The case where there was no crack in 1.5 mm grinding was rated as ◯, the case where the crack could be removed by additional 1 mm grinding was rated as △, and the case where the crack was deeper than that was rated as x.
結果を表３に示した。
発明鋼である実施例１〜１０は鋳片の表面１．５ｍｍ研削後に割れが無く、良好な鋳片品質であった。
比較例１１は鋼中に含まれる介在物に規定する介在物が含まれていたが、Ｃｒｅｑ／Ｎｉｅｑが１．３を下回っており、鋳片の割れ評価は×であった。
比較例１２はＣｒｅｑ／Ｎｉｅｑが１．３を下回っており、更に鋼中に含まれる介在物も規定の介在物を含んでおらず、鋳片の割れ評価は×であった。
比較例１３はＣｒｅｑ／Ｎｉｅｑが１．３を超えたが、鋼中に規定する介在物が含まれておらず、鋳片の割れ評価は△であった。
比較例１４はＣｒｅｑ／Ｎｉｅｑが１．３を超えたが、鋼中に規定する介在物が含まれておらず、鋳片の割れ評価は△であった。
比較例１５はＣｒｅｑ／Ｎｉｅｑが１．３を下回っており、更に鋼中に含まれる介在物も規定の介在物を含んでおらず、鋳片の割れ評価は×であった。
The results are shown in Table 3.
Inventive steels of Examples 1 to 10 had good slab quality without cracks after grinding the surface of the slab by 1.5 mm.
In Comparative Example 11, inclusions defined in the inclusions contained in the steel were included, but Creq / Nieq was less than 1.3, and the crack evaluation of the slab was x.
In Comparative Example 12, Creq / Nieq was less than 1.3, and inclusions contained in the steel did not contain any specified inclusions, and the crack evaluation of the slab was x.
In Comparative Example 13, Creq / Nieq exceeded 1.3, but inclusions specified in the steel were not included, and the crack evaluation of the slab was Δ.
In Comparative Example 14, Creq / Nieq exceeded 1.3, but inclusions specified in the steel were not included, and the crack evaluation of the slab was Δ.
In Comparative Example 15, Creq / Nieq was less than 1.3, and the inclusions contained in the steel did not contain any specified inclusions, and the evaluation of cracking of the slab was x.
Claims (2)
Ｃ：≦０．２５％、
Ｓｉ：１．５〜４％、
Ｍｎ：≦２．０％、
Ｐ：≦０．０４５％、
Ｓ：≦０．００１５％、
Ｃｒ：１６〜２６％、
Ｎｉ：８．０〜２２．０％、
Ｍｏ：０．０１〜３．０％、
Ｃｕ：０．０１〜２．５％、
Ａｌ：０．００３〜０．２％、
Ｎ：≦０．１％、
Ｃａ：０．０００１〜０．００５％、
Ｍｇ：０．０００１〜０．００５％、
を満足し、残部Ｆｅおよび不可避的不純物よりなり、かつ下記（１）で表されるＣｒｅｑ／Ｎｉｅｑが１．３以上であり、
前記のステンレス鋼中に含まれる非金属介在物として、ＭｇＯ・Ａｌ２Ｏ３系、Ａｌ２Ｏ３系の介在物をいずれも含有せず、
前記の非金属介在物が、ＣａＯ、ＭｇＯ、ＣａＳ、ＣａＯ−Ａｌ２Ｏ３−ＭｇＯ系酸化物の１種または２種以上からなる
ことを特徴とする製造性に優れた高Ｓｉ含有のオーステナイト系ステンレス鋼。
Ｃｒｅｑ／Ｎｉｅｑ＝（［Ｃｒ］＋１．３７×［Ｍｏ］＋１．５×［Ｓｉ］）／（［Ｎｉ］＋０．３１×［Ｍｎ］＋［Ｃｕ］＋２２×［Ｃ］＋１４．２×［Ｎ］）・・・（１）
但し、式中の［元素名］は、当該元素の含有質量％を意味する。 % By mass
C: ≦ 0.25%
Si: 1.5-4%,
Mn: ≦ 2.0%,
P: ≦ 0.045%
S: ≦ 0.0015%,
Cr: 16 to 26%,
Ni: 8.0 to 22.0%,
Mo: 0.01 to 3.0%,
Cu: 0.01 to 2.5%,
Al: 0.003 to 0.2%,
N: ≦ 0.1%
Ca: 0.0001 to 0.005%,
Mg: 0.0001 to 0.005%,
Satisfying the above, consisting of the balance Fe and inevitable impurities, and Creq / Nieq represented by the following (1) is 1.3 or more,
As the non-metallic inclusions contained in the stainless steel, MgO · Al 2 O 3 -based and Al 2 O 3 -based inclusions are not included,
The non-metallic inclusions are composed of one or more of CaO, MgO, CaS, and CaO—Al 2 O 3 —MgO-based oxides. Stainless steel.
Creq / Nieq = ([Cr] + 1.37 × [Mo] + 1.5 × [Si]) / ([Ni] + 0.31 × [Mn] + [Cu] + 22 × [C] + 14.2 × [N ]) ... (1)
However, [element name] in the formula means the mass% of the element.
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