KR20030047470A - The hot rolled sheet steel with the excellent anti-corrosion resistance to sulfuric acid - Google Patents
The hot rolled sheet steel with the excellent anti-corrosion resistance to sulfuric acid Download PDFInfo
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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Abstract
Description
본 발명은 발전소 예열기, 보일러 배관 및 주변부품의 소재로 사용되는 내황산 부식특성이 우수한 열연강판에 관한 것으로, 보다 상세하게는 저온-저황산 농도 구간에서 부식속도를 크게 향상 시키고 고온 산화를 지연하며, 연속주조 또는 열간압연공정에서 다량의 Cu첨가에 의한 표면결함을 방지하기 위해 다른 첨가원소를 적당량 첨가하여 고온-저황산 농도 구간에서 내황산 부식특성이 우수한 열연강판에 관한 것이다.The present invention relates to a hot rolled steel sheet having excellent sulfuric acid corrosion resistance, which is used as a material for power plant preheater, boiler pipe, and peripheral parts. More specifically, the corrosion rate is greatly improved in the low-low sulfuric acid concentration range, and high-temperature oxidation is delayed. The present invention relates to a hot rolled steel sheet having excellent sulfuric acid corrosion resistance in a high temperature-low sulfuric acid concentration range by adding an appropriate amount of other additive elements to prevent surface defects caused by a large amount of Cu in continuous casting or hot rolling.
내황산 부식특성이 우수한 강은 아황산가스가 함유된 배기가스와 접촉하는 화력발전소 예열기의 300℃이하의 저온부에 사용되는 소재, 보일러의 배관 등 황산에 의한 부식이 심한 부품의 소재로 사용되고 있다. 일반적으로 내황산 부식강은 황산분위기에서 일반강 보다 부식속도를 지연시키기 위하여 강중에 Cu를 다량 첨가하는 것으로 알려져 왔다. Cu는 다른 첨가 원소에 비해 황산 부식속도를 크게 지연시키는 효과가 월등하지만 많이 첨가할 경우 열간압연시 크랙발생등의 이유로 Cu를 적당량 첨가하고 다른 원소를 복합첨가하는 강이 개발되어 있다. 그 대표적인 예가 일본 특허공개공보 평 9-25536호, 평10-110237호가 있다.Steels with excellent sulfuric acid corrosion resistance are used as materials used in low temperature parts below 300 ° C of thermal power plant preheaters that come into contact with exhaust gas containing sulfurous acid gas, and components that are highly corrosive by sulfuric acid, such as boiler piping. In general, sulfuric acid resistant steel has been known to add a large amount of Cu in the steel in order to retard the corrosion rate in the sulfuric acid atmosphere than ordinary steel. Although Cu has a great effect of significantly delaying the corrosion rate of sulfuric acid compared to other additive elements, a steel has been developed that adds an appropriate amount of Cu and complexly adds other elements due to cracking during hot rolling. Representative examples thereof include Japanese Patent Laid-Open Nos. 9-25536 and 10-110237.
일본 특허 특개평9-25536호는 C-Si-Mn-P-S-Al-Cu의 기본성분계에 Ni, Cr, V, Nb, Ti, Sn, Sb, B의 합금원소를 첨가하여 열간가공성을 확보하면서 내황산부식특성을 개선하는 기술이다. 일본 특허공개공보 평10-110237호는 C-Si-Mn-P-S-Al-Cu의 기본성분계에 Ni, Cr, V, Nb, Ti, Sn, Sb, B, Mo의 합금원소를 첨가하여 열간가공성을 확보하면서 내황산부식특성을 개선하는 기술이다.Japanese Patent Application Laid-open No. Hei 9-25536 adds alloying elements of Ni, Cr, V, Nb, Ti, Sn, Sb, and B to the basic component system of C-Si-Mn-PS-Al-Cu to secure hot workability. It is a technology to improve sulfuric acid corrosion resistance. Japanese Patent Application Laid-Open No. 10-110237 discloses hot workability by adding alloying elements of Ni, Cr, V, Nb, Ti, Sn, Sb, B, and Mo to the basic component system of C-Si-Mn-PS-Al-Cu. It is a technology to improve sulfuric acid corrosion resistance while securing
그러나, 이들 선행기술에서는 다량의 합금원소를 첨가하고 있으면서도 저온-저황산농도 구간에서는 여전히 부식속도가 높은 문제점이 있다. 또한, 고온에서 일어나는 산화에 의한 부식 및 연속주조 또는 열간압연시 표면결함이 발생하는 문제점이 있다.However, these prior art has a problem that the corrosion rate is still high in the low-temperature sulfuric acid concentration range while adding a large amount of alloying elements. In addition, there is a problem that the surface defects during corrosion and continuous casting or hot rolling caused by oxidation occurring at a high temperature.
따라서 본 발명은 상기 문제점을 해결하기 위해 저온-저황산 농도 구간에서 부식속도를 크게 향상 시키고 고온 산화를 지연하며, 연속주조 또는 열간압연공정에서 다량의 Cu첨가에 의한 표면결함을 방지하기 위해 합금원소를 적당량 첨가하여 고온-저황산 농도 구간에서 내황산 부식특성이 우수한 열연강판을 제공하는데, 그 목적이 있다.Therefore, in order to solve the problem, the present invention greatly improves the corrosion rate in the low-low sulfuric acid concentration section, delays high temperature oxidation, and prevents surface defects due to the addition of a large amount of Cu in continuous casting or hot rolling. In order to provide a hot rolled steel sheet excellent in sulfuric acid corrosion resistance in the high temperature-low sulfuric acid concentration range by adding an appropriate amount, the purpose.
상기 목적을 달성하기 위한 본 발명의 열연강판은, 중량%로 C:0.15%이하, Si:1.0%이하, Mn:1.5%이하, S:0.03%이하, P:0.02%이하, Al:0.01-0.1%, Cu:0.2-1.0%, Co:0.02-0.1%, Cr:0.05-0.5, Ni:0.1-2.0%, Ni/Cu원자비: 0.5-2.0를 만족하고 나머지 Fe와 기타 불가피한 불순물로 조성된다.Hot-rolled steel sheet of the present invention for achieving the above object, by weight% C: 0.15% or less, Si: 1.0% or less, Mn: 1.5% or less, S: 0.03% or less, P: 0.02% or less, Al: 0.01- 0.1%, Cu: 0.2-1.0%, Co: 0.02-0.1%, Cr: 0.05-0.5, Ni: 0.1-2.0%, Ni / Cu atomic ratio: 0.5-2.0, satisfying the composition of remaining Fe and other unavoidable impurities do.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
·C: 0.15%이하 · C: 0.15% or less
상기 C의 첨가량이 0.15%을 초과할 경우 용접을 하여 사용할때 용접성이 크게 나빠져 결함발생 가능성이 높다. 따라서 C함량의 상한값을 0.15%로 하는 것이 바람직하다.When the amount of C added exceeds 0.15%, weldability is greatly deteriorated when welding is used, and thus defects are high. Therefore, it is preferable to make the upper limit of C content into 0.15%.
·Si: 1.0%이하 · Si: 1.0% or less
상기 Si는 주로 강도를 향상하기 위해 첨가하는 원소로 1.0%초과에서는 내황산부식특성이 크게 나빠지므로 상한값을 1.0%로 하는 것이 바람직하다.Since Si is an element mainly added to improve strength, the sulfuric acid corrosion resistance is greatly deteriorated at more than 1.0%, so the upper limit is preferably 1.0%.
·Mn: 1.5%이하 · Mn: 1.5% or less
상기 Mn은 통상 강중 고용 황을 망간황화물로 석출하여 고용 황에 의한적열취성(Hot shortness)을 방지하기 위해 첨가하는데 본 발명에서는 적열취성 방지의 목적과 강도 향상을 목적으로 첨가한다. Mn함량 1.5%초과의 경우 내황산 부식특성이 나빠지므로 상한값을 1.5%로 하는 것이 바람직하다.The Mn is usually added to prevent hot shortness due to solid solution of precipitated sulfur in steel as manganese sulfide in the present invention. If the Mn content is more than 1.5%, sulfuric acid corrosion resistance is deteriorated, so the upper limit is preferably 1.5%.
·P: 0.02%이하 · P: 0.02% or less
상기 P는 0.02%초과의 경우 내황산 부식성이 크게 저하하므로 상한값을 0.02%로 제한하는 것이 바람직하다.When P is more than 0.02%, sulfuric acid corrosion resistance is greatly reduced, so it is preferable to limit the upper limit to 0.02%.
·S:0.03%이하 · S: 0.03% or less
상기 S는 가능한 낮게 첨가하는 것이 바람직하며, 0.03%이상 첨가될 경우 열간취성에 의한 결함발생 가능성이 높기 때문에 상한값을 0.03%로 하는 것이 바람직하다.It is preferable to add the S as low as possible, and if it is added 0.03% or more, the upper limit is preferably 0.03% because the possibility of defects due to hot brittleness is high.
·Al: 0.01~0.1% · Al: 0.01 ~ 0.1%
상기 Al은 탈산제로 첨가되는데 0.01%미만에서는 탈산효과가 적고 0.1%초과의 경우 Al산화물의 증가로 표면 결함 발생 확률이 높다.The Al is added as a deoxidizer, but less than 0.01% has a low deoxidation effect, and in the case of more than 0.1%, Al has a high probability of surface defects.
·Cu: 0.2~1.0% · Cu: 0.2 ~ 1.0%
상기 Cu는 내황산 부식성을 크게 증가하므로 첨가하는데, 0.2%이상에서부터 그 효과가 두드러지나 1.0%초과의 경우에는 첨가량의 증가에 비해 내식성 향상 효과는 크지 않다.The Cu is added to increase the sulfuric acid corrosion resistance greatly, but the effect is noticeable from 0.2% or more, but in the case of more than 1.0%, the effect of improving the corrosion resistance is not large compared to the increase of the addition amount.
·Co: 0.02~0.1% · Co: 0.02 ~ 0.1%
상기 Co는 Cu와 함께 특히 저온-저황산 농도 구간에서 내식성을 크게 향상하는 효과가 있어 첨가한다. 0.02%이상에서부터 그 효과가 두드러지나, 0.1%초과할 경우에는 첨가량 대비 내식성 향상이 미미하다.The Co is added with Cu, particularly in the low temperature-low sulfuric acid concentration section, thereby greatly improving the corrosion resistance. The effect is prominent from 0.02% or more, but when it exceeds 0.1%, the improvement of corrosion resistance is insignificant compared to the added amount.
·Cr: 0.05~0.5% · Cr: 0.05 ~ 0.5%
상기 Cr은 고온에서 Cr계 산화물을 표면에 생성하게 하여 내식성을 향상하기 위해 첨가한 것으로 첨가량 0.05%미만에서는 방식피막이 거의 생성되지 않으며, 첨가량이 증가할수록 방식피막의 발달이 용이하여 방식 효과는 크지만 0.5%초과의 경우 첨가량의 증가분에 따른 효과가 거의 없다.The Cr is added to improve the corrosion resistance by the formation of Cr-based oxide on the surface at a high temperature, almost no anticorrosive coating is produced when the addition amount is less than 0.05%, the anticorrosive coating is easy to develop as the addition amount is increased, but the anticorrosive effect is large. If it is more than 0.5%, there is little effect by the increase of the addition amount.
·Ni: 0.1~2.0% · Ni: 0.1 ~ 2.0%
상기 Ni는 Cu첨가강에서 연속주조 또는 열간압연중에 발생하는 표면결함을 방지하기 위해 첨가하는 것으로 Ni첨가량 0.1%이상에서 표면결함 발생이 없으며, 2.0%초과할 경우에는 제조원가가 크게 상승하므로 상한값을 1.0%로 제한하는 것이 바람직하다.The Ni is added to prevent surface defects occurring during continuous casting or hot rolling in Cu-added steel, and there is no surface defects in the Ni addition amount of 0.1% or more, and when it exceeds 2.0%, the manufacturing cost increases greatly, so the upper limit value is 1.0. It is desirable to limit to%.
·Ni/Cu의 원자비: 0.5~2.0 · Ni / atomic ratio of Cu: 0.5 ~ 2.0
Ni/Cu의 원자비는 연속주조 또는 열간압연시 표면결함의 발생을 방지하고 고가의Ni첨가량을 가능한 절감하여 제조원가를 낮게하기 위한 것으로 Ni/Cu의 원자비 0.5이하에서는 표면결함이 발생할 가능성이 크며 Ni/Cu의 원자비 2.0이상으로 할 경우 제조원가가 크게 상승하므로 Ni/Cu의 원자비를 2.0이하로 제한하는 것이 바람직하다.The atomic ratio of Ni / Cu is to prevent the occurrence of surface defects during continuous casting or hot rolling, and to reduce the production cost by reducing expensive Ni additions. Surface defects are likely to occur at the Ni / Cu atomic ratio of 0.5 or less. When the atomic ratio of Ni / Cu is 2.0 or more, the manufacturing cost is greatly increased, so it is preferable to limit the atomic ratio of Ni / Cu to 2.0 or less.
상기와 같이 조성되는 강을 통상의 방법으로 가열하여 원하는 두께로 열간압연하여 열연판을 제조한다. 통상의 조건으로 열간압연하더라도 내황산 부식특성의 변화가 거의 없다.The steel formed as described above is heated by a conventional method and hot rolled to a desired thickness to produce a hot rolled sheet. Even under hot rolling under normal conditions, there is little change in sulfuric acid corrosion resistance.
이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
하기 표 1과 같은 조성을 만족하도록 용해하여 제조한 강괴를 1250℃가열로에 1시간 유지후 열간압연을 실시하였다. 이때 열간마무리 압연개시온도는 1100℃, 권취온도는 650℃로 하여 최종두께를 3.2mm로 하였다. 열간압연된 시편은 저온-저농도 조건에서 내황산 부식특성을 조사하기 위해 70℃-50% 및 140℃-80% 황산 용액 에 시편을 1시간 동안 침적하여 각 시편의 부식감량을 측정하였다.The steel ingot prepared by dissolving the composition as shown in Table 1 was maintained for 1 hour in a 1250 ° C. heating furnace, and then hot rolled. At this time, the hot finish rolling start temperature was 1100 ° C, the winding temperature was 650 ° C, and the final thickness was 3.2mm. In order to investigate the corrosion resistance of sulfuric acid at low temperature and low concentration, hot-rolled specimens were immersed in 70 ℃ -50% and 140 ℃ -80% sulfuric acid solution for 1 hour to measure the corrosion loss of each specimen.
상기 표 1, 2에서 본 발명 범위에 속하는 강은 평균 부식감량 15mg/cm2hr이하로서 매우 우수한 내황산 부식특성을 나타내며 표면상태도 결함이 발생하지 않아 매우 양호하다.그러나 비교강 1은 Co의 첨가량이 본 발명의 범위에 벗어나 50%-70oC 및80%-140oC 황산용액 조건에서 부식감량이 매우 높아 평균 부식감량은 28.25mg/cm2hr로 매우 높다. 비교강 2의 경우 저온-저농도 구간에서는 양호하나, Cr함량이 본 발명의 범위에서 벗어나 80%-140oC 황산용액 조건에서 부식감량이 매우 높아 평균 부식감량은 22.85mg/cm2hr로 매우 높다. 비교강 3의 경우 Cu의 함량이 본 발명의 범위에서 벗어나 50%-70oC 및 80%-140oC 황산용액 조건에서 부식감량이 매우 높아 평균 부식감량은 40.4mg/cm2hr로 매우 높다. 비교강 4의 경우 Cu, Co 및 Cr은 본 발명강의 범위에 속하여 내황산 부식성은 양호하나 Ni첨가량이 본 발명에서 제한하는 범위 보다 낮아 표면 결함이 발생하였다.In Tables 1 and 2, the steels belonging to the present invention have an average corrosion loss of 15 mg / cm 2 hr or less, and exhibit very excellent sulfuric acid corrosion resistance. The amount of addition is outside the scope of the present invention, the corrosion loss is very high under the conditions of 50% -70 o C and 80% -140 o C sulfuric acid solution, the average corrosion loss is very high, 28.25mg / cm 2 hr. Comparative steel 2 is good in the low temperature-low concentration range, but the Cr content is out of the scope of the present invention, the corrosion loss is very high under the condition of 80% -140 o C sulfuric acid solution, the average corrosion loss is very high, 22.85mg / cm 2 hr. . In case of Comparative Steel 3, the Cu content is out of the scope of the present invention and the corrosion loss is very high under the conditions of 50% -70 o C and 80% -140 o C sulfuric acid solution, and the average corrosion loss is very high as 40.4 mg / cm 2 hr. . In the case of Comparative Steel 4, Cu, Co, and Cr belonged to the range of the present invention, so that sulfuric acid corrosion resistance was good, but Ni was lower than the range limited by the present invention, resulting in surface defects.
상술한 바와 같이 본 발명에 의하면 내황산 부식특성이 우수한 열연강판이 제공되어, 황산 노점 부식이 발생하는 발전소 예열기의 비교적 두꺼운 두께를 요구하는 소재 및 보일러의 배관 및 주변 장치의 소재의 수명을 크게 연장하는 효과가 유용한 효과가 있는 것이다.As described above, according to the present invention, a hot rolled steel sheet having excellent sulfuric acid corrosion resistance is provided, which greatly extends the lifespan of materials requiring relatively thick thicknesses of power plant preheaters where sulfuric acid dew point corrosion occurs and materials of boiler piping and peripheral devices. The effect is to have a useful effect.
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EP1951922A1 (en) * | 2005-10-25 | 2008-08-06 | Posco | Corrosion resistance improved steel sheet for autmotive muffler and method of producing the steel sheet |
US11939489B2 (en) | 2016-09-28 | 2024-03-26 | Posco Co., Ltd | Solution composition for surface treatment of steel sheet and surface-treated steel sheet using same |
US12030082B2 (en) | 2018-12-19 | 2024-07-09 | Posco Co., Ltd | Bilayer composition for surface treatment of steel plate and surface-treated steel plate using same |
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JP3584636B2 (en) * | 1996-10-08 | 2004-11-04 | 住友金属工業株式会社 | Sulfuric acid / hydrochloric acid dew-point corrosion resistant steel with excellent hot workability |
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EP1951922A4 (en) * | 2005-10-25 | 2010-06-09 | Posco | Corrosion resistance improved steel sheet for autmotive muffler and method of producing the steel sheet |
US7922968B2 (en) | 2005-10-25 | 2011-04-12 | Posco | Corrosion resistance improved steel sheet for automotive muffler and method of producing the steel sheet |
US11939489B2 (en) | 2016-09-28 | 2024-03-26 | Posco Co., Ltd | Solution composition for surface treatment of steel sheet and surface-treated steel sheet using same |
US12030082B2 (en) | 2018-12-19 | 2024-07-09 | Posco Co., Ltd | Bilayer composition for surface treatment of steel plate and surface-treated steel plate using same |
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