KR890001829B1 - Hot dip zinc plated basin - Google Patents
Hot dip zinc plated basin Download PDFInfo
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- KR890001829B1 KR890001829B1 KR8205192A KR820005192A KR890001829B1 KR 890001829 B1 KR890001829 B1 KR 890001829B1 KR 8205192 A KR8205192 A KR 8205192A KR 820005192 A KR820005192 A KR 820005192A KR 890001829 B1 KR890001829 B1 KR 890001829B1
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- coating
- plating bath
- corrosion resistance
- zinc
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- 239000011701 zinc Substances 0.000 title claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052725 zinc Inorganic materials 0.000 title claims description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000007747 plating Methods 0.000 claims description 60
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005246 galvanizing Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 30
- 238000005260 corrosion Methods 0.000 abstract description 30
- 229910000831 Steel Inorganic materials 0.000 abstract description 19
- 239000010959 steel Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 6
- 238000000576 coating method Methods 0.000 abstract 6
- 238000005097 cold rolling Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001327 Rimmed steel Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- 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
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
Abstract
Description
본 발명은 내식성과 피복성(Coatability)이 극히 우수한 아연 용융도금 강판(hot-dip Zinc-plated Steel sheets)의 제조방법에 관한 것이다.The present invention relates to a method for producing hot-dip zinc-plated steel sheets having extremely excellent corrosion resistance and coatability.
오늘날 아연 용융도금 강판의 용도는 매우 복잡 다양해졌다. 예전에는 이러한 강판을 지붕이나 벽에 사용하였으나, 현재는 자동차의 착색 강판으로 미리 피복된 재료로서도 사용한다. 이경우, 그 강판은 굽힘(bending)이나 디프 드로잉(deep drawing)등과 같은 심한 소성가공을 하여야 하는데, 완성된 제품표면의 질과 외관이 아주 좋지않으면 안된다. 결국, 기판과 합금층의 가공성에 있어서는 물론, 가공부의 합금층의 내식성에 있어서도 재래식의 것보다 훨씬 우수한 제품의 필요성이 절실해졌다.The use of zinc hot-dip steel sheets today has become very complex and varied. Previously, these steel sheets were used for roofs and walls, but now they are also used as pre-coated materials with colored steel plates for automobiles. In this case, the steel sheet must be subjected to severe plastic processing such as bending or deep drawing, and the quality and appearance of the finished product surface must be very poor. As a result, there is an urgent need for a product that is much superior to conventional ones not only in the processability of the substrate and the alloy layer but also in the corrosion resistance of the alloy layer of the processed portion.
지금까지 아연 용융 도금 강판의 내식성을 개선시키는데 사용한 방법은 두가지가 있었는데, 그중 하나는 아연 도금층의 두께를 증가시키는 것과, 다른 하나는 도금욕속에 다른 원소를 첨가함으로써 아연 도금층 그자체의 질을 개선시키는 것이었다.So far, there have been two methods used to improve the corrosion resistance of galvanized steel sheets, one of which is to increase the thickness of the zinc plating layer, and the other is to improve the quality of the zinc plating layer itself by adding another element to the plating bath. Was.
전자는 기판을 위한 아연 도금층의 보호작용을 향상시키기는 하지만, 그 두꺼운 도금층으로 인하여, 도금판을 가공할때 도금층이 균열되어 벗겨져서, 외관을 해치는 결과를 초래한다. 따라서, 이러한 방법은 사실상 바람직하지 못하다.The former improves the protective action of the zinc plated layer for the substrate, but due to its thick plated layer, the plated layer cracks and peels off when the plated is processed, resulting in damage to the appearance. Thus, such a method is not practically desirable.
후자의 방법에 관한 것으로서 미합중국 특허 제4, 027, 478호에서는 Al 0.2 내지 17%, Mg 0.003 내지 0.15% 및 pb 0.02 내지 0.15%를 함유시킨 아연욕(Zine bath)을 제안한바 있는데 이 아연욕을 사용하면 내식성을 상당히 개선시키기는 하나 충분할 정도까지는 개선하지 못함은 물론, 만족스럽게 피복된 강판을 얻을 수도 없다. 그 이유는, 본 발명자의 상세한 조사결과, Al, Mg 및 pb와 같은 첨가원소들간의 비율이 잘 맞지않기 때문이라고 추측할 수 있었다. 특히, pb의 함량은 대단히 높은 반면에 이에 대한 Mg의 함량은 충분치가 못하다.As for the latter method, U.S. Patent Nos. 4,027 and 478 proposed a zinc bath containing 0.2 to 17% Al, 0.003 to 0.15% Mg and 0.02 to 0.15% pb. When used, the corrosion resistance is significantly improved, but not enough, and a satisfactory coated steel sheet cannot be obtained. The reason for this was that, as a result of the detailed investigation by the present inventors, the ratio between the additive elements such as Al, Mg, and pb does not match well. In particular, the content of pb is very high while the content of Mg is not sufficient.
또한, 아연 도금 강판의 외관과 기계적인 성질을 개선시키기 위하여 통상 사용하는 방법은 도금된 아연이 응고하기 직전에 그 도금강판에 물을 분무하여 냉각시켜 아연결정입자의 크기를 최소화시키거나, 또는 스트렛춰 레벨링(Srertcher leveling)과 탬버롤링(temperrolling)에 의해서 그 강판의 표면을 부드럽게 하는것이다. 그러나, 도금층을 급속히 냉각시키거나 기계적인 방법으로 부드럽게 하면, 부식의 시발점이 되는 활성점(activated point)의 수가 증가한다. 따라서, 내식성의 관점에서 볼때 이러한 방법들은 바람직하지 못하며, 특히 과도한 템퍼롤링을 해서는 안된다.In addition, the method commonly used to improve the appearance and mechanical properties of the galvanized steel sheet is sprayed with water to cool the coated steel sheet immediately before the plated zinc solidifies to minimize the size of the zinc crystal grains, or By surface leveling and tamperrolling, the surface of the steel sheet is smoothed. However, rapidly cooling the plating layer or softening it mechanically increases the number of activated points that are the starting point of corrosion. Therefore, from the standpoint of corrosion resistance, these methods are undesirable, and in particular, excessive tempering should not be performed.
아울러, 아연 도금강판을 예비 피복강판(precoated Sheets)이나 자동차용 재료로 사용할때에는 성형 및 용접가공을 해야되기 때문에 도금층을 얇게 형성시키는 것이 바람직하다. 따라서, 도금층이 얇으면서도 내식성이 강한 강판이 필요하다. 현재, 도금층의 두께 조절은 고속으로 작업하면서 (160-200m/min)개스로 세척하는 방식(gas-wiping)으로 한다. 이러한 고속 작업시에 공지의 아연 도금옥(Al 0.15-0.18%)도금시킬 수 있는 아연 도금량은 면(面)당 45-60g/㎡의 범위(이하 아연 도금층의 양은 면적에 대하여 표시한다)이다. 그러나, 이러한 범위의 양은 아연 도금강판을 가공할때 필요한 30g/㎡미만이라는 값을 훨씬 상회하는 것이다. 이러한 아연 도금량을 줄이기 위하여 통상 사용하는 방법이 도금속도를 표준치에서 20 내지 30%만큼 낮추어서 개스 세척효과를 증대시키는 것이다. 그러나, 이러한 방법은 생산성을 저하시키는 것이므로 산업적으로는 바람직하지 못하다.In addition, when the galvanized steel sheet is used as precoated sheets or automotive materials, it is preferable to form a thin plated layer because it must be formed and welded. Therefore, a steel plate with a thin plating layer and strong corrosion resistance is required. At present, the thickness control of the plating layer is performed by gas-wiping while working at high speed (160-200 m / min). In this high-speed operation, the zinc plating amount which can be plated with a known galvanized jade (Al 0.15-0.18%) is in the range of 45-60 g / m2 per surface (hereinafter, the amount of the galvanized layer is expressed in terms of area). However, the amount in this range far exceeds the value of less than 30g / ㎡ required when machining galvanized steel sheet. In order to reduce the amount of zinc plating, a commonly used method is to lower the plating rate by 20 to 30% at a standard value to increase the gas cleaning effect. However, this method is not industrially desirable because it lowers productivity.
본 발명자는 상기한 바의 문제점을 연구한 결과 그 근본적인 해결책이 도금욕의 성질에 있다는 것을 찾아내고서 본 발명을 완성하였다.The present inventors have completed the present invention by finding that the fundamental solution lies in the properties of the plating bath as a result of studying the above problems.
본 발명에 의한 신규한 아연 도금욕은 기본적으로 Al 0.35 내지 3.0% Mg 0.15 내지 1.0%, 나머지는 Zn과 불가피한 불순물이 되도록 구성하여 pb함량은 0.015%이하가 되게끔한 것이다.The novel zinc plating bath according to the present invention is basically composed of Al 0.35 to 3.0% Mg 0.15 to 1.0%, the rest of which is an inevitable impurity with Zn so that the pb content is less than 0.015%.
또한, 용융 아연 도금강판의 제조방법은 도금욕이 기본적으로 Al 0.35 내지 3.0% Mg 0.15 내지 1.0%, 나머지는 Zn과 불가피한 불순물이 되도록 구성되어 pb함량은 0.015%이하로 되게끔한 것을 특징으로 한다.In addition, the method of manufacturing a hot-dip galvanized steel sheet is characterized in that the plating bath is basically composed of Al 0.35 to 3.0% Mg 0.15 to 1.0%, the remainder is Zn and inevitable impurities, so that the pb content is less than 0.015%.
양호한 실시예에서, 아연 도금량은 면당 30g/㎡이하이다. 아울러 도금판은 가열하여 합금층이 형성되게끔 한다.In a preferred embodiment, the zinc plating amount is 30 g / m 2 or less per side. In addition, the plate is heated so that the alloy layer is formed.
바람직하기로는 도금욕의 조성을 Al 0.35 내지 2.0%와 Mg 0.15 내지 0.8%로 하여 그 나머지가 Zn과 불가피한 불순물이 되도록 구성함으로써 pb함량이 0.01%이하가 되게끔 한 것이다.Preferably, the composition of the plating bath is 0.35 to 2.0% of Al and 0.15 to 0.8% of Mg so that the remainder is made of Zn and inevitable impurities so that the pb content is 0.01% or less.
더욱 바람직하기로는 도금욕의 조성을 Al 0.35 내지 1.0%와 Mg 0.15 내지 0.5%로 하여 그 나머지가 Zn과 불가피한 불순물이 되도록 구성함으로써 pb함량이 0.007%이하가 되게끔 구성한 것이다.More preferably, the composition of the plating bath is 0.35 to 1.0% of Al and 0.15 to 0.5% of Mg so that the remainder is made of Zn and unavoidable impurities so that the pb content is set to be 0.007% or less.
불가피한 불순물이라 함은 시판되고 있는 Zn에 함유된 불순물, 즉 Cd 0.01%이하, Sn 0.01%이하, 및 Fe 1.0%이하를 의미한다.Unavoidable impurities mean impurities contained in commercially available Zn, that is, Cd 0.01% or less, Sn 0.01% or less, and Fe 1.0% or less.
본 발명에는 다음과 같은 잇점이 존재한다.The present invention has the following advantages.
1. 본 발명의 도금욕으로 제조한 제품의 내식성은 Al이 0.15 내지 0.18%함유되어 있는 공지의 도금욕으로 제조한 제품의 내식성보다 3배 이상이 된다.1. The corrosion resistance of the product manufactured by the plating bath of this invention becomes three times or more than the corrosion resistance of the product manufactured by the well-known plating bath which contains 0.15-0.18% of Al.
2. 강판이 도금욕을 통과한 후 특별히 급냉시키지 않더라도 스팽글(Spangle)이 최소로 유지된 반듯한 도금판을 얻을 수 있다.2. Even if the steel sheet passes through the plating bath, even if it is not particularly quenched, a smooth plate with a minimum spangle can be obtained.
3. 강판을 본 발명의 도금욕으로 도금시킨 후 약 1.0%정도의 축소율로 가볍게 템퍼 롤링시키면 외관과 기계적인 성질이 극히 우수한 제품을 얻을 수 있다.3. After the steel plate is plated with the plating bath of the present invention, lightly temper rolling with a shrinkage of about 1.0% yields an excellent product with excellent appearance and mechanical properties.
4. 본 발명의 도금욕에서는 Al의 함량을 공지의 것에 비해 2.5 내지 20배로 증가시킨 결과 도금욕의 유동성이 향상되어 동일 온도에서의 동일 개스 세척 조건하에서 개스 세척시에 그 세척효과가 증대되어 도금층이 더욱 얇아진 제품을 얻을 수 있다.4. In the plating bath of the present invention, the Al content is increased by 2.5 to 20 times compared with the known one, and the fluidity of the plating bath is improved, and the washing effect is increased when the gas is washed under the same gas washing conditions at the same temperature. This thinner product can be obtained.
이제 도금욕 조성물의 각 성분과 그 농도에 관해서 설명하고자 한다.Now, each component of the plating bath composition and its concentration will be described.
1. 알루미늄(Al)Aluminum
아연 용융 도금욕중 알루미늄의 함량을 증가시키면, 동일 온도에서 도금욕의 유동성이 공지의 것보다 현저하게 향상된다. 예컨대, 알루미늄의 함량을 공지의 0.15%에서 0.3%이상으로 증가시키면, 도금욕의 유동성이 1.5 내지 2.0%정도 향상된다. 따라서, 본 발명의 도금욕중 알루미늄 함량의 하한치는 0.35%로 한다. 또한, 그 상한치는 3.0%로 하는데, 그 이유는 이 값을 초과하게 되면 Zn-Al공정조직이 뚜렷해져서 그 공정상(共晶相)과 Zn 相상간에 국부 전지가 형성되어 내식성을 손상시키기 때문이다.Increasing the aluminum content in the zinc hot dip plating bath significantly improves the flowability of the plating bath at the same temperature than the known one. For example, when the content of aluminum is increased from 0.15% to 0.3% or more, the fluidity of the plating bath is improved by 1.5 to 2.0%. Therefore, the lower limit of the aluminum content in the plating bath of the present invention is 0.35%. In addition, the upper limit thereof is 3.0% because the Zn-Al process structure becomes clear when the value is exceeded, and a local battery is formed between the process phase and the Zn phase phase, thereby impairing the corrosion resistance. to be.
2. 마그네슘(Mg)2. Magnesium (Mg)
마그네슘은 내식성을 향상시키기 위하여 첨가하는 원소들중의 하나이다. 도금욕중 마그네슘의 함량이 0.15%이상일 때 도금층의 내식성이 현저하게 향상된다. 따라서, 마그네슘 함량이 증가함에 따라 도금층의 내식성이 향상되는 것은 사실이나, 1%를 초과시키게 되면 도금층의 표면에 주름이 잡혀서 외관을 해치게 되고 표면의 산화작용이 점차로 증대됨은 물론, 도금욕 표면의 산화작용(찌꺼기가 형성됨)이 커서 도금욕을 폐기화시키게 되는 결과를 초래한다. 따라서, 마그네슘 함량의 상한 허용치는 1.0%이다.Magnesium is one of the elements added to improve the corrosion resistance. When the magnesium content in the plating bath is 0.15% or more, the corrosion resistance of the plating layer is remarkably improved. Therefore, it is true that the corrosion resistance of the plating layer is improved as the magnesium content is increased, but when it exceeds 1%, the surface of the plating layer is corrugated to damage the appearance and the oxidation of the surface is gradually increased, as well as oxidation of the surface of the plating bath. The action (debris is formed) is large, resulting in a waste of the plating bath. Therefore, the upper limit of magnesium content is 1.0%.
3. 납(pb)3. Lead (pb)
납은 표준온도에서 아연속에 고용(固溶)상태로서는 거의 존재할 수 없기 때문에 결정립(Crystal grain)내에 또는 입계(grain bounolary)에 미립자(微粒子)로서 석출되어 국지 전위를 형성함으로써 내식성을 손상시키는 한 원인이 된다. 따라서, 납의 함량은 가능한한 낮추는 것이 좋다. 상세한 조사결과 납의 함량을 0.015%이하로만 유지시키면, 현미경적으로 도금층의 결정립이나 입계에 납의 석출현상과 입계간 부식현상을 발견할 수 없음은 물론 시각적으로는 아연 결정의 스팽글 현상도 거의 찾아볼 수 없다. 따라서 납의 함량은 0.015%이하로 한다.Since lead can hardly exist in the solid state in zinc at the standard temperature, it is precipitated as a fine particle in crystal grains or grain bounolary and forms a local potential, thereby impairing corrosion resistance. Becomes Therefore, the lead content should be as low as possible. As a result of detailed investigation, if lead content is kept below 0.015%, microscopic deposition of lead and intergranular corrosion at the grains or grain boundaries of the plating layer can not be observed microscopically, and zinc sequins can be found visually. none. Therefore, the content of lead is less than 0.015%.
상기한 바와같은 조성의 아연 도금욕을 사용함으로써, 공지 기술에서와 같은 작업 조건하에서도 매우 짧은 도금층(30g/㎡이하)과 우수한 외관 및 내식성을 갖는 아연 도금강판을 얻을 수 있다.By using the zinc plating bath having the composition described above, a galvanized steel sheet having a very short plating layer (less than 30 g / m 2) and excellent appearance and corrosion resistance can be obtained even under working conditions as in the known art.
아연 도금층의 두께를 얇게하는 것이 본 발명의 특징이기는 하지만, 개스세척 조건을 변화시킴으로써 아연 도금량이 변화될 수 있게 때문에 도금층을 더 두껍게 할 수 있음은 물론이다. 이제, 본 발명을 실시예에 의해 상세히 설명한다.Although thinning the thickness of the zinc plating layer is a feature of the present invention, it is of course possible to make the plating layer thicker because the zinc plating amount can be changed by changing the gas washing conditions. The present invention will now be described in detail by way of examples.
[실시예 1]Example 1
표1에 표시한 바와같은 조성의 아연 도금욕을 사용하여 두께가 04mm, 폭이 300mm인 소둔시키지 않은 림드강판(rimmed Steel Sheet)을 공지의 개스 환원방식 도금장치(gas reduction plating apparatus)로 다음과 같은 조건하에서 아연도금 하였다.Using a zinc plating bath having a composition as shown in Table 1, an annealed rimmed steel sheet having a thickness of 04 mm and a width of 300 mm was obtained using a known gas reduction plating apparatus. Galvanized under the same conditions.
선처리(pre-treatment)Pre-treatment
비산화로(non-oxidizing furnace)의 출구에서의At the exit of a non-oxidizing furnace
강판온도 : 590 내지 600℃Steel plate temperature: 590 ~ 600 ℃
환원로 개스 조성 : H275%, N225%Reduction furnace gas composition: H 2 75%, N 2 25%
환원로의 출구에서의At the exit of the reduction furnace
개스 온도 : 700 내지 720℃Gas temperature: 700 to 720 ℃
도금욕 온도 : 460℃ ±5℃Plating bath temperature: 460 ℃ ± 5 ℃
도금층의 양 : 면당 120g/㎡The amount of plating layer: 120g / ㎡ per side
후처리(after-treatment)After-treatment
템퍼롤링 : 안했음Tempering: No
크롬산으로 후처리 : 안했음Post-treatment with chromic acid: no
최종제품의 검사 및 그 결과를 평가하는 방법은 다음과 같이 하였다.The inspection of the final product and the method of evaluating the results were as follows.
스팽글의 크기 : 육안으로 관찰Sequin size: visually observed
도금층의 부착성 : 도금강판을 록크-폼(lock-formed)가공하여 그 가공부위에 셀로판 접착 테이프를 붙였다가 떼어낸 다음 도금층의 부착상태를 관찰하여 도금층이 하나도 벗겨지지 않았으면 "양호"라고 표시하였다.Adhesion of the plating layer: After locking-formed the plated steel plate, attach the cellophane adhesive tape to the machined part and peel it off. Then observe the adhesion state of the plating layer, and if it is not peeled off, mark "good". It was.
결정립 및 입계에 존재하는 납(pb)의 양 : 전자주사 현미경(Scanning electron microscole)으로 측정하여 대(大), 중(中), 소(小), 미(微)로 표시하였다.The amount of lead (pb) present in grains and grain boundaries was measured by scanning electron microscole and displayed in large, medium, small, and micro.
내식성 : (1)염수 분무시험법(ASTM B 117-73)으로 붉은 녹(red rust)이 생길 때까지의 시간을 측정하였다.Corrosion resistance: (1) The time until the formation of red rust was measured by the salt spray test method (ASTM B 117-73).
(2) 염수시험(ASTM B 117-13)을 한 200시간후의 부식으로 손실된 중량(g/㎡)을 측정하였다.(2) The weight (g / m 2) lost by corrosion after 200 hours of salt water test (ASTM B 117-13) was measured.
[표 1]TABLE 1
표 1은 시험결과를 도금욕의 조성과 함께 요약해 놓은 것으로서, 본 발명의 방법에 의한 제품의 특성과 공지기술에 의한 것을 비교하여 설명하면 다음과 같다.Table 1 summarizes the test results together with the composition of the plating bath, which is described below by comparing the properties of the product by the method of the present invention with those of the known technology.
1. 스팽글의 크기1. The size of the sequins
본 발명의 방법에 의한 제품은 도금판이 자연적으로 서냉되었음에도 불구하고 아주 적은 스팽글만이 발견되었다. 표1에서 "미"(微)라고 한 말은 육안으로는 스팽글을 거의 찾아볼 수 없음과 아울러 외관이 극히 반듯함을 의미한다. 이와 대조적으로, 공지기술에 의한 시편에서는 자연적으로 서냉시켰을때 육안으로는 "대" 및 "중"의 스팽글을 뚜렷이 관찰할 수 있었다. 다만, 강제냉각(수냉)을 시킨 10번 시편의 경우에서만 스팽글이 "소"로 나타났을 뿐이다. 물론, 공지기술에 의한 시편을 모두 수냉시키면 스팽글의 크기는 작게할수 있으나, 균일성이 좋지않다. 공지기술에 의한 도금판을 수냉시키지 않았을 경우에는 스팽글이 뚜렷하게 나타나고 표면이 상당히 거칠기 때문에 그 표면을 반듯하게 하기 위해서는 템퍼롤링의 수준을 더 높여야 했다.Products by the method of the present invention found only very few sequins even though the plate was naturally slow cooled. The word "mi" in Table 1 means that the sequins are hardly found by the naked eye and the appearance is extremely straight. In contrast, in the specimens according to the known art, the spangles of "large" and "heavy" were clearly observed with the naked eye when naturally cooled. The sequins only appeared as “small” in the case of forced cooling (water cooling). Of course, if all the specimens according to the known technology is water-cooled, the size of the sequins can be reduced, but the uniformity is not good. When the plated plate according to the prior art was not water-cooled, sequins appeared clearly and the surface was considerably rough. Therefore, in order to smooth the surface, it was necessary to further increase the level of tempering.
2. 도금층의 부착성2. Adhesion of Plating Layer
본 발명에 의한 도금강판에서나 공지기술에 의한 도금강판에서나 그 자체만으로서는 도금층의 부착성에 하등의 문제가 제거되지 않았지만, 도금강판을 굽혔을 경우에는 그 굽힌 부위의 도금층에서 본 발명에 의한것에서는 균일현상이 거의 나타나지 않은 반면에 공지기술에 의한 것에서는 결정립 및 입계에서 균일현상이 뚜렷하게 나타났다. 따라서, 본 발명에 의한 제품이 공지기술에 의한 것보다 훨씬 우수함을 알 수 있었다.In the plated steel sheet according to the present invention or in the plated steel sheet according to the known art alone, no problem of adhesion to the plated layer has been eliminated. On the other hand, in the case of the known technique, uniform phenomena were clearly observed in grains and grain boundaries. Thus, it was found that the product according to the present invention is much better than that according to the known art.
3. 결정립 및 입계에 존재하는 납(pb)의 양3. The amount of lead (pb) present in grains and grain boundaries
본 발명에서는 납의 함량을 0.015%이하로 제한시켰기 때문에 입자 속 및 입계에 존재하는 납의 양은 아주 미세한 정도로서 전자주사 현미경 사진에서도 거의 찾아볼 수 없었다. 반면에 납의 함량이 높은 공지기술에 의한 시편에서는 14번 시편만을 제외하고 모두 임자속 및 입계에서 납의 존재를 뚜렷이 볼 수 있었다.In the present invention, since the content of lead is limited to 0.015% or less, the amount of lead in the particles and grain boundaries is very fine and hardly found in the electron scanning micrograph. On the other hand, in the specimens according to the known technology with a high content of lead, all but the 14 specimens clearly showed the presence of lead in the flux and grain boundaries.
4. 내식성4. Corrosion resistance
본 발명에 의한 제품은 시편에 붉은 녹이 생길때까지의 시간이 모두 1000시간 이상이었고, 부식에 의한 중량 손실은 30g/㎡이였으나, 공지기술에 의한 것에서는 비교적 상태가 양호한 11번 시편이 800시간 이하이고 상태가 나쁜 10번과 12번 시편은 모두 200시간 이하였다. 공지기술에 의한 시편의 부식으로 인한 중량손실은 본 발명에 의한 시편의 2 내지 6배 정도였다.In the product according to the present invention, the time until the red rust on the specimen was all 1000 hours or more, and the weight loss due to corrosion was 30 g / m 2, but according to the known technique, the specimen 11 was relatively good in 800 hours. Less than 10 and poor specimens were less than 200 hours. The weight loss due to corrosion of the test piece according to the known art was about 2 to 6 times that of the test piece according to the present invention.
[실시예 2]Example 2
표 2에 표시한 바와같은 조성의 아연 용융 도금욕을 사용하여 실시예 1에서와 같은 장치로 다음과 같은 조건하에서 강판을 아주 얇게 아연도금시켰다.Using a zinc hot dip bath having a composition as shown in Table 2, the steel sheet was galvanized very thinly under the following conditions by the same apparatus as in Example 1.
기판 : 0.4mm 두께의 림드강판Substrate: 0.4mm thick rim steel sheet
선처리 : 실시예 1과 동일Pretreatment: same as Example 1
도금층의 두께에 대한 개스 세척조건 :Gas cleaning conditions for the thickness of the plating layer:
개스압력 : 0.35kg/c㎡Gas pressure: 0.35kg / c㎡
노즐의 위치 : 도금욕 표면에서 150mmPosition of nozzle: 150mm from the surface of plating bath
강판과 노즐끝 사이의 거리 : 6mmDistance between steel plate and nozzle tip: 6mm
후처리 :After treatment :
템퍼롤링 : 안했음Tempering: No
크롬산으로 후처리 : 안했음Post-treatment with chromic acid: no
이 시험결과와 도금욕의 조성은 표 2로서 요약한 바, 본 발명에 의한 제품의 특징과 공지기술에 의한 것을 비교하여 설명하면 다음과 같다.The test results and the composition of the plating bath are summarized as Table 2, and the characteristics of the product according to the present invention and the description according to the known technology are as follows.
[표 2]TABLE 2
1. 아연 도금량1. Zinc plating amount
본 발명에 의한 제품의 면당 아연 도금량은 10g/㎡정도로서 극히 얇은 반면 공지기술에 의한 것은 이것의 두배 가량됨을 알 수 있다. 따라서, 본 발명에 의하면 개스 세척으로 도금층의 두께를 아주 효과적으로 조절할 수 있다.The zinc plating amount per surface of the product according to the present invention is about 10 g / m 2, which is extremely thin, while the known technology is about twice that amount. Therefore, according to the present invention, the thickness of the plating layer can be controlled very effectively by gas washing.
2. 내식성2. Corrosion resistance
본 발명에 의해서 도금한 시편의 도금층의 두께는 아주 얇기 때문에 내식성에 문제가 있을 것으로 우려되지만 표 2를 보면 알 수 있는 바 본 발명에 의한 도금층은 내식성도 상당히 높다. 즉, 본 발명에 의한 17번, 16번 및 18번 시편 각각에 대하여 그 도금층 표면에 붉은 녹이 생길때까지의 시간을 보면 차례로 270시간, 140시간, 및 180시간, 그 표면의 30%를 붉은 녹이 덮을때까지 시간을 보면 차례로 840시간, 520시간, 및 580시간이었다. 즉, 부식속도가 상당히 느림은 물론 내식성이 우수함을 알 수 있다. 반면에, 공지기술에 의한 도금층의 두께는 본 발명에 의한 것의 두배 가량되었음에도 불구하고 그 표면의 30%를 붉은 녹이 덮을때까지의 시간을 보면 19번 시편의 경구가 100시간, 이보다 도금층이 더 두꺼운 20번 시편의 경우도 450시간 밖에 안되었다. 따라서, 내식성에 있어서도 본 발명에 의한 제품이 공지기술에 의한 것보다 우수함을 알 수 있다.Since the thickness of the plated layer of the specimen plated by the present invention is very thin, there is a concern that the corrosion resistance may be a problem, but it can be seen from Table 2 that the plated layer according to the present invention also has high corrosion resistance. That is, for each of the specimens 17, 16, and 18 according to the present invention, the time until the red rust is formed on the surface of the plating layer is sequentially 270 hours, 140 hours, and 180 hours, and 30% of the surface is red rust. The time to cover was 840 hours, 520 hours, and 580 hours in turn. That is, it can be seen that the corrosion rate is significantly slow and excellent corrosion resistance. On the other hand, even though the thickness of the plating layer according to the known technology is about twice the thickness according to the present invention, when the time until the red rust is covered 30% of the surface, the oral number of specimen 19 is 100 hours, the plating layer is thicker than this. Psalm 20 also had only 450 hours. Accordingly, it can be seen that the product according to the present invention also has superior corrosion resistance than that according to the known art.
물론, 본 발명에 의한 아연도금 강판을 열처리한 아연도금 합금 강판(alloyed zinc plated sheet)의 경우도 공지의 도금욕에 의한 것보다 내식성이 훨씬 우수하다.Of course, the galvanized alloy steel sheet (alloyed zinc plated sheet) heat-treated galvanized steel sheet according to the present invention is also much better corrosion resistance than that by a known plating bath.
또한, 도금방지제(plating inhibitor)를 사용하여 시험적으로 제조된 자동차용 일면 아연도금 강판의 경우도 내식성 및 가공성이 모두 우수하다.In addition, the one-side galvanized steel sheet for automobiles manufactured experimentally using a plating inhibitor is excellent in both corrosion resistance and workability.
끝으로, 본 발명의 방법에 의해 제조된 아연 도금강판은 지붕 및 벽재와 같은 공지의 용도로는 물론 착색용 예비 피복강판, 자동차용 재료, 가전기구용 재료와 더불어 앞으로 개발될 용도로서도 잘 이용할 수 있다.Finally, the galvanized steel sheet produced by the method of the present invention can be used not only for well-known uses such as roofing and walling materials but also for future development with coloring precoated steel sheets for automobiles, automotive materials, and appliances. have.
Claims (3)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP183653 | 1981-11-18 | ||
| JP56-183653 | 1981-11-18 | ||
| JP56183653A JPS5891162A (en) | 1981-11-18 | 1981-11-18 | Manufacture of galvanized steel plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR840002463A KR840002463A (en) | 1984-07-02 |
| KR890001829B1 true KR890001829B1 (en) | 1989-05-25 |
Family
ID=16139561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR8205192A KR890001829B1 (en) | 1981-11-18 | 1982-11-17 | Hot dip zinc plated basin |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5891162A (en) |
| KR (1) | KR890001829B1 (en) |
| AU (1) | AU540419B2 (en) |
| CA (1) | CA1190353A (en) |
| DE (1) | DE3242625C2 (en) |
| FR (1) | FR2537161B1 (en) |
| GB (1) | GB2110248B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3375971D1 (en) * | 1982-12-06 | 1988-04-14 | Siemens Ag | Housing for electronic equipments |
| JP2755387B2 (en) * | 1988-04-12 | 1998-05-20 | 大洋製鋼株式会社 | Manufacturing method of hot-dip zinc-alloy-plated steel sheet for pre-coated steel sheet and pre-coated steel sheet |
| JP4173990B2 (en) * | 2002-12-27 | 2008-10-29 | 新日本製鐵株式会社 | Zinc-based alloy-plated steel for welding and its ERW steel pipe |
| CN103320738A (en) | 2004-06-29 | 2013-09-25 | 塔塔钢铁艾默伊登有限责任公司 | Steel sheet with hot dip galvanized zinc alloy coating and process to produce it |
| EP1621645A1 (en) * | 2004-07-28 | 2006-02-01 | Corus Staal BV | Steel sheet with hot dip galvanized zinc alloy coating |
| EP1693477A1 (en) * | 2005-02-22 | 2006-08-23 | ThyssenKrupp Steel AG | Coated steel plate |
| US7413769B2 (en) * | 2005-07-01 | 2008-08-19 | Mcdevitt Erin T | Process for applying a metallic coating, an intermediate coated product, and a finish coated product |
| PL1857566T3 (en) | 2006-05-15 | 2017-10-31 | Thyssenkrupp Steel Europe Ag | Flat steel product provided with a corrosion protection coating and method of its manufacture |
| ES2629109T3 (en) * | 2006-05-15 | 2017-08-07 | Thyssenkrupp Steel Europe Ag | Procedure for the manufacture of a flat steel product coated with a corrosion protection system |
| US8721809B2 (en) | 2007-02-23 | 2014-05-13 | Tata Steel Ijmuiden B.V. | Method of thermomechanical shaping a final product with very high strength and a product produced thereby |
| DE202007006168U1 (en) | 2007-04-19 | 2007-07-19 | Rothfuss, Thomas | Wire grid for wire baskets, has steel core provided with coating that is made from alloy of zinc and aluminum, where coating has specific thickness and alloy is applied on steel core |
| CN105821199B (en) | 2007-07-19 | 2018-09-04 | 穆尔和本德公司 | For the method to annealing in length direction steel band with different thickness |
| DE102007048504B4 (en) | 2007-10-10 | 2013-11-07 | Voestalpine Stahl Gmbh | Anti-corrosion coating for steel sheets and method of conditioning a corrosion protection coating |
| EP2119804A1 (en) * | 2008-05-14 | 2009-11-18 | ArcelorMittal France | Method of manufacturing a covered metal strip with improved appearance |
| KR102568479B1 (en) * | 2017-05-25 | 2023-08-18 | 타타 스틸 이즈무이덴 베.뷔. | Method for producing continuous hot-dip galvanized steel strip and hot-dip galvanized steel sheet |
| DE102020119911B3 (en) | 2020-07-28 | 2021-12-09 | Johannes Hülshorst | Profile tube punch and working method |
| CN112322968A (en) * | 2020-09-28 | 2021-02-05 | 日照钢铁控股集团有限公司 | Thermal-base non-flower high-strength galvanized plate for photovoltaic support and preparation process thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3320040A (en) * | 1963-08-01 | 1967-05-16 | American Smelting Refining | Galvanized ferrous article |
| FR1446872A (en) * | 1964-09-15 | 1966-07-22 | Inland Steel Co | Protective coating made of zinc-based alloys |
| GB1131951A (en) * | 1965-06-08 | 1968-10-30 | Hitachi Ltd | Method of and apparatus for continuous hot dip metal coating |
| US4152472A (en) * | 1973-03-19 | 1979-05-01 | Nippon Steel Corporation | Galvanized ferrous article for later application of paint coating |
| IT984964B (en) * | 1973-05-09 | 1974-11-20 | Centro Speriment Metallurg | ZINC-BASED COATING FOR THE PROTECTION OF IRON SURFACES AND METALLIC BODY FROM CORRO SION IN THIS WAY OBTAINED |
| US4029478A (en) * | 1976-01-05 | 1977-06-14 | Inland Steel Company | Zn-Al hot-dip coated ferrous sheet |
| JPS5641359A (en) * | 1979-09-10 | 1981-04-18 | Nippon Steel Corp | Manufacture of corrosion resistant zinc alloy-plated steel products by galvanizing |
| JPS5696062A (en) * | 1979-12-28 | 1981-08-03 | Nippon Steel Corp | Manufacture of corrosion resistant steel products coated with zinc alloy by hot dipping |
| AU525668B2 (en) * | 1980-04-25 | 1982-11-18 | Nippon Steel Corporation | Hot dip galvanizing steel strip with zinc based alloys |
-
1981
- 1981-11-18 JP JP56183653A patent/JPS5891162A/en active Granted
-
1982
- 1982-11-04 CA CA000414918A patent/CA1190353A/en not_active Expired
- 1982-11-08 AU AU90229/82A patent/AU540419B2/en not_active Ceased
- 1982-11-17 GB GB08232830A patent/GB2110248B/en not_active Expired
- 1982-11-17 KR KR8205192A patent/KR890001829B1/en active
- 1982-11-18 DE DE3242625A patent/DE3242625C2/en not_active Expired
- 1982-11-18 FR FR8219309A patent/FR2537161B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2537161A1 (en) | 1984-06-08 |
| GB2110248A (en) | 1983-06-15 |
| KR840002463A (en) | 1984-07-02 |
| AU540419B2 (en) | 1984-11-15 |
| JPS5891162A (en) | 1983-05-31 |
| DE3242625C2 (en) | 1985-01-03 |
| FR2537161B1 (en) | 1986-08-08 |
| CA1190353A (en) | 1985-07-16 |
| GB2110248B (en) | 1985-09-25 |
| AU9022982A (en) | 1983-05-26 |
| JPS6330984B2 (en) | 1988-06-21 |
| DE3242625A1 (en) | 1983-05-26 |
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