KR100368728B1 - Manufacturing method of hot-dip galvanized steel sheet containing silicon - Google Patents
Manufacturing method of hot-dip galvanized steel sheet containing silicon Download PDFInfo
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- KR100368728B1 KR100368728B1 KR10-1998-0060222A KR19980060222A KR100368728B1 KR 100368728 B1 KR100368728 B1 KR 100368728B1 KR 19980060222 A KR19980060222 A KR 19980060222A KR 100368728 B1 KR100368728 B1 KR 100368728B1
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- Prior art keywords
- hot
- steel sheet
- rolled steel
- silicon
- plating
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- 239000010703 silicon Substances 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229910001335 Galvanized steel Inorganic materials 0.000 title description 3
- 239000008397 galvanized steel Substances 0.000 title description 3
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 52
- 239000010959 steel Substances 0.000 claims abstract description 52
- 238000007747 plating Methods 0.000 claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 238000005246 galvanizing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 21
- 238000005554 pickling Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
본 발명은 난도금성 원소인 실리콘을 함유한 열연강판의 표면에 형성된 스케일(scale)층을 산세공정이나 기계적 박리공정에서 제거시키지 않고, 도금조 이전에 설치되어 있는 환원가열대에서 열연판의 스케일층을 환원시키므로서 스케일 제거로 유발되는 환경 문제 뿐만 아니라 실리콘 함유강판의 젖음성을 향상시키기 위한 예비도금(pre-coating) 등을 생략시킬 수 있고, 제조원가를 절감시키면서 기존의 용융아연도금 열연강판과 동등 이상의 도금밀착성을 가질 수 있는 실리콘 함유 용융아연도금 열연강판의 제조방법에 관한 것이다.The present invention does not remove the scale layer formed on the surface of the hot-rolled steel sheet containing silicon, which is a non-plating element, in the pickling process or the mechanical peeling process, and the scale layer of the hot-rolled sheet in the reduction heating table installed before the plating bath. By reducing it, it is possible to omit pre-coating to improve the wettability of silicon-containing steel sheet as well as environmental problems caused by scale removal, and to reduce the manufacturing cost while plating more than or equal to the existing hot-dip galvanized hot rolled steel sheet. It relates to a method for producing a silicon-containing hot dip galvanized hot rolled steel sheet that can have adhesion.
본 발명은 난도금성 원소인 실리콘을 0.1% 이상 함유하는 고장력 및 고가공성 열연강판을 용융아연도금하기 위한 열연강판의 제조방법에 있어서, 도금욕조 이전 공정인 환원가열로에서의 열처리 온도를 650 내지 750 ℃, 유지시간은 60초 이상, 수소농도는 30% 이상으로 유지하면서 열연강판의 스케일층을 선택적으로 환원처리하는 단계와; 도금욕 이전의 제어 냉각 속도를 5 내지 25 ℃/sec 범위로 설정하여 특정 스케일 조성으로 형성시킨 다음에 용융아연도금을 실시하는 단계로 이루어진 것을 특징으로 한다.The present invention provides a method of manufacturing a hot rolled steel sheet for hot-dip galvanizing high tensile and high process hot rolled steel sheet containing 0.1% or more of silicon, which is a non-plating element, wherein the heat treatment temperature in a reduction heating furnace before the plating bath is 650 to 750. Selectively reducing the scale layer of the hot-rolled steel sheet while maintaining the holding time of 60 seconds or more and the hydrogen concentration of 30% or more; The control cooling rate before the plating bath is set to a range of 5 to 25 ℃ / sec to form a specific scale composition characterized in that the step consisting of hot-dip galvanizing.
Description
본 발명은 실리콘 함유 용융아연도금 열연강판의 제조방법에 관한 것으로서, 특히 제철의 용융아연도금 열연강판의 제조 공정(Pickling & Galvanizing Line)에 있어서, 난도금성 원소인 실리콘을 함유한 열연강판의 표면에 형성된 스케일(scale)층을 산세공정이나 기계적 박리공정에서 제거시키지 않고, 도금조 이전에 설치되어 있는 환원가열대에서 열연판의 스케일층을 환원시키므로서 스케일 제거로 유발되는 환경 문제 뿐만 아니라 실리콘 함유강판의 젖음성을 향상시키기 위한 예비도금(pre-coating) 등을 생략시킬 수 있고, 제조원가를 절감시키면서 기존의 용융아연도금 열연강판과 동등 이상의 도금밀착성을 가질 수 있는 실리콘 함유 용융아연도금 열연강판의 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a silicon-containing hot dip galvanized hot rolled steel sheet, and more particularly, in the pickling and galvanizing line of a hot-dip galvanized hot rolled steel sheet, the surface of a hot-rolled steel sheet containing silicon as a non-plating element. Instead of removing the scale layer formed in the pickling process or the mechanical peeling process, and reducing the scale layer of the hot rolled sheet in the reduction heating stage installed before the plating bath, the silicon-containing steel sheet as well as the environmental problem caused by the scale removal In the manufacturing method of silicon-containing hot-dip galvanized hot-rolled steel sheet which can omit pre-coating to improve the wettability and can reduce the manufacturing cost and have plating adhesion equal to or higher than that of the existing hot-dip galvanized hot-rolled steel sheet. It is about.
최근에 자동차 재료의 고 강도화 및 고 가공성이 요구되고 있어 실리콘을 0.2 중량% 이상 함유하는 실리콘첨가강이 많이 사용되고 있다. 실리콘은 연성을 감소시키지 않고 강도를 향상시키는 잇점이 있어 실리콘 함유강판은 자동차용 고강도 용융아연도금 열연강판으로 사용이 전망된다. 그러나, 0.1 중량% 이상의 실리콘이 첨가된 열연강판에서는 열연스케일층과 소지철 계면에서 저융점 화합물인 페올라이트-뷔스타이트 공정 화합물(Fe2SiO4-FeO)을 형성시켜 산세공정 후에도 잔존하는 스케일 결함을 유발시키므로 젖음성 확보가 더욱 곤란하게 되어 미도금 현상이 다발하게 되고, 도금이 되더라도 도금 밀착성이 열화되어 가공시 도금박리가 발생하게 된다. 또한, 실리콘은 산화되기가 용이하기 때문에 종래 방법에 의한 산세후 도금전의 열처리 공정에서 강판표면으로 확산되어 표면층에서의 실리콘 농도는 강중의 농도보다 약 10 내지 100 배 높게 된다.Recently, high strength and high workability of automobile materials are required, and silicon-added steels containing 0.2% by weight or more of silicon are frequently used. Silicon has the advantage of improving the strength without reducing the ductility, silicon-containing steel sheet is expected to be used as a high-strength hot dip galvanized hot rolled steel sheet for automobiles. However, in a hot rolled steel sheet containing 0.1 wt% or more of silicon, a low-melting point compound, a low melting point compound, is formed of a Feolite-Busite process compound (Fe 2 SiO 4 -FeO) at the interface between the hot-rolled scale layer and the ferrous iron. Since the wettability is more difficult to secure, the unplating phenomenon occurs frequently. Even when plating, plating adhesion deteriorates and plating peeling occurs during processing. In addition, since silicon is easily oxidized, it diffuses to the surface of the steel sheet in the heat treatment step before plating after pickling by the conventional method, so that the silicon concentration in the surface layer is about 10 to 100 times higher than the concentration in steel.
이와 같이 결정입계나 입내에 농화된 실리콘은 가열로 분위기 중의 극미량 수분이나 불순물과 반응하여 실리콘 산화물(SiO2)을 강판 표면에 형성시키므로서 도금공정에서 용융아연과의 젖음성을 급격히 저하시킨다.In this way, the silicon concentrated in the grain boundary or in the mouth reacts with a very small amount of moisture or impurities in the heating furnace atmosphere to form silicon oxide (SiO 2 ) on the surface of the steel sheet, thereby rapidly decreasing wettability with molten zinc in the plating process.
그러므로, 이와 같은 문제점을 해결하기 위해 안출된 종래의 공지기술로,Therefore, in the prior art known to solve this problem,
첫째, 환원 열처리로의 수소가스의 유량증가 또는 노내압 상승 등에 의한 산소가스 혼합방지 및 재료시간 연장으로 환원능을 증가시키는 방법이 있으나, 실리콘 함유강판에 대해서는 큰 효과가 없으며 생산라인의 속도를 감속시켜야 하므로 생산성 저하의 문제가 있다.First, there is a method of increasing the reducing capacity by preventing the mixing of oxygen gas and increasing the material time by increasing the flow rate of hydrogen gas or increasing the internal pressure of the reduction heat treatment furnace, but it does not have a great effect on the silicon-containing steel sheet and slows down the production line. There is a problem of reduced productivity because it must be.
둘째, 용융아연 도금욕의 알루미늄 첨가량을 증가시키므로서 실리콘 산화층의 환원 효과를 얻을 수 있으므로 계면의 합금원소 산화층으로 인한 용융아연의 젖음성 저하를 방지하고자 하였으나, 도금욕의 알루미늄 증가조업은 도금욕의 불순물인 납과의 공존에 의한 입계부식으로 인한 경시도금 박리 문제와 도금욕 상부드로스(top dross) 발생의 증가에 의한 도금층 표면결함 유발 가능성이 높게 된다.Second, since the reduction effect of the silicon oxide layer can be obtained by increasing the amount of aluminum added to the hot dip galvanizing bath, the wettability of the hot dip galvanized due to the alloy element oxide layer at the interface was prevented. The possibility of plating over time due to intergranular corrosion due to coexistence with lead and the occurrence of surface defects in the plating layer due to an increase in the occurrence of top dross in the plating bath are increased.
셋째, 용융도금전 강판에 미리 Fe, Ni, Cu 또는 Fe-Mn 등을 전해도금(일본특허공보 소 60-56418, 특개평 5-156416)하므로서 고온 소둔에 의해서 소지철 계면에 합금원소가 농화되어도 전해도금층 하부에 농화되므로 소둔과정 또는 가열과정에서의 분위기 가스 중의 수분과의 반응을 차단하여 합금원소의 산화가 방지되기 때문에 소지철의 요철이 큰 열연 산세강판을 도금 소재로 하는 경우 짧은 도금공정에 의해 요철부의 도금부착량 편차가 발생하게 된다.Third, even if the alloying element is concentrated at the base iron interface by high temperature annealing by electroplating Fe, Ni, Cu, or Fe-Mn, etc. on the steel sheet before hot-dip galvanization Since it is concentrated in the lower part of the electroplating layer, it prevents oxidation of alloying elements by blocking reaction with moisture in the atmosphere gas during annealing or heating process. This causes variations in the coating amount of the uneven portion.
또한, 이를 방지하기 위해 전해도금 공정을 길게 하거나 감속 작업을 행하는 경우가 있는데, 이 방법으로 패인 부분의 미도금은 해결 가능하나 돌출부는 과도금 될 것이다. 또 예비도금하는 합금원소는 경도가 크고 연성이 부족한 원소로 도금 부착량이 큰 경우 가공시에 도금박리의 문제가 있다.In addition, in order to prevent this, there are cases in which the electroplating process is lengthened or deceleration is performed. In this way, unplated portions of the recesses can be solved, but the protrusions will be overplated. In addition, the alloying element to be pre-plated has a problem of plating peeling at the time of processing when the plating adhesion amount of the alloy element having a high hardness and insufficient ductility.
따라서, 본 발명의 목적은 상기한 문제점을 해결하기 위해 열연강판의 스케일층의 제거 공정을 생략하고 환원 가열처리 공정에서 실리콘 함유 열연강판의 표면에 형성된 스케일층을 환원시켜 스케일층을 스폰지 상의 다공질 구조로 선택적으로 환원시키므로서 소지철 표면에 실리콘이 농화되는 것에 기인된 미도금 없이 난도금성 원소인 실리콘 함유 용융아연도금 열연강판의 제조방법을 제공하는데 있다.Accordingly, an object of the present invention is to omit the step of removing the scale layer of the hot-rolled steel sheet in order to solve the above problems, and to reduce the scale layer formed on the surface of the silicon-containing hot-rolled steel sheet in the reduction heat treatment step to reduce the scale layer of the porous structure on the sponge The present invention provides a method for producing a hot-dip galvanized steel sheet containing silicon, which is a non-plating element without unplating due to the concentration of silicon on the surface of a ferrous iron by selectively reducing it.
도 1은 종래 방법에 의한 제조공정과 본 발명에 의한 제조공정을 비교한 개략도.1 is a schematic view comparing the manufacturing process according to the present invention with the manufacturing process according to the conventional method.
도 2는 본 발명에 의한 실리콘 함유 용융아연도금 열연강판의 단면 미세조직도.Figure 2 is a cross-sectional microstructure of the silicon-containing hot dip galvanized hot rolled steel sheet according to the present invention.
도 3은 본 발명에 의해 제조된 실리콘 함유 용융아연도금 열연강판의 제조 조건별 도금 밀착성 비교 결과도.Figure 3 is a comparison result of the plating adhesion according to the manufacturing conditions of the silicon-containing hot dip galvanized hot-rolled steel sheet produced by the present invention.
상기 목적을 달성하기 위한 본 발명은 난도금성 원소인 실리콘을 0.1% 이상 함유하는 고장력 및 고가공성 열연강판을 용융아연도금하기 위한 열연강판의 제조 방법에 있어서, 산세공정 및 예비도금 공정을 생략하면서 도금욕조 이전 공정인 환원 가열로에서의 열처리 온도를 650 내지 750 ℃, 유지시간은 60 내지 400초, 수소농도는 30%로 유지하면서 열연강판의 스케일층을 선택적으로 환원처리한 후, 도금욕 이전의 제어 냉각 속도를 5 내지 25 ℃/sec 범위로 설정하여 특정 스케일 조성으로 형성시킨 다음에 용융아연도금을 하는 것을 특징으로 한다.The present invention for achieving the above object in the method of manufacturing a hot-rolled steel sheet for hot-dip galvanizing high tensile and high-processing hot-rolled steel sheet containing 0.1% or more of silicon as a non-plating element, plating while omitting the pickling process and pre-plating process After the reduction of the scale layer of the hot-rolled steel sheet while maintaining the heat treatment temperature in the reduction heating furnace of the bath before the process 650 to 750 ℃, holding time 60 to 400 seconds, hydrogen concentration 30%, and before the plating bath The controlled cooling rate is set in a range of 5 to 25 ° C./sec to form a specific scale composition, followed by hot dip galvanizing.
이하, 첨부된 도면을 참조하여 본 발명을 상세히 설명하기로 한다.Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.
도 1은 기존 실리콘 함유 용융아연도금 열연강판 제조공정과 본 발명에 의한 제조공정의 개략도이고, 도 2는 본 발명에 의한 실리콘 함유 용융아연도금 열연강판 단면의 미세 조직도이고, 도 3은 본 발명에 의해 제조된 실리콘 함유 용융아연도금 열연강판의 제조 조건별 도금 밀착성 비교 결과도이다.1 is a schematic diagram of a conventional silicon-containing hot-dip galvanized hot-rolled steel sheet manufacturing process and the manufacturing process according to the present invention, Figure 2 is a microstructure of the cross-section of the silicon-containing hot-dip galvanized hot rolled steel sheet according to the present invention, Figure 3 is a present invention It is a result of the plating adhesion comparison according to the manufacturing conditions of the silicon-containing hot dip galvanized hot rolled steel sheet manufactured by the above.
본 발명에서는 기존 방법에서의 산세후 가열대에서 환원처리할 때 실리콘이 표면으로 농화되는 현상을 방지함과 아울러 미산세 혹은 과산세에 의한 도금강판의 표면결함을 해소시키기 위하여 기존 방법에서의 중요공정인 열연강판 스케일층 산세를 위한 3단계 산세설비와, 수세설비 및 건조설비가 생략되어 제조공정 라인의길이단축 및 산세공정에 기인된 환경문제를 해소시킬 수 있다. 그러므로, 기존의 용융아연도금 열연강판의 제조 공정에서 산세성을 향상시키기 위한 염산용액과 황산용액의 혼합 비율, 철손실, 산세비용 증가 및 산세 피트(pit) 형성 등의 과산세를 방지하기 위한 부식 억제제의 첨가량 그리고 산세속도를 증가시키기 위한 산세조의 온도관리 등의 복잡한 조업조건을 적정하게 관리하지 않아도 되기 때문에 매우 간편하게 작업할 수 있다. 또한, 실리콘이 표면에서 농화되어 미도금을 유발하는 실리콘 산화물 형성을 방지시키거나 용융 아연도금층과 직접 접촉되지 않도록 하기 위하여 Cu, Ni, Nn 등의 합금원소를 미리 도금처리 하는 예비도금 공정과 이에 따른 수세 및 건조공정을 생략할 수 있어 제조 원가를 크게 절감할 수 있을 것이다.In the present invention, in order to prevent the phenomenon that the silicon is concentrated to the surface when the reduction treatment in the heating table after pickling in the existing method, and to solve the surface defects of the plated steel sheet by the micro acid or peracid washing, The three-stage pickling facility for pickling hot rolled steel sheet, the flushing device and the drying facility can be omitted to solve the environmental problems caused by the shortening of the manufacturing process line and the pickling process. Therefore, in the manufacturing process of the hot-dip galvanized hot-rolled steel sheet, corrosion to prevent the pickling of hydrochloric acid and sulfuric acid solution to improve pickling properties, iron loss, pickling cost increase and pickling pit formation This can be done very simply because complex operating conditions, such as the addition of inhibitors and the temperature control of the pickling bath to increase the pickling rate, are not properly managed. In addition, in order to prevent the formation of silicon oxide that causes silicon to be unplated by being concentrated on the surface or to prevent direct contact with the hot dip galvanized layer, a pre-plating process for pre-plating alloy elements such as Cu, Ni, and Nn, and thus Since water washing and drying processes can be omitted, manufacturing costs can be greatly reduced.
실리콘 함유강은 열연강판 제조 공정 중 산화될 때 실리콘이 이온화되므로서 스케일 중에 중성의 공공을 형성시키게 되며, 이 공공은 조대화되어 기공으로 된다. 또한 실리콘은 열연 스케일층과 소지철 계면에 농화되는 합금원소로서 실리콘과 철산화물의 공정 화합물을 형성시켜 소지철과 열연 스케일의 계면 밀착성을 향상시키는 작용을 한다. 실리콘 함유강의 열연 스케일은 열연공정에서 슬라브(slab)의 재가열 온도에 따라 차이가 있으나, 1180 ℃ 이상에서 형성된 열연 스케일층은 기공을 다소 보유하고 있어 용융아연도금 공정의 환원 가열대에서 오히려 환원을 촉진시키는 작용을 할 것이나 실리콘 미함유강에 비해 열연 스케일층이 약 10 내지 30 % 정도 두껍기 때문에 환원 열처리 소요시간이 다소 길어질 것이다. 환원처리를 하게 되면, 열연 스케일층은 다공질로 변화되고, 스폰지 상의 기공 및 터널을 따라모세관 현상에 의해 용융아연은 스케일층에 채워질 것이며, 또한 스케일층과 소지철 계면에 존재하는 페올라이트 화합물과 반응하여 Fe-Al-Zn-Si 계 화합물을 형성시키므로서 도금 밀착성을 향상시킬 수 있다. 실리콘 함유 열연강판의 스케일층을 환원시키기 위한 환원 가열대 온도는 550 ℃ 이상이면 가능하나, 환원 열처리에 의한 기계적 성질의 변화를 우려하여 최대한 짧은 시간으로 할 목적으로 Ar3변태점 근처인 650 내지 750 ℃로 하였으며, 570 ℃ 이상에서 안정한 스케일 조성인 뷔스타이트가 도금욕 온도인 450 ℃로 냉각될 때의 온도구간에서 환원성이 나쁜 마그네타이트와 순철로 변태되지 않도록 하기 위해서 환원 가열 온도후 도금욕 온도로 제어 냉각될 때의 냉각속도가 5 내지 25 ℃/sec로 되도록 하는 것이 도금 밀착성이 우수한 실리콘을 함유한 용융아연도금 열연강판을 제조할 수 있다.When silicon-containing steel is oxidized during the hot rolled steel sheet manufacturing process, silicon is ionized to form neutral pores in the scale, and these pores are coarsened to form pores. In addition, silicon serves as an alloying element concentrated at the interface between the hot rolled scale layer and the base iron, thereby forming a process compound of silicon and iron oxide to improve interfacial adhesion between the base iron and the hot rolled scale. The hot rolled scale of silicon-containing steel differs depending on the slab reheating temperature in the hot rolled process, but the hot rolled scale layer formed at 1180 ° C or higher retains some pores, which promotes reduction in the reduction heating zone of the hot dip galvanizing process. It will work, but the time required for reduction heat treatment will be somewhat longer because the hot rolled scale layer is about 10 to 30% thicker than silicon-free steel. Upon reduction, the hot rolled scale layer is changed to porous, and the molten zinc will be filled in the scale layer by capillary action along the pores and tunnels on the sponge, and also react with the pholite compound present at the scale layer and the ferrous iron interface. By forming a Fe-Al-Zn-Si-based compound, the plating adhesion can be improved. The reduction heating zone temperature for reducing the scale layer of the silicon-containing hot rolled steel sheet may be 550 ° C. or higher, but it may be reduced to 650 to 750 ° C. near the Ar 3 transformation point for the purpose of making it as short as possible due to the change in mechanical properties due to reduction heat treatment. In order to prevent the transformation of bustite which is stable at 570 ° C or higher to 450 ° C, which is a stable scale composition, to prevent transformation into magnetite and pure iron having poor reducibility, it is controlled and cooled to the plating bath temperature after reduction heating temperature. It is possible to produce a hot-dip galvanized hot-rolled steel sheet containing silicon having excellent plating adhesion by setting the cooling rate at the time of 5 to 25 ° C / sec.
이하, 본 발명의 구체적인 실시예를 설명한다.Hereinafter, specific embodiments of the present invention will be described.
(실시예)(Example)
본 발명에 의한 난도금성 원소인 실리콘을 함유한 용융아연도금 열연강판을 제조하기 위해서 하기 표 1에 나타낸 일반 저탄소강과 실리콘 함유 열연강판을 100(㎜) ×220(㎜) ×1.2(㎜)의 크기로 절단하여 탐지한 후, 용융도금 시뮬레이터를 이용, 서로 비교하기 위하여 열연 스케일 상태의 열연판과 산세처리한 열연판에 대해서 가열대의 열처리 온도 550 내지 750 ℃, 열처리 유치시간 60 내지 400 초, 수소농도 30%로 유지시키면서 환원 열처리한 다음에 5 내지 25 ℃/sec의 냉각속도로 도금소재를 제어 냉각시킨 후 도금욕의 알루미늄 성분이 약 0.2%, 그리고 450℃로 유지된 용융도금조에서 도금한 다음에 스케일층의 환원상태, 도금층 미세조직 및 계면의 도금 밀착성을 분석할 목적으로 단면의 현미경 미세조직을 관찰한 결과, 도 2에 도시된 바와 같이 열연 스케일층 내부에 선택적으로 Fe-Zn-Al 화합물이 형성되어 아연도금층과 스케일층 및 소지철을 단단하게 결속시켜 주는 역할을 함을 알 수 있다.In order to manufacture a hot-dip galvanized hot-rolled steel sheet containing silicon, which is a non-plating element according to the present invention, the general low carbon steel and silicon-containing hot-rolled steel sheet shown in Table 1 are 100 (mm) x 220 (mm) x 1.2 (mm) in size. After the detection by cutting with a hot-dip galvanizing simulator, the hot-rolled sheet in the hot-rolled scale and the pickled hot-rolled sheet for comparison with each other, the heat treatment temperature of the heating table 550 to 750 ℃, the heat treatment retention time 60 to 400 seconds, hydrogen concentration After the reduction heat treatment while maintaining at 30%, the plated material is controlled and cooled at a cooling rate of 5 to 25 ℃ / sec, and then plated in a molten plating tank in which the aluminum component of the plating bath is maintained at about 0.2%, and 450 ℃ As a result of observing the microscopic microstructure of the cross section for the purpose of analyzing the reduced state of the scale layer, the plating layer microstructure, and the plating adhesion of the interface, as shown in FIG. Is optionally Fe-Zn-Al compound to the inside is formed it can be seen that the role to firmly bond the zinc-plated layer and the scale layer and possessing iron.
그리고 도금 밀착성을 평가하기 위해서 굽힙 시험기(bending machine)를 이용하여 용융아연 도금강판을 180°로 굽힘시험하는 0 두께(zero thickness) 벤딩 시험을 행한 대표적인 결과로 20℃/sec로 제어 냉각된 후 용융아연도금된 예를 도 3에 도시하였다. 여기서 알 수 있듯이, 550 ℃에서는 시간에 무관하게 비교재 및 실리콘 함유재 모두 도금 밀착성이 나쁘며, 650 ℃ 및 750 ℃의 경우는 60초 이상의 환원 열처리 시간에서는 도금 밀착성이 양호함을 알 수 있다.In order to evaluate the adhesion of the plating, a typical result of a zero thickness bending test of bending a hot-dip galvanized steel sheet at 180 ° by using a bending machine was performed. A galvanized example is shown in FIG. As can be seen here, at 550 ° C., both the comparative material and the silicon-containing material have poor plating adhesion regardless of time, and at 650 ° C. and 750 ° C., the plating adhesion is good at the reduction heat treatment time of 60 seconds or more.
본 발명에서는 소정의 환원 열처리 온도, 유지 시간 및 도금욕 이전의 제어 냉각 속도를 적정하게 유지하며, 소정의 알루미늄 농도로 유지된 도금욕조에서 도금을 실시하므로서 산세공정이나 예비도금 공정이 필요없이 도금 밀착성이 우수한 실리콘 함유강에 대한 용융 아연도금 열연강판을 제조할 수 있다.The present invention maintains a predetermined reduction heat treatment temperature, a holding time and a controlled cooling rate before the plating bath, and performs plating in a plating bath maintained at a predetermined aluminum concentration, thereby eliminating the need for a pickling process or a preplating process. A hot dip galvanized hot rolled steel sheet for this excellent silicon-containing steel can be produced.
[표 1]TABLE 1
상술한 바와 같이, 본 발명에 의하면 난도금성 원소인 실리콘이 0.1% 이상 함유된 열연강판에 산세공정을 실시할 필요가 없게되면서 도금 밀착성 향상을 위한 예비도금 공정이 필요없이 미도금의 문제를 해결할 수 있으며, 도금 밀착성이 우수한 실리콘 함유강에 대한 용융아연도금 열연강판을 제조하는 것이 가능하다. 또한, 종래의 습식산세 공정을 생략시킬 수 있으므로 복잡하게 관리 운용되고 있던 습식산세 및 주변설비를 생략할 수 있어 향후 환경친화적 제조 공정을 구축할 수 있는 효과가 있다.As described above, according to the present invention, it is not necessary to perform a pickling process on a hot rolled steel sheet containing 0.1% or more of silicon, which is a non-plating element, so that the problem of unplating can be solved without the need of a preplating process for improving plating adhesion. In addition, it is possible to manufacture a hot-dip galvanized hot rolled steel sheet for a silicon-containing steel having excellent plating adhesion. In addition, since the conventional wet pickling process can be omitted, it is possible to omit the wet pickling and the peripheral facilities which have been complicatedly managed and operated, and thus an environmentally friendly manufacturing process can be constructed in the future.
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1998-0060222A KR100368728B1 (en) | 1998-12-29 | 1998-12-29 | Manufacturing method of hot-dip galvanized steel sheet containing silicon |
| TW088119842A TW418122B (en) | 1998-12-29 | 1999-11-15 | Method for manufacturing hot rolled galvanized steel sheet at high speed, with pickling skipped |
| GB9928173A GB2345492B (en) | 1998-12-29 | 1999-11-29 | Methods of manufacturing hot rolled galvanized steel sheet at high speed |
| JP11364786A JP2000199017A (en) | 1998-12-29 | 1999-12-22 | Production of hot-rolled galvanized steel sheet at high speed omitting pickling |
| BE9900835A BE1014992A3 (en) | 1998-12-29 | 1999-12-24 | Method for manufacturing steel plates galvanized hot rolled high speed and without stripping. |
| US09/473,641 US6258186B1 (en) | 1998-12-29 | 1999-12-28 | Method for manufacturing hot rolled galvanized steel sheet at high speed, with pickling skipped |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1998-0060222A KR100368728B1 (en) | 1998-12-29 | 1998-12-29 | Manufacturing method of hot-dip galvanized steel sheet containing silicon |
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| KR20000043801A KR20000043801A (en) | 2000-07-15 |
| KR100368728B1 true KR100368728B1 (en) | 2003-03-31 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100902216B1 (en) * | 2002-09-12 | 2009-06-11 | 주식회사 포스코 | Method of manufacturing a hot dip galvanizing steel sheet containing Si |
| KR100905667B1 (en) | 2002-12-27 | 2009-06-30 | 주식회사 포스코 | Method for manufacturing cold rolled steel sheet without pickling process |
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| CN111015131B (en) * | 2019-12-31 | 2021-06-29 | 福建金锐达金属包装有限公司 | Preparation process of tinplate can cover |
| CN112485009B (en) * | 2020-11-17 | 2023-01-24 | 潍柴动力股份有限公司 | Ambient temperature detection method and device, controller and vehicle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07216524A (en) * | 1994-01-25 | 1995-08-15 | Nisshin Steel Co Ltd | Hot dipping method of high tensile strength hot rolled steel plate |
| KR970043254A (en) * | 1995-12-29 | 1997-07-26 | 김종진 | Method for manufacturing hot dip galvanized steel sheet by no pickling |
| KR19990041446A (en) * | 1997-11-21 | 1999-06-15 | 이구택 | Method for manufacturing hot-dip galvanized steel sheet, eliminating descale process with excellent corrosion resistance and plating adhesion |
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1998
- 1998-12-29 KR KR10-1998-0060222A patent/KR100368728B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07216524A (en) * | 1994-01-25 | 1995-08-15 | Nisshin Steel Co Ltd | Hot dipping method of high tensile strength hot rolled steel plate |
| KR970043254A (en) * | 1995-12-29 | 1997-07-26 | 김종진 | Method for manufacturing hot dip galvanized steel sheet by no pickling |
| KR19990041446A (en) * | 1997-11-21 | 1999-06-15 | 이구택 | Method for manufacturing hot-dip galvanized steel sheet, eliminating descale process with excellent corrosion resistance and plating adhesion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100902216B1 (en) * | 2002-09-12 | 2009-06-11 | 주식회사 포스코 | Method of manufacturing a hot dip galvanizing steel sheet containing Si |
| KR100905667B1 (en) | 2002-12-27 | 2009-06-30 | 주식회사 포스코 | Method for manufacturing cold rolled steel sheet without pickling process |
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| KR20000043801A (en) | 2000-07-15 |
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