JP2005320556A - Highly corrosion resistant galvannealed steel sheet - Google Patents
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本発明は、高耐食性合金化溶融亜鉛めっき鋼板に関するものである。 The present invention relates to a high corrosion resistance galvannealed steel sheet.
耐食性に優れた溶融Ｚｎ系めっき鋼板については従来より多くの提案がなされており、本発明者等もすでに特許文献１においてＺｎ−Ｍｇ−Ａｌめっき鋼板、特許文献２でＺｎ−Ｍｇ−Ａｌ−Ｓｎめっき鋼板を提案している。
本Ｚｎ−Ｍｇ−Ａｌ系めっき鋼板は、未塗装状態での耐食性が極めて優れることから、建材、土木用途に幅広く使用されている。一方、自動車車体あるいはシャッター等においては、塗装状態の合金化溶融Ｚｎめっき鋼板が使用され、塗装後の耐食性、特に塗膜密着性及び塗装ブリスター性などに優れた鋼板であるが、塗膜に疵が入った場合の疵部（未塗装状態）の耐赤錆性についての耐食性向上が望まれていた。 This Zn-Mg-Al-based plated steel sheet is widely used in building materials and civil engineering applications because of its extremely excellent corrosion resistance in an unpainted state. On the other hand, in an automobile body or a shutter, etc., a coated alloyed hot-dip Zn-plated steel sheet is used, and it is a steel sheet having excellent corrosion resistance after painting, particularly coating film adhesion and coating blistering properties. Improvement of corrosion resistance for red rust resistance of the buttocks (unpainted state) in the case of entering is desired.
本発明者等は、Ｚｎ−Ｍｇ−Ａｌめっき鋼板のめっき層のＭｇが特に未塗装状態の裸耐食性に優れることに着目して検討を重ねたところ、表層にＭｇ濃化層を有する合金化溶融Ｚｎめっき層が塗装疵部の耐赤錆性が向上することを見いだすに至り、下記の本発明を完成したものである。
即ち、本発明は、鋼板の表面に、Ｍｇ：０．０５−３質量％、Ａｌ：０．１−１質量％、Ｆｅ：８−１５質量％、残部がＺｎおよび不可避的不純物よりなる合金化溶融Ｚｎめっき層を有する鋼板であって、表層にＭｇ濃化層を有することを特徴とする高耐食性合金化溶融Ｚｎめっき鋼板、
上記Ｍｇ濃化層は表面から２μｍまでのＭｇ濃度が上記合金化溶融Ｚｎめっき層の平均Ｍｇ濃度の１．６−４倍で有ることを特徴とする高耐食性合金化溶融Ｚｎめっき鋼板、
上記合金化溶融Ｚｎめっき層が添加元素としてＮｉ、Ｓｉ、Ｔｉ、Ｂ、Ｓｎの単独あるいは複合で３％以内含有することを特徴とする高耐食性合金化溶融Ｚｎめっき鋼板、
さらにはこれらのめっき層の地鉄界面にＮｉ−Ｆｅ−Ａｌ−Ｚｎ層があることを特徴とするめっき密着性に優れた高耐食性合金化溶融Ｚｎめっき鋼板、
である。
The inventors of the present invention have repeatedly studied paying attention to the fact that Mg of the coating layer of the Zn—Mg—Al plated steel sheet is particularly excellent in bare corrosion resistance in an unpainted state. The Zn plating layer has been found to improve the red rust resistance of the painted collar, and the following invention has been completed.
That is, the present invention provides an alloying process in which the surface of the steel sheet is Mg: 0.05-3 mass%, Al: 0.1-1 mass%, Fe: 8-15 mass%, the balance being Zn and inevitable impurities. A steel plate having a hot-dip Zn plating layer, and a high corrosion resistance alloyed hot-dip Zn plating steel plate characterized by having a Mg-concentrated layer on the surface layer,
The Mg-enriched layer has a Mg concentration from the surface to 2 μm, which is 1.6-4 times the average Mg concentration of the alloyed hot-dip Zn plating layer, and a high corrosion resistance alloyed hot-dip Zn-plated steel sheet,
The alloyed hot-dip Zn-plated steel sheet is characterized by containing within 3% of Ni, Si, Ti, B, Sn alone or in combination as an additive element,
Furthermore, a highly corrosion-resistant alloyed hot-dip Zn-plated steel sheet excellent in plating adhesion, characterized in that there is a Ni-Fe-Al-Zn layer at the iron-iron interface of these plated layers,
It is.
本発明によれば、従来の塗膜後耐食性（塗膜密着性及び塗装ブリスター性）に加えて塗装疵部の耐赤錆性に優れた合金化溶融Ｚｎめっき鋼板を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, in addition to the conventional post-coating corrosion resistance (coating-film adhesion and coating blister property), the alloyed hot-dip Zn-plated steel plate excellent in the red rust resistance of a coating collar part can be provided.
以下、本発明の実施の形態を詳細に説明する。
本発明は合金化溶融Ｚｎめっき層の構造が、表層にＭｇ濃化層を有することに最大の特徴があり、これにより従来の合金化溶融Ｚｎめっき鋼板よりも塗装疵部の耐赤錆性が向上する点に最大の技術のポイントがある。
本発明のめっき層中にはＭｇを０．０５〜３質量％、Ａｌを０．１〜１質量％含有させる。めっき層中のＭｇ含有量の下限を０．０５質量％としたのは、塗装疵部の耐食性に効果を発揮するためである。上限を３質量％としたのはこれを超えるとめっき層が硬くしかも脆くなりすぎるためにめっき密着性が劣化するためである。
めっき層中のＡｌ含有量の下限を０．１質量％としたのは、めっき密着性が良好となるためである。また、上限を１質量％としたのは、１質量％を超えると溶接性が劣化するためである。また、Ｆｅ含有量の下限を８質量％としたのは、塗膜密着性を確保するためである。また、Ｆｅ含有量の上限を１５質量％としたのは１５％を超えるとめっき密着性が劣化するためである。
Hereinafter, embodiments of the present invention will be described in detail.
The present invention has the greatest feature in that the structure of the alloyed hot-dip Zn plating layer has a Mg-concentrated layer on the surface layer, which improves the red rust resistance of the painted collar than the conventional alloyed hot-dip Zn-plated steel sheet. The biggest technical point is to do.
The plating layer of the present invention contains 0.05 to 3% by mass of Mg and 0.1 to 1% by mass of Al. The reason why the lower limit of the Mg content in the plating layer is set to 0.05% by mass is to exert an effect on the corrosion resistance of the coating collar. The reason why the upper limit is 3 mass% is that when the upper limit is exceeded, the plating layer becomes too hard and too brittle, so that the plating adhesion deteriorates.
The reason why the lower limit of the Al content in the plating layer is set to 0.1% by mass is that the plating adhesion is good. Further, the upper limit is set to 1% by mass because when the content exceeds 1% by mass, the weldability deteriorates. Moreover, the reason why the lower limit of the Fe content is 8% by mass is to ensure the adhesion of the coating film. Further, the upper limit of the Fe content is set to 15% by mass because if it exceeds 15%, the plating adhesion deteriorates.
表層にＭｇ濃化層を有することとしたのは、これにより塗装疵部の耐赤錆性が向上するためである。
上記Ｍｇ濃化層は表面から２μｍまでのＭｇ濃度が上記合金化溶融Ｚｎめっき層の平均Ｍｇ濃度の１．６−４倍であることとしたのは、これにより特に塗装疵部の耐赤錆性が特に向上するためである。
上記合金化溶融Ｚｎめっき層が添加元素としてＮｉ、Ｓｉ、Ｔｉ、Ｂ、Ｓｎの単独あるいは複合で３質量％以内含有することとしたのは、この場合にも塗装疵部の耐赤錆性が特に向上するためである。
また、下層にＮｉ−Ａｌ−Ｆｅ−Ｚｎ合金層を設けることとしたのは、加工性特にめっき密着性をさらに向上させるためである。めっき層下層にＮｉ−Ａｌ−Ｆｅ−Ｚｎ合金層を有する場合にめっき密着性が良好となる理由は、めっき層−地鉄界面に生成したＮｉ−Ａｌ−Ｆｅ−Ｚｎ合金層が一種のバインダーの役割を果たすことによるものと考えられる。
The reason why the Mg layer is included in the surface layer is that the red rust resistance of the painted heel portion is thereby improved.
The Mg concentration layer has a Mg concentration from the surface of 2 μm to 1.6-4 times the average Mg concentration of the alloyed hot-dip Zn plating layer. This is because of particularly improved.
The alloyed hot-dip Zn plating layer contains Ni, Si, Ti, B, Sn as an additive element alone or in combination within 3% by mass. It is for improving.
The reason why the Ni—Al—Fe—Zn alloy layer is provided in the lower layer is to further improve the workability, particularly the plating adhesion. The reason why the plating adhesion is good when the Ni—Al—Fe—Zn alloy layer is present in the lower layer of the plating layer is that the Ni—Al—Fe—Zn alloy layer formed at the plating layer-ground iron interface is a kind of binder. This is thought to be due to playing a role.
さらに、製造法として、溶融めっき前の前処理としては、まず、通常の還元法として加熱還元、冷却後、溶融めっきし、ワイピングで付着量を調整した後に４８０−６００℃の温度範囲で５−１００ｓ程度再加熱する方法が最適である。また、加熱還元前にＮｉめっき、ＮｉとＰ、Ｂ、Ｍｏ、Ｗなどの合金めっきあるいはＮｉ以外のＣｕ、Ｓｎ、Ｆｅ等のプレめっきを施しても良い。また、純粋なプレめっき法としてはプレＮｉめっき、加熱後、溶融めっきする方法が適用できる。これらのプレめっき方法は、純粋なＮｉめっきのみでなく、ＮｉとＰ、Ｂ、Ｍｏ、Ｗなどの合金めっきであっても良い。プレめっき量については特に制限は設けないが、０．２−２ｇ／ｍ２程度が好ましい。
溶融めっきの付着量については特に限定しないが１０−１００ｇ／ｍ２程度が望ましい。耐食性の観点から１０ｇ／ｍ２以上、加工性の観点からすると１００ｇ／ｍ２以下が最適なためである。
Further, as a pretreatment before hot dipping as a manufacturing method, first, heat reduction as a normal reduction method, cooling, hot dipping, hot dipping, adjusting the amount of adhesion by wiping, and then in a temperature range of 480-600 ° C. A method of reheating for about 100 seconds is optimal. Further, before the heat reduction, Ni plating, alloy plating such as Ni and P, B, Mo, W, or pre-plating such as Cu, Sn, Fe other than Ni may be performed. Further, as a pure pre-plating method, pre-Ni plating, a method of hot dipping after heating can be applied. These pre-plating methods may be not only pure Ni plating but also alloy plating of Ni and P, B, Mo, W, or the like. The pre-plating amount is not particularly limited, but is preferably about 0.2-2 g / m 2 .
The adhesion amount of hot dip plating is not particularly limited, but is preferably about 10-100 g / m 2 . This is because 10 g / m 2 or more is optimal from the viewpoint of corrosion resistance, and 100 g / m 2 or less is optimal from the viewpoint of workability.
下地鋼板としては、熱延鋼板、冷延鋼板共に使用でき、鋼種の制約もなく、例えばＡｌキルド鋼、Ｔｉ等の炭窒化物形成元素を添加した極低炭素鋼板およびこれに強化元素（Ｐ、Ｓｉ、Ｍｎ等）を添加した高強度鋼板等種々のものが適用できる。 As the base steel plate, both hot-rolled steel plates and cold-rolled steel plates can be used, and there are no restrictions on the steel type. For example, an ultra-low carbon steel plate to which carbonitride-forming elements such as Al killed steel and Ti are added, and a strengthening element (P, Various materials such as a high-strength steel sheet to which Si, Mn, etc.) are added can be applied.
以下、実施例を用いて本発明をさらに詳細に説明する。
図１に本発明の代表的めっき層構造をＥＰＭＡで分析した結果と模式図を示す。
また、実施例の一覧を表１に示す。
Ａｌキルド熱延鋼板（板厚１．６ｍｍ）にプレＮｉを施さない場合はＨ２１５％＋Ｎ２雰囲気中で６００℃まで加熱後、４５０℃まで冷却した状態で、また、プレＮｉを０．５ｇ／ｍ２施し、Ｈ２３％＋Ｎ２雰囲気中で４５０℃まで加熱し、４５０℃のＺｎ合金めっき浴で３ｓ溶融めっきを行い、Ｎ２ワイピングで付着量を６０ｇ／ｍ２に調整した後、溶融状態のめっき層を５００℃で３０ｓ再加熱で合金化処理を行った。得られためっき層に通常の化成処理（リン酸塩処理２．５ｇ／ｍ２）及びエポキシ系電着塗装（２０μｍ）を施した後、ナイフで塗装面にクロスカット疵を入れ、腐食サイクルテスト（ＪＡＳＯ）による疵部の耐赤錆性評価を行った。
（ＪＡＳＯ：ＳＳＴ(３５℃、５％ＮａＣｌ)２ｈｒ→乾燥（６０℃、３０％）４ｈｒ→湿潤(５０℃、９５％)２ｈｒ、３サイクル／日）耐食性はＪＡＳＯ９サイクル後の疵部の赤錆発生状況および疵部からの塗装ブリスターの大きさで評価した。
Hereinafter, the present invention will be described in more detail with reference to examples.
FIG. 1 shows a result and a schematic diagram of a typical plating layer structure of the present invention analyzed by EPMA.
A list of examples is shown in Table 1.
When pre-Ni is not applied to an Al-killed hot-rolled steel sheet (thickness 1.6 mm), it is heated to 600 ° C. in an H 2 15% + N 2 atmosphere, cooled to 450 ° C. After applying 5 g / m 2 , heating to 450 ° C. in an atmosphere of 3% H 2 + N 2 , performing 3 s hot dipping in a 450 ° C. Zn alloy plating bath, and adjusting the adhesion amount to 60 g / m 2 by N 2 wiping The molten plating layer was alloyed by reheating at 500 ° C. for 30 s. After applying the usual chemical conversion treatment (phosphate treatment 2.5 g / m 2 ) and epoxy-based electrodeposition coating (20 μm) to the resulting plating layer, a cross-cut flaw is put on the coated surface with a knife, and a corrosion cycle test (JASO) was used to evaluate the rust resistance of the buttocks.
(JASO: SST (35 ° C., 5% NaCl) 2 hr → dry (60 ° C., 30%) 4 hr → wet (50 ° C., 95%) 2 hr, 3 cycles / day) The situation and the size of the painted blister from the buttock were evaluated.
以下に耐食性の評価基準を示す。（評点３以上が合格）
評点 疵部の耐赤錆性 塗装ブリスターの大きさ
５・・・赤錆まったくなし 極微小
４・・・赤錆極微少 微小
３・・・赤錆微少ない 小
２・・・赤錆少 中
１・・・赤錆多 大
また、めっき密着性は、６０度Ｖ曲げ後、あらかじめ貼っておいた内面のシールをはがしてめっき剥離幅で評価した。（評点３以上が合格）
５・・・剥離幅極微小
４・・・剥離幅微小
３・・・剥離幅小
２・・・剥離幅中
１・・・剥離幅大
The evaluation criteria for corrosion resistance are shown below. (Grade 3 or higher is acceptable)
Ratings Red rust resistance of the buttocks Size of coating blister 5 ... No red rust at all Very small 4 ... Red rust very small Small 3 ... Red rust very small Small 2 ... Red rust small Medium 1 ... Red rust many The plating adhesion was evaluated by the plating peeling width by peeling off the seal on the inner surface previously pasted after bending at 60 degrees V. (Grade 3 or higher is acceptable)
5: Peeling width is extremely small 4 ... Peeling width is very small 3 ... Peeling width is small 2 ... Peeling width is medium 1 ... Peeling width is large
以上の評価結果を表１に示す。
本発明のめっき鋼板(Ｎｏ．１−１０、１５、１６)は、塗装疵部の耐赤錆性、塗装ブリスター性ともに優れている。
これに対して、本発明範囲を逸脱する比較例(Ｎｏ．１１−１４)は、本発明鋼板に比較して塗装疵部の耐赤錆性が劣る。
The above evaluation results are shown in Table 1.
The plated steel sheets (Nos. 1-10, 15, 16) of the present invention are excellent in both red rust resistance and paint blistering properties of the coating saddle.
On the other hand, the comparative example (No. 11-14) which deviates from the scope of the present invention is inferior in the red rust resistance of the painted collar compared with the steel sheet of the present invention.
本発明のめっき鋼板は、従来にない優れた耐食性、特に塗装疵部の耐赤錆性に優れるので、車体、シャッターなどの部品用途にも有用である。 The plated steel sheet of the present invention is excellent in unprecedented corrosion resistance, in particular, red rust resistance of the painted collar, and is also useful for parts such as car bodies and shutters.
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| WO2023098125A1 (en) * | 2021-11-30 | 2023-06-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium alloy coated steel containing v and b and preparation method therefor |
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