KR960009199B1 - Vacuum deposite mn/galvannealed steel sheets and the method therefor - Google Patents
Vacuum deposite mn/galvannealed steel sheets and the method therefor Download PDFInfo
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- KR960009199B1 KR960009199B1 KR1019930031358A KR930031358A KR960009199B1 KR 960009199 B1 KR960009199 B1 KR 960009199B1 KR 1019930031358 A KR1019930031358 A KR 1019930031358A KR 930031358 A KR930031358 A KR 930031358A KR 960009199 B1 KR960009199 B1 KR 960009199B1
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 29
- 239000010959 steel Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title description 6
- 239000011572 manganese Substances 0.000 claims abstract description 46
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 24
- 239000008397 galvanized steel Substances 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 abstract description 33
- 230000007797 corrosion Effects 0.000 abstract description 33
- 238000007747 plating Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 5
- 238000005244 galvannealing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001771 vacuum deposition Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- 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
- C23C2/26—After-treatment
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
제1도는 본 발명에 의한 망간/합금화 용융아연 2층도금강판의 깊이 방향에 따른 도금층의 조성의 그로우 디스차지 램프 스팩트 로스코피(GDLS : Glow discharge lamp spectroscopy)분석결과를 나타낸 것임.Figure 1 shows the results of the glow discharge lamp spectroscopy (GDLS) analysis of the composition of the plating layer according to the depth direction of the manganese / alloyed molten zinc two-layer plated steel sheet according to the present invention.
(a)는 합금화 용융아연도금강판(50g/m2)의 조성변화를 나타낸 것이고,(a) shows the composition change of the alloyed hot-dip galvanized steel sheet (50g / m 2 ),
(b)는 합금화 용융아연도금강판 위에 진공중착법으로 망간을 10g/m2증착한 후 조성변화를 나타낸 것이고,(b) shows the composition change after depositing 10 g / m 2 of manganese by vacuum deposition on an alloyed hot-dip galvanized steel sheet,
(c)는 상기의 (b)시편을 1800시간의 염수분무 시험후에 조성 변화를 나타낸 것임.(c) shows the composition change of the above (b) specimen after the salt spray test for 1800 hours.
본 발명은 내식성을 증가시키기 위해, 용융도금법으로 도금된 아연도금강판을 합금화 열처리를 통해 합금화 용융아연도금강판(Galvannealed steel sheet)을 만든후, 상층에 진공증착법으로 망간을 도금하여 하층은합금화 용융아연도금, 상층은 망간을 도금하는 것을 특징으로 하는 망간/합금화 용융아연 2층도금강판 및 그 제조방법에 관한 것이다.In order to increase the corrosion resistance, the present invention is to produce a galvanized galvanized steel sheet (galvannealed steel sheet) by galvanizing the galvanized steel plate plated by hot dip galvanizing method, and then the upper layer is plated with manganese by vacuum vapor deposition. Plating, the upper layer relates to a manganese / alloyed hot-dip galvanized two-layer plated steel sheet characterized in that the manganese plating.
강판은 원래 강판자체의 기계적 성질이 우수하고 가공성이 양호하며 자원이 풍부하여 자동차, 가전제품 및 건재 등의 구조재로 널리 이용되고 있다. 그러나 강판자제의 내식성이 떨어지기 때문에 부식을 방지하기 위해 아연이나 아연합금 등을 도금한 표면처리강판이 널리 사용되고 있다. 특히 최근 자동차의 외판재로 사용하는 경우 자동차의 사용수명을 연장시키기 위한 차체의 방청규제가 점차 엄격해짐에 따라 고내식성을 가지는 표면처리 강판의 요구가 있으며 보다 내식성이 우수한 새로운 도금계를 찾고자 하는 시도가 활발히 이루어지고 있다.Steel sheets are widely used as structural materials for automobiles, home appliances, and building materials due to their excellent mechanical properties, good processability, and abundant resources. However, since the corrosion resistance of the steel sheet material is poor, in order to prevent corrosion, a surface-treated steel sheet plated with zinc or zinc alloy is widely used. In particular, in recent years, when used as an exterior material of automobiles, as the anti-rust regulation of the body to extend the service life of automobiles becomes stricter, there is a demand for a surface treated steel sheet having high corrosion resistance and an attempt to find a new plating system with better corrosion resistance. Is actively being done.
지금까지 개발되어온 고내식성 도금강판에는 전기도금법을 이용한 Zn-Fe, Zn-Ni, Zn-Co, Zn-Mn등의 아연합금도금강판이 있는데, 그 중에서도 Zn-Mn 합금도금강판은 내식성이 매우 우수한 것으로 알려져 있다. 또한 최근에는 전기도금법이 아닌 증착도금범으로도 Zn-Mn 도금강판이 개발되었는데 여기서 망간의 중량비는 15wt%에서 75wt%에서 내식성이 우수하다고 보고 되었다. (일본특허공보 소 64-42572호) 한편 아연도금계를 하층으로 하고 Fe-Mn을 상층으로 하는 2층전기도금강판의 제조방법이 발표된바 있는 데, 여기서는 하층을 아연, 아연-철 도는 아연-니켈도금으로 하고 상층에 망간농도가 60wt% 이하인 Fe-Mn으로 구성하는 도금계이다. 이처럼 합금상태에서 망간이 고내식성을 유지하는 이유는 부식분위기 속에서 도금강판의 표면에 형성되는 망간산화물이 부식진행을 억제하는 효과를 가져오기 때문이다.The high corrosion-resistant plated steel sheet developed so far includes zinc alloy plated steel sheets such as Zn-Fe, Zn-Ni, Zn-Co, and Zn-Mn by electroplating. Among them, Zn-Mn alloy plated steel sheets have excellent corrosion resistance. It is known. Recently, Zn-Mn plated steel sheets have been developed as depositors rather than electroplating methods, where the weight ratio of manganese is reported to be excellent in corrosion resistance at 15 wt% to 75 wt%. (Japanese Patent Publication No. 64-42572) Meanwhile, a method for manufacturing a two-layer electroplating steel sheet having a zinc-plated layer as the lower layer and an Fe-Mn layer as the upper layer has been announced, in which the lower layer is zinc, zinc-iron or zinc. It is a plating system composed of nickel-plated and composed of Fe-Mn having a manganese concentration of 60wt% or less in the upper layer. The reason why manganese maintains high corrosion resistance in the alloy state is that the manganese oxide formed on the surface of the plated steel sheet in the corrosion atmosphere has an effect of inhibiting the progress of corrosion.
그러나 전기도금이든 증착도금이든 합금형태로 도금되는 합금도금을 실제 공업화하는데 있어서는 합금조성을 정확히 유지하는데에 어려움이 따르는 단점이 있다. 또한 합금도금층이 금속학적으로 단일상을 형성하는 경우도 있으나 2상 이상의 혼합상을 형성하는 경우도 많은데 이경우에는 도금후 도장 등을 위한 화성처리 조건의 설정이 까다로워지며 화성피막의 균일성에도 문제가 있다. 그리고 합금형태로 망간을 도금하여 충분한 내식성을 얻으려면 망간의 함유량이 적어도 50wt%가 되어야 하는데, 이는 값이 비싼 망간을 다량 요구하는 것이기 때문에 상업적으로 비용이 많이 들게 되는 단점이 있다.However, in actual industrialization of the alloy plating plated in the form of alloy, whether electroplating or deposition plating, there is a disadvantage in that it is difficult to maintain the alloy composition correctly. In addition, the alloy plating layer may form a single phase metallically, but in many cases, a mixed phase of two or more phases is formed. In this case, it is difficult to set the conversion treatment conditions for coating after plating, and there is a problem in uniformity of the coating film. have. To obtain sufficient corrosion resistance by plating manganese in an alloy form, the content of manganese should be at least 50 wt%, which is disadvantageous because it requires a large amount of expensive manganese.
이러한 문제점들은 부식특성이 우수한 단원소를 상층으로 하는 2층도금강판으로 해결할 수 있다. 이층도금강판은 제조공정이 단순하며 도금표층에 단일금속인 상층피막이 존재하게 되므로 적절한 도금계를 선택하면 화성처리성도 양호하다. 그리고 내식성이 우수한 망간을 상층에 소량 도금하여도 부식분위기에서 바깥층의 망간이 먼저 부식인자와 반응하여 도금층 표면에 망간의 산화물이 형성되기 때문에 기판을 보호할 수 있다. 이러한 2층도금 제조공정에 가장 적합한 것은 상층에 진공증착법을 적용하는 것이다. 진공증착법을 적용하게 되면 하층에 영향을 주지 않고 상층 피막을 제조할 수 있으며, 필요시에는 증착온도 등의 증착조건을 조절하여 합금화층을 형성시킬 수도 있다는 장점이 있어 적용하기에 용이하다.These problems can be solved by a two-layer plated steel sheet having a single unit having excellent corrosion characteristics. Since the manufacturing process of the two-layer plated steel sheet is simple and there is a single layer of upper metal film on the surface of the plating, if the appropriate plating system is selected, the chemical conversion treatment is good. Even if a small amount of manganese having excellent corrosion resistance is plated on the upper layer, manganese in the outer layer reacts with the corrosion factor first in the corrosion atmosphere, thereby forming a manganese oxide on the surface of the plating layer, thereby protecting the substrate. The most suitable for this two-layer plating manufacturing process is to apply a vacuum deposition method to the upper layer. When the vacuum deposition method is applied, the upper layer can be manufactured without affecting the lower layer, and if necessary, the alloy layer can be formed by adjusting the deposition conditions such as the deposition temperature, and thus it is easy to apply.
본 발명의 목적은 망간의 우수한 내식특성을 이용하여 일반 아연도금 강판보다 도장성, 가공성 및 용접성이 우수한 합금화 아연도금 강판을 하층으로 하고, 상층에 망간을 진공증착한 2층도금강판을 제공하는데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a two-layer plated steel sheet in which an alloyed galvanized steel sheet having a lower coating layer, workability and weldability than a general galvanized steel sheet using manganese excellent corrosion resistance, and vacuum-manganese deposited on the upper layer. .
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
먼저 소지기판인 합금화 용융아연도금강판을 아세톤 및 알콜 용액에서 초음파 세척을 하여 전처리를 실시하였다. 이때 사용된 합금화 용융아연도금강판은 용융도금법으로 아연의 부착량을 50g/m2도금시킨 후 650℃에서 열처리를 하여 도금층의 조직이 Zn7Fe이 되도록 제조하였다. 이때 재질은 자동차용으로 사용되는 심가공용(Extra deep Drawing Quality)을 사용하였다. 전처리를 마친 합금화 용융아연도금강판은 진공증착 챔버내에 장입시킨 후, 망간 금속 낟알(grain)을 수냉식 구리 도가니에 채운후 진공배기시키고 전자빔을 이용하여 망간을 진공증착법으로 도금시켰다.First, an alloyed hot-dip galvanized steel sheet, which is a substrate, was pretreated by ultrasonic cleaning in acetone and alcohol solution. In this case, the alloyed hot-dip galvanized steel sheet used was prepared by plating the deposition amount of zinc by hot-dip plating at 50 g / m 2 and heat-processing at 650 ° C. to form Zn 7 Fe. In this case, the material used was an deep deep drawing quality used for automobiles. After pretreatment, the alloyed hot-dip galvanized steel sheet was charged into a vacuum deposition chamber. The manganese metal grains were filled in a water-cooled copper crucible, evacuated, and the manganese was plated by vacuum deposition using an electron beam.
이때 기판온도는 250℃ 이하에서 유지시켜야 한다. 여기서 기판온도가 250℃ 이하로 유지하는 이유는 기판온도가 250℃를 넘으면 하층으로 사용되는 합금화 용융아연도금강판내의 아연성분이 고온으로 인해 재증발하기 때문에 내식성 효과가 떨어지기 때문이다. 그리고 상층에 부착되는 망간의 부착량은 3g/m2이상 도금시켜야 한다. 왜냐하면 소지기판으로 사용되는 합금화 용융아연도금강판은 표면에 많은 요철(凹凸)을 가지고 있기 때문에 망간의 부착량이 3g/m2미만이 되면 망간이 표면을 충분히 덮어주지 못하기 때문이다. 또한 망간의 부착량이 20g/m2이상이 되면 내식성의 증가가 뚜렷하지 않기 때문에 상업적 측면을 고려하면 망간의 부착량을 20g/m2이상까지 도금시킬 필요는 없다.At this time, the substrate temperature should be maintained below 250 ℃. The reason why the substrate temperature is maintained at 250 ° C. or lower is because the zinc component in the alloyed hot-dip galvanized steel sheet used as the lower layer when the substrate temperature exceeds 250 ° C. re-evaporates due to high temperature, thereby reducing the corrosion resistance effect. And the amount of manganese attached to the upper layer should be plated more than 3g / m 2 . Because the alloyed hot-dip galvanized steel sheet used as the base plate has a lot of irregularities on the surface, manganese does not cover the surface sufficiently when the amount of manganese adhesion is less than 3g / m 2 . In addition, there is no consideration of the commercial aspects necessary to plate the adhesion amount of manganese up to 20g / m 2 or more, because an adhesion amount of manganese does not increase the corrosion resistance pronounced when the 20g / m 2 or more.
본 발명을 구체적인 실시예를 들어 설명하면 다음과 같다.The present invention will be described with reference to specific examples as follows.
(실시예 (1∼7))(Examples (1-7))
본 발명에서는 용융도금법으로 아연을 50g/m2도금시킨 아연도금강판을 650℃에서 열처리하여 합금화 용융아연도금강판을 제조한 후, 아세톤 및 알콜용액에서 초음파세척을 하여 전처리를 실시하였다. 이렇게 전처리를 거친 강판을 진공조에 장입하여 10-4Torr까지 진공배기하였다. 진공배기 후 기판을 상온에서 250℃ 온도까지 가열하고 전자빔을 이용하여 망간의 부착량을 3g/m2에서 20g/m2까지 증착하여 Mn/GA 2층도금강판을 제조하였다. 여기에서, GA는 합금화 용융아연도금강판(Galvanneald steel sheet)를 의미한다.In the present invention, a zinc-plated steel sheet plated with 50 g / m 2 of zinc by hot dip plating is heat-treated at 650 ° C. to produce an alloyed hot dip galvanized steel sheet, and then pretreated by ultrasonic washing in acetone and alcohol solution. The pretreated steel sheet was charged into a vacuum chamber and evacuated to 10 -4 Torr. After evacuating the substrate is heated from room temperature to 250 ℃ temperature and deposited using an electron beam in a coating weight of manganese 3g / m 2 to 20g / m 2 to prepare a Mn / GA 2 layer coated steel sheets. Here, GA means galvanized galvanized steel sheet (Galvanneald steel sheet).
상기와 같이 제조된 시편은 나내식성을 비교, 평가하기 위해 10cm×15cm의 크기의 시편을 ASTM B3317-73에 의거 염수분무장치에서 내식성을 평가하였다. 나내식성평가는 염수분무시험중 24시간을 단위로 시편 표면에 적청이 5% 발생하는 시점을 기준으로 하여 실시하였다. 결과는 표 1에 기재하였다.The specimen prepared as described above was evaluated for corrosion resistance in a salt spray device according to ASTM B3317-73 specimen of size of 10cm × 15cm to compare and evaluate the corrosion resistance. The corrosion resistance evaluation was performed on the basis of the time when 5% of red blue color occurred on the surface of the specimen during 24 hours during the salt spray test. The results are shown in Table 1.
(비교예 1)(Comparative Example 1)
비교예 1은 부착량이 50g/m2인 합금화 용융아연도금강판에 망간을 증착시키지 않고 그대로 내식성 평가를 실시하였다.In Comparative Example 1, corrosion resistance was evaluated as it is without depositing manganese on an alloyed hot dip galvanized steel sheet having an adhesion amount of 50 g / m 2 .
(비교예 2)(Comparative Example 2)
비교예 2은 일반냉연강판 위에 진공증착방법으로 200℃의 기판온도에서 망간을 20g/m2도금시킨 후 내식성 평가를 실시하였다.In Comparative Example 2, 20 g / m 2 of manganese was plated at a substrate temperature of 200 ° C. by vacuum deposition on a general cold rolled steel sheet, and corrosion resistance was evaluated.
(비교예 3)(Comparative Example 3)
상기의 실시에(1∼7)에서 처럼 부착량이 50g/m2인 합금화 용융아연도금강판 위에 진공증착범으로 200℃의 기판온도에서 망간을 2g/m2도금시킨 후 내식성 평가를 실시하였다.As in the above embodiments (1 to 7), corrosion resistance was evaluated after plating 2 g / m 2 of manganese at a substrate temperature of 200 ° C. on a alloyed hot-dip galvanized steel sheet having an adhesion amount of 50 g / m 2 at a vacuum evaporator.
(비교예 4)(Comparative Example 4)
상기의 실시예에서 처럼 부착량이 50g/m2인 합금화 용융아연도금강판 위에 진공증착법으로 300℃의 기판온도에서 망간을 10g/m2도금시킨 후 내식성 평가를 실시하였다. 비교예의 결과는 표 2에 기재하였다.As in the above embodiment, 10 g / m 2 of manganese was plated at a substrate temperature of 300 ° C. by vacuum deposition on an alloyed hot-dip galvanized steel sheet having an adhesion amount of 50 g / m 2 , and corrosion resistance was evaluated. The results of the comparative example are shown in Table 2.
표 1에서 보여주듯이 망간을 기판온도 250℃ 이하에서 증착시킨 망간/합금화 용융아연 2층도금강판은 기존의 합금화 용융아연도금강판(비교예 1)이나 망간이 단독으로 도금된 강판(비교예 2) 보다 내식성이 10배이상 증가하였다. 그리고 망간의 부착량이 2g/m2인 비교예 3이나, 기판온도를 300℃에서 증착한 비교예 4에서 뚜렷한 내식성 효과를 얻지 못했다.As shown in Table 1, the manganese / alloyed hot-dip galvanized steel sheet in which manganese was deposited at a substrate temperature of 250 ° C. or lower is a conventional alloyed hot-dip galvanized steel sheet (Comparative Example 1) or manganese plated steel alone (Comparative Example 2). Corrosion resistance increased more than 10 times. And, in Comparative Example 3 having a deposition amount of manganese of 2 g / m 2 or Comparative Example 4 in which the substrate temperature was deposited at 300 ° C., no obvious corrosion resistance effect was obtained.
제1도는 본 발명에 의한 망간/합금화 용융아연 2층도금강판의 깊이방향에 따른 도금층의 조성분석결과를 보여주는 그림이다. 그런데 그림(b)에서 볼 수 있듯이 상층에 진공증착법으로 기판온도 200℃에서 8g/m2도금된 망간이, 하층의 합금화 용융아연도금층에 특별한 영향을 주지 않고 2층도금강판의 제조가 가능한 것을 보여주고 있다. 그림(c)는 상기의 (b)시편을 1800시간의 염수분무시험 후에 조성변화를 보여주는 그림인데 도금층 바같쪽에 망간산화물로 예상되는 산소의 강도가 검출되고 있다. 이는 X-ray 분석결과 γ-Mn2O3임을 알 수 있있는데, 표면에 형성된 이 부식생성물이 부식의 지연을 방지했다고 말할 수 있다.1 is a view showing the composition analysis results of the plating layer in the depth direction of the manganese / alloyed molten zinc two-layer plated steel sheet according to the present invention. However, as shown in Fig. (B), the manganese plated with 8 g / m 2 at the substrate temperature of 200 ° C. by vacuum deposition on the upper layer shows that it is possible to manufacture a two-layer plated steel sheet without affecting the alloying hot dip galvanized layer of the lower layer. Giving. Figure (c) shows the change in composition after 1800 hours of salt spray test (b) above, and the strength of oxygen expected to be manganese oxide is detected on the bar. X-ray analysis shows that γ-Mn 2 O 3 , which can be said that the corrosion product formed on the surface prevented the delay of corrosion.
상술한 바와 같이 본 발명은 기존의 합금화 용융아연도금강판 위에 망간을 진공증착법으로 도금시켜, 내식성이 우수한 망간/합금화 용융아연 2층도금강판의 제조가 가능하다. 그리고 하층으로 사용된 합금화 용융아연도금의 특성을 그대로 이용할 수 있기 때문에 자동차의 판재 등의 용도로 사용이 가능하다.As described above, the present invention enables the production of manganese / alloyed hot dip galvanized steel sheet having excellent corrosion resistance by plating manganese on a conventional hot dip galvanized steel sheet by vacuum deposition. And since the characteristics of the alloyed hot-dip galvanizing used in the lower layer can be used as it is, it can be used for applications such as plate of the automobile.
[표 1]. Mn/GA 이층도금강판의 내식성평가TABLE 1 Corrosion Resistance Evaluation of Mn / GA Laminated Steel Sheet
[표 2]TABLE 2
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