JP2022511464A - 耐酸用鋼板およびその製造方法 - Google Patents
耐酸用鋼板およびその製造方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 99
- 239000010959 steel Substances 0.000 title claims abstract description 99
- 239000002253 acid Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims description 42
- 238000005260 corrosion Methods 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 4
- 238000005097 cold rolling Methods 0.000 claims description 4
- 238000005098 hot rolling Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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Abstract
Description
伸び率が30%以上であり得る。
熱延鋼板を製造する段階で、仕上げ圧延温度はAr3以上であり得る。
Ar3=910-310×[C]-80×[Mn]-20×[Cu]-15×[Cr]-55×[Ni]-80×[Mo]-(0.35×(25.4-8))
熱延鋼板を製造する段階の後、熱延鋼板を冷間圧延する段階をさらに含み得る。
熱延鋼板を製造する段階の後、熱延鋼板を焼鈍する段階をさらに含み得る。
本発明の一実施形態による耐酸用鋼板は、Crのような高価な合金成分を添加せずとも、優れた耐酸性と加工性を得ることができる。
本発明の一実施形態による耐酸用鋼板は、Si濃化層が形成されており、酸による腐食環境で優れた耐食性を有することによって素材の寿命を効果的に延長させることができる。
以下、各成分別に詳細に説明する。
Cは含有量が高いほど強度が増加するので所望する降伏強度および引張強度を得るために適正量のCを添加する。しかし、Cの含有量が過度に高い場合は伸び率が減少して成形性が低下し得る。したがって、Cを0.1重量%以下で含み得る。より具体的にはCを0.001~0.1重量%含み得る。さらに具体的にはCを0.01~0.09重量%含み得る。
Siは少量添加されて脱炭剤として使用できる元素であり、固溶強化による強度の向上に寄与することができる。本発明の一実施形態におけるSiは、非常に重要な添加元素としてSiの添加および表面濃化により表面にSi系酸化層を形成させることによって酸に対する耐食性を大きく向上させることができる。Siが過度に少なく添加される場合、前述した効果を得難い。逆にSiが過多に添加される場合はB2またはDO3規則相の形成によって加工性が大きく低下し得る。したがって、Siを2.0~4.0重量%含み得る。より具体的にはSiを2.5~3.5重量%含み得る。
マンガン(Mn)は鋼中の固溶Sと結合してMnSとして析出されることによって固溶Sによる赤熱脆性(Hot shortness)を防止する元素である。このような効果を出すために、Mnをさらに含む場合、0.1重量%以上含まれ得る。しかし、Mnを0.5重量%を超える場合は材質が硬化して軟性を低下させ得る。より具体的にはMnを0.15~0.35重量%含み得る。
Alは脱酸効果が非常に大きい元素であり、鋼中のNと反応してAlNを析出させることによって固溶Nによる成形性が低下することを防止するので、さらに含まれ得る。しかし、多量添加される場合は軟性が急激に低下するので、含有量を0.1重量%以下に制限する。より具体的にはAlを0.01~0.05重量%さらに含み得る。
一定量以下のPの添加は鋼の軟性を大きく減少させず強度を上げることができる元素であるが、0.01重量%を超えて添加すると結晶粒界に偏析して鋼を硬化させるので0.01重量%以下に制限し得る。より具体的にはPを0.001~0.01重量%さらに含み得る。
Sは固溶時赤熱脆性を誘発する元素であるので、Mnの添加によりMnSの析出が誘導されなければならない。しかし、MnSの過多な析出は鋼を硬化させるので好ましくない。したがって、Sの上限を0.01重量%に制限する。より具体的にはSを0.001~0.01重量%さらに含み得る。
Nは鋼中に不可避な元素として含有される場合が多く、析出されず固溶された状態で存在するNは軟性を低下させ、耐時効性を悪化させるだけでなく加工性を落とす。またTi、Nbなどの元素と結合して析出物を形成する場合は耐食性を大きく悪化させるので上限を0.01重量%に制限する。より具体的にはNを0.001~0.005重量%さらに含み得る。
先にスラブを加熱する。
スラブの合金組成については前述した耐酸用鋼板で説明したので、重複する説明は省略する。耐酸用鋼板の製造過程で合金成分が実質的に変動しないので、耐酸用鋼板の合金組成とスラブの合金組成は実質的に同一である。
このとき、仕上げ圧延温度はAr3以上であり得る。
Ar3=910-310×[C]-80×[Mn]-20×[Cu]-15×[Cr]-55×[Ni]-80×[Mo]-(0.35×(25.4-8))
本発明の一実施形態で酸処理により表面部20にSiを濃化させることによって、優れた耐酸性を確保することができる。
下記表1の組成を有する鋼を製造し、成分は実績値を表記したものである。このような表1の組成を有する鋼スラブを1250℃で再加熱して、900℃以上で熱間圧延を実施して、620℃で巻き取りして、表1の酸処理条件で塩酸による表面処理を実施して、最終的に3mm厚さの熱延鋼板を得た。
20 表面部
Claims (11)
- 重量%で、C:0.1%以下(0%を除く)およびSi:2.0~4.0%を含み、残部Feおよび不可避不純物を含み、
鋼板表面から内部方向に深さ10μmまでの表面部のSi含有量が15重量%以上である、耐酸用鋼板。 - Mn:0.1~0.5重量%、Al:0.1重量%以下、P:0.01重量%以下、S:0.01重量%以下およびN:0.01重量%以下のうち1種以上をさらに含む、請求項1に記載の耐酸用鋼板。
- Cr:0.1重量%以下、Ni:0.1重量%以下、Cu:0.1重量%以下、Nb:0.1重量%以下およびMo:0.1重量%以下のうち1種以上をさらに含む、請求項1に記載の耐酸用鋼板。
- 1重量%の硫酸水溶液に70℃で1時間の間浸漬するとき、平均腐食速度が3.5mg/cm2・h以下である、請求項1に記載の耐酸用鋼板。
- 伸び率が30%以上である、請求項1に記載の耐酸用鋼板。
- 重量%で、C:0.1%以下(0%を除く)およびSi:2.0~4.0%を含み、残部Feおよび不可避不純物を含むスラブを加熱する段階;
前記スラブを熱間圧延して熱延鋼板を製造する段階;および
前記熱延鋼板を25重量%以上の酸水溶液に10秒以上酸処理する段階
を含む、耐酸用鋼板の製造方法。 - 前記スラブを加熱する段階で、
前記スラブを1200℃以上加熱する、請求項6に記載の耐酸用鋼板の製造方法。 - 前記熱延鋼板を製造する段階で、
仕上げ圧延温度はAr3以上である、請求項6に記載の耐酸用鋼板の製造方法。 - 前記熱延鋼板を製造する段階の後、
前記熱延鋼板を550~750℃で巻き取りする段階をさらに含む、請求項6に記載の耐酸用鋼板の製造方法。 - 前記熱延鋼板を製造する段階の後、
前記熱延鋼板を冷間圧延する段階をさらに含む、請求項6に記載の耐酸用鋼板の製造方法。 - 前記熱延鋼板を製造する段階の後、
前記熱延鋼板を焼鈍する段階をさらに含む、請求項6に記載の耐酸用鋼板の製造方法。
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KR102178809B1 (ko) | 2020-11-13 |
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