KR20120067145A - Method for manufacturing high strength hot dip galvanized steel sheet having excellent coating adhesion - Google Patents
Method for manufacturing high strength hot dip galvanized steel sheet having excellent coating adhesion Download PDFInfo
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- KR20120067145A KR20120067145A KR1020100128598A KR20100128598A KR20120067145A KR 20120067145 A KR20120067145 A KR 20120067145A KR 1020100128598 A KR1020100128598 A KR 1020100128598A KR 20100128598 A KR20100128598 A KR 20100128598A KR 20120067145 A KR20120067145 A KR 20120067145A
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- galvanized steel
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 28
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title abstract 4
- 238000000576 coating method Methods 0.000 title abstract 4
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 230000003746 surface roughness Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- 238000003303 reheating Methods 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims description 45
- 229910000831 Steel Inorganic materials 0.000 claims description 26
- 239000010959 steel Substances 0.000 claims description 26
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 239000002344 surface layer Substances 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 9
- 238000005246 galvanizing Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003082 abrasive agent Substances 0.000 claims 1
- 229910001566 austenite Inorganic materials 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 230000009466 transformation Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910015372 FeAl Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910001563 bainite Inorganic materials 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000794 TRIP steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Classifications
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- 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
- C23C2/0224—Two or more thermal pretreatments
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
-
- 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
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
Abstract
Description
본 발명은 용융아연도금강판에 관한 것으로서, 보다 상세하게는 난도금성 성분을 다량 함유하는 고강도 냉연강판의 용융도금시 도금 젖음성을 향상시킬 수 있는 용융아연도금강판의 제조방법에 관한 것이다.The present invention relates to a hot-dip galvanized steel sheet, and more particularly, to a method for manufacturing a hot-dip galvanized steel sheet which can improve plating wettability during hot-dip plating of a high strength cold rolled steel sheet containing a large amount of non-plating components.
최근 자동차의 연비규제에 대한 해결방안으로 강판의 고강도화를 통한 자동차의 차체 경량화를 위한 노력들이 많이 이루어지고 있다. 이러한 고강도화를 위한 노력의 일환으로 변태 유기 소성(Transformation Induced Plasticity, TRIP)강이 있다.
Recently, as a solution to the fuel economy regulation of automobiles, a lot of efforts have been made to reduce the weight of automobile bodies by increasing the strength of steel sheets. In an effort to increase the strength, transformation induced plasticity (TRIP) steels are used.
상기 TRIP강은 0.05~0.3wt%정도의 C과 0.5~2.0wt%의 Si 및 0.5~3.0wt% 정도의 Mn을 기본적인 합금원소로 강 중에 첨가하여, 냉간압연 후 이상역에서 열처리를 한 후 약 400℃전후의 온도에서 베이나이트 변태를 시킴으로써 미세 균질하게 분산된 잔류 오스테나이트를 강 중에 함유함으로 상온에서 가공 시 마르텐사이트 변태를 유도하여 고강도 및 고연성을 확보한 강이다.
In the TRIP steel, about 0.05-0.3 wt% of C, 0.5-2.0 wt% of Si, and 0.5-3.0 wt% of Mn are added to the steel as a basic alloying element, and after cold rolling, heat treatment is performed in an ideal region. By bainite transformation at temperatures around 400 ° C, the steel contains fine a homogeneously dispersed residual austenite in steel to induce martensite transformation during processing at room temperature to ensure high strength and high ductility.
그러나 위의 TRIP 고강도강의 경우 난도금성 성분인 Si, Mn이 약 1~2% 첨가되는데, 이들 난도금 성분은, 소둔시 산화물 생성의 핵으로 작용함으로 Si, Mn 산화물 피막을 형성하며 표층에 다량 분포하게 됨으로써 용융아연과의 젖음성(Wettability)을 악화시킨다. 그 결과 도금 부착성 확보가 어려우며 미도금(Bare spot)들이 발생하고, 계면 억제층(Inhibition layer) 즉 Fe-Al 금속간 화합물인 Fe2Al5, FeAl3 가 도금층과 소지층 계면 사이에 균일하게 형성되지 못하여 도금 밀착성이 열화됨으로 가공시 도금박리가 나타나고 가공성 확보에 어려움이 있다.
However, in the case of the TRIP high-strength steel, about 1 to 2% of the non-plating components Si and Mn are added, and these components are formed as a nucleus of oxide formation during annealing, forming a Si, Mn oxide film and distributed in a large amount on the surface layer. This deteriorates wettability with molten zinc. As a result, it is difficult to secure the adhesion of plating, and bare spots are generated. Inhibition layers, that is, Fe 2 Al 5 and FeAl 3, which are Fe-Al intermetallic compounds, are uniformly interposed between the plating layer and the base layer interface. It is difficult to form the plating peeling during processing due to the deterioration of the adhesion of the plating due to the formation is difficult.
이러한 난도금성을 해결하기 위해 다양한 방법이 개발되었다. 일본 특허공개공보 2000-292869호, 일본 특허공개공보 2000-239788호에서는 강 중에 Ni이나 Zr을 첨가하여 소둔 후 표층에 산화시킴으로 SiO2, Mn2SiO4, MnSiO3의 표층 산화막 형성을 억제하는 방법으로 도금성을 개선하는 방법을 제시하였다. 그러나 이러한 방법은 고가의 Ni, Zr등을 강 중에 첨가함으로 인하여 제조원가 상승의 문제점을 가지고 있다.
Various methods have been developed to solve this difficulty. In Japanese Patent Laid-Open Publication No. 2000-292869 and Japanese Patent Laid-Open Publication No. 2000-239788, Ni or Zr is added to steel to oxidize the surface layer after annealing, thereby suppressing the surface oxide film formation of SiO 2 , Mn 2 SiO 4 , and MnSiO 3 . It was proposed a method of improving the plating property. However, this method has a problem of manufacturing cost increase due to the addition of expensive Ni, Zr, etc. in the steel.
다른 방법으로, 일본 특허공개공보 2001-279409호에서는 전처리 공정에서 선도금(Pre-plating)을 행하는 것으로, Fe계 전기도금처리를 통해 0.05~1㎛ 두께의 산화피막을 형성하여 도금성을 개선하는 방법이 제기되었다. 그러나, 이러한 경우는 전기도금 설비를 추가적으로 적용해야 한다는 단점이 있으며, 전기 도금 처리한 Fe, Ni 등의 두께가 얇거나 균일하지 않을 경우에는 Si, Mn계의 산화물이 표층으로 올라와 용융도금성을 개선하지 못하는 단점이 있다.
Alternatively, Japanese Patent Laid-Open No. 2001-279409 performs pre-plating in a pretreatment process, and forms an oxide film having a thickness of 0.05 to 1 μm through Fe-based electroplating to improve plating properties. The method was raised. However, in this case, there is a disadvantage in that an additional electroplating equipment is applied. When the thickness of Fe, Ni, etc., which is electroplated is not thin or uniform, oxides of Si and Mn are raised to the surface layer to improve melt plating property. There is a drawback to not doing it.
또다른 방법으로 일본 특허공개공보 2001-131698호에서는 산화-환원법을 이용하여 산화 분위기에서 1차로 열처리를 한 후 환원분위기에서 2차로 환원하여 Si, Mn 산화물의 표층 분포를 억제하는 방법이 있다. 이러한 방법의 경우, 산화 분위기에서 생성된 FeO층의 두께를 조절하는 것이 관건이며, FeO층의 두께가 얇게 형성되면 환원 공정 중 Si, Mn이 Fe 산화물 층을 뚫고 표층으로 확산되어 Si, Mn계 산화물을 형성하는 문제점이 있다. 또한 산화 분위기에서 형성된 FeO 산화물층의 두께가 두꺼울 경우에는 환원과정에서 FeO 산화물을 모두 환원하지 못하여 용융도금성을 열화 시키는 단점이 있으며, Fe 산화물층과 소지층 계면상에 Si, Mn계 산화물이 띠형태로 형성되어, 가공 시 계면 부위에서 도금박리가 일어날 우려가 있다.
As another method, Japanese Patent Application Laid-Open No. 2001-131698 discloses a method of suppressing the surface layer distribution of Si and Mn oxides by performing a first heat treatment in an oxidizing atmosphere using an oxidation-reduction method and then reducing it secondarily in a reducing atmosphere. In such a method, it is important to control the thickness of the FeO layer formed in the oxidizing atmosphere, and when the thickness of the FeO layer is thin, the Si and Mn diffuse through the Fe oxide layer to the surface layer during the reduction process and the Si, Mn-based oxide There is a problem to form. In addition, when the thickness of the FeO oxide layer formed in the oxidizing atmosphere is thick, the FeO oxide may not be reduced during the reduction process, thereby deteriorating the hot-plating property.Si, Mn-based oxides may be formed on the interface between the Fe oxide layer and the base layer. It is formed in the shape, there is a fear that plating peeling occurs at the interface portion during processing.
도금 밀착성이 우수한 고강도 합금화 용융아연도금강판의 제조를 위한 다양한 방법들을 정리해 보면, 강 중에 특수 원소를 첨가하거나 전기도금을 이용한 선도금을 통하여 Si, Mn 산화물이 표층확산을 막거나 산화-환원법에 의한 내부산화의 방법으로 분리된다. 이러한 방법은 모두 소둔 공정상에서 Si, Mn계 산화물이 표층 확산방지에 초점이 맞추어져 있어 간접적인 방법이며, 근본적으로 Si, Mn 산화물을 제거하는 방법은 아니다.Various methods for manufacturing high-strength alloyed hot-dip galvanized steel sheet with excellent plating adhesion can be summarized as follows. By adding special elements to the steel or using lead plating using electroplating, Si and Mn oxides can prevent surface diffusion or by oxidation-reduction method. It is separated by internal oxidation. All of these methods are indirect because they focus on preventing surface diffusion of Si and Mn oxides in the annealing process, and are not fundamentally a method of removing Si and Mn oxides.
본 발명의 일측면은 용융아연도금강판의 도금 밀착성을 향상시킬 수 있는 고강도 용융아연도금강판의 제조방법을 제공하고자 하는 것이다. One aspect of the present invention is to provide a method of manufacturing a high strength hot dip galvanized steel sheet that can improve the plating adhesion of the hot dip galvanized steel sheet.
본 발명은 냉연강판을 탈지 후 700~900℃로 가열하고 냉각하는 1차 소둔단계; The present invention is the first annealing step of heating and cooling to 700 ~ 900 ℃ after degreasing the cold rolled steel sheet;
상기 냉연강판의 표층에 고압수 및 연마재가 혼합된 슬러리(Slurry)를 고압 분사하는 단계;Spraying a slurry of high pressure water and a slurry mixed with the surface layer of the cold rolled steel sheet at high pressure;
상기 냉연강판을 400~550℃로 재가열하는 2차 소둔단계; 및 A second annealing step of reheating the cold rolled steel sheet at 400˜550 ° C .; And
용융아연도금하는 단계를 포함하는 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법을 제공한다.Provided is a method for producing a high strength hot dip galvanized steel sheet having excellent plating adhesion, including hot dip galvanizing.
본 발명에 의하면, 1차 소둔 후 발생한 Si, Mn계 산화물 등을 제거하고, 표면 조도를 제어함으로서, 미도금이 발생되지 않고, 도금 밀착성이 우수한 고강도 용융아연도금강판을 제공함으로서, 용융아연도금강판의 품질특성 향상의 효과가 있다.According to the present invention, by removing the Si, Mn-based oxide, etc. generated after the primary annealing, and controlling the surface roughness, unplated is not generated, by providing a high-strength hot dip galvanized steel sheet excellent in plating adhesion, hot-dip galvanized steel sheet Has the effect of improving the quality characteristics.
도 1은 본 발명의 고강도 용융아연도금강판의 제조 공정도임.
도 2는 본 발명의 슬러리 고압 분사를 나타낸 모식도임.1 is a manufacturing process diagram of the high strength hot-dip galvanized steel sheet of the present invention.
Figure 2 is a schematic diagram showing the slurry high pressure injection of the present invention.
이하, 본 발명에 대하여 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명에 제조방법에 따른 공정 구성도를 도 1에 간략히 나타내었다. 도 1에 나타난 바와 같이, 본 발명의 제조방법은 탈지조를 거친 냉연강판을 1차 소둔 가열로에서 가열처리하고, 슬러리 고압분사 후 2차 소둔 가열로에서 가열처리 후 용융 도금조에서 용융아연도금을 행한다.
The process block diagram according to the manufacturing method of the present invention is briefly shown in FIG. As shown in Figure 1, the production method of the present invention is the hot-rolled cold-rolled steel sheet subjected to the degreasing tank heat treatment in the first annealing furnace, after the high pressure slurry slurry heat treatment in the secondary annealing furnace after hot-dip galvanizing Is done.
이하, 본 발명의 고강도 용융아연도금강판의 제조방법에 대하여 상세히 설명한다. 먼저, 냉연강판을 탈지 후 700~900℃로 가열하고 냉각하는 1차 소둔공정을 행한다. 상기 1차 소둔은 소둔로 온도 700~900℃에서 행하고, 소둔로의 분위기는 통상적인 소둔 분위기에서 행한다. 바람직한 일예로는 H2 5~10%, N2 90~95%이고, 이슬점은 -20~-60℃가 바람직하다.
Hereinafter, the manufacturing method of the high strength hot-dip galvanized steel sheet of this invention is demonstrated in detail. First, after degreasing the cold rolled steel sheet, a first annealing step of heating and cooling to 700 to 900 ° C is performed. The primary annealing is performed at annealing furnace temperature of 700 to 900 占 폚, and the atmosphere of the annealing furnace is performed in a normal annealing atmosphere. As a preferable example, H 2 5-10%, N 2 90-95%, and the dew point is preferably -20 to -60 ℃.
상기 1차 소둔과정에서 강중에 포함되어 있는 Si, Mn 등 난도금 성분이 표층으로 확산되어, SiO2, Fe2SiO4, Mn2SiO4, MnSiO3 등이 강판 표면에 농화되어, 도금시 용융아연과의 젖음성을 저하시킨다. 상기와 같은 Si, Mn계 산화물의 표면 형성으로 인하여 종래의 방법으로 용융아연도금강판을 제조할 경우에 다량의 미도금(Bare Spot)이 발생한다.
In the first annealing process, hardening components such as Si and Mn contained in the steel are diffused to the surface layer, and SiO 2 , Fe 2 SiO 4 , Mn 2 SiO 4 , MnSiO 3, etc. are concentrated on the surface of the steel sheet and melted during plating. Decreases the wettability with zinc. Due to the surface formation of Si, Mn-based oxides as described above, a large amount of bare spots are generated when the hot-dip galvanized steel sheet is manufactured by a conventional method.
이에, 본 발명에서는 상기 소둔공정 후 상기 냉연강판의 표층에 농화된 Si, Mn계 산화물을 고압수와 연마재를 혼합한 슬러리(Slurry)를 고압 분사하여 제거한다. 도 2는 본 발명이 적용되는 슬러리 고압분사를 모사한 것이다. 도 2에 나타난 바와 같이, 슬러리 고압분사 공정은 고압수의 분사에 의해 형성된 음압을 통해 빨려 들어오는 연마재가 혼합되어 슬러리 형태를 이루고, 고압수의 운동에너지로 고압의 슬러리 스트림(stream)을 형성시킨 후 이를 폭 방향으로 균일하게 분사하여 강판 표층에 형성된 Si, Mn계 산화물층을 제거하게 된다.
Thus, in the present invention, after the annealing process, the slurry (Slurry) mixed with high-pressure water and abrasive is removed from the Si, Mn-based oxide concentrated in the surface layer of the cold rolled steel sheet by high pressure spraying. Figure 2 is a simulation of the slurry high pressure spray to which the present invention is applied. As shown in Figure 2, the slurry high-pressure spraying process is a mixture of abrasive sucked through the negative pressure formed by the injection of high pressure water to form a slurry, after forming a high pressure slurry stream with the kinetic energy of the high pressure water It is sprayed uniformly in the width direction to remove the Si, Mn-based oxide layer formed on the steel sheet surface layer.
상기 슬러리 형성에 필요한 연마재는 글라스 비드(glass bead), 숏 볼(shot ball), 스틸 그릿트(steel grit), 세라믹 비드(ceramic bead), 스테인리스 비드(stainless bead) 등이 사용될 수 있다.
The abrasive required to form the slurry may be glass beads, shot balls, steel grit, ceramic beads, stainless beads, or the like.
상기 연마재의 직경은 10~400㎛인 것이 바람직하다. 상기 연마재의 직경이 10㎛ 미만이면, Si, Mn계 산화물의 제거가 미흡하게 되고, 400㎛를 초과하는 것이면, 표면 조도가 너무 크게되어 목표로 하는 도금품질의 확보가 곤란하다.
It is preferable that the diameter of the said abrasive is 10-400 micrometers. If the diameter of the abrasive is less than 10 mu m, the removal of Si and Mn-based oxides is insufficient, and if the diameter exceeds 400 mu m, the surface roughness becomes too large to secure the target plating quality.
냉연강판에 분사되는 연마재의 속도는 20~200m/s가 바람직하다. 연마재 속도가 20m/s 미만이면, Si, Mn 계 산화물의 제거능이 부족하며, 연마재 속도가 200m/s를 초과하게 되면 강판 표면에 결함을 남기고, 표면조도가 너무 높게 된다.
The speed of the abrasive injected into the cold rolled steel sheet is preferably 20 ~ 200m / s. If the abrasive velocity is less than 20 m / s, the removal ability of Si and Mn-based oxides is insufficient. If the abrasive velocity exceeds 200 m / s, the surface of the steel sheet will be left with defects, and the surface roughness will be too high.
상기 슬러리 고압 분사시 고압수의 분사압력은 50~300bar로 하는 것이 바람직하다. 상기 분사압력이 50bar 미만이면 Si, Mn 계 산화물의 제거효율이 미흡하고, 300bar를 초과하는 압력에서는 냉연강판의 표면조도 증가 및 전력비, 설비비 증가를 초래하게 된다.
In the slurry high pressure injection, the injection pressure of the high pressure water is preferably 50 ~ 300bar. When the injection pressure is less than 50bar, the removal efficiency of Si and Mn-based oxides is insufficient, and when the pressure exceeds 300bar, the surface roughness of the cold rolled steel sheet is increased, and the power ratio and equipment cost are increased.
분사노즐은 개개의 헤드에 냉연강판의 폭에 따라 노즐 분사각도 및 강판과의 거리를 고려하여 일정한 간격으로 냉연강판의 상, 하부에 동일하게 설치하여 균일한 분사패턴을 이루어야 한다. 이와 같이 설치된 슬러리 고압분사에 의해서 제거되는 Si, Mn 계 산화물은 라인 스피드나 설치되는 헤드의 개수에 따라 달라질 수 있으나, 적정한 조건 하에서 표층부 Si, Mn 계 산화물을 제거할 수 있다.
Spray nozzles should be uniformly installed on the upper and lower parts of the cold rolled steel sheet at regular intervals in consideration of the nozzle spraying angle and the distance to the steel sheet according to the width of the cold rolled steel sheet in each head. Si and Mn-based oxides removed by the slurry high pressure injection provided in this way may vary depending on the line speed or the number of heads installed, but may remove surface layer Si and Mn-based oxides under appropriate conditions.
상기 슬러리 고압 분사공정 후의 냉연강판의 표면조도는 슬러리 고압 분사 조건에 따라 조절이 가능하며, 연마재의 충돌에 의해 발생된 표면 요철은 Fe와 Zn의 밀착강도를 증가시킨다. 슬러리 고압분사 후의 냉연강판의 표면 평균조도(Ra)는 0.5~2.0㎛가 바람직하다, 조도가 0.5㎛ 미만일 경우에는 표면이 너무 평탄하여 용융아연의 젖음성이 좋지 못하고 흘러내리는 현상이 발생하며, 표면조도가 2.0㎛를 초과하는 경우에는 강판의 요철이 너무 심하여 용융도금 공정 이후에도 이러한 요철이 표면에 잔존하게 되므로, 표면 평균조도가 0.5~2.0㎛이 되도록 하는 것이 바람직하다.
The surface roughness of the cold rolled steel sheet after the slurry high pressure spraying process can be adjusted according to the slurry high pressure spraying conditions, and the surface irregularities generated by the collision of the abrasive increases the adhesion strength between Fe and Zn. The surface average roughness (Ra) of the cold rolled steel sheet after slurry high-pressure injection is preferably 0.5 to 2.0 μm. When the roughness is less than 0.5 μm, the surface is too flat, so that wettability of molten zinc does not occur, and the surface roughness occurs. When the thickness exceeds 2.0 μm, the unevenness of the steel sheet is so severe that such unevenness remains on the surface even after the hot dip plating process, so that the surface average roughness is preferably 0.5 to 2.0 μm.
Si, Mn계 산화물을 제거한 후, 2차 소둔을 행한다. 이때 2차 소둔 가열로는 N2 90~95%, H2 5~10%, 이슬점은 -20~-60℃의 통상적인 환원 분위기에서 400~550℃ 온도에서 강판은 가열된다. 2차 소둔 가열로의 온도는 Si, Mn의 표층확산을 최소화할 수 있는 온도이어야 하기 때문에 강판의 온도는 550℃를 초과해서는 안되고, 용융도금을 수행하기 위해서는 용융아연의 용융점과 유사한 온도가 최소한 필요하기 때문에 강판 가열온도는 400℃이상이 바람직하다.
After the Si and Mn-based oxides are removed, secondary annealing is performed. At this time, as the second annealing heating is N 2 90 ~ 95%, H 2 5 ~ 10%, the dew point is in the conventional reducing atmosphere at -20 ~ -60 ℃ 400 ~ 550 ℃ temperature of the steel sheet is heated. Since the temperature of the secondary annealing furnace should be such that the surface diffusion of Si and Mn can be minimized, the temperature of the steel sheet should not exceed 550 ℃, and at least a temperature similar to the melting point of molten zinc is required to perform hot dip plating. Therefore, the steel sheet heating temperature is preferably 400 ° C or higher.
상기 가열된 냉연강판을 용융도금욕에 침지하여 용융아연도금을 행한다. 상기 용융도금욕의 Al 농도는 0.12~0.25wt%가 바람직하다. 도금욕 중 Al의 함량이 0.25wt%를 초과해서는 도금욕 내에 상부 드로스 발생이 심화되는 문제가 있어 도금품질을 저해하며, 0.12wt% 미만에서는 소지층과 도금층 사이에 형성되는 금속간 화합물인 Fe2Al5, FeAl3의 치밀한 형성이 미미하여 밀착성을 약화시키므로, 그 함량을 0.12~0.25wt%로 하는 것이 바람직하다.
The heated cold rolled steel sheet is immersed in a hot dip plating bath to perform hot dip galvanizing. The Al concentration of the hot dip bath is preferably 0.12 to 0.25 wt%. If the Al content in the plating bath exceeds 0.25wt%, there is a problem in that the upper dross occurs in the plating bath, which hinders the plating quality. If the Al content is less than 0.12wt%, Fe, an intermetallic compound formed between the base layer and the plating layer, Since dense formation of 2 Al 5 and FeAl 3 is insignificant and the adhesion is weakened, the content thereof is preferably 0.12 to 0.25 wt%.
본 발명의 용융아연도금강판은 Si 및 Mn을 포함하는 고강도강이며, 그 종류를 한정하는 것은 아니다. 본 발명의 용융아연도금강판에 사용될 수 있는 냉연강판의 일예로는 중량%로, C: 0.05~0.3%, Si: 0.5~2.0%, Mn: 0.5~3.0%, 나머지는 Fe 및 불가피한 불순물을 포함하는 냉연강판을 사용하는 것이 바람직하다.
The hot-dip galvanized steel sheet of this invention is a high strength steel containing Si and Mn, and does not limit the kind. An example of a cold rolled steel sheet that can be used in the hot-dip galvanized steel sheet of the present invention is by weight, C: 0.05-0.3%, Si: 0.5-2.0%, Mn: 0.5-3.0%, the rest includes Fe and unavoidable impurities It is preferable to use a cold rolled steel sheet.
상기 냉연강판에서 C는 오스테나이트 안정화 원소이면서 2상 공존온도 영역 및 베이나이트 변태온도 영역에서 페라이트로부터 이동하여 오스테나이트에 농화된다. 그 결과 상온까지 냉각시켜도 안정화된 오스테나이트가 2~20% 수준으로 잔류하여 변태유기 소성에 의한 성형성 확보가 가능하게 된다. C가 0.05wt% 미만인 경우에는 2% 이상의 잔류 오스테나이트 조직을 확보하기가 곤란하며, 반면 C가 0.3wt%를 초과하여 첨가되면 용접성이 악화되므로, 그 함량은 0.05~0.3wt%가 바람직하다.
In the cold rolled steel sheet, C is an austenite stabilizing element and moves from ferrite in the two-phase coexistence temperature region and the bainite transformation temperature region to concentrate on austenite. As a result, even when cooled to room temperature, stabilized austenite remains at a level of 2 to 20%, thereby securing moldability due to transformation of organic plastics. When C is less than 0.05 wt%, it is difficult to secure 2% or more of the retained austenite structure. On the other hand, when C is added in excess of 0.3 wt%, weldability is deteriorated, and the content thereof is preferably 0.05 to 0.3 wt%.
상기 Si는 세멘타이트에 고용되지 않고 세멘타이트의 석출을 억제시킴에 따라 350~600℃의 온도에서 오스테나이트로부터의 변태를 지연시킨다. 따라서 오스테나이트로 C가 농화되는 것을 촉진시킬 수 있어 오스테나이트의 화학적 안정성을 향상시킬 수 있고 변태유기 소성을 일으켜 성형성을 좋게 하는 잔류 오스테나이트를 확보할 수 있게 된다. Si 함량이 0.5wt% 미만인 경우에는 이러한 효과가 적은 반면, 2.0wt%를 초과하여 첨가되면 도금성이 악화될 수 있으므로 Si의 첨가량은 0.5~2.0wt%로 하는 것이 바람직하다.
Si does not dissolve in cementite and inhibits the precipitation of cementite, thus delaying the transformation from austenite at a temperature of 350 to 600 ° C. Therefore, it is possible to promote the concentration of austenite C, thereby improving the chemical stability of the austenite, and it is possible to secure residual moldable austenite, which causes transformation organic plasticity and improves moldability. In the case where the Si content is less than 0.5wt%, such an effect is small, but when the content is added in excess of 2.0wt%, the plating property may deteriorate, so the amount of Si is preferably 0.5 to 2.0wt%.
상기 Mn은 오스테나이트 형성을 촉진하는 원소이면서 이상온도영역에서 소둔 후 350~600℃로 냉각하는 과정에서 오스테나이트가 펄라이트로 분해되는 것을 방지하여 상온까지의 냉각과정에서 금속조직에 오스테나이트를 잔류하도록 한다. 따라서, 본 발명에서는 오스테나이트의 잔류 및 펄라이트로의 분해를 억제하기 위하여 0.5wt% 이상 첨가하나, 그 함량이 3.0wt%를 초과하면 밴드조직이 많이 나타나 물성이 저하된다.
The Mn is an element that promotes austenite formation and prevents austenite from being decomposed into pearlite during annealing in an abnormal temperature range and then cooled to 350 to 600 ° C. so that austenite remains in the metal structure during cooling to room temperature. do. Therefore, in the present invention, 0.5wt% or more is added in order to suppress residual austenite and decomposition into pearlite. However, when the content exceeds 3.0wt%, a large number of band structures appear, thereby deteriorating physical properties.
본 발명의 제조방법에 의해 제조된 용융아연도금강판은 미도금이 발생하지 않고, 도금 밀착성이 우수하다. 1차 소둔 공정에서 표층에 생성된 Si, Mn계 산화물은 슬러리(Slurry) 고압 분사 공정을 통하여 표면에서 제거된다. Si, Mn 계 산화물의 제거를 수행한 후 2차 저온 소둔한 강판은 강판 표면의 Fe와 도금욕내의 Al과의 반응이 원활하여 미려하고 치밀한 Fe2Al5(Zn)조직을 계면에 형성한다. 이를 통해 계면의 밀착성은 기존의 도금 강판에 대비 현저하게 우수하며, 또한 슬러리 고압분사에 의한 연마재 충돌로 형성된 소둔 강판 표면의 요철은 용융아연과의 젖음성(wettability)을 향상시킨다.
The hot-dip galvanized steel sheet produced by the manufacturing method of the present invention does not generate unplated and has excellent plating adhesion. In the first annealing process, the Si and Mn-based oxides formed on the surface layer are removed from the surface through a slurry high pressure spray process. After the removal of Si and Mn-based oxides, the steel sheet subjected to secondary low temperature annealing smoothly reacts with Fe in the surface of the steel plate and Al in the plating bath to form a beautiful and dense Fe 2 Al 5 (Zn) structure at the interface. As a result, the adhesion of the interface is remarkably superior to that of the conventional plated steel sheet, and the unevenness of the surface of the annealed steel sheet formed by the abrasive collision due to the slurry high pressure injection improves the wettability with the molten zinc.
이하, 본 발명의 실시예에 대하여 상세히 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 것으로, 하기 실시예에 의해서 본 발명이 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in detail. The following examples are provided to aid the understanding of the present invention, and the present invention is not limited by the following examples.
(실시예)(Example)
C:0.09wt%, Si:1.2wt%, Mn:1.7wt% 함유한 590MPa급 변태 유기 소성강을 대상으로, 1차 소둔은 800℃에서 30초간 유지하여, 20℃/s의 냉각속도로 냉각하였다. 상기 냉각 후 슬러리 고압분사를 행하고, 이때 연마재의 종류 및 고압수 압력은 표 1과 같이 달리 실시하였다. 상기 고압분사 후, 400℃에서 30초간 2차 소둔을 행하였다. 상기 1차, 2차 소둔시 소둔 분위기는 H2 5%, N2 95%, 이슬점은 -60℃에서 수행하였다.
For 590MPa grade organic plastics containing C: 0.09wt%, Si: 1.2wt%, Mn: 1.7wt%, the primary annealing is maintained at 800 ° C for 30 seconds and cooled at a cooling rate of 20 ° C / s. It was. After cooling, slurry high pressure injection was performed, and the type of abrasive and the high pressure water pressure were differently performed as shown in Table 1. After the high pressure injection, secondary annealing was performed at 400 ° C. for 30 seconds. The annealing atmosphere during the first and second annealing was performed at H 2 5%, N 2 95%, and dew point at -60 ° C.
상기 2차 소둔 후 용융아연도금을 행하고, 도금욕 온도는 460℃, 도금욕 중 Al의 함유량은 0.2wt%로 행하고, 도금 부착량은 편면 기준 60g/㎡으로 행하였다. 한편 비교재는 슬러리 고압분사를 하지 않은 용융아연도금강판을 사용하였다.
After the second annealing, hot dip galvanizing was carried out, the plating bath temperature was 460 占 폚, the Al content in the plating bath was 0.2 wt%, and the plating deposition amount was performed at 60 g / m 2 based on one side. On the other hand, the comparative material used a hot-dip galvanized steel sheet without slurry high-pressure injection.
각 용융아연도금강판에 대하여, 표면외관 및 180° 밴딩 시험을 실시하여 그 결과를 표 1에 나타내었다. 180° 밴딩 시험은 박리 여부로 평가하였고, 표면외관에 대한 평가는 아래와 같이 평가하였다.Each hot dip galvanized steel sheet was subjected to a surface appearance and a 180 ° bending test, and the results are shown in Table 1. The 180 ° bending test was evaluated by peeling, and the evaluation on the surface appearance was evaluated as follows.
평점 1 : 미도금 발생면적 0%Rating 1: 0% unplated area
평점 2 : 미도금 발생면적 0.1% 미만, 미도금 크기 0.1 mm 이하 Rating 2: Less than 0.1% of unplated area, 0.1 mm or less of unplated size
평점 3 : 미도금 발생면적 0.1~0.3% 미만, 미도금 크기 0.5 mm 이하Rating 3: Less than 0.1 ~ 0.3% of unplated area, less than 0.5 mm of unplated size
평점 4 : 미도금 발생면적 0.3~0.5% 미만, 미도금 크기 1 mm 이하Rating 4: Less than 0.3 ~ 0.5% of unplated area, less than 1 mm of unplated size
평점 5 : 미도금 발생면적 0.5% 이상, 미도금 크기 3 mm 이상
Rating 5: More than 0.5% of unplated area, more than 3 mm of unplated size
(bar)High pressure water pressure
(bar)
(㎛)Abrasive size
(Μm)
상기 결과에서 알 수 있듯이 1차 소둔 후 슬러리 고압분사를 하여, Si, Mn계 산화물을 제거한 냉연강판의 도금성은 비교예 대비 매우 우수하였으며, 도금 밀착성 또한 향상된 것을 확인할 수 있다.As can be seen from the above results, after the first annealing, the slurry was subjected to high pressure injection, and the plating property of the cold rolled steel sheet from which the Si and Mn-based oxides were removed was much better than that of the comparative example, and the adhesion of the plating was also improved.
Claims (9)
상기 냉연강판의 표층에 고압수 및 연마재가 혼합된 슬러리(Slurry)를 고압 분사하는 단계;
상기 냉연강판을 400~550℃로 재가열하는 2차 소둔단계; 및
용융아연도금하는 단계
를 포함하는 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
A first annealing step of heating and cooling the cold rolled steel sheet to 700 to 900 ° C. after degreasing;
Spraying a slurry of high pressure water and a slurry mixed with the surface layer of the cold rolled steel sheet at high pressure;
A second annealing step of reheating the cold rolled steel sheet at 400˜550 ° C .; And
Hot dip galvanizing step
Method for producing a high-strength hot-dip galvanized steel sheet excellent plating adhesion comprising a.
상기 슬러리 고압 분사는 고압수의 분사에 의해 형성된 음압을 통해 빨려 들어오는 연마재가 혼합되어 슬러리 형태로 분사되는 것인 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
The slurry high pressure injection is a method of manufacturing a high strength hot-dip galvanized steel sheet in which the abrasive sucked through the negative pressure formed by the injection of high pressure water is mixed and sprayed in the form of a slurry.
상기 고압 분사 후 냉연강판의 평균 표면 조도는 0.8~2.0㎛인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
Method of producing a high-strength hot-dip galvanized steel sheet having excellent plating adhesion of the average surface roughness of the cold rolled steel sheet after the high pressure injection.
상기 냉연강판은 중량%로, C: 0.05~0.3%, Si: 0.5~2.0%, Mn: 0.5~3.0%, 나머지는 Fe 및 불가피한 불순물을 포함하는 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
The cold rolled steel sheet is a weight%, C: 0.05 ~ 0.3%, Si: 0.5 ~ 2.0%, Mn: 0.5 ~ 3.0%, the remainder is a method of producing a high strength hot-dip galvanized steel sheet excellent plating adhesion containing Fe and unavoidable impurities .
상기 연마재는 글라스 비드(glass bead), 숏 볼(shot ball), 스틸 그릿트(steel grit), 세라믹 비드(ceramic bead) 및 스테인리스 비드(stainless bead)로 이루어진 그룹에서 선택된 1종 이상인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
The abrasive material has excellent plating adhesion, which is at least one selected from the group consisting of glass beads, shot balls, steel grit, ceramic beads, and stainless beads. Method for producing high strength hot dip galvanized steel sheet.
상기 연마재의 직경은 10~400㎛인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
A method of producing a high strength hot dip galvanized steel sheet having excellent plating adhesion of the abrasive is 10 ~ 400㎛ diameter.
상기 연마재의 분사속도는 20~200m/s인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
Method of producing a high-strength hot-dip galvanized steel sheet having excellent plating adhesion of the abrasive is 20 ~ 200m / s.
상기 고압수의 분사압력은 50~300bar인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.
The method according to claim 1,
The injection pressure of the high-pressure water is 50 ~ 300bar of the high-strength hot-dip galvanized steel sheet excellent plating adhesion.
상기 용융아연도금시, 도금욕의 조성은 Al 0.12~0.25wt%, 나머지는 Zn 및 불가피한 불순물을 포함하는 것인 도금 밀착성이 우수한 고강도 용융아연도금강판의 제조방법.The method according to claim 1,
When the hot dip galvanizing, the composition of the plating bath is Al 0.12 ~ 0.25 wt%, the rest is Zn and the manufacturing method of high strength hot-dip galvanized steel sheet excellent plating adhesion that contains an unavoidable impurity.
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