JP2005272922A - HOT DIP Zn-Al-BASED ALLOY COATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND BENDING WORKABILITY AND METHOD FOR MANUFACTURING THE SAME - Google Patents
HOT DIP Zn-Al-BASED ALLOY COATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND BENDING WORKABILITY AND METHOD FOR MANUFACTURING THE SAME Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
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- 238000007598 dipping method Methods 0.000 claims description 4
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- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、建材や家庭用電気器具等の分野で広く利用されている、溶融Zn−Al系合金めっき鋼板、特に耐食性および曲げ加工性を向上した溶融Zn−Al系合金めっき鋼板およびその製造方法に関するものである。 The present invention is widely used in the fields of building materials, household electric appliances, and the like, and is a hot-dip Zn-Al alloy-plated steel plate, in particular, a hot-dip Zn-Al-base alloy-plated steel plate with improved corrosion resistance and bending workability, and a method for producing the same. It is about.
溶融Znめっき鋼板は、軽量で、かつ防水性、Znの鋼板に対する犠牲防食性および施工性に優れていることから、デッキプレートや軽天井をはじめとして屋根やサイデイング等に到る、広い範囲で使用されている。特に、最近は住宅リサイクル法が制定され、住宅の長寿命化のニーズが高まっていることもあり、個人住宅向けを中心に、従来より高い耐食性をもつ、例えば溶融55mass％Al−1.6mass％Si−Zn合金めっき鋼板などが大きく需要を伸ばしている。 Hot-dip Zn-plated steel sheet is lightweight, waterproof, and excellent in sacrificial corrosion resistance and workability for Zn steel sheet, so it can be used in a wide range from deck plates and light ceilings to roofs and siding. Has been. In particular, recently, the Housing Recycling Law has been enacted, and there is an increasing need for extending the lifespan of homes. With a focus on personal housing, it has higher corrosion resistance than conventional ones, such as molten 55 mass% Al-1.6 mass% Si. -Zn alloy-plated steel sheets and other products are growing in demand.
このめっき鋼板は、めっき層中のAl濃度を55mass％まで高めることにより、Znの犠牲防食能に加えて、Alによる保護性に優れた腐食生成物により、溶融Znめっき鋼板の２〜５倍の耐食性を示すことが広く知られている。しかし、Al濃度が高いため、めっき層が固く曲げ曲げ加工性に劣り、さらに曲げ加工部や切断部の鋼板が露出している領域では、その曝露初期に赤錆が発生しやすいという、欠点があった。 By increasing the Al concentration in the plating layer to 55 mass%, this plated steel sheet is 2-5 times the hot-dip Zn-plated steel sheet due to the corrosion product excellent in protection by Al in addition to the sacrificial anticorrosive ability of Zn. It is widely known that it exhibits corrosion resistance. However, since the Al concentration is high, the plating layer is hard and inferior in bending and bending workability. Further, in the areas where the steel sheet in the bent and cut parts is exposed, red rust is likely to occur at the initial exposure stage. It was.
上記の加工部並びに切断部の耐食性を改善させるために、Zn−Al系合金めっき鋼板においてMgを添加することが、例えば特許文献１に提案されている。 In order to improve the corrosion resistance of the processed part and the cut part, for example, Patent Document 1 proposes to add Mg to the Zn-Al alloy-plated steel sheet.
Mgの添加によって、確かに加工部および切断部を含む耐食性は改善されるが、一方で曲げ加工性、とりわけ曲げ曲げ加工性に劣るところに問題を残していた。すなわち、この種のめっき鋼板を住宅向けの使途とする場合には、曲げ加工が施された際に、めっき層にクラックが発生しないことが肝要である。なぜなら、これらのクラック発生部位では、鋼板が露出し赤錆が発生しやすいことに加え、鋼板が0.6mm以下と薄い場合は、エンボス加工時に鋼板が破断するという危険性もあるからである。 Although the corrosion resistance including the processed part and the cut part is certainly improved by the addition of Mg, there remains a problem in that it is inferior in bending workability, particularly bending bending workability. That is, when this type of plated steel sheet is used for a house, it is important that the plated layer does not crack when bending is performed. This is because, at these crack generation sites, the steel plate is exposed and red rust is easily generated, and if the steel plate is as thin as 0.6 mm or less, there is a risk that the steel plate will break during embossing.
しかしながら、特許文献１に記載の技術では、この曲げ加工性については何ら考慮されておらず、上記の用途においては、この曲げ加工性の改善が必須であった。 However, in the technique described in Patent Document 1, this bending workability is not taken into consideration at all, and in the above applications, it is essential to improve the bending workability.
また、特許文献２には、Zn−Al系めっき鋼板中のMgを１mass％未満とし、Ca、NaおよびBaを選択添加する技術が開示されている。この場合、Mgの単独添加に比べて、加工部および切断部の耐食性をさらに改善することが可能であるが、曲げ加工性については、やはり考慮されていない。 Patent Document 2 discloses a technique in which Mg in a Zn-Al-based plated steel sheet is less than 1 mass% and Ca, Na, and Ba are selectively added. In this case, it is possible to further improve the corrosion resistance of the processed part and the cut part as compared with the addition of Mg alone, but the bending workability is still not taken into consideration.
ここに、高曲げ加工性のZn−Al系めっき鋼板について、特許文献３には、16〜28mass％の中濃度のAlにMgを選択添加した溶融めっき鋼板に、５％以上の圧下率で冷間圧延を施すことが記載されている。しかしながら、特許文献３の技術は、主に制振性を向上するためのものであり、さらに、ここで述べられている曲げ加工性はプレス成形性に関する機械的性質であり、めっき層の曲げ曲げ加工性は何ら考慮されていない。
本発明は、Mgを添加して耐食性を向上したZn−Al系合金めっき鋼板において、さらに曲げ曲げ加工性をも改善する手法を確立することによって、耐食性および曲げ曲げ加工性に共に優れた溶融Zn−Al系めっき鋼板を、その製造方法に併せて提供することを目的とするものである。 The present invention is a Zn-Al alloy-plated steel sheet that has been improved in corrosion resistance by adding Mg, and by establishing a technique for further improving the bending and bending workability, molten Zn that is excellent in both corrosion resistance and bending and bending workability. The purpose of the present invention is to provide an Al-based plated steel sheet together with its manufacturing method.
発明者らは、Zn−0.14mass％Al、Zn−６mass％Al、Zn−11mass％Al、Zn−22％Al−0.5mass％Si、Zn−45mass％Al−1.3mass％SiおよびZn−55mass％Al−1.6mass％Siの各組成を有する溶融めっき浴に、Zn−20mass％MgまたはAl−10mass％Mg母合金を適宜用いてMgを最高５mass％まで順次増量しながら、片面めっき厚が20±2.5μmとなるようにめっきを施したのち、JIS Ｚ2248−1996に規定される密着曲げに準拠して、鋼板に０Ｔ曲げを行った加工部および切断部とそれ以外の平面部の耐食性を、JIS Ｋ5621−2003耐複合サイクル防食性に準拠した、複合サイクル腐食試験により調査した。
この調査によれば、特に加工部の耐食性が他よりも劣ることが判明した。そこで、各めっき鋼板について、０Ｔ曲げを行っためっき層の曲げ加工部を実体顕微鏡で観察したところ、めっき層にクラックが発生していることが判明した。
The inventors have made Zn-0.14 mass% Al, Zn-6 mass% Al, Zn-11 mass% Al, Zn-22% Al-0.5 mass% Si, Zn-45 mass% Al-1.3 mass% Si and Zn-55 mass%. One-side plating thickness is 20 ± while increasing the Mg up to 5 mass% by using Zn-20mass% Mg or Al-10mass% Mg master alloy as appropriate in the hot dipping bath having each composition of Al-1.6mass% Si. After plating to 2.5 μm, the corrosion resistance of the processed and cut parts where the steel sheet was subjected to 0T bending and other flat parts was determined according to JIS Z2248-1996. It investigated by the combined cycle corrosion test based on K5621-2003 combined cycle corrosion resistance.
According to this investigation, it was found that the corrosion resistance of the processed part was inferior to that of others. Then, about each plating steel plate, when the bending process part of the plating layer which performed 0T bending was observed with the stereomicroscope, it turned out that the crack has generate | occur | produced in the plating layer.
さらに、この原因について鋭意究明したところ、Mgを添加した場合に生じる、MgZn2、Mg2Si、Zn／Al／MgZn2共晶など、Mg系金属間化合物の単独または複合組織が粗大化し、これら組織がクラックの起点となることを知見した。
以上の知見に基づき、さらに実験を重ねた結果、通常はめっき層中に均一に存在するMgが、めっき層の表面およびその近傍に濃化していると、曲げ曲げ加工性が向上することを新たに見出した。
Furthermore, as a result of earnest investigation on the cause, Mg-based intermetallic compounds such as MgZn 2 , Mg 2 Si, Zn / Al / MgZn 2 eutectic, etc., which are generated when Mg is added, are coarsened, and these microstructures become coarse. It was found that the structure was the starting point of cracks.
Based on the above knowledge, as a result of further experiments, it was found that the bending and bending workability is improved when Mg, which is normally present in the plating layer, is concentrated on the surface of the plating layer and its vicinity. I found it.
本発明は、上記の知見に立脚するものである。すなわち、本発明の要旨構成は次のとおりである。
（１）鋼板の表面にZn−Al系合金めっき層を有する溶融めっき鋼板において、該めっき層は、Al：15mass％以上40mass％未満、Si：（0.0005×〔mass％Al〕）〜（0.05×〔mass％Al〕）mass％およびMg：0.005〜３mass％を含有し、残部はZnおよび不可避的不純物の成分組成を有し、かつ、めっき層の表層におけるMg濃度が、めっき層の平均Mg濃度よりも高いことを特徴とする耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板。
The present invention is based on the above findings. That is, the gist configuration of the present invention is as follows.
(1) In a hot-dip plated steel sheet having a Zn-Al alloy plated layer on the surface of the steel sheet, the plated layer is made of Al: 15 mass% or more and less than 40 mass%, Si: (0.0005 × [mass% Al]) to (0.05 × [Mass% Al]) mass% and Mg: 0.005 to 3 mass%, the balance has a component composition of Zn and inevitable impurities, and the Mg concentration in the surface layer of the plating layer is the average Mg concentration of the plating layer A hot-dip Zn-Al alloy-plated steel sheet excellent in corrosion resistance and bending workability, characterized by being higher than that.
（２）前記めっき層の表層におけるMg濃度が、めっき層の平均Mg濃度の２倍以上であることを特徴とする上記（１）に記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板。 (2) The molten Zn-Al system having excellent corrosion resistance and bending workability as described in (1) above, wherein the Mg concentration in the surface layer of the plating layer is at least twice the average Mg concentration of the plating layer Alloy-plated steel sheet.
（３）鋼板の表面にZn−Al系合金めっき層を有する溶融めっき鋼板において、該めっき層は、Al：15mass％以上40mass％未満およびSi：（0.0005×〔mass％Al〕）〜（0.05×〔mass％Al〕）mass％を含み、さらにMgとMg含有量の1/2以下のCaとを合計で0.005〜３mass％含有し、残部はZnおよび不可避的不純物の成分組成を有し、かつめっき層の表層におけるMgおよびCaの合計濃度がめっき層のMgおよびCaの合計濃度の平均よりも高いことを特徴とする耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板。 (3) In the hot dip galvanized steel sheet having a Zn-Al based alloy plating layer on the surface of the steel sheet, the plating layer includes Al: 15 mass% or more and less than 40 mass%, and Si: (0.0005 × [mass% Al]) to (0.05 × [Mass% Al]) containing mass%, further containing 0.005 to 3 mass% of Mg and Ca less than or equal to 1/2 of the Mg content, the balance having a composition of Zn and inevitable impurities, and A molten Zn-Al alloy-plated steel sheet excellent in corrosion resistance and bending workability, characterized in that the total concentration of Mg and Ca in the surface layer of the plating layer is higher than the average of the total concentration of Mg and Ca in the plating layer.
（４）前記めっき層の表層におけるMgおよびCaの合計濃度が、めっき層のMgおよびCaの合計濃度の平均の２倍以上であることを特徴とする上記（３）に記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板。
ここで、上記めっき層の表層とは、めっき表面から、めっき厚の１／５深さまでと定義する。
(4) Corrosion resistance and bending as described in (3) above, wherein the total concentration of Mg and Ca in the surface layer of the plating layer is at least twice the average of the total concentration of Mg and Ca in the plating layer Hot-dip Zn-Al alloy-plated steel sheet with excellent properties.
Here, the surface layer of the plating layer is defined as from the plating surface to 1/5 depth of the plating thickness.
（５）前記めっき層は、さらにCr，Mn，NiおよびCoのうちから選ばれる１種または２種以上を合計で0.002〜２mass％含有することを特徴とする上記（１）〜（４）のいずれかに記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板。 (5) The plating layer further includes 0.002 to 2 mass% of one or more selected from Cr, Mn, Ni and Co in total of 0.002 to 2 mass%. A hot-dip Zn-Al alloy-plated steel sheet excellent in corrosion resistance and bending workability according to any one of the above.
（６）Al：15mass％以上40mass％未満およびSi：（0.0005×〔mass％Al〕）〜（0.05×〔mass％Al〕）mass％を含み、残部はZnおよび不可避的不純物の組成になる溶融めっき浴に、鋼板を浸漬してめっき層を形成し、次いで鋼板をめっき浴から引き上げたのち、めっき層が凝固するまでの間に、Mgイオンを0.1mol／リットル以上含有する溶液をめっき層の表面に付着させることを特徴とする耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板の製造方法。 (6) Al: 15 mass% or more and less than 40 mass% and Si: (0.0005 × [mass% Al]) to (0.05 × [mass% Al]) mass%, with the balance being the composition of Zn and inevitable impurities After the steel plate is immersed in the plating bath to form a plating layer, and after the steel plate is pulled out of the plating bath, a solution containing 0.1 mol / liter or more of Mg ions is added to the plating layer until the plating layer solidifies. A method for producing a hot-dip Zn-Al alloy-plated steel sheet having excellent corrosion resistance and bending workability, characterized by adhering to a surface.
（７）Al：15mass％以上40mass％未満およびSi：（0.0005×〔mass％Al〕）〜（0.05×〔mass％Al〕）mass％を含み、残部はZnおよび不可避的不純物の組成になる溶融めっき浴に、鋼板を浸漬してめっき層を形成し、次いで鋼板をめっき浴から引き上げたのち、めっき層が凝固するまでの間に、MgイオンおよびMgイオンの1/2以下の量のCaイオンを合計で0.1mol／リットル以上含有する溶液をめっき層の表面に付着させることを特徴とする耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板の製造方法。 (7) Al: 15 mass% or more and less than 40 mass% and Si: (0.0005 × [mass% Al]) to (0.05 × [mass% Al]) mass%, with the balance being a composition of Zn and inevitable impurities After the steel plate is immersed in the plating bath to form a plating layer, and then the steel plate is lifted from the plating bath, the amount of Ca ions is less than 1/2 of the Mg ions and Mg ions until the plating layer solidifies. A method for producing a hot-dip Zn-Al alloy-plated steel sheet excellent in corrosion resistance and bending workability, characterized in that a solution containing 0.1 mol / liter or more in total is adhered to the surface of the plating layer.
（８）前記めっき浴に、さらにMg：0.005〜１mass％を添加することを特徴とする上記（６）または（７）に記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板の製造方法。 (8) The molten Zn-Al alloy-plated steel sheet having excellent corrosion resistance and bending workability according to (6) or (7), wherein Mg: 0.005 to 1 mass% is further added to the plating bath. Manufacturing method.
（９）前記めっき浴に、さらにMgとMg含有量の1/2以下のCaとを合計で0.005〜１mass％添加することを特徴とする上記（６）または（７）に記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板の製造方法。 (9) Corrosion resistance and bending as described in (6) or (7) above, wherein 0.005 to 1 mass% of Mg and less than 1/2 of Mg content are further added to the plating bath. Manufacturing method of hot-dip Zn-Al alloy-plated steel sheet with excellent workability.
（１０）前記めっき浴に、さらにCr，Mn，NiおよびCoのうちから選ばれる１種または２種以上を合計で0.002〜２mass％添加することを特徴とする上記（６）〜（９）のいずれかに記載の耐食性および曲げ加工性に優れた溶融Zn−Al系合金めっき鋼板の製造方法。 (10) In the above (6) to (9), one or more selected from Cr, Mn, Ni and Co are further added to the plating bath in a total amount of 0.002 to 2 mass%. The manufacturing method of the hot-dip Zn-Al type alloy plating steel plate excellent in corrosion resistance and bending workability in any one.
本発明によれば、優れた耐食性および曲げ曲げ加工性を兼ね備えた溶融Zn−Al系めっき鋼板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the hot-dip Zn-Al system plated steel plate which has the outstanding corrosion resistance and bending workability can be provided.
以下、本発明の溶融Zn−Al系合金めっき鋼板について、具体的に説明する。まず、めっき層の成分組成から順に述べる。
Al：15mass％以上40mass％未満
Alの含有量が15mass％より少ないと、耐食性が劣化し、Zn−55％Al−1.6％Siめっき鋼板と同等レベル程度の耐食性しか得られなくなるため、15mass％以上とする。一方、40mass％以上では、めっきのままでは曲げ曲げ加工性に劣るものとなる。より好適な範囲は、微細な共析組織を得やすい18〜25mass％である。
Hereinafter, the hot-dip Zn-Al alloy-plated steel sheet of the present invention will be specifically described. First, the component composition of the plating layer will be described in order.
Al: 15mass% or more and less than 40mass%
If the Al content is less than 15 mass%, the corrosion resistance deteriorates and only the corrosion resistance equivalent to that of a Zn-55% Al-1.6% Si-plated steel sheet can be obtained. On the other hand, if it is 40 mass% or more, it is inferior in bending and bending workability as it is plated. A more preferable range is 18 to 25 mass% at which a fine eutectoid structure is easily obtained.
Si：（0.0005×〔mass％Al〕）〜（0.05×〔mass％Al〕）mass％
Siは、鋼板とAlとの合金化を抑制するために添加する元素であり、（0.0005×〔mass％Al〕）mass％より少ないと合金層が生成し、この合金層を起点としてめっき層厚み方向にクラックが発生しやすくなるため、曲げ加工性が劣化する。よってSiは（0.0005×〔mass％Al〕）mass％以上とする。逆に、（0.05×〔mass％Al〕）mass％より多いと、Mg2Siが粗大化しやすくなり、曲げ曲げ加工性が劣化し、さらには加工部および切断部の耐食性が劣化するため、（0.05×〔mass％Al〕）mass％以下とする。より好適な範囲は、（0.005〜0.03）×〔mass％Al〕である。
Si: (0.0005 × [mass% Al]) to (0.05 × [mass% Al]) mass%
Si is an element added to suppress alloying between the steel sheet and Al, and if less than (0.0005 × [mass% Al]) mass%, an alloy layer is formed, and the plating layer thickness starts from this alloy layer. Since cracks tend to occur in the direction, bending workability deteriorates. Therefore, Si is set to (0.0005 × [mass% Al]) mass% or more. On the other hand, if it is more than (0.05 × [mass% Al]) mass%, Mg 2 Si tends to be coarsened, the bending workability deteriorates, and further the corrosion resistance of the processed part and the cut part deteriorates. 0.05 × [mass% Al]) mass% or less. A more preferable range is (0.005 to 0.03) × [mass% Al].
Mg：0.005〜３mass％
Mgは、特に加工部および切断部の耐食性を改善させることができる。そのメカニズムは必ずしも明らかではないが、0.005〜３mass％の範囲において有効である。すなわち、0.005mass％より少ないと、耐食性の改善効果が認められない。一方、３mass％を超えると、めっき層が凝固する間にMg，CaとZnまたはSiの金属間化合物の単独またはZn／Alとの共晶組織が粗大析出しやすくなり、曲げ曲げ加工性、さらに加工部および切断部の耐食性が劣化する。より好適な範囲は、0.05〜２mass％である。
Mg: 0.005-3 mass%
Mg can particularly improve the corrosion resistance of the processed part and the cut part. Although the mechanism is not necessarily clear, it is effective in the range of 0.005 to 3 mass%. That is, when it is less than 0.005 mass%, the effect of improving the corrosion resistance is not recognized. On the other hand, if it exceeds 3 mass%, the eutectic structure of Mg, Ca and Zn or Si intermetallic compound alone or Zn / Al tends to precipitate during the solidification of the plating layer, and bending and bending workability, Corrosion resistance of processed parts and cut parts deteriorates. A more preferable range is 0.05 to 2 mass%.
MgとMg含有量の1/2以下のCaとを合計で0.005〜３mass％
Mg とともに、Caを複合して添加することにより、さらに加工部および切断部の耐食性を改善させることができる。なお、合計添加量における上下限の限定理由は、上記Mgの単独添加の場合と同様である。
なお、Caの含有量は、Mg含有量の1/2以下とする。なぜなら、Caは、単独添加では耐食性改善効果がなく、理由は必ずしも明らかではないが、Mgとともに少量添加することで耐食性が改善され、Caの含有量が、Mgの1/2を超えると、複合添加による耐食性の改善効果が乏しくなるからである。
0.005-3 mass% in total of Mg and Ca less than 1/2 of Mg content
By adding Ca in combination with Mg, the corrosion resistance of the processed part and the cut part can be further improved. In addition, the reason for limiting the upper and lower limits in the total addition amount is the same as in the case of adding Mg alone.
Note that the Ca content is 1/2 or less of the Mg content. This is because Ca does not have an effect of improving corrosion resistance when added alone, and the reason is not necessarily clear, but adding a small amount together with Mg improves the corrosion resistance, and if the Ca content exceeds 1/2 of Mg, This is because the effect of improving the corrosion resistance by the addition becomes poor.
ここで、めっき層の表層におけるMg濃度がめっき層の平均Mg濃度よりも高いこと、つまり（めっき層の表層のMg濃度）／（めっき層の平均Mg濃度）比が1.0超であることが肝要である。なぜなら、Mgを添加した場合の曲げ曲げ加工性の劣化は、上記したMg系金属間化合物組織の粗大化に起因していることは上述の通りであり、このMg系金属間化合物組織の粗大化は、Mg濃度を、めっき層の表面およびその近傍に濃化することによって、回避することができるからである。 Here, it is important that the Mg concentration in the surface layer of the plating layer is higher than the average Mg concentration in the plating layer, that is, the ratio of (Mg concentration in the surface layer of the plating layer) / (Average Mg concentration in the plating layer) is more than 1.0. It is. This is because the deterioration of the bending workability when Mg is added is due to the coarsening of the Mg-based intermetallic structure described above, and the coarsening of this Mg-based intermetallic structure. This is because the Mg concentration can be avoided by concentrating on the surface of the plating layer and in the vicinity thereof.
なお、めっき層の表層におけるMg濃度が、めっき層の平均Mg濃度の２倍以上であることがより好ましい。 In addition, it is more preferable that the Mg concentration in the surface layer of the plating layer is at least twice the average Mg concentration of the plating layer.
また、Mg とともに、Caを複合して添加する場合は、Mgの単独添加の場合と同様、めっき層の表層におけるMgおよびCaの合計濃度を、めっき層のMgおよびCaの合計濃度の平均よりも高く、つまり（めっき層の表層のMg＋Ca濃度）／（めっき層の平均Mg＋Ca濃度）比を1.0超とする。より好ましくは、めっき層の表層におけるMgおよびCaの合計濃度を、めっき層のMgおよびCaの合計濃度の平均の２倍以上とする。Mg単独と同様に、めっき層の表面およびその近傍にMgおよびCaが濃化することによって、上記Mg系金属間化合物組織の粗大化を回避することができるからである。 In addition, when adding Ca together with Mg, as in the case of adding Mg alone, the total concentration of Mg and Ca in the surface layer of the plating layer is more than the average of the total concentration of Mg and Ca in the plating layer. That is, the ratio of (Mg + Ca concentration of the surface layer of the plating layer) / (Average Mg + Ca concentration of the plating layer) is more than 1.0. More preferably, the total concentration of Mg and Ca in the surface layer of the plating layer is at least twice the average of the total concentration of Mg and Ca in the plating layer. This is because, as in the case of Mg alone, when Mg and Ca are concentrated on the surface of the plating layer and in the vicinity thereof, coarsening of the Mg-based intermetallic compound structure can be avoided.
本発明では、さらに耐食性の向上を目的として、Cr，Mn，NiおよびCoのうちから選ばれる１種または２種以上を合計で0.002〜２mass％添加してもよい。添加量が0.002mass％より少ないと、耐食性の向上効果が認められず、２mass％より多いと、浴温が上昇し、ドロスも大量発生するので、操業性が著しく低下する。より好適な範囲は0.01〜1.0mass％である。 In the present invention, for the purpose of further improving the corrosion resistance, one or more selected from Cr, Mn, Ni and Co may be added in a total amount of 0.002 to 2 mass%. When the amount added is less than 0.002 mass%, the effect of improving the corrosion resistance is not recognized. When the amount added is more than 2 mass%, the bath temperature rises and dross is generated in large quantities, so that the operability is remarkably lowered. A more preferable range is 0.01 to 1.0 mass%.
なお、Cr，Mn，NiおよびCoのうちから選ばれる１種または２種以上を添加する場合は、ドロスの発生を抑えめっき性を改善する目的で、Srを0.002〜0.1mass％添加することができる。これより少ないと効果がなく、多すぎるとめっき層中にSrが粗大析出し、耐食性が低下するので好ましくない。好適範囲は、上記金属元素の添加量（mass％）の0.005〜0.02mass％である。 When adding one or more selected from Cr, Mn, Ni and Co, 0.002 to 0.1 mass% of Sr may be added for the purpose of suppressing the generation of dross and improving the plating property. it can. If it is less than this, there will be no effect, and if it is too much, Sr will coarsely precipitate in the plating layer and the corrosion resistance will decrease, which is not preferred. A suitable range is 0.005 to 0.02 mass% of the amount of addition (mass%) of the metal element.
次に、上記しためっき層組織とするための製造方法について説明する。
まず、本発明における被めっき鋼板としては、通常の方法で製造した鋼板、たとえば低炭素アルミキルド鋼板や極低炭素鋼板等がいずれも好適に使用できる。本発明では、これらの鋼板を溶融Zn−Al系合金めっき浴に浸漬する、いわゆる熱浸めっきを行い、該鋼板をめっき浴から引き上げてガスワイピング等で付着量を調整した後、冷却し溶融Zn−Al系合金めっき層を形成する。
Next, a manufacturing method for obtaining the above-described plating layer structure will be described.
First, as the steel plate to be plated in the present invention, any steel plate produced by a normal method, for example, a low carbon aluminum killed steel plate or an ultra low carbon steel plate can be suitably used. In the present invention, these steel sheets are immersed in a molten Zn-Al alloy plating bath, so-called hot immersion plating is performed, the steel sheet is pulled up from the plating bath, the amount of adhesion is adjusted by gas wiping, etc., and then cooled and molten Zn. -An Al alloy plating layer is formed.
この溶融Zn−Al系合金めっき浴の浴組成は、Alを15mass％以上40mass％未満、そしてSiをAl量（mass％）の（0.0005〜0.05）倍の範囲で含有し、残部はZnおよび不可避的不純物の組成になるように調整しなければならない。この不可避的不純物とは、Fe，Pb，Sn，Cd等であり、これらは合計で0.05mass％を超えることは好ましくない。 The bath composition of this hot-dip Zn-Al alloy plating bath contains 15 mass% or more and less than 40 mass% of Al, and Si in the range of (0.0005 to 0.05) times the amount of Al (mass%), with the balance being Zn and inevitable It must be adjusted so as to obtain a composition of the target impurities. The inevitable impurities are Fe, Pb, Sn, Cd, etc., and it is not preferable that these total exceed 0.05 mass%.
ここで、本発明になるめっき層は、Mgを必須とし、必要に応じてMgの１／２のCaを合計で0.005〜３mass％を含有し、しかもめっき表層のMgまたは、MgおよびCaの合計濃度をめっき層の平均濃度より高くするところに特徴があることから、上記めっき浴から引き上げ後の鋼板に対して、そのめっき層が凝固するまでの間に、Mgイオンを必須として、必要に応じてMgイオンの1/2以下の量のCaイオンを合計で0.01mol／リットル以上含有する溶液を、当該めっき層の表面に付着させることが、肝要である。 Here, the plating layer according to the present invention essentially contains Mg, and if necessary, contains a total of 0.005 to 3 mass% of Ca that is 1/2 of Mg, and furthermore, Mg of the plating surface layer or the total of Mg and Ca Since the concentration is higher than the average concentration of the plating layer, Mg ions are indispensable for the steel plate after being pulled up from the plating bath until the plating layer solidifies, and if necessary Thus, it is important to attach a solution containing a total of 0.01 mol / liter or more of Ca ions in an amount of 1/2 or less of Mg ions to the surface of the plating layer.
めっき層に付着させる溶液におけるMg濃度または、MgおよびCaの合計濃度は、0.1mol／リットル未満ではめっき表層のMgまたは、MgおよびCaの合計濃度をめっき層の平均濃度より高くすることが難しくなる。一方、溶液におけるMg濃度または、MgおよびCaの合計濃度が3.5mol／リットルを超えると、溶液を噴霧するためのノズルが詰まりやすくなるので、3.5mol／リットル以下とすることが好ましい。
なお、MgおよびCaは、これらの塩化物を添加して溶液に含有させることが好ましい。また、MgまたはMgおよびCaを含有する溶液は水溶液であることが好ましいが、水以外の溶媒を含んでいてもよい。
If the Mg concentration or the total concentration of Mg and Ca in the solution adhered to the plating layer is less than 0.1 mol / liter, it is difficult to make the total concentration of Mg or Mg and Ca on the plating surface layer higher than the average concentration of the plating layer. . On the other hand, when the Mg concentration in the solution or the total concentration of Mg and Ca exceeds 3.5 mol / liter, the nozzle for spraying the solution is likely to be clogged, and therefore it is preferably 3.5 mol / liter or less.
In addition, it is preferable to add Mg and Ca to the solution by adding these chlorides. The solution containing Mg or Mg and Ca is preferably an aqueous solution, but may contain a solvent other than water.
また、上記めっき浴には、耐食性のさらなる改善を目的に、Mgを単独で、または MgおよびCaを複合して、添加することができる。すなわち、Mgまたは、MgおよびCaをめっき浴に添加する場合は、Mg単独または、MgおよびMgの１／２のCaを合計で0.005〜１mass％の範囲で添加する。ここで、１mass％を超えると、めっき層の凝固途中にて、MgおよびCaとZnおよびSiとの金属間化合物が粗大に析出しやすくなり、一方0.005mass％未満では、耐食性改善の効果が認められなくなるからである。さらにCaの添加量が、Mgの１／２を超えると、複合添加による耐食性の改善効果が小さくなるからである。 In addition, Mg can be added to the plating bath alone or in combination with Mg and Ca for the purpose of further improving the corrosion resistance. That is, when adding Mg or Mg and Ca to the plating bath, Mg alone or 1/2 of Mg and Mg is added in a range of 0.005 to 1 mass% in total. Here, if it exceeds 1 mass%, an intermetallic compound of Mg, Ca, Zn, and Si tends to precipitate coarsely during the solidification of the plating layer, while if it is less than 0.005 mass%, an effect of improving corrosion resistance is recognized. It is because it becomes impossible. Further, when the Ca addition amount exceeds 1/2 of Mg, the effect of improving the corrosion resistance by the composite addition becomes small.
さらに、耐食性の向上の観点から、必要に応じてCr、Mn、NiおよびCoのうちから選ばれる１種または２種以上を添加することができる。耐食性の向上を期待するには、少なくとも１種または２種以上の合計が0.002mass％以上であることが好ましく、一方
操業性の観点からは２mass％以下、より好ましくは１mass％以下とするとよい。
Furthermore, from the viewpoint of improving corrosion resistance, one or more selected from Cr, Mn, Ni and Co can be added as necessary. In order to expect improvement in corrosion resistance, the total of at least one or two or more is preferably 0.002 mass% or more, and from the viewpoint of operability, it is preferably 2 mass% or less, more preferably 1 mass% or less.
なお、めっき鋼板の冷却後、コイル巻取りまでの間に形状矯正を目的としたテンションレベラー、めっき表面の平滑化を目的としたスキンパス圧延を必要に応じて行うことができる。さらに、化成処理と一層または二層のカラー塗装を行うこともできる。 In addition, the tension leveler for the purpose of shape correction and the skin pass rolling for the purpose of smoothing the plating surface can be performed as needed after cooling the plated steel sheet and before winding the coil. Furthermore, a chemical conversion treatment and one or two layers of color coating can be performed.
Ｃ：0.039mass％、Si：0.012mass％、Mn：0.15mass％、Ｓ：0.008mass％およびAl：0.022mass％を含有し、残部はFeおよび不可避的不純物の組成になる、板厚：0.8mmの低炭素アルミキルド鋼板に、連続式溶融めっき設備によって、溶融Zn−Al合金めっきを施した。溶融めっき浴は、99.99mass％Zn、Alインゴット、25mass％Si−Al、20mass％Mg−Zn、1.2mass％Cr−Zn、５mass％Cr−Al、10mass％Mn−Zn、５mass％Ni−Zn、そして5.5mass％Co−Znの各合金インゴットを用いた。めっき浴およびめっき層の組成分析結果を、表１に示す。 Contains C: 0.039 mass%, Si: 0.012 mass%, Mn: 0.15 mass%, S: 0.008 mass%, and Al: 0.022 mass%, the balance being the composition of Fe and inevitable impurities, Plate thickness: 0.8 mm The low-carbon aluminum killed steel plate was subjected to hot-dip Zn-Al alloy plating using a continuous hot-dip plating facility. The hot dipping bath is 99.99 mass% Zn, Al ingot, 25 mass% Si-Al, 20 mass% Mg-Zn, 1.2 mass% Cr-Zn, 5 mass% Cr-Al, 10 mass% Mn-Zn, 5 mass% Ni-Zn, Each alloy ingot of 5.5 mass% Co—Zn was used. Table 1 shows the composition analysis results of the plating bath and the plating layer.
めっき処理は、めっき浴への浸漬時間を約１秒とし、目標めっき層厚（片面当たり）が20μmとなるようにめっき付着量をワイパーによって制御して行った。このめっき処理において、鋼板をめっき浴から引き上げたのち、めっき層の凝固が完了するまでの間に、表２に示す濃度で塩化Mgを脱イオン水に添加した水溶液を、めっき層表面に１〜３秒間噴霧しながら冷却した。 The plating treatment was performed by setting the amount of plating adhesion with a wiper so that the immersion time in the plating bath was about 1 second and the target plating layer thickness (per one side) was 20 μm. In this plating treatment, an aqueous solution in which Mg chloride is added to deionized water at a concentration shown in Table 2 until the solidification of the plating layer is completed after the steel plate is lifted from the plating bath is applied to the surface of the plating layer. Cooled while spraying for 3 seconds.
かくして得られた溶融Zn−Al系合金めっき鋼板から、めっき層の組成分析用に幅50mmおよび長さ50mmの試験片を各２枚ずつ採取し、また平面部、曲げ加工部、切断部の耐食性評価用に幅70mmおよび長さ150mmの試験片を各３枚ずつ採取した。 Two specimens each having a width of 50 mm and a length of 50 mm were collected from the hot-dip Zn-Al alloy-plated steel sheet thus obtained for composition analysis of the plating layer, and the corrosion resistance of the flat part, the bent part and the cut part. Three test pieces each having a width of 70 mm and a length of 150 mm were collected for evaluation.
なお、めっき層の組成は、1枚をそのまま、もう1枚を表面から１／５深さまでを研削で除去した後に、裏面をシール後、ISO溶解液（塩酸50mass％水溶液＋0.35mass％ヘキサメチレンテトラミン）30mlに浸漬してめっき層のみを溶解した溶解液を水100mlで希釈し、ICP発光分光分析法により定量した。表面から１／５深さまでの表層およびめっき層平均のMg濃度の比は以下の式から求めた。
Ｓ／ａ＝５−４ｂ／ａ
ここに、Ｓはめっき表面から１／５深さまでのMg濃度の計算値、ａはめっき層全体の平均のMgの定量結果（mass％）、ｂは表面から１／５深さまでを除去した試料からのMgの定量結果(mass％)である。
The composition of the plating layer is as follows: one sheet is left as it is, the other sheet is removed by grinding to 1/5 depth from the front surface, the back surface is sealed, and then the ISO solution (50 mass% hydrochloric acid aqueous solution + 0.35 mass% hexamethylene) is sealed. A solution obtained by dissolving only the plating layer by immersing in 30 ml of tetramine) was diluted with 100 ml of water and quantified by ICP emission spectroscopy. The ratio of the average Mg concentration of the surface layer and the plating layer from the surface to 1/5 depth was obtained from the following equation.
S / a = 5-4b / a
Here, S is a calculated value of Mg concentration from the plating surface to 1/5 depth, a is a quantitative result (mass%) of average Mg of the entire plating layer, and b is a sample from which 1/5 depth is removed from the surface. Is the quantitative result (mass%) of Mg from
耐食性の評価は、平面部と曲げ加工部用の試験片の裏面とエッジをテープシールした。曲げ加工部用は、さらに長さ75mm位置でJIS Ｚ2248−1996に規定される密着曲げに準拠して０Ｔ曲げを行い、曲げた外側の部位を、また切断部用の試験片は長手方向の両側面部が下バリとなるように切断し、その裏面と上下側面部とをテープで覆い、JIS Ｋ5621−2003耐複合サイクル防食性に準拠したサイクルに設定した複合サイクル腐食試験装置に入れ、面積率で５％赤錆発生までの時間（サイクル数）を測定した。このサイクル数が300以上であれば、優れた耐食性が得られていると判断できる。 For the evaluation of corrosion resistance, the back surface and the edge of the test piece for the flat portion and the bent portion were tape-sealed. For the bent part, further, 0T bend is performed at 75mm length in accordance with the close contact bending specified in JIS Z2248-1996, the outer part is bent, and the test piece for the cut part is on both sides in the longitudinal direction. Cut the surface part to become a lower burr, cover the back and upper and lower side parts with tape, put it in a combined cycle corrosion tester set to a cycle conforming to JIS K5621-2003 combined cycle anti-corrosion resistance, and by area ratio The time until the occurrence of 5% red rust (number of cycles) was measured. If the number of cycles is 300 or more, it can be determined that excellent corrosion resistance is obtained.
さらに、溶融Zn−Al系合金めっき鋼板から、めっき層の曲げ曲げ加工性評価用に幅70mmおよび長さ100mmの試験片を各５枚ずつ採取し、長さ50mm位置でJIS Ｚ2248−1996に規定される密着曲げに準拠して０Ｔ曲げ試験に供して、曲げ外側の部位を真上から100倍の実体顕微鏡で１試験片について１視野を観察し、次に示す５段階レベルの評価をし、５試験片計５視野の平均を求めた。
評価５：クラック全くなし
評価４：鋼素地まで達しないヘアクラックが１本／視野〜10本／視野
評価３：鋼素地まで達しないヘアクラックが11本／視野以上（ただし、鋼素地に達する粗大クラックなし）
評価２：鋼素地まで達する粗大クラックが１本／視野〜５本／視野
評価１：鋼素地まで達する粗大クラックが６本／視野以上
Furthermore, five specimens each having a width of 70mm and a length of 100mm were collected from the hot-dip Zn-Al alloy-plated steel sheet for the evaluation of the bending and bending workability of the plating layer, and specified in JIS Z2248-1996 at a length of 50mm. In accordance with the close contact bending, a 0T bending test was performed, and one field of view was observed for one test piece with a stereomicroscope at a magnification of 100 times from directly above, and the following five-level evaluation was performed. The average of 5 visual fields of 5 specimens was determined.
Evaluation 5: No crack at all Evaluation 4: One hair crack that does not reach the steel substrate / 10 to 10 / field of view Evaluation 3: 11 hair cracks that do not reach the steel substrate / more than the visual field (however, the coarse that reaches the steel substrate) No crack)
Evaluation 2: One coarse crack reaching the steel substrate / one field of view to five / field of view Evaluation 1: Six coarse cracks reaching the steel substrate / more than the field of view
以上の測定並びに評価の各結果を、表３に示す。同表から、本発明により、平面部曲げ加工部および切断部の耐食性がともに優れ、かつめっき層の曲げ加工性にも優れた溶融Zn−Al系合金めっき鋼板が得られることがわかる。 Table 3 shows the results of the above measurements and evaluations. From the same table, it can be seen that the present invention can provide a hot-dip Zn-Al alloy-plated steel sheet that has excellent corrosion resistance at both the flat-surface bent portion and the cut portion and is excellent in the bending property of the plating layer.
Ｃ：0.0012mass％、Mn：0.10mass％、Ｓ：0.007mass％およびAl：0.023mass％を含有し、残部はFeおよび不可避的不純物の組成になる、板厚：0.8mmの極低炭素アルミキルド鋼板に、連続式溶融めっき設備によって、溶融Zn−Al合金めっきを施した。溶融めっき浴は、99.99mass％Zn、Alインゴット、25mass％Si−Al、10mass％Ca−Al、20mass％Mg−Zn、1.2mass％Cr−Zn、５mass％Cr−Al、10mass％Mn−Zn、５mass％Ni−Zn、そして5.5mass％Co−Znの各合金インゴットを用いた。めっき浴およびめっき層の組成分析結果を表４に示す。 C: 0.0012 mass%, Mn: 0.10 mass%, S: 0.007 mass% and Al: 0.023 mass%, with the balance being Fe and inevitable impurities, ultra-low carbon aluminum killed steel sheet with a thickness of 0.8 mm In addition, hot-dip Zn-Al alloy plating was performed using a continuous hot-dip plating facility. The hot dipping bath is 99.99 mass% Zn, Al ingot, 25 mass% Si-Al, 10 mass% Ca-Al, 20 mass% Mg-Zn, 1.2 mass% Cr-Zn, 5 mass% Cr-Al, 10 mass% Mn-Zn, Each alloy ingot of 5 mass% Ni-Zn and 5.5 mass% Co-Zn was used. Table 4 shows the composition analysis results of the plating bath and the plating layer.
めっき処理は、めっき浴への浸漬時間を約１秒とし、目標めっき層厚（片面当たり）が20μmとなるようにめっき付着量をワイパーによって制御して行った。このめっき処理において鋼板をめっき浴から引き上げたのち、めっき層の凝固が完了するまでの間に、表５に示す濃度で塩化Mg、塩化Caを脱イオン水に添加した水溶液を、めっき層表面に１〜３秒間噴霧しながら冷却した。
その後、実施例１と同様にして、Ｓ／ａ、平面部、０Ｔ曲げ加工部および切断端面部（下バリ）の耐食性を評価するとともに、曲げ加工性も評価した。その測定並びに評価結果を、表６に示す。
同表から本発明により、平面部、曲げ加工部および切断部の耐食性がともに優れ、かつめっき層の曲げ加工性にも優れた溶融Zn−Al系合金めっき鋼板が得られることがわかる。
The plating treatment was performed by setting the amount of plating adhesion with a wiper so that the immersion time in the plating bath was about 1 second and the target plating layer thickness (per one side) was 20 μm. In this plating process, after the steel sheet is pulled out of the plating bath, an aqueous solution in which Mg chloride and Ca chloride are added to deionized water at the concentrations shown in Table 5 until the solidification of the plating layer is completed is applied to the surface of the plating layer. Cooled while spraying for 1-3 seconds.
Thereafter, in the same manner as in Example 1, the corrosion resistance of S / a, the flat surface portion, the 0T bent portion and the cut end surface portion (lower burr) was evaluated, and the bending workability was also evaluated. The measurement and evaluation results are shown in Table 6.
It can be seen from the table that the present invention provides a hot-dip Zn-Al alloy-plated steel sheet that has excellent corrosion resistance at the flat portion, the bent portion, and the cut portion, and is also excellent in the bending property of the plating layer.
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