JP2005264188A - HOT DIP Zn-Al ALLOY PLATED STEEL HAVING EXCELLENT BENDABILITY, AND ITS MANUFACTURING METHOD - Google Patents
HOT DIP Zn-Al ALLOY PLATED STEEL HAVING EXCELLENT BENDABILITY, AND ITS MANUFACTURING METHOD Download PDFInfo
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本発明は、建材、自動車、家電用途に使用される溶融めっき鋼材に関するものである。特に、主として建材用途分野で要求される高耐食性能を有し、かつ、めっき層の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材及びその製造方法に関するものである。 The present invention relates to a hot dipped steel used for building materials, automobiles, and home appliances. In particular, the present invention relates to a hot-dip Zn-Al alloy-plated steel material having high corrosion resistance, which is mainly required in the field of building material applications, and excellent in the bending workability of a plating layer, and a method for producing the same.
従来から、鋼材の表面にＺｎめっきを施して鋼材の耐食性を改善することは、広く知られており、現在もＺｎめっきが施された鋼材は、大量に生産され、使用されている。しかしながら、多くの用途に対し、Ｚｎめっきのみでは耐食性が不充分な場合が生じており、そこで、めっき層の耐食性を向上すべく、Ａｌを添加した溶融Ｚｎ−Ａｌ合金めっき鋼板（ガルバリウム鋼板）が使用されている。例えば、特公昭６１−２８７４８号公報（特許文献１）に開示されている溶融Ｚｎ−Ａｌ合金めっきは、２５〜７５質量％のＡｌと、Ａｌ含有量の０．５％以上のＳｉ、及び残部は本質的にＺｎより成る合金めっきを施し、良好な耐食性が得られている。 Conventionally, it is widely known to improve the corrosion resistance of steel materials by applying Zn plating to the surface of steel materials, and steel materials to which Zn plating has been applied are produced and used in large quantities. However, for many applications, corrosion resistance is insufficient only with Zn plating. Therefore, in order to improve the corrosion resistance of the plating layer, a molten Zn-Al alloy plated steel sheet (galvalume steel sheet) to which Al is added is provided. in use. For example, the hot-dip Zn-Al alloy plating disclosed in Japanese Patent Publication No. 61-28748 (Patent Document 1) is 25 to 75% by mass of Al, Si having an Al content of 0.5% or more, and the balance. Has been subjected to alloy plating consisting essentially of Zn, and good corrosion resistance has been obtained.
しかしながら、近年、主として建材用途分野で、更なる耐食性向上要求が生じており、これに応えるため、発明者は、既に特開２００２−３５６７５９号公報（特許文献２）に開示される、Ｚｎ−Ａｌめっき層にＣｒ、更にはＭｇを添加した合金めっき層を施す、従来の溶融Ｚｎ−Ａｌ合金めっき鋼板（ガルバリウム鋼板）を超える高耐食性のＺｎ−Ａｌ−Ｃｒ系合金めっき鋼材を開発した。しかし、このめっき鋼材を そのままもしくは塗装した後、曲げ変形を加えると、めっき層にクラックが発生し、曲げ加工部の外観を損なったり、耐食性低下原因となる問題を生じることが散見された。 However, in recent years, there has been a demand for further improvement in corrosion resistance mainly in the field of building material use. In order to meet this demand, the inventor has already disclosed Zn-Al, which is disclosed in JP-A-2002-356759 (Patent Document 2). A high corrosion resistance Zn-Al-Cr alloy-plated steel material, which exceeds the conventional hot-dip Zn-Al alloy-plated steel plate (galvalume steel plate), was developed by applying an alloy plating layer to which Cr or Mg was added to the plating layer. However, it has been found that if this plated steel material is subjected to bending deformation as it is or after coating, cracks occur in the plating layer, resulting in damage to the appearance of the bent portion or a problem that causes a decrease in corrosion resistance.
そこで、本発明は、Ｚｎ−Ａｌ−Ｃｒ系合金めっき鋼材における上記問題点を解決し、高耐食性であり、かつめっき層の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材及びその製造方法を提供することを目的とする。 Therefore, the present invention solves the above-mentioned problems in Zn-Al-Cr alloy-plated steel materials, has a high corrosion resistance and is excellent in bending workability of the plating layer, and a method for producing the same. The purpose is to provide.
発明者は、Ｚｎ−Ａｌ系合金めっき鋼材のめっき層組織、及び、製造条件とめっき層の折り曲げ加工性について、種々調査検討を行い、その結果、下記に開示する技術を適用することで、めっき層の曲げ加工性に優れるＺｎ−Ａｌ系合金めっき鋼材及びその製造方法が得られることを見出し、本発明を完成した。
（１）質量％で、Ａｌ：２５〜８５％、Ｃｒ、Ｍｎの１種又は２種：０．０５〜５％、Ｓｉ：Ａｌの含有量の０．５〜１０％を含有し、残部はＺｎ及び不可避的不純物からなるめっき層を有し、かつ、めっき表面のスパングルサイズの平均値が０．５ｍｍ以上であることを特徴とする曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材。
The inventor conducted various investigations and studies on the plating layer structure of the Zn-Al-based alloy-plated steel material, the manufacturing conditions and the bending workability of the plating layer, and as a result, by applying the technology disclosed below, plating The present inventors have found that a Zn—Al-based alloy-plated steel material excellent in layer bending workability and a method for producing the same can be obtained, and the present invention has been completed.
(1) By mass%, Al: 25 to 85%, one or two of Cr and Mn: 0.05 to 5%, Si: Al content of 0.5 to 10%, the balance being A molten Zn-Al-based alloy-plated steel material that has a plating layer made of Zn and inevitable impurities and has an excellent bending workability, characterized in that the average value of spangle sizes on the plating surface is 0.5 mm or more.
（２）前記めっき層が、Ｍｇ：０．１〜５質量％を、さらに含有することを特徴とす（１）に記載の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材。
（３）前記めっき層と鋼材との界面に、Ｃｒ、Ｍｎの１種又は２種を含有する合金化層を有することを特徴とする（１）又は（２）に記載の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材。
(2) The molten Zn—Al-based alloy-plated steel material having excellent bending workability according to (1), wherein the plating layer further contains Mg: 0.1 to 5% by mass.
(3) It has an alloying layer containing one or two of Cr and Mn at the interface between the plating layer and the steel material, and is excellent in bending workability according to (1) or (2) Hot-dip Zn-Al alloy plated steel.
（４）（１）〜（３）のいずれかに記載の溶融Ｚｎ−Ａｌ系合金めっき鋼材の製造方法であって、鋼材を、質量％で、Ａｌ：２５〜８５％、Ｃｒ、Ｍｎの１種又は２種以上：０．０５〜５％、Ｓｉ：Ａｌの含有量の０．５〜１０％を含有し、残部はＺｎ及び不可避的不純物からなるめっき浴に浸漬して、溶融めっき後、めっき層の凝固が完了する温度までのめっき鋼材の冷却速度が２０℃／ｓｅｃ以下であることを特徴とする曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材の製造方法。 (4) It is a manufacturing method of the hot dip Zn-Al system alloy plating steel materials in any one of (1)-(3), Comprising: Steel materials are mass%, Al: 25-85%, Cr, 1 of Mn Species or 2 or more types: 0.05 to 5%, Si: Al content of 0.5 to 10%, the remainder is immersed in a plating bath consisting of Zn and inevitable impurities, after hot dipping, A method for producing a molten Zn-Al alloy-plated steel material excellent in bending workability, wherein the cooling rate of the plated steel material to a temperature at which solidification of the plating layer is completed is 20 ° C / sec or less.
（５）前記めっき浴が、さらにＭｇ：０．１〜５質量％を含有することを特徴とする（４）に記載の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材の製造方法。
（６）前記溶融Ｚｎ−Ａｌ系合金めっき鋼材を、下記（１）式に規定される条件で保温することを特徴とする（４）に記載の曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材の製造方法にある。
ｙ≧７．５×１０9 ×ｔ-4.5 … （１）
（ここで、ｔは１００〜２５０℃のめっき鋼材の保温温度、ｙは保温時間（ｈｒ）を表す。）
(5) The method for producing a molten Zn-Al alloy-plated steel material having excellent bending workability according to (4), wherein the plating bath further contains Mg: 0.1 to 5% by mass.
(6) The molten Zn-Al alloy-plated steel material having excellent bending workability according to (4), wherein the molten Zn-Al alloy-plated steel material is kept warm under the conditions defined by the following formula (1): It exists in the manufacturing method of steel materials.
y ≧ 7.5 × 10 9 × t −4.5 (1)
(Here, t represents the heat retaining temperature of the plated steel material of 100 to 250 ° C., and y represents the heat retaining time (hr).)
本発明の溶融Ｚｎ−Ａｌ系合金めっき鋼材は、良好なめっき層の曲げ加工性を有するため、鋼材の曲げ加工が多々要求される建材、自動車、家電用途分野に好適に用いることができ、産業上の利用価値が極めて高い。また、本発明のめっき鋼材の製造方法は、既存の溶融めっき設備をそのまま使用することができ、製造コストの大幅な上昇を伴なうことなく、簡便に効率良く製造することができる。 Since the hot-dip Zn-Al alloy-plated steel material of the present invention has a good plating layer bending property, it can be suitably used in the fields of building materials, automobiles, and home appliances that require many bending of steel materials. The above utility value is extremely high. Moreover, the manufacturing method of the plated steel material of this invention can use the existing hot dipping equipment as it is, and can manufacture it simply and efficiently, without accompanying a significant raise in manufacturing cost.
以下、本発明を詳細に説明する。
本発明の耐食性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材は、めっき層の組成としてＡｌ：２５〜７５質量％、Ｃｒ、Ｍｎの１種又は２種：０．０５〜５質量％、Ｓｉ：Ａｌ含有量の０．５〜１０質量％を含有し、残部はＺｎ及び不可避的不純物であることを特徴とし、Ｍｇ：０．１〜５質量％を、さらに含有することが好ましい。ここで、被めっき鋼材とは、鋼板、鋼管及び鋼線等の鉄鋼材料である。
Hereinafter, the present invention will be described in detail.
The hot-dip Zn-Al alloy-plated steel material having excellent corrosion resistance according to the present invention has a plating layer composition of Al: 25 to 75 mass%, one or two of Cr and Mn: 0.05 to 5 mass%, Si: Al It contains 0.5 to 10% by mass of the content, and the balance is Zn and inevitable impurities, and it is preferable to further contain Mg: 0.1 to 5% by mass. Here, to-be-plated steel materials are steel materials, such as a steel plate, a steel pipe, and a steel wire.
めっき層組成の内、Ａｌは２５〜７５質量％とする。Ａｌが２５質量％未満の場合は、裸耐食性が低下する。一方、７５質量％を超えると切断端面の耐食性が低下し、また、合金めっき浴の温度を高く維持する必要が生じ、製造コストが高くなる等の問題が生じる。また、めっき総組成の内、Ｃｒ、Ｍｎの１種又は２種は０．０５〜５質量％とする。Ｃｒ、Ｍｎの１種又は２種が０．０５質量％未満の場合は耐食性向上効果が不充分であり、５質量％を超えるとめっき浴のドロス発生量が増大する等の問題が生じる。耐食性の観点からは０．１質量％を超えて含有されることが好ましい。 Of the plating layer composition, Al is 25 to 75 mass%. When Al is less than 25% by mass, the bare corrosion resistance decreases. On the other hand, if it exceeds 75% by mass, the corrosion resistance of the cut end face is lowered, and the temperature of the alloy plating bath needs to be kept high, which causes problems such as an increase in manufacturing cost. Moreover, 1 type or 2 types of Cr and Mn is 0.05-5 mass% among plating total composition. When one or two of Cr and Mn is less than 0.05% by mass, the effect of improving the corrosion resistance is insufficient, and when it exceeds 5% by mass, problems such as an increase in the amount of dross generated in the plating bath occur. From the viewpoint of corrosion resistance, it is preferable to contain more than 0.1% by mass.
また、めっき層組成の内、ＳｉはＡｌ含有量の０．５質量％以上添加する。鋼材にめっき層を形成するにあたり、鋼材表面とめっき層との界面におけるＦｅ−Ａｌ系合金層が過剰に厚く形成されることを抑制して、鋼材表面とめっき層の密着性を向上することができる。また、ＳｉをＡｌ含有量の１０質量％を超えて含有すると、Ｆｅ−Ａｌ合金化層の形成を抑制する効果が飽和すると共に、めっき層の加工性の低下を招く恐れがあるので、Ａｌ含有量の１０質量％を上限とする。めっき層の加工性を重視する場合は、Ａｌ含有量の５質量％を上限とすることが好ましい。 Of the plating layer composition, Si is added by 0.5 mass% or more of the Al content. In forming the plating layer on the steel material, it is possible to suppress the formation of an excessively thick Fe-Al alloy layer at the interface between the steel material surface and the plating layer, and to improve the adhesion between the steel material surface and the plating layer. it can. Further, if Si is contained in an amount exceeding 10% by mass of the Al content, the effect of suppressing the formation of the Fe—Al alloyed layer is saturated and the workability of the plating layer may be reduced. The upper limit is 10% by mass of the amount. When emphasizing the workability of the plating layer, it is preferable that the upper limit is 5% by mass of the Al content.
また、めっき層の組織として、スパングルサイズの平均値を０．５ｍｍ以上とする。ここで、スパングルサイズの測定は、めっき表面からの光学顕微鏡観察で行う。凝固組織としてＡｌデンドライト組織が認められるが、デンドライト組織の中心間の距離を２０倍ないし５０倍程度の倍率にて観察測定する。スパングルサイズの平均値が０．５ｍｍ未満であると、めっき層を曲げ加工した際、クラックが多数発生し、曲げ加工性が低下する。また、本めっき鋼材の特徴であるスパングル模様が目視で認識できなくなり外観を損なう。尚、より高いレベルの曲げ加工性が要求される場合には、スパングルサイズの平均値を１．０ｍｍ以上、より好ましくは３．０ｍｍ以上とすると良い。 Moreover, the average value of spangle size is 0.5 mm or more as the structure of the plating layer. Here, the spangle size is measured by observation with an optical microscope from the plating surface. An Al dendrite structure is recognized as a solidified structure, and the distance between centers of the dendrite structure is observed and measured at a magnification of about 20 to 50 times. When the average value of the spangle size is less than 0.5 mm, when the plating layer is bent, a large number of cracks are generated and bending workability is deteriorated. Moreover, the spangle pattern which is the characteristic of this plated steel material cannot be recognized visually, and an external appearance is impaired. In addition, when a higher level of bending workability is required, the average value of spangle size should be 1.0 mm or more, more preferably 3.0 mm or more.
ここで上限については、特に規定するものではないが、スパングルサイズが粗大となると、逆に外観を損なうので、通常は１０ｍｍ以下であることが好ましい。ここで、スパングルサイズがめっき層の加工性に影響する理由は、現時点で必ずしも明らかではないが、溶融めっき後のめっき層が凝固完了するまでの冷却速度が速い場合は、スパングルサイズ微細化し、かつ同時にめっき層硬度が高くなるため、曲げ変形を受けた際、めっき層のクラック発生が多くなると考えられる。さらに、めっき層組成として、Ｍｇを０．１〜５質量％含有させることにより、更に高い耐食性を得ることができる。０．１質量％未満の添加では、耐食性向上に寄与する添加効果が見られない。一方、添加量が５質量％を超える場合は、耐食性向上効果が飽和すると共に、めっき浴のドロス発生量が増大する等の問題を生じる可能性が高くなる。 Here, the upper limit is not particularly specified, but when the spangle size becomes coarse, the appearance is adversely affected. Therefore, the upper limit is usually preferably 10 mm or less. Here, the reason that spangle size affects the processability of the plating layer is not necessarily clear at this time, but if the cooling rate until the plating layer after hot dipping is solidified is high, the spangle size is refined, and At the same time, the plating layer hardness increases, so that it is considered that cracking of the plating layer increases when subjected to bending deformation. Furthermore, higher corrosion resistance can be obtained by containing 0.1 to 5% by mass of Mg as the plating layer composition. If the addition is less than 0.1% by mass, the addition effect contributing to the improvement of corrosion resistance is not observed. On the other hand, when the addition amount exceeds 5% by mass, the corrosion resistance improving effect is saturated, and there is a high possibility that problems such as an increase in the amount of dross generated in the plating bath will occur.
そして、めっき層の組織として、めっき層と素地鋼材界面に形成されるＦｅ−Ａｌ系の合金化層に、Ｃｒ、Ｍｎの１種又は２種を含有することが好ましい。Ｆｅ−Ａｌ系合金化層に濃化したＣｒ、Ｍｎは、腐食進行に伴いめっき層が溶解し素地鋼材表面の一部が露出する段階で、Ｃｒによる不働態化作用、Ｍｎによる犠牲防食作用により、素地鋼材の腐食を抑制、耐食性を向上させる作用を有すると考えられる。 And as a structure of a plating layer, it is preferable to contain 1 type or 2 types of Cr and Mn in the Fe-Al type alloying layer formed in a plating layer and a base steel material interface. Cr and Mn concentrated in the Fe-Al alloyed layer are in a stage where the plating layer dissolves and a part of the surface of the base steel material is exposed as the corrosion progresses. It is thought that it has the effect | action which suppresses corrosion of a base steel material and improves corrosion resistance.
Ｃｒ、Ｍｎを含有する合金化層は、めっき層断面のＥＰＭＡ分析又はＧＤＳ分析により確認できる。合金化層の膜厚は、特に限定されるものではないが、０．０５μｍ以上で形成効果が得られ、一方、厚くなり過ぎるとめっき層の折曲げ加工性が低下するので、好ましくは３μｍ以下が良い。また、合金化層の形成は、被めっき鋼材を溶融めっき浴に浸漬した直後より開始し、その後めっき層が凝固完了、めっき鋼材の温度が約４００℃以下となるまで進行する。したがって、合金化層の厚さの制御は、めっき浴温度、被めっき鋼材浸漬時間、めっき後冷却速度等を調整することで可能である。 The alloying layer containing Cr and Mn can be confirmed by EPMA analysis or GDS analysis of the plating layer cross section. The film thickness of the alloyed layer is not particularly limited, but a forming effect is obtained at 0.05 μm or more. On the other hand, if it is too thick, the bending workability of the plating layer is reduced, and is preferably 3 μm or less. Is good. The formation of the alloying layer starts immediately after the steel material to be plated is immersed in the hot dipping bath, and then proceeds until the plating layer is completely solidified and the temperature of the plated steel material is about 400 ° C. or lower. Therefore, the thickness of the alloying layer can be controlled by adjusting the plating bath temperature, the steel material immersion time, the cooling rate after plating, and the like.
めっき層の組成として、Ａｌ、Ｃｒ、Ｍｎ、Ｓｉを除く残部は、亜鉛及び不可避的不純物である。ここで、不可避的不純物とは、Ｐｂ、Ｓｂ、Ｓｎ、Ｃｄ、Ｆｅ、Ｎｉ、Ｃｕ、Ｔｉ等のめっき合金原料の製造過程で不可避的に混入する元素、及び、めっき鋼材製造過程で鋼材より又はめっき釜材料よりめっき浴中に溶解混入する元素を意味し、これら不可避的不純物の含有量が合計で１質量％まで含まれても良い。めっき膜厚は、特に限定するものではないが、薄すぎるとめっき層による耐食性向上効果が不足する一方で、厚すぎるとめっき層の折り曲げ加工性が低下しクラック発生等の問題が生じ易くなることから、膜厚範囲を５〜４０μｍとすることが好ましい。特に、良好な曲げ加工性を必要とする場合には、膜厚上限を１５μｍ以下とすると良い。 As the composition of the plating layer, the balance excluding Al, Cr, Mn, and Si is zinc and inevitable impurities. Here, the inevitable impurities are elements inevitably mixed in the production process of plating alloy raw materials such as Pb, Sb, Sn, Cd, Fe, Ni, Cu, and Ti, and the steel material in the production process of the plated steel material or It means an element dissolved and mixed in the plating bath from the plating pot material, and the content of these inevitable impurities may be contained up to 1% by mass in total. The plating film thickness is not particularly limited, but if it is too thin, the effect of improving the corrosion resistance by the plating layer is insufficient. On the other hand, if it is too thick, the bending workability of the plating layer is reduced and problems such as cracking are likely to occur. Therefore, the film thickness range is preferably 5 to 40 μm. In particular, when good bending workability is required, the upper limit of the film thickness is preferably 15 μm or less.
本発明のめっき鋼材の製造方法としては、被めっき鋼材を、質量％で、Ａｌ：２５〜８５％、Ｃｒ、Ｍｎの１種又は２種以上：０．０５〜５％、Ｓｉ：Ａｌの含有量の０．５〜１０％、必要に応じてＭｇ：０．１〜５質量％を含有し、残部はＺｎ及び不可避的不純物からなるめっき浴に浸漬して、溶融めっき後、めっき層が凝固が完了する温度までのめっき鋼材の冷却速度が２０℃／ｓｅｃ以下とする。被めっき鋼材をめっき浴に浸漬する前に、めっき濡れ性、めっき密着性を改善する等の目的で、アルカリ脱脂処理、酸洗処理を施しても良い。 As a method for producing a plated steel material of the present invention, the steel material to be plated is, by mass%, Al: 25 to 85%, one or more of Cr and Mn: 0.05 to 5%, Si: Al content 0.5-10% of the amount, if necessary Mg: 0.1-5% by mass, the remainder is immersed in a plating bath consisting of Zn and inevitable impurities, and after hot dipping, the plating layer is solidified The cooling rate of the plated steel material up to the temperature at which is completed is 20 ° C./sec or less. Prior to immersing the steel to be plated in the plating bath, alkali degreasing treatment and pickling treatment may be performed for the purpose of improving plating wettability and plating adhesion.
被めっき鋼材をめっきする方法して、無酸化炉→還元炉もしくは全還元炉を用いて、被めっき鋼材を加熱還元焼鈍した後、めっき浴に浸漬引き上げを行う。続いて、ガスワイピング方式で所定のめっき付着量制御を行い、その後冷却する工程を連続的適用する方法を用いることができる。また、被めっき鋼材表面に、塩化亜鉛、塩化アンモニウム、他の薬剤を用いたフラックス処理を施した上で、めっき浴に浸漬してめっきする方法を適用しても良い。 As a method of plating a steel material to be plated, the steel material to be plated is heat-reduced and annealed using a non-oxidation furnace → reduction furnace or a total reduction furnace, and then immersed in a plating bath. Subsequently, a method in which a predetermined plating adhesion amount control is performed by a gas wiping method and then a cooling process is continuously applied can be used. Alternatively, a method may be applied in which the surface of the steel material to be plated is subjected to flux treatment using zinc chloride, ammonium chloride, or other chemicals, and then immersed in a plating bath for plating.
めっき浴の調合方法として、本発明に示される範囲の組成に予め調合された合金を加熱溶解しても良いし、各金属単体もしくは２種以上の合金を組み合わせて加熱溶解し、所定の組成にする方法を適用しても良い。加熱溶解方法として、めっき合金をめっき浴に直接溶解する方法を用いても良いし、また、予備溶解炉で事前に溶解した後めっき浴槽に移送する方法を用いても良い。予備溶解炉を用いる方法は、設備設置費用が高くなるものの、めっき合金溶解時に発生するドロス等の不純物除去がし易い、めっき浴の温度管理がし易い等の利点がある。 As a method for preparing the plating bath, an alloy prepared in advance in the composition shown in the present invention may be heated and dissolved, or each metal alone or a combination of two or more alloys is heated and dissolved to obtain a predetermined composition. You may apply the method to do. As a heating and melting method, a method of directly dissolving a plating alloy in a plating bath may be used, or a method of dissolving in advance in a preliminary melting furnace and then transferring the plating alloy to a plating bath may be used. The method using the preliminary melting furnace has advantages such as easy removal of impurities such as dross generated when the plating alloy is melted and easy temperature control of the plating bath, although the cost of installing the equipment is high.
めっき浴の表面が大気と接することで発生する酸化物系のドロス発生量を低減させる目的で、めっき浴表面にセラミックス、ガラスウール等の耐熱物で覆っても良い。溶融めっき層の冷却凝固までの冷却速度を２０℃／ｓｅｃ以下とすることで、スパングルサイズの平均値が０．５ｍｍ以上となり、良好な加工性が得られる。これを超える冷却速度とすると、スパングルサイズが微細化し、めっき層の曲げ加工性が低下するばかりでなく、表面外観も損なわれる。 In order to reduce the amount of oxide-based dross generated when the surface of the plating bath is in contact with the atmosphere, the surface of the plating bath may be covered with a heat-resistant material such as ceramics or glass wool. By setting the cooling rate until the cooling and solidification of the hot-dip plated layer to 20 ° C./sec or less, the average value of the spangle size becomes 0.5 mm or more, and good workability is obtained. If the cooling rate exceeds this, the spangle size becomes finer, not only the bending workability of the plating layer is lowered, but also the surface appearance is impaired.
溶融めっき後のめっき鋼材の冷却速度制御は、めっき鋼材が溶融めっき浴をでた後、めっき層の凝固が完了するまでの区間で行われる。具体的方法は、めっき鋼材周囲の雰囲気温度調整やめっき鋼材への相対風速調整、又は、必要に応じて誘導加熱や燃焼式加熱バーナーを用いて加熱することにより、調整することができる。なお、めっき鋼材の冷却速度は、めっき鋼材が溶融めっき浴から出た後、溶融めっき層の凝固が完了するまでの時間を測定することで計算できる。ここで、溶融めっき層の凝固完了は、目視で表面状態変化を観察することにより確認できる。また、凝固までの時間は、めっき層凝固が完了するまでの距離を製造速度で割ることにより求められる。 The cooling rate control of the plated steel material after the hot dip plating is performed in a section from when the plated steel material comes out of the hot dip plating bath until the solidification of the plating layer is completed. The specific method can be adjusted by adjusting the ambient temperature around the plated steel material, adjusting the relative wind speed to the plated steel material, or by heating using an induction heating or a combustion heating burner as necessary. It should be noted that the cooling rate of the plated steel material can be calculated by measuring the time until the solidification of the hot-dip plating layer is completed after the hot-dip plating bath is removed from the hot-dip plating bath. Here, completion of solidification of the hot dipped layer can be confirmed by visually observing a change in the surface state. The time until solidification is obtained by dividing the distance until the plating layer solidification is completed by the production rate.
めっき層の凝固が完了した後のめっき鋼材の冷却速度は、特に規定するものではないが、３０℃／ｓｅｃ以上で冷却した方が、めっき層の曲げ加工性の改善効果がより向上する。さらに、めっき鋼材を製造後、下記式に規定される条件で保温することにより、めっき層の曲げ加工性をさらに改善することができる。
ｙ≧７．５×１０9×ｔ-4.5
（ここで、ｔは１００〜２５０℃のめっき鋼材の保温温度、ｙは保温時間（ｈｒ）である。）
Although the cooling rate of the plated steel material after the solidification of the plating layer is not particularly defined, the effect of improving the bending workability of the plating layer is further improved by cooling at 30 ° C./sec or more. Furthermore, after manufacturing a plated steel material, the bending workability of a plating layer can be further improved by maintaining the temperature under the conditions defined by the following formula.
y ≧ 7.5 × 10 9 × t −4.5
(Here, t is the heat retention temperature of the plated steel material of 100 to 250 ° C., and y is the heat retention time (hr).)
図１に、めっき組成：５５％Ａｌ−１．５％Ｓｉ−０．２％Ｃｒ−１％Ｍｇ−残Ｚｎ、めっき層膜厚１５μｍのめっき材に、加熱保温処理を施し、保温温度及び保温時間とめっき層の曲げ加工性の関係について調べた結果を示す。ここで、めっき層の曲げ加工性試験は、３ｍｍＴ曲げ加工後、曲げ加工頂上部を顕微鏡にて観察し、下記の基準にて判定を行った。
◎：曲げクラック無し（保温加熱処理無し材に比較して顕著な改善効果有り）
○：曲げクラック１〜５個（保温加熱処理無し材に比較して改善効果有り）
△：曲げクラック６〜１０個（保温加熱処理無し材と同等レベル）
１００℃未満の場合は、曲げ加工性の改善効果を得るために長時間の保温を必要とし、生産性低下の問題が生じる。また、２５０℃を超える場合には更なる改善効果が得られない。
FIG. 1 shows a plating composition: 55% Al-1.5% Si-0.2% Cr-1% Mg-residual Zn, plating material having a plating layer thickness of 15 [mu] m, which is subjected to heat and heat treatment to keep the heat and temperature. The result of having investigated about the relationship between time and the bending workability of a plating layer is shown. Here, the bending workability test of the plating layer was carried out by observing the top of the bending work with a microscope after 3 mmT bending work, and making the determination according to the following criteria.
◎: No bending crack (There is a remarkable improvement effect compared to the material without heat insulation and heat treatment)
○: 1 to 5 bending cracks (improvement effect compared to materials without heat insulation and heat treatment)
Δ: 6 to 10 bending cracks (equivalent to a material without heat treatment)
When the temperature is lower than 100 ° C., it is necessary to keep the heat for a long time in order to obtain the effect of improving the bending workability, which causes a problem of lowering the productivity. Moreover, when it exceeds 250 degreeC, the further improvement effect is not acquired.
上式は、図１に示される、実験で得られためっき層の曲げ加工性の改善効果の得られる条件について、保温温度と保温時間の関係を累乗近似して求めた式である。なお、加熱保温処理によりめっき層の加工性が更に改善する理由は、以下のメカニズムを推定している。めっき材製造ままの状態では、めっき層内に微細析出粒子が多数存在する。微細析出粒子は、めっき層の曲げ変形時、転移の移動を妨げ、めっき層の加工性を低下させる。加熱保温処理を施すことにより微細析出粒子を粗大化させ、めっき層の加工性を改善する。なお、２５０℃を超える保温加熱処理を施した場合は、粗大析出粒子自体がめっき層内で溶解し、めっき材を冷却した際、再び微細析出粒子が生じ、めっき層の加工性改善効果が得られないものと推定される。 The above equation is an equation obtained by approximating the relationship between the heat retention temperature and the heat retention time with respect to the conditions for obtaining the effect of improving the bending workability of the plating layer obtained in the experiment shown in FIG. The reason why the workability of the plating layer is further improved by the heat insulation treatment is presumed as follows. In the state as the plating material is manufactured, a large number of fine precipitated particles exist in the plating layer. The fine precipitated particles hinder the movement of transition during bending deformation of the plating layer and reduce the workability of the plating layer. By applying heat and heat treatment, the fine precipitated particles are coarsened to improve the workability of the plating layer. In addition, when heat-retaining heat treatment exceeding 250 ° C. is performed, coarse precipitated particles themselves are dissolved in the plating layer, and when the plating material is cooled, fine precipitated particles are generated again, and the effect of improving the workability of the plating layer is obtained. It is estimated that it is not possible.
保温方法としては、連続溶融めっき製造時、本発明に規定される温度条件以上にめっき鋼材の温度を保ちながら巻き取り、そのまま保温する方法、連続溶融めっき製造後、めっき鋼材の温度が本発明に規定される温度条件以下に冷やされている場合は、加熱保温箱等を用いてめっき鋼材を加熱し保温する方法、めっき鋼材を一旦巻き解き、誘導加熱装置や連続式加熱炉を用いて所定の温度まで再加熱した上で巻き取り、保温する方法等が適用できる。 As a heat retention method, during continuous hot dipping, the temperature of the plated steel material is maintained while maintaining the temperature of the plated steel material above the temperature condition specified in the present invention. If it is cooled below the specified temperature condition, heat the plated steel material using a heat insulation box, etc., unwind the plated steel material, and then use the induction heating device or continuous heating furnace to A method of winding and keeping warm after reheating to temperature can be applied.
また、本発明の溶融Ｚｎ−Ａｌ系合金めっき鋼材の表面に、ポリエステル樹脂系、アクリル樹脂系、フッ素樹脂系、塩化ビニル樹脂系、ウレタン樹脂系、エポキシ樹脂系等の塗料を、ロール塗装、スプレー塗装、カーテンフロー塗装、ディップ塗装、あるいは、アクリル樹脂フィルム等のプラスチックフィルムを積層するフィルムラミネート法等を行っても良い。このようにめっき層上に皮膜を形成した場合、腐食性雰囲気下で、平面部、切断端面部、及び折り曲げ加工部において優れた耐食性が発揮させることができる。 In addition, on the surface of the molten Zn-Al alloy-plated steel material of the present invention, a paint such as polyester resin, acrylic resin, fluororesin, vinyl chloride resin, urethane resin, and epoxy resin is applied by roll coating or spraying. Coating, curtain flow coating, dip coating, or a film laminating method in which a plastic film such as an acrylic resin film is laminated may be performed. Thus, when a membrane | film | coat is formed on a plating layer, the outstanding corrosion resistance can be exhibited in a plane part, a cut end surface part, and a bending process part in corrosive atmosphere.
以下、本発明を実施例によってさらに詳細に説明する。
表１に示す組成の溶融めっき金属槽に、被めっき鋼材を浸漬し、その後、表１に示す条件で処理することにより、合金めっき鋼材を製造した。ここで、本発明例Ｎｏ．１〜１８及び比較例Ｎｏ．１９〜２１は、板厚０．８ｍｍの冷延鋼板を、めっき前にアルカリ脱脂後、Ｎ2−１０％Ｈ2雰囲気中で８００℃まで加熱還元焼鈍し、続いて５８０℃まで冷却した後、溶融めっき金属槽に２秒間浸漬して、合金めっき層を表面に形成した。めっき膜厚は、１０〜１５μｍに制御した。溶融めっき浴温度は本発明例Ｎｏ．９は５６０℃、本発明例Ｎｏ．１０は６４０℃、それ以外は６０５℃にした。
Hereinafter, the present invention will be described in more detail by way of examples.
An alloy-plated steel material was manufactured by immersing the steel material to be plated in a hot dipped metal tank having the composition shown in Table 1 and then treating it under the conditions shown in Table 1. Here, Example No. of the present invention. 1-18 and Comparative Example No. 19-21, after cold degreasing the cold-rolled steel plate having a thickness of 0.8 mm before plating, heat-reduction annealing to 800 ° C. in an N 2 -10% H 2 atmosphere, and subsequently cooling to 580 ° C., An alloy plating layer was formed on the surface by dipping in a hot dipped metal bath for 2 seconds. The plating film thickness was controlled to 10-15 μm. The hot dip bath temperature is the same as that of the present invention example No. 9 is 560 ° C., Example No. of the present invention. 10 was set to 640 ° C., and other temperatures were set to 605 ° C.
（折り曲げ加工性試験）
合金めっき鋼材を、３０ｍｍ×４０ｍｍの寸法に切断し、めっき層の曲げ加工試験を行った。めっき層の曲げ加工性試験は、３ｍｍＴ曲げ加工後、曲げ加工頂上部を顕微鏡にて観察し、下記の基準にて判定を行い、△以上を合格とした。
◎：曲げクラック無し
○：曲げクラック１〜５個
△：曲げクラック６〜１０個
×：曲げクラック１０個以上
(Bending workability test)
The alloy-plated steel material was cut into a size of 30 mm × 40 mm, and a bending test of the plating layer was performed. The bending workability test of the plating layer was carried out by observing the top of the bending work with a microscope after 3 mmT bending work, making a determination based on the following criteria, and setting a value of Δ or more as acceptable.
◎: No bending crack ○: Bending crack 1 to 5 △: Bending crack 6 to 10 ×: Bending crack 10 or more
（裸耐食性試験）
合金めっきした鋼材の塩水噴霧試験を２０日間行った。めっき腐食減量の測定方法は、腐食試験後材をＣｒＯ3２００ｇ／Ｌの処理浴に温度８０℃で３分間浸漬、腐食生成物を溶解除去した。腐食に伴うめっき腐食減量を質量測定した。下記評価基準にて裸耐食性を判定し、○以上を合格とした。
◎：めっき腐食減量５ｇ／ｍ2以下
○：めっき腐食減量５ｇ／ｍ2超１０ｇ／ｍ2以下
△：めっき腐食減量１０ｇ／ｍ2超２０ｇ／ｍ2以下
×：めっき腐食減量２０ｇ／ｍ2超
(Nude corrosion resistance test)
The salt spray test of the alloy-plated steel was performed for 20 days. The plating corrosion weight loss was measured by immersing the material after the corrosion test in a CrO 3 200 g / L treatment bath at a temperature of 80 ° C. for 3 minutes to dissolve and remove the corrosion product. The weight loss of plating corrosion due to corrosion was measured. Bare corrosion resistance was determined according to the following evaluation criteria, and a value of ○ or higher was determined to be acceptable.
◎: Plating corrosion weight loss 5g / m 2 or less ○: Plating corrosion weight loss 5g / m 2 ultra-10g / m 2 or less △: Plating corrosion weight loss 10g / m 2 ultra-20g / m 2 or less ×: Plating corrosion weight loss 20g / m 2 more than
表１から明らかなように、本発明例Ｎｏ．１〜１８は、何れも良好な曲げ加工性及び耐食性を有する。特に、Ｎｏ．２、３は、Ｎｏ．１に比較して、また、Ｎｏ．１２、１３は、Ｎｏ．１１に比較して、めっき後の冷却速度を低くすることで、スパングルサイズを大きくさせたため、より良好な曲げ加工性が得られた。Ｎｏ．１５〜１８は、めっき後の保温加熱処理を施すことにより、めっき層の曲げクラック発生が認められず、極めて良好な結果を得た。これに対し、比較例Ｎｏ．１９〜２１は、めっき後の冷却速度が速く、スパングルサイズが小さいため、曲げ加工性が不良である。更に、比較例Ｎｏ．２１については、めっき層にＣｒ、Ｍｎを含まないため、耐食性が不足である。 As is apparent from Table 1, Example No. of the present invention. Nos. 1 to 18 all have good bending workability and corrosion resistance. In particular, no. 2, 3 are No. No. 1 and no. Nos. 12 and 13 are No. Compared to 11, the spangle size was increased by lowering the cooling rate after plating, so that better bending workability was obtained. No. In Nos. 15 to 18, by performing the heat insulation heat treatment after plating, the occurrence of bending cracks in the plating layer was not observed, and very good results were obtained. In contrast, Comparative Example No. Nos. 19 to 21 have poor bending workability because the cooling rate after plating is fast and the spangle size is small. Further, Comparative Example No. About 21, since a plating layer does not contain Cr and Mn, corrosion resistance is insufficient.
Claims (6)
Ａｌ：２５〜８５％、
Ｃｒ、Ｍｎの１種又は２種以上：０．０５〜５％、
Ｓｉ：Ａｌの含有量の０．５〜１０％
を含有し、残部はＺｎ及び不可避的不純物からなるめっき層を有し、かつ、めっき表面のスパングルサイズの平均値が０．５ｍｍ以上であることを特徴とする曲げ加工性に優れる溶融Ｚｎ−Ａｌ系合金めっき鋼材。 % By mass
Al: 25 to 85%,
One or more of Cr and Mn: 0.05 to 5%,
0.5 to 10% of Si: Al content
And the balance has a plating layer made of Zn and unavoidable impurities, and the average value of the spangle size of the plating surface is 0.5 mm or more. Alloy-plated steel.
ｙ≧７．５×１０9×ｔ-4.5 … （１）
（ここで、ｔは１００〜２５０℃のめっき鋼材の保温温度、ｙは保温時間（ｈｒ）を表す。） The hot-melted Zn-Al alloy-plated steel material having excellent bending workability according to claim 4, wherein the hot-dip Zn-Al-based alloy plated steel material is kept warm under the conditions defined by the following formula (1). Method.
y ≧ 7.5 × 10 9 × t −4.5 (1)
(Here, t represents the heat retaining temperature of the plated steel material of 100 to 250 ° C., and y represents the heat retaining time (hr).)
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| TW200710286A (en) | 2007-03-16 |
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