JP2010229483A - Zn-Al BASED PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE, AND METHOD FOR MANUFACTURING THE SAME - Google Patents

Zn-Al BASED PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE, AND METHOD FOR MANUFACTURING THE SAME Download PDF

Info

Publication number
JP2010229483A
JP2010229483A JP2009077769A JP2009077769A JP2010229483A JP 2010229483 A JP2010229483 A JP 2010229483A JP 2009077769 A JP2009077769 A JP 2009077769A JP 2009077769 A JP2009077769 A JP 2009077769A JP 2010229483 A JP2010229483 A JP 2010229483A
Authority
JP
Japan
Prior art keywords
plating
steel sheet
plated steel
plating layer
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2009077769A
Other languages
Japanese (ja)
Other versions
JP5404126B2 (en
Inventor
Fukio Yoshizaki
布貴男 吉崎
Nobuhiko Yamaki
信彦 山木
Takeshi Shimizu
剛 清水
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Nisshin Co Ltd
Original Assignee
Nisshin Steel Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Priority to JP2009077769A priority Critical patent/JP5404126B2/en
Publication of JP2010229483A publication Critical patent/JP2010229483A/en
Application granted granted Critical
Publication of JP5404126B2 publication Critical patent/JP5404126B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Zn-Al based plated steel sheet containing Mg-Si and having notably improved corrosion resistance. <P>SOLUTION: In the Zn-Al based plated steel sheet having excellent corrosion resistance and having a Zn-Al based plating layer having an average composition, by mass%, of Al:25 to 75%, Si:1 to 10% and Mg:0.5 to 6%, further containing one or more of Ti and B in the range of ≤0.1% in total if needed and having the balance consisting of Zn and inevitable impurities, the plating layer includes a Zn rich part, an Al rich part, and an Si rich part, the Zn rich part has a region having ≥4.5 mass% Mg concentration, and the Al rich part and the Si rich part have organization states where a region having ≥4.5 mass% Mg concentration is not observed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、Mg・Si含有Zn−Al系めっき鋼板であって、めっき層中のMgが、Siリッチ部ではなく、Znリッチ部に主として分布する特異なめっき層組織を有する高耐食性めっき鋼板、およびその製造方法に関する。   The present invention is a Mg-Si-containing Zn-Al-based plated steel sheet, wherein Mg in the plating layer has a unique plating layer structure in which the Mg is mainly distributed in the Zn-rich part instead of the Si-rich part, And a manufacturing method thereof.

Znめっき鋼板が有する犠牲防食作用と、Alめっき鋼板が有するめっき表面の高耐食性とをバランス良く兼ね備えためっき鋼板として、25〜75%のAlを含有するZn−Al系めっき鋼板が知られており、例えば溶融Zn−55%Al−1.5%Si合金めっき鋼板などが実用化されている。本明細書ではこのようなSiを含有するZn−Al系めっきを「Si含有Zn−Al系めっき」と呼んでいる。近年ではさらに高耐食性の要求が高まり、Si含有Zn−Al系めっきをベースに数%のMgを含有させた「Mg・Si含有Zn−Al系めっき」が検討され(特許文献1〜4など)、例えば溶融Zn−55%Al−1.5%Si−2%Mg合金めっき鋼板などが開示されている。   As a plated steel sheet having a good balance between the sacrificial anticorrosive action of the Zn-plated steel sheet and the high corrosion resistance of the plated surface of the Al-plated steel sheet, a Zn-Al-based plated steel sheet containing 25 to 75% Al is known. For example, a molten Zn-55% Al-1.5% Si alloy-plated steel sheet has been put into practical use. In this specification, such a Zn-Al-based plating containing Si is referred to as “Si-containing Zn—Al-based plating”. In recent years, the demand for higher corrosion resistance has increased, and "Mg.Si-containing Zn-Al plating" containing several percent of Mg based on Si-containing Zn-Al plating has been studied (Patent Documents 1 to 4, etc.) For example, a molten Zn-55% Al-1.5% Si-2% Mg alloy-plated steel sheet is disclosed.

特開2000−104153号公報JP 2000-104153 A 特開2000−328214号公報JP 2000-328214 A 特開2002−322527号公報JP 2002-322527 A 特開2001−115247号公報JP 2001-115247 A

Mg・Si含有Zn−Al系めっき鋼板は、Mgを含有しないものと比べ、平坦部(めっき表面)および切断端面の耐食性に向上が認められる。この種の溶融めっき鋼板のめっき層中において、Mgの大部分はMg−Si系金属間化合物(Mg2Siなど)として「Siリッチ部」に存在しており、その他、Zn−Mg系金属間化合物(Zn2Mgなど)も「Znリッチ部」に見られる。めっき層中のMgは、めっき層が腐食する際に保護性の高いMg含有Zn系腐食生成物を形成し、主としてこれによって耐食性が向上するものと考えられている。 The Mg · Si-containing Zn—Al-plated steel sheet is improved in the corrosion resistance of the flat portion (plated surface) and the cut end face as compared with the steel containing no Mg. In the plated layer of this type of hot-dip steel sheet, most of Mg is present in the “Si-rich portion” as an Mg—Si intermetallic compound (Mg 2 Si, etc.). Compounds (such as Zn 2 Mg) are also found in the “Zn-rich part”. It is considered that Mg in the plating layer forms a highly protective Mg-containing Zn-based corrosion product when the plating layer corrodes, and this mainly improves the corrosion resistance.

しかしながら、このようなMg・Si含有Zn−Al系めっき鋼板においても、Mgを含有しないSi含有Zn−Al系めっき鋼板で問題となるような腐食が見られることがあり、耐食性向上効果は必ずしも十分とは言えない。また、溶融めっき浴中にMgを含有すると、めっき面の表面性状が劣化しやすいという問題もある。このようなことから、Mg・Si含有Zn−Al系めっき鋼板はほとんど普及していないのが現状である。   However, even in such Mg · Si-containing Zn—Al-based plated steel sheets, corrosion that causes problems in Si-containing Zn—Al-based plated steel sheets that do not contain Mg may be seen, and the effect of improving corrosion resistance is not always sufficient. It can not be said. Further, when Mg is contained in the hot dipping bath, there is a problem that the surface properties of the plated surface are likely to deteriorate. For these reasons, Mg / Si-containing Zn—Al-based plated steel sheets are rarely used.

発明者らの検討によれば、Mg・Si含有Zn−Al系めっき鋼板の耐食性改善効果が不十分となる原因として、Mgの大部分がSiリッチ部に存在していることが考えられる。Zn−Al系めっき鋼板ではめっき層中のZnリッチ部がAlリッチ部よりも選択的に腐食されやすい傾向を有することから、MgがZnリッチ部に少量しか分布していないことは、保護性の高いMg含有Zn系腐食生成物の形成に有利とは言えない。また、Mg2Si相自体は耐食性が良好でなく、Mg2Si相が多量に生成していることもめっき層の耐食性低下要因となっているものと考えられる。 According to the study by the inventors, it can be considered that most of Mg is present in the Si-rich portion as a cause of insufficient effect of improving the corrosion resistance of the Mg · Si-containing Zn—Al-based plated steel sheet. In the Zn-Al-based plated steel sheet, the Zn-rich portion in the plating layer tends to be selectively corroded more than the Al-rich portion, so that only a small amount of Mg is distributed in the Zn-rich portion is a protective property. It is not advantageous for the formation of high Mg-containing Zn-based corrosion products. In addition, the Mg 2 Si phase itself does not have good corrosion resistance, and a large amount of the Mg 2 Si phase is considered to be a factor that lowers the corrosion resistance of the plating layer.

本発明はこのような現状に鑑み、Mg・Si含有Zn−Al系めっき鋼板において、従来のものより耐食性に優れるものを提供することを目的とする。   In view of such a current situation, the present invention aims to provide a Mg · Si-containing Zn—Al-based plated steel sheet that has better corrosion resistance than conventional ones.

上記目的は、平均組成が質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜6%であり、必要に応じてさらにTi、Bの1種または2種を合計0.1%以下の範囲で含有し、残部Znおよび不可避的不純物であるZn−Al系めっき層を有するめっき鋼板であって、当該めっき層は、Znリッチ部、Alリッチ部およびSiリッチ部からなり、Znリッチ部にはMg濃度4.5質量%以上の領域があり、Alリッチ部およびSiリッチ部にはMg濃度4.5質量%以上の領域が観測されない組織状態を呈する耐食性に優れたZn−Al系めっき鋼板によって達成される。鋼板片面当たりのめっき付着量は例えば30〜200g/m2である。 The above-mentioned object is that Al: 25 to 75%, Si: 1 to 10%, Mg: 0.5 to 6% in terms of mass composition, and Ti or B, if necessary, for one or two of Ti and B. A plated steel sheet having a total content of 0.1% or less and having a remaining Zn and a Zn—Al-based plating layer that is an inevitable impurity, the plating layer comprising a Zn-rich portion, an Al-rich portion, and a Si-rich portion The Zn-rich part has a region with an Mg concentration of 4.5% by mass or more, and the Al-rich part and the Si-rich part have an excellent corrosion resistance with a structure state in which a region with an Mg concentration of 4.5% by mass or more is not observed. This is achieved by using a Zn-Al-based plated steel sheet. The plating adhesion amount per one side of the steel plate is, for example, 30 to 200 g / m 2 .

このめっき鋼板の製造方法として、鋼板を基材として、下記めっき要件を満たすように、質量%でSi:1〜12%、Zn:0〜10%、残部Alおよび不可避的不純物からなる第1の溶融めっきを施して第1めっき層を形成させ、その上に質量%でAl:3〜22%、Mg:1〜10%、Si:0〜2%、Ti:0〜0.1%、B:0〜0.05%、残部Znおよび不可避的不純物からなる第2の溶融めっきを施して第2めっき層を形成させることにより重層めっき鋼板を製造し、その後、当該重層めっき鋼板を500〜650℃に加熱し、第2めっき層を溶融させて第1めっき層と反応させることにより第1めっき層中に新たに溶融したZnリッチ部を生成させ、第2の溶融めっきに由来するZnおよびMgがめっき層の厚み全域に分布したのち冷却する手法が提供される。
〔めっき要件〕
めっき層全体の平均組成においてAl、SiおよびMgの含有量が、質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜6%となるように、第1および第2の溶融めっきにおける浴組成およびめっき付着量をそれぞれ設定する。
As a manufacturing method of this plated steel sheet, the first steel consisting of Si: 1 to 12%, Zn: 0 to 10%, the balance Al and unavoidable impurities in mass% so as to satisfy the following plating requirements using the steel sheet as a base material. A first plating layer is formed by hot dip plating, and Al: 3 to 22%, Mg: 1 to 10%, Si: 0 to 2%, Ti: 0 to 0.1%, and B on the mass. : A multi-layer plated steel sheet is produced by forming a second plated layer by applying a second hot dipping comprising 0 to 0.05%, the balance Zn and unavoidable impurities, and then the multi-layer plated steel sheet is 500 to 650 Zn and Mg derived from the second hot dipping are generated by heating to 0 ° C., causing the second plating layer to melt and reacting with the first plating layer to produce a newly melted Zn rich portion in the first plating layer. Is distributed throughout the thickness of the plating layer. Method of cooling later is provided.
[Plating requirements]
In the average composition of the whole plating layer, the first and the second so that the content of Al, Si and Mg is Al: 25 to 75%, Si: 1 to 10%, Mg: 0.5 to 6% by mass%. The bath composition and the plating adhesion amount in the second hot dipping are set.

重層めっき鋼板の前記加熱において、例えば加熱温度を550〜650℃とし、加熱時間を均熱0〜5秒とすることができる。   In the heating of the multi-layer plated steel sheet, for example, the heating temperature can be set to 550 to 650 ° C., and the heating time can be set to 0 to 5 seconds for soaking.

本発明によれば、めっき層中のMgがSiリッチ部ではなくZnリッチ部に主として存在するMg・Si含有Zn−Al系めっき鋼板を工業的に製造することが可能になった。このようなめっき層組織を有するMg・Si含有Zn−Al系めっき鋼板は、従来のめっき層組織を有するものと比べ耐食性に優れる。   According to the present invention, it has become possible to industrially produce an Mg · Si-containing Zn—Al-based plated steel sheet in which Mg in the plating layer is mainly present in the Zn-rich portion, not in the Si-rich portion. The Mg · Si-containing Zn—Al-based plated steel sheet having such a plated layer structure is superior in corrosion resistance as compared with those having a conventional plated layer structure.

本発明例のMg・Si含有Zn−Al系めっき鋼板におけるめっき層断面SEM写真。The plating layer cross-sectional SEM photograph in the Mg * Si containing Zn-Al type plated steel plate of the example of this invention. 図1に対応する領域におけるZnのEPMA面分析結果を示す画像。The image which shows the EPMA surface analysis result of Zn in the area | region corresponding to FIG. 図1に対応する領域におけるAlのEPMA面分析結果を示す画像。The image which shows the EPMA surface analysis result of Al in the area | region corresponding to FIG. 図1に対応する領域におけるMgのEPMA面分析結果を示す画像。The image which shows the EPMA surface analysis result of Mg in the area | region corresponding to FIG. 図1に対応する領域におけるSiのEPMA面分析結果を示す画像。The image which shows the EPMA surface analysis result of Si in the area | region corresponding to FIG. 図1に対応する領域におけるFeのEPMA面分析結果を示す画像。The image which shows the EPMA surface analysis result of Fe in the area | region corresponding to FIG. 1浴めっきにて製造された従来のSi含有Zn−Al系めっき鋼板およびMg・Si含有Zn−Al系めっき鋼板についてのめっき層断面SEM写真およびEDX分析結果を示す図。The figure which shows the plating layer cross-sectional SEM photograph and EDX analysis result about the conventional Si containing Zn-Al type plated steel plate manufactured by 1 bath plating, and Mg * Si containing Zn-Al type plated steel plate. CCT150サイクル後のめっき層の断面写真。The cross-sectional photograph of the plating layer after CCT150 cycle.

従来、55%前後のAlを含有するZn−Al系めっき鋼板は、他の一般的な溶融めっき鋼板と同様、基材鋼板を合金めっき浴に1回浸漬することによって製造されている。めっき浴への浸漬回数が1回であることから、本明細書ではこれを「1浴めっき」と呼ぶ。1浴めっきによりSi含有Zn−Al系めっきを行うと、めっき層はZnリッチ部、Alリッチ部およびSiリッチ部からなる組織を呈するものとなる。本明細書では、めっき層に含まれる金属元素のうち、質量%でZn含有量が最も高い部分を「Znリッチ部」、Al含有量が最も高い部分を「Alリッチ部」、Si含有量が最も高い部分を「Siリッチ部」と呼んでいる。Mg・Si含有Zn−Al系めっき鋼板の場合も、めっき層はZnリッチ部、Alリッチ部およびSiリッチ部からなるものとなる。Mgリッチ部は形成されず、Mgは主としてSiリッチ部に金属間化合物として存在する。めっき後に加熱して拡散処理を行った場合でも、Siリッチ部に濃化したMgをめっき層中に拡散させることは困難であり、Znリッチ部にMgが濃化した金属組織を得ることはできない。   Conventionally, a Zn—Al-based plated steel sheet containing about 55% Al is manufactured by immersing a base steel sheet once in an alloy plating bath, as with other general hot-dip plated steel sheets. Since the number of immersions in the plating bath is one, this is referred to as “one-bath plating” in this specification. When Si-containing Zn—Al-based plating is performed by one bath plating, the plating layer exhibits a structure composed of a Zn-rich portion, an Al-rich portion, and a Si-rich portion. In the present specification, among the metal elements contained in the plating layer, the portion with the highest Zn content in mass% is “Zn-rich portion”, the portion with the highest Al content is “Al-rich portion”, and the Si content is The highest part is called “Si rich part”. Also in the case of the Mg · Si-containing Zn—Al-based plated steel sheet, the plating layer is composed of a Zn-rich portion, an Al-rich portion, and a Si-rich portion. The Mg rich part is not formed, and Mg exists mainly as an intermetallic compound in the Si rich part. Even when the diffusion treatment is performed by heating after plating, it is difficult to diffuse Mg concentrated in the Si-rich portion into the plating layer, and a metal structure in which Mg is concentrated in the Zn-rich portion cannot be obtained. .

本発明では、1浴めっきではなく、2浴めっき+拡散処理によって、MgがZnリッチ部に主として存在するめっき層組織を有するMg・Si含有Zn−Al系めっき鋼板を得る。2浴めっきは、基材表面に第1の溶融めっきを施し、その上に別のめっき浴にて第2の溶融めっきを施すことによって、重層構造のめっき層を形成させるものである。第1の溶融めっきに使用するめっき浴を「第1めっき浴」、それにより形成されためっき層を「第1めっき層」と呼ぶ。また、第2の溶融めっきに使用するめっき浴を「第2めっき浴」、それにより形成された新たなめっき層の部分を「第2めっき層」と呼ぶ。めっき浴あるいはめっき層の組成における「%」は特に断らない限り「質量%」を意味する。   In the present invention, a Mg · Si-containing Zn—Al-based plated steel sheet having a plating layer structure in which Mg mainly exists in the Zn-rich portion is obtained not by one-bath plating but by two-bath plating + diffusion treatment. In the two-bath plating, a first hot-dip plating is performed on the surface of a base material, and a second hot-dip plating is performed on the surface of the second hot-dip plating in another plating bath, thereby forming a plating layer having a multilayer structure. The plating bath used for the first hot dipping is referred to as “first plating bath”, and the plating layer formed thereby is referred to as “first plating layer”. A plating bath used for the second hot dipping is called a “second plating bath”, and a portion of a new plating layer formed thereby is called a “second plating layer”. “%” In the composition of the plating bath or plating layer means “% by mass” unless otherwise specified.

〔基材鋼板〕
めっき原板となる基材鋼板としては、従来一般的にZn系めっき鋼板、Al系めっき鋼板、Zn−Al系めっき鋼板などの溶融めっき鋼板の基材として使用されている各種鋼板が適用可能である。用途に応じて種々の鋼種が選択され、ステンレス鋼を適用することもできる。
[Base steel sheet]
Various steel plates that have been conventionally used as base materials for hot-dipped steel sheets such as Zn-based plated steel sheets, Al-based plated steel sheets, and Zn-Al-based plated steel sheets can be used as the base steel sheet that serves as the plating base plate. . Various steel types are selected according to the application, and stainless steel can also be applied.

〔第1の溶融めっき〕
第1の溶融めっきは、質量%でSi:1〜12%、Zn:0〜10%、残部Alおよび不可避的不純物からなる「Al系めっき」とする。ただし、第1の溶融めっきにおける浴組成およびめっき付着量は、第1のめっき層と第2のめっき層からなる重層めっき層における平均組成が後述の範囲となるように設定する必要がある。
[First hot dipping]
The first hot dipping is “Al-based plating” consisting of Si: 1 to 12% by mass, Zn: 0 to 10%, the balance Al and unavoidable impurities. However, the bath composition and plating adhesion amount in the first hot dipping must be set so that the average composition in the multilayer plating layer composed of the first plating layer and the second plating layer falls within the range described later.

第1の溶融めっきにおけるSiは、Al系めっき浴の液相線温度を低減する作用を有する。また、基材鋼板との界面に脆いFe−Al系反応層が厚く生成することを抑制し、薄いAl−Fe−Si系反応層を生成させる作用もある。ただし、めっき浴のSi含有量が12%を超えると共晶組成を過ぎて逆に液相線温度が上昇する領域に入りやすい。また、第1めっき浴にそのような多量のSiを含有させると第1めっき層/第2めっき層界面に多量のSi晶出相が形成して、拡散処理による組成の均一化を阻害する要因となり得る。このため、第1めっき浴のSi含有量は12%以下とする。   Si in the first hot dipping has an action of reducing the liquidus temperature of the Al-based plating bath. Moreover, it has the effect | action which suppresses that a brittle Fe-Al-type reaction layer produces | generates thick in an interface with a base-material steel plate, and produces | generates a thin Al-Fe-Si-type reaction layer. However, if the Si content of the plating bath exceeds 12%, the eutectic composition is passed and the liquidus temperature tends to rise. In addition, when such a large amount of Si is contained in the first plating bath, a large amount of Si crystallized phase is formed at the interface between the first plating layer and the second plating layer, and the factor that hinders the homogenization of the composition by the diffusion treatment Can be. For this reason, Si content of the 1st plating bath shall be 12% or less.

第1めっき浴中には必要に応じてZnを含有させることができるが、あまりZn含有量が多いとめっき層全体の平均組成を後述の範囲に調整する上で、第2めっき浴中のZn含有量を低めに設定する必要が生じ、Mg含有量が相対的に高くなって第2の溶融めっき性を低下させる要因となる。このため、第1めっき浴にZnを含有させる場合は10%以下の範囲で行う。   Zn can be contained in the first plating bath as necessary. However, if the Zn content is too large, Zn in the second plating bath is used to adjust the average composition of the entire plating layer to the range described later. It becomes necessary to set the content lower, and the Mg content becomes relatively high, which becomes a factor of reducing the second hot dipping property. For this reason, when Zn is contained in the first plating bath, it is performed in a range of 10% or less.

第1の溶融めっきにおけるSiとZnの残部は、Alおよび不可避的不純物である。不可避的不純物として2%以下の範囲でFeの混入が許容され、他の不純物元素は合計1%以下の範囲とすることが好ましい。第1の溶融めっきはAl系めっき鋼板の製造ラインをそのまま利用して実施することが可能である。   The balance of Si and Zn in the first hot dipping is Al and inevitable impurities. Inevitable impurities are allowed to be mixed in the range of 2% or less, and other impurity elements are preferably set to a range of 1% or less in total. The first hot dipping can be performed using the production line of the Al-based plated steel sheet as it is.

〔第2の溶融めっき〕
第2の溶融めっきは、質量%でAl:3〜22%、Mg:1〜10%、Si:0〜2%、Ti:0〜0.1%、B:0〜0.05%、残部Znおよび不可避的不純物からなる「Zn−Al−Mg系めっき」とする。ただし、第2の溶融めっきにおける浴組成およびめっき付着量は、第1のめっき層と第2のめっき層からなる重層めっき層における平均組成が後述の範囲となるように設定する必要がある。
[Second hot dipping]
The second hot-dip plating is Al: 3 to 22% by mass, Mg: 1 to 10%, Si: 0 to 2%, Ti: 0 to 0.1%, B: 0 to 0.05%, the balance This is “Zn—Al—Mg-based plating” made of Zn and inevitable impurities. However, the bath composition and the plating adhesion amount in the second hot dipping must be set so that the average composition in the multilayer plating layer composed of the first plating layer and the second plating layer falls within the range described later.

第2の溶融めっきは、主としてMgをめっき層中に供給する役割を担う。目標組成のSiとMgを1つの溶融めっき浴から1浴めっきで供給しようとすると、めっき浴の凝固過程においてMg2Si相の生成が避けられず、Mg添加による耐食性向上効果が十分に活かしきれない。そこで本発明ではSiを添加していないか、またはSi添加量を低く抑えた第2めっき浴を用いて、Mg含有めっき層を新たに形成させる。また、第1の溶融めっきがAl系めっきであるから、第2の溶融めっきでは目的とするZn−Al系めっき層の構成成分であるZnを供給する役割も有する。ただし、Zn系めっき浴にMgを含有させると、Mg酸化物系ドロスの生成によりめっき性が低下する。これを抑制するにはMg含有めっき浴中にAlを含有させることが有効である。また、Alは目的とするZn−Al系めっき層の主たる構成成分の1つであるから、第2めっき浴に添加することに問題はない。したがって、本発明では第2の溶融めっきをZn−Al−Mg系めっきとしている。 The second hot dipping is mainly responsible for supplying Mg into the plating layer. When trying to supply the target composition of Si and Mg from one hot dipping bath by one bath plating, the formation of Mg 2 Si phase is inevitable in the solidification process of the plating bath, and the effect of improving corrosion resistance by adding Mg can be fully utilized. Absent. Therefore, in the present invention, a Mg-containing plating layer is newly formed using a second plating bath in which Si is not added or the amount of Si added is kept low. Further, since the first hot dipping is Al-based plating, the second hot dipping also has a role of supplying Zn, which is a constituent component of the target Zn-Al-based plating layer. However, when Mg is contained in the Zn-based plating bath, the plating property is lowered due to the generation of Mg oxide-based dross. In order to suppress this, it is effective to contain Al in the Mg-containing plating bath. Moreover, since Al is one of the main components of the target Zn—Al-based plating layer, there is no problem in adding it to the second plating bath. Therefore, in the present invention, the second hot dipping is Zn—Al—Mg based plating.

最終的なめっき層において後述のMg含有量を確保するためには、第2の溶融めっき浴中のMg含有量は1%以上とすることが望まれる。2%以上に管理してもよい。一方、めっき浴中のMg含有量が多くなるとMg酸化物系ドロスが発生しやすくなる。このため第2めっき浴中のMg含有量は10%以下に規定され、8%以下とすることがより好ましく、7%以下あるいは6%以下に管理してもよい。めっき浴中のMgは、第1の溶融めっきにより形成されたAl系めっき層の表面酸化皮膜を還元し表面を活性化する作用を有しており、第1めっき層の上層に第2めっき層を密着性良く不めっきなどの欠陥を発生させずに健全に形成させるのにも役立っていると推察される。さらに、後述する加熱処理において第1めっき層/第2めっき層の界面における拡散を滑らかに進行させるのにも役立っていると推察される。   In order to ensure the later-described Mg content in the final plating layer, it is desirable that the Mg content in the second hot dipping bath is 1% or more. You may manage to 2% or more. On the other hand, when the Mg content in the plating bath increases, Mg oxide-based dross tends to occur. For this reason, the Mg content in the second plating bath is regulated to 10% or less, more preferably 8% or less, and may be controlled to 7% or less or 6% or less. Mg in the plating bath has a function of reducing the surface oxide film of the Al-based plating layer formed by the first hot dipping and activating the surface, and the second plating layer is formed on the first plating layer. It is presumed that it is also useful for forming a film with good adhesion without causing defects such as non-plating. Further, it is presumed that the heat treatment described later is also useful for smoothly promoting diffusion at the interface between the first plating layer and the second plating layer.

第2の溶融めっきにおけるAl含有量が3%を下回ると、Mg酸化物系ドロスの生成抑制効果が不十分となる。一方、めっき浴中のAl含有量が22%を超えるとめっき浴の融点が高くなり表面性状の良好なめっき面を得ることが難しくなる。第2めっき浴中のAl含有量は15%以下とすることがより好ましい。   When the Al content in the second hot dipping is less than 3%, the effect of suppressing the formation of Mg oxide-based dross becomes insufficient. On the other hand, if the Al content in the plating bath exceeds 22%, the melting point of the plating bath increases and it becomes difficult to obtain a plated surface with good surface properties. The Al content in the second plating bath is more preferably 15% or less.

第2めっき浴中には、さらにSi、Ti、Bの1種以上を含有させることができる。めっき浴中にSiを含有させると、めっき層の黒色化が防止され、表面の光沢性が維持されるので、拡散処理までの保管期間が長い場合などには有利となる。ただし、Si含有量が多くなるとMg2Si相の生成を招くので、第2めっき浴にSiを含有させる場合は2%以下の範囲で行う。Ti、Bの1種または2種を含有させると、斑点状の外観不良の要因となるZn11Mg2相の生成・成長が抑制される。また、表面性状の良い溶融Zn−Al−Mg系めっき層を得るための浴温および冷却速度の自由度が拡大する。Ti、Bの1種以上を含有させる場合は、Ti:0.1%以下、B:0.05%以下の範囲とすればよい。 The second plating bath can further contain one or more of Si, Ti, and B. When Si is contained in the plating bath, the plating layer is prevented from being blackened and the glossiness of the surface is maintained, which is advantageous when the storage period until the diffusion treatment is long. However, when the Si content is increased, the Mg 2 Si phase is generated, so when Si is contained in the second plating bath, it is performed in a range of 2% or less. Ti, the inclusion of one or two B, formation and growth of Zn 11 Mg 2 phase, which causes a patchy appearance defects are suppressed. In addition, the degree of freedom in bath temperature and cooling rate for obtaining a molten Zn—Al—Mg-based plating layer with good surface properties is expanded. When one or more of Ti and B are contained, the content of Ti is 0.1% or less and B is 0.05% or less.

第2の溶融めっきにおける上記元素以外の残部は、Znおよび不可避的不純物である。不可避的不純物として2%以下の範囲でFeの混入が許容され、他の不純物元素は合計1%以下の範囲とすることが好ましい。第2の溶融めっきはZn−Al−Mg系めっき鋼板の製造ラインをそのまま利用して実施することが可能である。   The balance other than the above elements in the second hot dipping is Zn and inevitable impurities. Inevitable impurities are allowed to be mixed in the range of 2% or less, and other impurity elements are preferably set to a range of 1% or less in total. The second hot dipping can be carried out using the production line of the Zn—Al—Mg plated steel sheet as it is.

〔拡散処理〕
以上のようにして重層構造のめっき層を形成したのち、加熱による拡散処理を行う。この加熱処理は実際のめっきラインにおいては、第2の溶融めっき後に引き続き加熱炉を通過させることにより実施することが可能である。加熱温度は500〜650℃の範囲とする。この温度域は、第2めっき層を溶融させて第1めっき層と反応させることで、第1めっき層中に新たに溶融したZnリッチ部を生成させる温度域であり、Siリッチ部は溶融しない温度域である。本発明ではめっき層中に溶融したZnリッチ部を生成させて、厚さ方向におけるめっき層組織の均一化を図る。その際、重層めっき層中のAlリッチ部も溶融して構わない。ただし、未溶融のSiリッチ部と溶融状態となった液相中のMgが反応すると、Siリッチ部にMg2Siが形成される恐れがあるので、加熱時間はできるだけ短時間とすることが望ましい。
[Diffusion treatment]
After forming the multi-layered plating layer as described above, diffusion treatment by heating is performed. In the actual plating line, this heat treatment can be carried out by continuously passing through a heating furnace after the second hot dipping. The heating temperature is in the range of 500 to 650 ° C. This temperature range is a temperature range in which a newly melted Zn-rich portion is generated in the first plating layer by melting the second plating layer and reacting with the first plating layer, and the Si-rich portion does not melt. It is a temperature range. In the present invention, a Zn-rich portion melted in the plating layer is generated to make the plating layer structure uniform in the thickness direction. At that time, the Al-rich portion in the multilayer plating layer may be melted. However, when Mg in the molten liquid phase reacts with the unmelted Si-rich part, Mg 2 Si may be formed in the Si-rich part. Therefore, it is desirable that the heating time be as short as possible. .

具体的には、第2の溶融めっきに由来するZnおよびMgがめっき層の厚み全域に分布するに足る加熱時間が確保できればよい。基材鋼板とめっき層の界面に介在するAl−Fe−Si系反応層近傍までMgが拡散して到達していれば、十分に拡散が進行したと判断できる。例えば、加熱温度を550〜650℃とし、加熱時間を均熱0〜5秒とすることができる。ここで「均熱」とはめっき層の温度が目標温度に達してから冷却するまでの時間である。例えば「600℃、均熱0秒」というときは、めっき層温度が600℃に到達した時点で、直ちに冷却する加熱パターンである。第1めっき層、第2めっき層の構成などに応じて、予め予備実験により最適な加熱パターンのデータを把握しておけばよい。加熱雰囲気は特に限定されるものではなく、大気雰囲気、N2ガスなどの非酸化性雰囲気、N2−H2ガスなどの還元性雰囲気とすることができる。 Specifically, it is only necessary to ensure a heating time sufficient for Zn and Mg derived from the second hot dipping to be distributed over the entire thickness of the plating layer. If Mg has diffused and reached the vicinity of the Al—Fe—Si reaction layer interposed at the interface between the base steel plate and the plating layer, it can be determined that the diffusion has sufficiently progressed. For example, the heating temperature can be 550 to 650 ° C., and the heating time can be soaking 0 to 5 seconds. Here, “soaking” is the time from when the temperature of the plating layer reaches the target temperature until cooling. For example, “600 ° C., soaking 0 seconds” is a heating pattern that immediately cools when the plating layer temperature reaches 600 ° C. According to the configuration of the first plating layer and the second plating layer, the data of the optimum heating pattern may be obtained in advance by preliminary experiments. Heating atmosphere is not particularly limited, it can be an air atmosphere, a non-oxidizing atmosphere such as N 2 gas, a reducing atmosphere such as N 2 -H 2 gas.

〔最終的なめっき層〕
拡散処理によって得られる最終的なめっき層(目的とするめっき層)の平均組成は、Al、SiおよびMgの含有量が、質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜6%となるようにする。第2の溶融めっきでTi、Bの1種または2種を添加する場合は、Ti、Bの1種または2種を合計0.1%以下の範囲で含有して構わない。残部元素はZnおよび不可避的不純物である。
[Final plating layer]
The average composition of the final plating layer (target plating layer) obtained by the diffusion treatment is such that the content of Al, Si, and Mg is Al: 25 to 75%, Si: 1 to 10%, Mg in mass%. : Set to 0.5 to 6%. When adding 1 type or 2 types of Ti and B by 2nd hot dipping, you may contain 1 type or 2 types of Ti and B in the range of a total 0.1% or less. The remaining elements are Zn and inevitable impurities.

Alは「めっき面の高耐食性」を付与する元素であり、Znは「犠牲防食作用」を付与する元素である。それらの特性バランスを考慮して、用途に応じてAl含有量を25〜75%の範囲で設定する。   Al is an element that imparts “high corrosion resistance of the plated surface”, and Zn is an element that imparts “sacrificial anticorrosive action”. In consideration of the balance of the characteristics, the Al content is set in the range of 25 to 75% according to the application.

Mgは保護性に優れたZn系腐食生成物を形成させ、めっき層の腐食の進行を抑制する作用を担う。そのためにはめっき層中のMg含有量は0.5%以上とする必要があり、1%以上とすることがより好ましく、2%以上が一層好ましい。ただし過剰のMgはめっき層の加工性を低下させる要因となり、また第2の溶融めっきでのMg添加量が増大するので、平均組成におけるMg含有量は6%以下の範囲とする。   Mg forms a Zn-based corrosion product having excellent protective properties and plays a role of suppressing the progress of corrosion of the plating layer. For this purpose, the Mg content in the plating layer needs to be 0.5% or more, more preferably 1% or more, and even more preferably 2% or more. However, excessive Mg causes a decrease in the workability of the plating layer, and the amount of Mg added in the second hot dipping increases, so the Mg content in the average composition is set to a range of 6% or less.

Siは上述のように基材鋼板とめっき層の間に生成する脆いFe−Al系反応層の生成を抑制する作用や、めっき層表面の黒色化を抑制する作用を有し、第1めっき浴あるいはさらに第2めっき浴に配合される。めっき層全体の平均組成においてSi含有量は1%以上となる。ただし、多量のSi含有は塊状の析出物の多量生成を招くことがあり、めっき層の加工性を低下させる要因となるので、平均組成におけるSi含有量は10%以下の範囲とする。   Si has the effect of suppressing the formation of a brittle Fe—Al-based reaction layer generated between the base steel plate and the plating layer as described above, and the effect of suppressing the blackening of the plating layer surface. Or it is further mix | blended with a 2nd plating bath. In the average composition of the entire plating layer, the Si content is 1% or more. However, since a large amount of Si content may cause a large amount of massive precipitates to be produced, which causes a decrease in the workability of the plating layer, the Si content in the average composition is made 10% or less.

上記の平均組成を有する重層構造のめっき層は、上記の拡散処理により、Znリッチ部、Alリッチ部およびSiリッチ部からなり、Znリッチ部にはMg濃度4.5質量%以上の領域があり、Alリッチ部およびSiリッチ部にはMg濃度4.5質量%以上の領域が観測されない組織状態を呈するものとなる。断面組織構造は、Alリッチ部の間をZnリッチ部が網目状に埋めるような構造を基本とし、部分的にSiリッチ部が存在する状態となる。   The plating layer having a multilayer structure having the above average composition is composed of a Zn-rich portion, an Al-rich portion, and a Si-rich portion by the above diffusion treatment, and the Zn-rich portion has a region having an Mg concentration of 4.5% by mass or more. In the Al-rich part and the Si-rich part, a structure state in which a region having an Mg concentration of 4.5 mass% or more is not observed is exhibited. The cross-sectional structure is basically a structure in which the Zn-rich portion is filled in a network between the Al-rich portions, and the Si-rich portion is partially present.

従来の1浴めっきによるMg・Si含有Zn−Al系めっき鋼板と最も相違する点は、本発明に従った場合、めっき層中のMgは、その大部分がZnリッチ部に分布する点である。Siリッチ部にはMgがほとんど検出されないか、あるいは非常に少量である。すなわちSiリッチ部をEDX等の微視的手段で分析したとき、Mg濃度4.5質量%以上の領域が観測されない。Siはほとんど金属Siの状態で存在していると考えられる。一方、Znリッチ部には、EDX等の微視的手段で分析したときにMg濃度が4.5質量%以上となる部分がある。このようにMgは腐食されやすいZnリッチ部に多く存在しているため、Znリッチ部に腐食が生じたときに迅速に保護性の高いMg含有Zn系腐食生成物が形成され、これが従来よりもめっき層の耐食性を大幅に向上させているものと考えられる。   The most different point from the conventional Mg · Si-containing Zn—Al-plated steel sheet by one-bath plating is that, according to the present invention, most of the Mg in the plating layer is distributed in the Zn-rich portion. . Almost no Mg is detected in the Si-rich portion, or the amount is very small. That is, when the Si rich portion is analyzed by microscopic means such as EDX, a region having an Mg concentration of 4.5% by mass or more is not observed. Si is considered to exist almost in the form of metallic Si. On the other hand, the Zn-rich part has a part where the Mg concentration becomes 4.5% by mass or more when analyzed by microscopic means such as EDX. Since Mg is present in a large amount in the Zn-rich portion that is easily corroded in this way, a highly protective Mg-containing Zn-based corrosion product is rapidly formed when corrosion occurs in the Zn-rich portion. It is thought that the corrosion resistance of the plating layer is greatly improved.

鋼板片面あたりのトータルのめっき付着量は30〜200g/m2とすることが望ましい。めっき付着量が少なすぎると鋼板の耐食性(特に長期耐食性)が不足し、多すぎると加工性の低下を招く。 It is desirable that the total plating adhesion amount per one side of the steel plate is 30 to 200 g / m 2 . If the coating amount is too small, the corrosion resistance (particularly long-term corrosion resistance) of the steel sheet is insufficient, and if it is too large, the workability is reduced.

〔本発明例〕
基材鋼板として板厚0.8mmの普通鋼冷延鋼板(C含有量:0.04質量%)を用意した。この基材鋼板をめっき原板として、溶融Al系めっきラインを用いて第1の溶融めっきを施し、片面あたりのめっき付着量75g/m2の溶融Al系めっき鋼板を得た。次いで、このめっき鋼板を原板として、溶融Zn−Al−Mg系めっきラインを用いて第2の溶融めっきを施し、片面あたりのめっき付着量60g/m2の第2めっき層を有する重層めっき鋼板を得た。めっき浴組成はそれぞれ以下のとおりである。
(第1めっき浴)
質量%でSi:9%、Zn:0%、残部Alおよび不可避的不純物
(第2めっき浴)
質量%でAl:6%、Mg:3%、Si:0.025%、Ti:0.02%、B:0.005%、残部Znおよび不可避的不純物
この場合、めっき層全体の平均組成においてAl、SiおよびMgの含有量は以下のようになる。
(平均組成)
質量%でAl:53.2%、Si:5.0%、Mg:1.3%
[Invention Example]
A plain steel cold-rolled steel sheet having a thickness of 0.8 mm (C content: 0.04 mass%) was prepared as a base steel sheet. The base steel plate was used as a plating original plate, and the first hot dip plating was performed using a hot dip Al plating line to obtain a hot dip Al plated steel plate having a coating adhesion amount of 75 g / m 2 per side. Next, using this plated steel plate as a base plate, a second hot-dip plating is performed using a hot-dip Zn—Al—Mg-based plating line, and a multi-layer plated steel plate having a second plating layer with a plating adhesion amount of 60 g / m 2 per side is obtained. Obtained. The plating bath compositions are as follows.
(First plating bath)
In mass%, Si: 9%, Zn: 0%, balance Al and inevitable impurities (second plating bath)
In mass%, Al: 6%, Mg: 3%, Si: 0.025%, Ti: 0.02%, B: 0.005%, the balance Zn and inevitable impurities In this case, in the average composition of the entire plating layer The contents of Al, Si and Mg are as follows.
(Average composition)
In mass%, Al: 53.2%, Si: 5.0%, Mg: 1.3%

上記の重層めっき鋼板を、大気雰囲気中にて600℃、均熱0秒の加熱パターンで加熱することにより拡散処理を施し、Mg・Si含有Zn−Al系めっき鋼板を得た。   The multi-layer plated steel sheet was subjected to diffusion treatment by heating in an air atmosphere at a heating pattern of 600 ° C. and soaking for 0 seconds to obtain a Mg · Si-containing Zn—Al-based plated steel sheet.

このめっき鋼板の断面についてSEM観察を行うとともに、EPMAによる面分析を行った。図1にめっき層断面のSEM写真を例示する。また、図2〜図6にそれぞれ図1に対応する領域についてのZn、Al、Mg、Si、FeのEPMA面分析結果を示す。面分析画像において当該元素が検出された位置が白く表示されている。面分析の結果、めっき層は、Znリッチ部、Alリッチ部およびSiリッチ部からなり、MgはZnリッチ部に濃化していることがわかる。Siリッチ部にはMgの濃化が認められない。   While performing SEM observation about the section of this plated steel plate, surface analysis by EPMA was performed. FIG. 1 illustrates an SEM photograph of a cross section of the plating layer. 2 to 6 show the EPMA surface analysis results of Zn, Al, Mg, Si, and Fe for the regions corresponding to FIG. 1, respectively. The position where the element is detected in the surface analysis image is displayed in white. As a result of the surface analysis, the plating layer is composed of a Zn-rich portion, an Al-rich portion, and a Si-rich portion, and it can be seen that Mg is concentrated in the Zn-rich portion. Mg enrichment is not observed in the Si-rich part.

図1中に表示した1〜5の位置についてのEDX分析値(質量%)は以下のとおりである。
分析位置1; Zn:36.0%、Al:64.0%、Si:0%、Mg:0%
分析位置2; Zn:0%、Al:0%、Si:100%、Mg:0%
分析位置3; Zn:91.7%、Al:2.9%、Si:0%、Mg:5.4%
分析位置4; Zn:0%、Al:0%、Si:100%、Mg:0%
分析位置5; Zn:90.5%、Al:2.8%、Si:0%、Mg:6.7%
Znリッチ部(分析位置3、5)にはMg濃度4.5%以上の領域があり、Siリッチ部(分析箇所2、4)は金属Si相であると考えられる。
The EDX analysis values (mass%) for the positions 1 to 5 displayed in FIG. 1 are as follows.
Analysis position 1; Zn: 36.0%, Al: 64.0%, Si: 0%, Mg: 0%
Analysis position 2; Zn: 0%, Al: 0%, Si: 100%, Mg: 0%
Analysis position 3; Zn: 91.7%, Al: 2.9%, Si: 0%, Mg: 5.4%
Analysis position 4; Zn: 0%, Al: 0%, Si: 100%, Mg: 0%
Analysis position 5: Zn: 90.5%, Al: 2.8%, Si: 0%, Mg: 6.7%
The Zn-rich portion (analysis positions 3 and 5) has a region with an Mg concentration of 4.5% or more, and the Si-rich portion (analysis locations 2 and 4) is considered to be a metal Si phase.

〔従来例〕
1浴めっきにて製造されためっき鋼板として、Si含有Zn−Al系めっき鋼板(Zn−55%Al−1.5%Si合金めっき鋼板)、およびMg・Si含有Zn−Al系めっき鋼板(Zn−55%Al−1.5%Si−2%Mg合金めっき鋼板)を用意した。図7に、これらについてのめっき層断面のSEM写真を示す。図7中にはアルファベットで示した位置のEDX分析結果(質量%)を併記した。いずれもめっき層の断面組織はZnリッチ部、Alリッチ部およびSiリッチ部で構成されている。ただし、Mgを含有するものにおいては、MgはSiリッチ部に最も多く存在しており、別途X線回折を行ったところ、Mg2Si相の存在が認められた。
[Conventional example]
As a plated steel sheet produced by one bath plating, a Si-containing Zn-Al-based plated steel sheet (Zn-55% Al-1.5% Si alloy-plated steel sheet) and a Mg-Si-containing Zn-Al-based plated steel sheet (Zn -55% Al-1.5% Si-2% Mg alloy-plated steel sheet) was prepared. In FIG. 7, the SEM photograph of the plating layer cross section about these is shown. In FIG. 7, the EDX analysis results (mass%) at the positions indicated by alphabets are also shown. In any case, the cross-sectional structure of the plating layer is composed of a Zn-rich portion, an Al-rich portion, and a Si-rich portion. However, in the case of containing Mg, Mg is most abundant in the Si-rich portion, and when X-ray diffraction was performed separately, the presence of the Mg 2 Si phase was recognized.

《耐食性試験》
上記の本発明例および従来例のめっき鋼板から耐食性試験片を切り出し、複合サイクル腐食試験(CCT)に供した。試験片の寸法は75mm×150mm×板厚であり、ここではめっき面の耐食性を比べるために、切断端面と裏面全面を絶縁性テープにより被覆した。CCT条件はJIS H8502の中性塩水噴霧サイクル試験に準拠したもので、「塩水噴霧(5%NaCl水溶液、35℃)2h→乾燥(60℃、25%RH)4h→湿潤(50℃、98%RH)2h」のサイクルを1サイクルとするものである。150サイクル終了後に腐食生成物を液温70℃の10%塩化アンモニウム水溶液にて除去し、試験前との質量差から腐食減量を求めた。
その結果、腐食減量は以下のとおりであった。
1浴めっきによるSi含有Zn−Al系めっき鋼板; 31g/m2
1浴めっきによるMg・Si含有Zn−Al系めっき鋼板; 23g/m2
本発明例のMg・Si含有Zn−Al系めっき鋼板; 12g/m2
<Corrosion resistance test>
Corrosion resistance test pieces were cut out from the plated steel sheets of the present invention examples and the conventional examples and subjected to a combined cycle corrosion test (CCT). The dimension of the test piece is 75 mm × 150 mm × plate thickness. Here, in order to compare the corrosion resistance of the plated surface, the cut end surface and the entire back surface were covered with an insulating tape. The CCT conditions were based on the neutral salt spray cycle test of JIS H8502. “Salt spray (5% NaCl aqueous solution, 35 ° C.) 2 h → Dry (60 ° C., 25% RH) 4 h → Wet (50 ° C., 98% RH) 2h "is one cycle. After 150 cycles, the corrosion product was removed with a 10% aqueous ammonium chloride solution at a liquid temperature of 70 ° C., and the weight loss from the corrosion was determined from the difference in mass from before the test.
As a result, the corrosion weight loss was as follows.
Si-containing Zn-Al plated steel sheet by one bath plating; 31 g / m 2
Mg / Si-containing Zn-Al plated steel sheet by one bath plating; 23 g / m 2
Mg · Si-containing Zn—Al-based plated steel sheet of the present invention example: 12 g / m 2

図8に、上記CCT150サイクル後の代表的なめっき層の断面写真を例示する。
本発明例のものは、従来の1浴めっきによるMg・Si含有Zn−Al系めっき鋼板に比べ、めっき面の耐食性が顕著に改善された。
FIG. 8 illustrates a cross-sectional photograph of a typical plating layer after the CCT 150 cycle.
In the example of the present invention, the corrosion resistance of the plated surface was remarkably improved as compared with the conventional Mg · Si-containing Zn—Al-based plated steel sheet by one bath plating.

なお、別途パイロットラインにより第1の溶融めっきおよび第2の溶融めっきの浴組成を本発明に従う範囲で種々変えた重層構造のめっき鋼板(第2めっき浴にTi、B、Siを添加していないものを含む)を製造し、本発明に従う条件で拡散処理を施すことによって、本発明に該当するMg・Si含有Zn−Al系めっき鋼板を種々作製し、これらについて上記の耐食性試験を実施している。その結果、いずれも上記の従来例のものと比べ顕著な耐食性向上効果が確かめられた。   In addition, a plated steel sheet having a multi-layer structure in which the bath composition of the first hot dipping and the second hot dipping is variously changed within the range according to the present invention by a separate pilot line (Ti, B, Si are not added to the second plating bath) In addition, various Mg-Si-containing Zn-Al-plated steel sheets corresponding to the present invention are produced by carrying out diffusion treatment under the conditions according to the present invention, and the above corrosion resistance test is carried out on these. Yes. As a result, in each case, a remarkable corrosion resistance improvement effect was confirmed as compared with the conventional example.

Claims (5)

平均組成が質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜6%、残部Znおよび不可避的不純物であるZn−Al系めっき層を有するめっき鋼板であって、当該めっき層は、Znリッチ部、Alリッチ部およびSiリッチ部からなり、Znリッチ部にはMg濃度4.5質量%以上の領域があり、Alリッチ部およびSiリッチ部にはMg濃度4.5質量%以上の領域が観測されない組織状態を呈する耐食性に優れたZn−Al系めっき鋼板。   A plated steel sheet having an average composition of mass%, Al: 25 to 75%, Si: 1 to 10%, Mg: 0.5 to 6%, remaining Zn and Zn—Al based plating layer which is an unavoidable impurity, The plating layer is composed of a Zn-rich portion, an Al-rich portion, and an Si-rich portion. The Zn-rich portion includes a region having an Mg concentration of 4.5% by mass or more, and the Al-rich portion and the Si-rich portion have an Mg concentration of 4 A Zn-Al-based plated steel sheet excellent in corrosion resistance that exhibits a microstructure in which a region of 0.5 mass% or more is not observed. Zn−Al系めっき層の平均組成が質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜5%であり、さらにTi、Bの1種または2種を合計0.1%以下の範囲で含有し、残部Znおよび不可避的不純物である請求項1に記載のZn−Al系めっき鋼板。   The average composition of the Zn—Al-based plating layer is Al: 25 to 75%, Si: 1 to 10%, Mg: 0.5 to 5% in mass%, and one or two of Ti and B are added together. The Zn-Al-based plated steel sheet according to claim 1, which is contained in a range of 0.1% or less and is the balance Zn and inevitable impurities. 鋼板片面当たりのめっき付着量が30〜200g/m2である請求項1または2に記載のZn−Al系めっき鋼板。 Zn-Al-based plated steel sheet according to claim 1 or 2 coating weight per steel sheet one side is 30 to 200 g / m 2. 鋼板を基材として、下記めっき要件を満たすように、質量%でSi:1〜12%、Zn:0〜10%、残部Alおよび不可避的不純物からなる第1の溶融めっきを施して第1めっき層を形成させ、その上に質量%でAl:3〜22%、Mg:1〜10%、Si:0〜2%、Ti:0〜0.1%、B:0〜0.05%、残部Znおよび不可避的不純物からなる第2の溶融めっきを施して第2めっき層を形成させることにより重層めっき鋼板を製造し、その後、当該重層めっき鋼板を500〜650℃に加熱し、第2めっき層を溶融させて第1めっき層と反応させることにより第1めっき層中に新たに溶融したZnリッチ部を生成させ、第2の溶融めっきに由来するZnおよびMgがめっき層の厚み全域に分布したのち冷却する耐食性に優れたZn−Al系めっき鋼板の製造方法。
〔めっき要件〕
めっき層全体の平均組成においてAl、SiおよびMgの含有量が、質量%でAl:25〜75%、Si:1〜10%、Mg:0.5〜6%となるように、第1および第2の溶融めっきにおける浴組成およびめっき付着量をそれぞれ設定する。
First plating is performed by using a steel plate as a base material and applying the first hot dipping which consists of Si: 1 to 12%, Zn: 0 to 10%, the balance Al and inevitable impurities in mass% so as to satisfy the following plating requirements. A layer is formed, and Al: 3 to 22%, Mg: 1 to 10%, Si: 0 to 2%, Ti: 0 to 0.1%, B: 0 to 0.05%, A multi-layer plated steel sheet is manufactured by forming a second plating layer by applying a second hot-dip plating composed of the remaining Zn and inevitable impurities, and then heating the multi-layer plated steel sheet to 500 to 650 ° C. By melting the layer and reacting with the first plating layer, a newly melted Zn-rich portion is generated in the first plating layer, and Zn and Mg derived from the second hot-dip plating are distributed throughout the thickness of the plating layer. Zn with excellent corrosion resistance after cooling Method of manufacturing the Al-based plated steel sheet.
[Plating requirements]
In the average composition of the whole plating layer, the first and the second so that the content of Al, Si and Mg is Al: 25 to 75%, Si: 1 to 10%, Mg: 0.5 to 6% by mass%. The bath composition and the plating adhesion amount in the second hot dipping are set.
重層めっき鋼板の前記加熱において、加熱温度を550〜650℃とし、加熱時間を均熱0〜5秒とする請求項4に記載のZn−Al系めっき鋼板の製造方法。   5. The method for producing a Zn—Al-based plated steel sheet according to claim 4, wherein the heating of the multi-layer plated steel sheet is performed at a heating temperature of 550 to 650 ° C. and a heating time of 0 to 5 seconds for soaking.
JP2009077769A 2009-03-26 2009-03-26 Zn-Al plated steel sheet with excellent corrosion resistance and method for producing the same Active JP5404126B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009077769A JP5404126B2 (en) 2009-03-26 2009-03-26 Zn-Al plated steel sheet with excellent corrosion resistance and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009077769A JP5404126B2 (en) 2009-03-26 2009-03-26 Zn-Al plated steel sheet with excellent corrosion resistance and method for producing the same

Publications (2)

Publication Number Publication Date
JP2010229483A true JP2010229483A (en) 2010-10-14
JP5404126B2 JP5404126B2 (en) 2014-01-29

Family

ID=43045567

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009077769A Active JP5404126B2 (en) 2009-03-26 2009-03-26 Zn-Al plated steel sheet with excellent corrosion resistance and method for producing the same

Country Status (1)

Country Link
JP (1) JP5404126B2 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013027837A1 (en) * 2011-08-24 2013-02-28 新日鐵住金株式会社 Coated plated steel material
WO2013027827A1 (en) * 2011-08-24 2013-02-28 新日鐵住金株式会社 Surface-treated hot-dipped steel material
WO2014057771A1 (en) * 2012-10-12 2014-04-17 株式会社Neomaxマテリアル Metal substrate
CN104955975A (en) * 2013-01-31 2015-09-30 Jfe钢板株式会社 HOT-DIP Al-Zn GALVANIZED STEEL PLATE AND METHOD FOR PRODUCING SAME
US20180223409A1 (en) * 2015-07-30 2018-08-09 Arcelormittal Steel Sheet Coated with a Metallic Coating based on Aluminum
JP2019506525A (en) * 2015-12-24 2019-03-07 ポスコPosco Alloy-coated steel sheet and method for producing the same
US10655203B2 (en) 2015-10-26 2020-05-19 Nippon Steel Corporation Plated steel sheet
US10947608B2 (en) 2015-10-05 2021-03-16 Arcelormittal Steel sheet coated with a metallic coating based on aluminum and comprising titanium
CN112771197A (en) * 2018-09-27 2021-05-07 Posco公司 Highly corrosion-resistant plated steel sheet excellent in weld embrittlement resistance and plating adhesion
US11031162B2 (en) 2014-11-27 2021-06-08 Posco Grain-oriented electrical steel sheet and manufacturing method therefor
US11162153B2 (en) 2015-07-30 2021-11-02 Arcelormittal Method for the manufacture of a hardened part which does not have LME issues
US11414737B2 (en) 2015-07-30 2022-08-16 Arcelormittal Method for the manufacture of a phosphatable part starting from a steel sheet coated with a metallic coating based on aluminum
US11731397B2 (en) 2015-12-24 2023-08-22 Posco Co., Ltd Alloy-coated steel sheet and manufacturing method therefor
JP7393640B2 (en) 2020-01-22 2023-12-07 日本製鉄株式会社 Manufacturing method of multi-layer plated steel sheet

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000104153A (en) * 1998-09-28 2000-04-11 Daido Steel Sheet Corp Zinc-aluminum alloy plated steel sheet
JP2000265255A (en) * 1999-03-16 2000-09-26 Nisshin Steel Co Ltd HOT-DIP Zn-Al BASE ALLOY PLATED STEEL SHEET IMPROVED IN HEAT RESISTANCE AND ITS PRODUCTION
JP2001115247A (en) * 1999-08-09 2001-04-24 Nippon Steel Corp Zn-Al-Mg-Si ALLOY PLATED STEEL PRODUCT EXCELLENT IN CORROSION RESISTANCE, AND ITS MANUFACTURING METHOD
JP2002004017A (en) * 2000-06-15 2002-01-09 Nippon Steel Corp HOT-DIP Zn-Al-Mg-Si PLATED STEEL MATERIAL EXCELLENT IN SURFACE CHARACTERISTIC AND ITS PRODUCTION METHOD
JP2002275611A (en) * 2001-03-15 2002-09-25 Nippon Steel Corp Columnar material plated with zinc alloy, method for producing the same and flux used in the production method
JP2002322527A (en) * 2001-04-25 2002-11-08 Nippon Steel Corp Al-Zn-Mg BASED ALLOY PLATED STEEL PRODUCT
JP2003147500A (en) * 2001-11-09 2003-05-21 Nippon Steel Corp HOT DIP Zn-Al ALLOY PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AFTER WORKING, AND PRODUCTION METHOD THEREFOR

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000104153A (en) * 1998-09-28 2000-04-11 Daido Steel Sheet Corp Zinc-aluminum alloy plated steel sheet
JP2000265255A (en) * 1999-03-16 2000-09-26 Nisshin Steel Co Ltd HOT-DIP Zn-Al BASE ALLOY PLATED STEEL SHEET IMPROVED IN HEAT RESISTANCE AND ITS PRODUCTION
JP2001115247A (en) * 1999-08-09 2001-04-24 Nippon Steel Corp Zn-Al-Mg-Si ALLOY PLATED STEEL PRODUCT EXCELLENT IN CORROSION RESISTANCE, AND ITS MANUFACTURING METHOD
JP2002004017A (en) * 2000-06-15 2002-01-09 Nippon Steel Corp HOT-DIP Zn-Al-Mg-Si PLATED STEEL MATERIAL EXCELLENT IN SURFACE CHARACTERISTIC AND ITS PRODUCTION METHOD
JP2002275611A (en) * 2001-03-15 2002-09-25 Nippon Steel Corp Columnar material plated with zinc alloy, method for producing the same and flux used in the production method
JP2002322527A (en) * 2001-04-25 2002-11-08 Nippon Steel Corp Al-Zn-Mg BASED ALLOY PLATED STEEL PRODUCT
JP2003147500A (en) * 2001-11-09 2003-05-21 Nippon Steel Corp HOT DIP Zn-Al ALLOY PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AFTER WORKING, AND PRODUCTION METHOD THEREFOR

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013027827A1 (en) * 2011-08-24 2013-02-28 新日鐵住金株式会社 Surface-treated hot-dipped steel material
JP5408385B2 (en) * 2011-08-24 2014-02-05 新日鐵住金株式会社 Surface-treated hot-dip galvanized steel
JP5408384B2 (en) * 2011-08-24 2014-02-05 新日鐵住金株式会社 Painted steel
WO2013027837A1 (en) * 2011-08-24 2013-02-28 新日鐵住金株式会社 Coated plated steel material
WO2014057771A1 (en) * 2012-10-12 2014-04-17 株式会社Neomaxマテリアル Metal substrate
CN104955975A (en) * 2013-01-31 2015-09-30 Jfe钢板株式会社 HOT-DIP Al-Zn GALVANIZED STEEL PLATE AND METHOD FOR PRODUCING SAME
EP2957648A4 (en) * 2013-01-31 2016-02-10 Jfe Steel Corp HOT-DIP Al-Zn ALLOY COATED STEEL SHEET AND METHOD FOR PRODUCING SAME
AU2014212967B2 (en) * 2013-01-31 2016-05-19 Jfe Galvanizing & Coating Co., Ltd. Hot-dip Al-Zn alloy coated steel sheet and method for producing same
US11031162B2 (en) 2014-11-27 2021-06-08 Posco Grain-oriented electrical steel sheet and manufacturing method therefor
US20210395853A1 (en) * 2015-07-30 2021-12-23 Arcelormittal Hot formed pre-coated steel part
US11414737B2 (en) 2015-07-30 2022-08-16 Arcelormittal Method for the manufacture of a phosphatable part starting from a steel sheet coated with a metallic coating based on aluminum
US10889884B2 (en) 2015-07-30 2021-01-12 Arcelormittal Steel sheet coated with a metallic coating based on aluminum
US20180223409A1 (en) * 2015-07-30 2018-08-09 Arcelormittal Steel Sheet Coated with a Metallic Coating based on Aluminum
US20210395855A1 (en) * 2015-07-30 2021-12-23 Arcelormittal Method for manufacture of a pre-coated steel sheet
US20210395854A1 (en) * 2015-07-30 2021-12-23 Arcelormittal Pre-coated steel sheet
US11162153B2 (en) 2015-07-30 2021-11-02 Arcelormittal Method for the manufacture of a hardened part which does not have LME issues
US10947608B2 (en) 2015-10-05 2021-03-16 Arcelormittal Steel sheet coated with a metallic coating based on aluminum and comprising titanium
US10655203B2 (en) 2015-10-26 2020-05-19 Nippon Steel Corporation Plated steel sheet
JP2019506525A (en) * 2015-12-24 2019-03-07 ポスコPosco Alloy-coated steel sheet and method for producing the same
US11731397B2 (en) 2015-12-24 2023-08-22 Posco Co., Ltd Alloy-coated steel sheet and manufacturing method therefor
CN112771197A (en) * 2018-09-27 2021-05-07 Posco公司 Highly corrosion-resistant plated steel sheet excellent in weld embrittlement resistance and plating adhesion
US11530470B2 (en) 2018-09-27 2022-12-20 Posco Co., Ltd Highly corrosion-resistant plated steel sheet having excellent plating adhesion and resistance to liquid metal embrittlement
CN112771197B (en) * 2018-09-27 2024-04-02 浦项股份有限公司 High corrosion resistant plated steel sheet excellent in weld liquefaction brittleness resistance and plating adhesion
JP7393640B2 (en) 2020-01-22 2023-12-07 日本製鉄株式会社 Manufacturing method of multi-layer plated steel sheet

Also Published As

Publication number Publication date
JP5404126B2 (en) 2014-01-29

Similar Documents

Publication Publication Date Title
JP5404126B2 (en) Zn-Al plated steel sheet with excellent corrosion resistance and method for producing the same
JP4644314B2 (en) Hot-dip Zn-Al-Mg-Si-Cr alloy-plated steel with excellent corrosion resistance
JP5760150B2 (en) High manganese steel with excellent plating adhesion and method for producing hot dip galvanized steel sheet therefrom
CN113508186B (en) Molten Al-Zn-Mg-Si-Sr plated steel sheet and method for producing same
CN117026132A (en) Molten Al-Zn-Mg-Si-Sr plated steel sheet and method for producing same
WO2001059171A1 (en) STEEL SHEET HOT DIP COATED WITH Zn-Al-Mg HAVING HIGH Al CONTENT
JP5601771B2 (en) Multi-layer plated steel sheet and manufacturing method thereof
US20150184275A1 (en) Method and apparatus for producing zinc-aluminum alloy-coated steel sheet with superior workability and corrosion resistance
JP4264373B2 (en) Method for producing molten Al-based plated steel sheet with few plating defects
JP2003003238A (en) Zn-Al-Mg BASED HOT DIP PLATED STEEL HAVING EXCELLENT CORROSION RESISTANCE
JP6092969B2 (en) Nitrogen film forming equipment
JP4751168B2 (en) Fused Al-based plated steel sheet with excellent workability and method for producing the same
JP5660796B2 (en) Manufacturing method of hot dip galvanized high strength steel sheet
KR20150070841A (en) High-anticorosive coated steel sheet and method for manufacturing the same
JP5495921B2 (en) Manufacturing method of hot dip galvanized high strength steel sheet
JP2020105554A (en) Alloyed hot-dip galvanized film
JP6468493B2 (en) High corrosion resistance plated steel material and method for producing the same
WO2004033745A1 (en) HOT-DIPPED Sn-Zn PLATING PROVIDED STEEL PLATE OR SHEET EXCELLING IN CORROSION RESISTANCE AND WORKABILITY
JP5521932B2 (en) Sn-Zn hot-dip galvanized steel sheet excellent in corrosion resistance, solder strength and spot weldability and method for producing the same
KR100478725B1 (en) Manufacturing Method of High Strength Alloying Hot-Dip Galvanized Steel Sheet with Excellent Plating Adhesion and Alloying Process
JP4920356B2 (en) Manufacturing method of plated steel sheet
KR101612240B1 (en) High-anticorosive coated steel sheet and method for manufacturing the same
JP2023182581A (en) Hot-dipped steel sheet excellent in corrosion resistance and processability, and method for manufacturing the same
KR20200071366A (en) Method for manufacturing hot-dip plated steel sheet
JP2000119867A (en) Sn-Zn GROUP HOT DIP PLATING STEEL SHEET

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20110913

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20130823

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20131001

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20131008

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20131029

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20131029

R150 Certificate of patent or registration of utility model

Ref document number: 5404126

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313111

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350