JP2023027518A - Zn-Al-Mg BASED ALLOY PLATED STEEL PLATE AND METHOD FOR PRODUCING THE SAME - Google Patents
Zn-Al-Mg BASED ALLOY PLATED STEEL PLATE AND METHOD FOR PRODUCING THE SAME Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 76
- 239000000956 alloy Substances 0.000 title claims abstract description 76
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 74
- 239000010959 steel Substances 0.000 title claims abstract description 74
- 229910018134 Al-Mg Inorganic materials 0.000 title claims abstract description 53
- 229910018467 Al—Mg Inorganic materials 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000007747 plating Methods 0.000 claims abstract description 109
- 230000005496 eutectics Effects 0.000 claims abstract description 62
- 229910017708 MgZn2 Inorganic materials 0.000 claims abstract description 55
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 abstract description 51
- 230000007797 corrosion Effects 0.000 abstract description 51
- 239000010410 layer Substances 0.000 description 95
- 239000011701 zinc Substances 0.000 description 83
- 238000000034 method Methods 0.000 description 13
- 229910017706 MgZn Inorganic materials 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000005339 levitation Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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Abstract
Description
本発明は、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板に関し、特に、自動車、建築、土木、家電等の分野で利用される耐食性、摺動性および耐めっき剥離性に優れたＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板とその製造方法に関するものである。 The present invention relates to a Zn-Al-Mg-based alloy plated steel sheet, and in particular, a Zn-Al-Mg-based alloy plated steel sheet having excellent corrosion resistance, slidability, and peeling resistance, which is used in the fields of automobiles, construction, civil engineering, home appliances, etc. The present invention relates to an alloy plated steel sheet and its manufacturing method.
Ｚｎ－Ａｌ系合金めっき鋼板は、Ｚｎめっきに比べ優れた耐食性を有することから、従来より、自動車、建築、土木、家電等の分野で広く利用されてきた。このＺｎ－Ａｌ系合金めっき鋼板としては、めっき層中のＡｌ含有量が０．３０質量％以下の溶融亜鉛めっき鋼板、同Ａｌ含有量が約５質量％の溶融亜鉛－５％アルミニウム合金めっき鋼板、同Ａｌ含有量が約５５質量％の溶融５５％アルミニウム－亜鉛合金めっき鋼板が代表的である。一方で近年、耐食性を向上させる目的でＺｎ－Ａｌ系合金めっきにＭｇが添加されており、種々のＡｌ、Ｍｇ含有量および金属組織を有するＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板が開発されている。 Zn—Al alloy-plated steel sheets have been widely used in the fields of automobiles, construction, civil engineering, home appliances, and the like, because they have better corrosion resistance than Zn plating. The Zn-Al alloy plated steel sheet includes a hot-dip galvanized steel sheet with an Al content of 0.30% by mass or less in the coating layer, and a hot-dip zinc-5% aluminum alloy plated steel sheet with an Al content of about 5% by mass. and a hot-dip 55% aluminum-zinc alloy plated steel sheet having an Al content of about 55% by mass. On the other hand, in recent years, Mg has been added to Zn—Al alloy plating for the purpose of improving corrosion resistance, and Zn—Al—Mg alloy plated steel sheets having various Al and Mg contents and metal structures have been developed. .
Ｚｎ－Ａｌ－Ｍｇ系合金めっきは、さらなる耐食性の向上を目的として、めっき層中の組成や組織に着目した研究が行われている。特許文献１には、Ａｌ：４．０～１０．０重量％、Ｍｇ：１．０～４．０重量％、Ｔｉ：０．００２～０．１重量％、Ｂ：０．００１～０．０４５重量％、残部がＺｎおよび不可避的不純物からなる溶融めっき層が、Ａｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組織の素地中に初晶Ａｌ相が混在した金属組織を有する、耐食性および表面外観の良好な溶融Ｚｎ－Ａｌ－Ｍｇ系めっき鋼板が開示されている。また、特許文献２には、Ａｌ：２．０～７．０質量％、Ｍｇ：０．５～３．５質量％、残部がＺｎおよび不可避的不純物よりなり、Ｚｎ－Ａｌ－Ｍｇ三元共晶組織を体積比率で６０％以上含む結晶組織を有する溶融めっき皮膜を備えた加工性、耐食性および接着耐久性に優れたＺｎ－Ａｌ－Ｍｇ合金めっき鋼板が開示されている。一方、特許文献３には、Ａｌ：０．５～２．８重量％、Ｍｇ：０．５～２．８重量％、残部Ｚｎおよび不可避不純物を含む亜鉛合金めっき層の表面組織が、面積率で、Ｚｎ単相組織を４０％以下、及びＺｎ－Ａｌ－Ｍｇ系金属間化合物を６０％以上含む、リン酸塩処理性及びスポット溶接性に優れた亜鉛合金めっき鋼板が開示されている。 Zn--Al--Mg alloy plating has been studied with a focus on the composition and structure in the plating layer for the purpose of further improving corrosion resistance. In Patent Document 1, Al: 4.0-10.0% by weight, Mg: 1.0-4.0% by weight, Ti: 0.002-0.1% by weight, B: 0.001-0. 045% by weight, the balance being Zn and unavoidable impurities, the hot-dip plated layer has a metal structure in which the primary crystal Al phase is mixed in the base of the ternary eutectic structure of Al/Zn/Zn 2 Mg, corrosion resistance and surface A hot-dip Zn-Al-Mg plated steel sheet with good appearance is disclosed. Further, in Patent Document 2, Al: 2.0 to 7.0% by mass, Mg: 0.5 to 3.5% by mass, the balance being Zn and unavoidable impurities, Zn-Al-Mg ternary A Zn-Al-Mg alloy-plated steel sheet having excellent workability, corrosion resistance and adhesion durability and having a hot-dip coating having a crystal structure containing 60% or more of the crystal structure in volume ratio is disclosed. On the other hand, in Patent Document 3, the surface texture of the zinc alloy plating layer containing Al: 0.5 to 2.8% by weight, Mg: 0.5 to 2.8% by weight, the balance Zn and inevitable impurities is discloses a zinc alloy plated steel sheet that contains 40% or less of a Zn single-phase structure and 60% or more of a Zn-Al-Mg intermetallic compound and has excellent phosphating properties and spot weldability.
自動車、建築、土木、家電等の分野では、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板は、加工して用いられることが多く、平板部耐食性に加えて、加工部耐食性、摺動性および耐めっき剥離性が求められる。耐めっき剥離性とは、摺動時にめっきが粉末状に剥離するパウダリングや薄片上に剥離するフレーキングなどを抑制する性能を言う。しかしながら、特許文献１、２および３に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板はいずれも摺動性および耐めっき剥離性については検討されておらず、平板部耐食性、加工部耐食性、摺動性および耐めっき剥離性の全てを兼ね備えためっき組成およびめっき組織は明らかではない。 In the fields of automobiles, construction, civil engineering, home appliances, etc., Zn-Al-Mg alloy plated steel sheets are often processed and used. sexuality is required. The term "plating peeling resistance" refers to the ability to suppress powdering, in which the plating peels off in the form of powder during sliding, and flaking, in which the plating peels off on thin pieces. However, the Zn-Al-Mg-based alloy-plated steel sheets described in Patent Documents 1, 2 and 3 have not been examined for slidability and plating peeling resistance, and the flat plate portion corrosion resistance, the worked portion corrosion resistance, the sliding A plating composition and a plating structure that satisfy all of the properties and resistance to peeling of the plating have not been clarified.
本発明はかかる事情に鑑みてなされたものであり、平板部耐食性、加工部耐食性、摺動性および耐めっき剥離性に優れたＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板およびその製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and provides a Zn-Al-Mg alloy-plated steel sheet excellent in corrosion resistance of a flat portion, corrosion resistance of a worked portion, slidability and resistance to peeling of plating, and a method for producing the same. With the goal.
本発明者らは、上記課題を達成するために検討を行った結果、以下の知見を得た。
（１）Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板のめっき層表面に存在するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織のめっき層の表面全体に対する面積率が８０％以上であると、優れた平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性を示す。
（２）前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中に含まれるＭｇＺｎ２相の前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率が３５％以上であると、より優れた平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性を示す。
（３）前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の厚み方向断面における平均厚みが０．１０μｍ以上であれば、平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性がさらに向上する。
（４）前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織を前記Ｚｎ－Ａｌ－Ｍｇ系合金めっき層の表面全体に対する面積率が８０％以上で存在させる方法として、Ｚｎ－Ａｌ系合金めっき鋼板のめっき層上にＭｇまたはＭｇ－Ｚｎ層を形成し、加熱による熱処理を行う方法が好ましい。
（５）前記Ｚｎ－Ａｌ系合金めっき層上にＭｇまたはＭｇ－Ｚｎ層の付着量が鋼板片面当たり０．１ｇ／ｍ２以上となるように形成し、前記Ｚｎ－Ａｌ系合金めっき層の融点以上の温度で加熱による熱処理を行ったのち、平均冷却速度が１０℃／秒以下で冷却することで、めっき層の表面にＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織を、めっき層の表面全体に対する面積率が８０％以上で存在させやすくなり、好ましい。
The present inventors have obtained the following findings as a result of investigations to achieve the above-mentioned problems.
(1) Excellent if the area ratio of the Zn/Al/ MgZn ternary eutectic structure present on the surface of the coating layer of the Zn-Al-Mg alloy plated steel sheet to the entire surface of the coating layer is 80% or more. Corrosion resistance of flat part, corrosion resistance of processed part, slidability, and resistance to plating peeling.
(2) The area ratio of the MgZn2 phase contained in the Zn/Al/ MgZn2 ternary eutectic structure to the entire surface of the Zn/Al/ MgZn2 ternary eutectic structure is 35% or more. , exhibiting better corrosion resistance of flat plate parts, corrosion resistance of machined parts, slidability, and resistance to plating peeling.
(3) If the average thickness of the ternary eutectic structure of Zn/Al/ MgZn2 in the cross section in the thickness direction is 0.10 μm or more, the corrosion resistance of the flat plate portion, the corrosion resistance of the processed portion, the slidability, and the resistance to plating peeling are improved. Further improve.
(4) As a method for making the ternary eutectic structure of Zn/Al/ MgZn2 exist at an area ratio of 80% or more with respect to the entire surface of the Zn-Al-Mg-based alloy plating layer, a Zn-Al-based alloy plated steel sheet A preferred method is to form an Mg or Mg--Zn layer on the plated layer of and heat-treat it by heating.
(5) The Mg or Mg-Zn layer is formed on the Zn-Al alloy plating layer so that the adhesion amount of the Mg or Mg-Zn layer is 0.1 g / m 2 or more per side of the steel sheet, and the melting point of the Zn-Al alloy plating layer After heat treatment by heating at the above temperature, cooling is performed at an average cooling rate of 10 ° C./sec or less to form a ternary eutectic structure of Zn / Al / MgZn 2 on the surface of the coating layer. It becomes easy to exist when the area ratio to the whole is 80% or more, which is preferable.
本発明は、上記知見を基になされたものであり、本発明の要旨は次のとおりである。
［１］鋼板の少なくとも一方の表面にＺｎ－Ａｌ－Ｍｇ系合金めっき層を有するＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板であって、
前記Ｚｎ－Ａｌ－Ｍｇ系合金めっき層の表面に存在するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の前記めっき層の表面全体に対する面積率が８０％以上であることを特徴とする、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板。
［２］前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中に含まれるＭｇＺｎ２相の前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率が３５％以上であることを特徴とする、［１］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板。
［３］前記Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の厚み方向断面における平均厚みが０．１０μｍ以上であることを特徴とする、［１］または［２］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板。
［４］前記Ｚｎ－Ａｌ－Ｍｇ系合金めっき層は、Ａｌを１．０～１５質量％含有することを特徴とする、［１］～［３］のいずれかに記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板。
［５］前記Ｚｎ－Ａｌ－Ｍｇ系合金めっき層は、さらにＮｉを０．００５～０．１質量％含有することを特徴とする、［４］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板。
［６］Ｚｎ－Ａｌ系合金めっき層を有するＺｎ－Ａｌ系合金めっき鋼板の前記Ｚｎ－Ａｌ系合金めっき層上に、ＭｇまたはＭｇ－Ｚｎ層を形成し、前記Ｚｎ－Ａｌ系合金めっき層の融点以上の加熱温度で加熱する熱処理を行ったのち、
前記加熱温度から、前記Ｚｎ－Ａｌ系合金めっき層の融点－１０℃まで温度域を、平均冷却速度１０℃／秒以下で冷却することを特徴とする、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板の製造方法。
［７］前記ＭｇまたはＭｇ－Ｚｎ層の付着量が、鋼板片面当たり０．１ｇ／ｍ２以上であることを特徴とする、［６］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板の製造方法。
［８］前記Ｚｎ－Ａｌ系合金めっき層は、Ａｌを１．０～１５質量％含有することを特徴とする、［６］または［７］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板の製造方法。
［９］前記Ｚｎ－Ａｌ系合金めっき層は、さらにＮｉを０．００５～０．１質量％含有することを特徴とする、［８］に記載のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板の製造方法。
The present invention was made based on the above findings, and the gist of the present invention is as follows.
[1] A Zn-Al-Mg alloy plated steel sheet having a Zn-Al-Mg alloy plating layer on at least one surface of the steel sheet,
Zn, characterized in that the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 present on the surface of the Zn-Al-Mg-based alloy plating layer to the entire surface of the plating layer is 80% or more. - Al-Mg alloy plated steel sheet.
[2] The area ratio of the MgZn2 phase contained in the Zn/Al/ MgZn2 ternary eutectic structure to the entire surface of the Zn/Al/ MgZn2 ternary eutectic structure is 35% or more. The Zn-Al-Mg alloy plated steel sheet according to [1], characterized by
[3] Zn-Al- according to [1] or [2], characterized in that the ternary eutectic structure of Zn/Al/ MgZn2 has an average thickness of 0.10 μm or more in a cross section in the thickness direction. Mg-based alloy plated steel sheet.
[4] The Zn-Al-Mg according to any one of [1] to [3], wherein the Zn-Al-Mg alloy plating layer contains 1.0 to 15% by mass of Al. alloy plated steel sheet.
[5] The Zn-Al-Mg alloy plated steel sheet according to [4], wherein the Zn-Al-Mg alloy plating layer further contains 0.005 to 0.1% by mass of Ni. .
[6] Forming an Mg or Mg-Zn layer on the Zn-Al alloy plated layer of a Zn-Al alloy plated steel sheet having a Zn-Al alloy plated layer, After performing heat treatment to heat at a heating temperature above the melting point,
A Zn-Al-Mg alloy-plated steel sheet, characterized in that the temperature range from the heating temperature to the melting point of the Zn-Al-based alloy plating layer -10 ° C. is cooled at an average cooling rate of 10 ° C./sec or less. Production method.
[7] Manufacture of the Zn-Al-Mg alloy plated steel sheet according to [6], wherein the amount of the Mg or Mg-Zn layer deposited is 0.1 g/m 2 or more per side of the steel sheet. Method.
[8] The Zn-Al-Mg alloy-plated steel sheet according to [6] or [7], wherein the Zn-Al-based alloy plating layer contains 1.0 to 15% by mass of Al. Production method.
[9] Manufacture of the Zn-Al-Mg alloy-plated steel sheet according to [8], wherein the Zn-Al-based alloy plating layer further contains 0.005 to 0.1% by mass of Ni. Method.
本発明によれば、平板部耐食性、加工部耐食性、摺動性および耐めっき剥離性に優れたＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板を提供することができる。本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板は自動車用途、家電用途、建材用途など、様々な用途に好適である。 According to the present invention, it is possible to provide a Zn--Al--Mg alloy-plated steel sheet which is excellent in corrosion resistance of a flat portion, corrosion resistance of a worked portion, slidability, and resistance to plating peeling. The Zn--Al--Mg alloy-plated steel sheet of the present invention is suitable for various uses such as automobile use, home appliance use and building material use.
以下、本発明の実施形態について説明する。なお、以下の説明は、本発明の好適な一実施態様を示すものであり、本発明は、以下の説明によって何ら限定されるものではない。 Embodiments of the present invention will be described below. The following description shows a preferred embodiment of the present invention, and the present invention is not limited by the following description.
本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき層の付着量は、優れた平板部耐食性および加工部耐食性を得るために、片面あたり１０ｇ／ｍ２以上が好ましい。より好ましくは６０ｇ／ｍ２以上である。 The amount of the Zn--Al--Mg-based alloy plating layer of the present invention is preferably 10 g/m 2 or more per side in order to obtain excellent corrosion resistance of flat parts and processed parts. More preferably, it is 60 g/m 2 or more.
本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき層は、Ｚｎ、Ａｌ、Ｍｇおよび不可避的不純物からなり、さらにめっき層の表面において、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、めっき層の表面全体に対する面積率が８０％以上で存在していることを特徴とする。以下、その限定理由について説明する。 The Zn-Al-Mg-based alloy plating layer of the present invention consists of Zn, Al, Mg and unavoidable impurities, and furthermore, on the surface of the plating layer, the ternary eutectic structure of Zn/Al/ MgZn2 It is characterized by having an area ratio of 80% or more with respect to the entire surface. The reason for the limitation will be described below.
本発明者らは、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、めっき層の表面全体に対する面積率で８０％以上であると平板部耐食性および加工部耐食性が著しく向上することを見出した。なお、ここでの平板部耐食性とは、端面を除く平面部における耐食性のことを言う。腐食環境では、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇは、優先溶出し、保護性の高い腐食生成物である塩基性塩化亜鉛中に取り込まれ、生成した腐食生成物を安定化させる効果を示す。さらに、溶出したＭｇは腐食環境下において、Ｍｇ（ＯＨ）２とＭｇイオンとして存在し、これらの共存により、酸、アルカリのいずれに対してもｐＨ緩衝効果を示すことで、腐食を遅延させる。一方、Ａｌは難溶性の不動態皮膜からなるバリア層を形成することで、腐食を遅延させる。以上の効果により、平板部耐食性は向上する。一方、めっき鋼板に曲げ加工や張り出し加工などの加工を施すと、めっき層中に存在する硬い合金相の部分でクラックが入り、クラックが地鉄まで到達し、早期に地鉄の腐食が進行する恐れがある。しかし、本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき層では、硬質相であるＭｇＺｎ２相は、三元共晶組織中で微細に存在しており、かつＭｇＺｎ２相が含まれる三元共晶組織は最表層に存在しているため、微細なクラックが表層でのみ発生する。したがって、地鉄に到達するクラックが抑制できるとともに、微細なクラック部では、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶中のＭｇが溶出し、上記Ｍｇの作用により加工部耐食性にも優れる。以上より、本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板においては、めっき層の表面全体に対するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率は８０％以上とする。より好ましくは９０％以上である。 The present inventors found that when the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 to the entire surface of the plating layer is 80% or more, the corrosion resistance of the plate portion and the corrosion resistance of the worked portion are significantly improved. . The corrosion resistance of the flat plate portion here means the corrosion resistance of the flat portion excluding the end faces. In a corrosive environment, Mg in the ternary eutectic structure of Zn/Al/ MgZn2 is preferentially eluted and taken into basic zinc chloride, which is a highly protective corrosion product, and stabilizes the generated corrosion product. It shows the effect of making Furthermore, the eluted Mg exists as Mg(OH) 2 and Mg ions in a corrosive environment, and the coexistence of these exhibits a pH buffering effect against both acids and alkalis, thereby retarding corrosion. On the other hand, Al retards corrosion by forming a barrier layer consisting of a poorly soluble passive film. Due to the above effects, the corrosion resistance of the flat plate portion is improved. On the other hand, when a plated steel sheet is subjected to processing such as bending or overhanging, cracks occur in the hard alloy phase part existing in the coating layer, and the cracks reach the base steel, and corrosion of the base steel progresses early. There is fear. However, in the Zn-Al-Mg-based alloy plated layer of the present invention, the MgZn 2 phase, which is a hard phase, exists finely in the ternary eutectic structure, and the ternary eutectic containing the MgZn 2 phase Since the structure exists in the outermost layer, fine cracks occur only in the surface layer. Therefore, cracks reaching the base iron can be suppressed, and Mg in the ternary eutectic of Zn/Al/ MgZn2 is eluted in fine crack portions, and the action of Mg provides excellent corrosion resistance in the worked portion. As described above, in the Zn-Al-Mg alloy plated steel sheet of the present invention, the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 to the entire surface of the coating layer is set to 80% or more. More preferably, it is 90% or more.
また本発明者らは、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、めっき層の表面全体に対する面積率で８０％以上であると、摺動性および耐めっき剥離性が著しく向上することを見出した。本発明におけるＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織では、Ａｌ相およびＭｇＺｎ２相は三元共晶組織中に均一、かつ微細に分布している。そのため、めっき層の表面全体におけるＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率が８０％以上であると、めっき層の最表層のほぼ全面にＡｌ、Ｍｇを含む緻密な酸化物層が形成され、金型による摺動を受けた際には、凝集力の高い金属同士の接触ではなく、凝集力の低い酸化物と金属との接触となり、摩擦係数が低下する。また摺動を受けた後の金型には、Ａｌ、Ｍｇ系酸化物が移着し、金型が平滑化されるため、摩擦係数はさらに低下し、摺動性が向上する。一方で、めっき層の表面が金型などで摺動を受けると、せん断応力が発生し、めっき層内部を伝搬することでパウダリングやフレーキングが起こると考えられる。そのため上記のように摩擦係数が低下すると、耐めっき剥離性も向上すると考えられる。 In addition, the present inventors have found that when the ternary eutectic structure of Zn/Al/ MgZn2 has an area ratio of 80% or more with respect to the entire surface of the plating layer, the slidability and resistance to plating peeling are significantly improved. I found In the ternary eutectic structure of Zn/Al/ MgZn2 in the present invention, the Al phase and the MgZn2 phase are uniformly and finely distributed in the ternary eutectic structure. Therefore, when the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 in the entire surface of the plating layer is 80% or more, a dense oxide layer containing Al and Mg is formed on almost the entire surface of the outermost layer of the plating layer. is formed, and when it is slid by a mold, the contact is not between metals with high cohesive force but between oxides with low cohesive force and metal, resulting in a decrease in the coefficient of friction. In addition, Al- and Mg-based oxides are transferred to the mold after being slid, and the mold is smoothed, so that the coefficient of friction is further reduced and the slidability is improved. On the other hand, when the surface of the plating layer is slid by a mold or the like, shear stress is generated and propagates inside the plating layer to cause powdering and flaking. Therefore, it is considered that when the coefficient of friction is lowered as described above, the resistance to peeling of plating is also improved.
さらに本発明者らは、めっき層の表面におけるＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相が、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率で３５％以上であると、平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性がより向上することを見出した。 Furthermore, the present inventors have found that the MgZn2 phase in the ternary eutectic structure of Zn/Al/ MgZn2 on the surface of the plating layer is the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 to the entire surface. It has been found that when the content is 35% or more, the corrosion resistance of the flat portion, the corrosion resistance of the worked portion, the slidability, and the resistance to peeling of the plating are further improved.
Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相がＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率で３５％以上であれば、平部、加工部ともに腐食環境中に溶出するＭｇ量が増加するため、上記Ｍｇの効果が大きくなり、平板部耐食性および加工部耐食性がさらに向上する。Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相の前記面積率は好ましくは５０％以上である。 If the area ratio of the MgZn2 phase in the ternary eutectic structure of Zn/Al/ MgZn2 to the entire surface of the ternary eutectic structure of Zn/Al/MgZn2 is 35% or more, both the flat part and the processed part Since the amount of Mg eluted into the corrosive environment increases, the effect of Mg is enhanced, and the corrosion resistance of the flat portion and the corrosion resistance of the processed portion are further improved. The area ratio of the MgZn2 phase in the ternary eutectic structure of Zn/Al/ MgZn2 is preferably 50% or more.
また、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相がＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率で３５％以上であると、めっき層の表面硬度が高くなる結果、摩擦係数は低下し、摺動性および耐めっき剥離性はさらに向上する。 In addition, when the MgZn2 phase in the ternary eutectic structure of Zn/Al/ MgZn2 has an area ratio of 35% or more with respect to the entire surface of the ternary eutectic structure of Zn/Al/MgZn2, the surface of the plating layer As a result of the higher hardness, the coefficient of friction is lowered, and the slidability and resistance to plating peeling are further improved.
なお、めっき層の表面におけるＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織は微細組織であるため、ＭｇＺｎ２相の面積率を算出する際には、表面のＳＥＭ像を倍率１００００倍以上で取得し、画像解析ソフトを用いて面積率を算出するのが好ましい。 In addition, since the ternary eutectic structure of Zn/Al/ MgZn2 on the surface of the plating layer is a fine structure, when calculating the area ratio of the MgZn2 phase, an SEM image of the surface is obtained at a magnification of 10000 times or more. Then, it is preferable to calculate the area ratio using image analysis software.
さらに本発明者らは、めっき層の表面に存在しているＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、厚み方向断面における平均厚みで０．１０μｍ以上であると平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性がさらに向上することを見出した。 Furthermore, the present inventors found that the ternary eutectic structure of Zn/Al/ MgZn2 present on the surface of the plating layer has an average thickness of 0.10 μm or more in the cross section in the thickness direction. It was found that corrosion resistance, slidability, and resistance to plating peeling are further improved.
Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、厚み方向断面における平均厚みで０．１０μｍ以上であると、めっき層の表層でのＭｇによる腐食遅延効果が持続的に発揮されるため、耐食性は向上する。前記平均厚みは、好ましくは０．５０μｍ以上である。 When the ternary eutectic structure of Zn/Al/ MgZn2 has an average thickness of 0.10 μm or more in the cross section in the thickness direction, the corrosion retarding effect of Mg on the surface layer of the plating layer is continuously exhibited, so corrosion resistance improves. The average thickness is preferably 0.50 μm or more.
また、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が、厚み方向断面における平均厚みで０．１０μｍ以上であると、めっき層の表層に存在するＡｌ、Ｍｇ系酸化物が摺動時に欠損しても、新たなＡｌ、Ｍｇ系酸化物が生成するため、長い距離の摺動や繰り返しの摺動においても摩擦係数が低減され、優れた摺動性および耐めっき剥離性を示す。 In addition, when the ternary eutectic structure of Zn/Al/ MgZn2 has an average thickness of 0.10 μm or more in the cross section in the thickness direction, the Al and Mg oxides present on the surface layer of the plating layer are damaged during sliding. However, since new Al- and Mg-based oxides are generated, the friction coefficient is reduced even in long-distance sliding and repeated sliding, and excellent slidability and plating peeling resistance are exhibited.
本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板のめっき層中のＡｌ含有量は１．０～１５質量％とすることが好ましい。Ａｌ含有量が１．０質量％以上であると、めっき層の最表層に形成されるＡｌ酸化物の量が増大するため、摺動性および耐めっき剥離性をより向上しやすくなる。Ａｌ含有量は、好ましくは４．０質量％以上とする。一方で、Ａｌ含有量が１５質量％以下であると、めっき層の表面においてＺｎ／Ａｌ二元共晶の割合が増加するのを抑制でき、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率を確保しやすくなるため、耐食性、摺動性、および耐めっき剥離性をより向上しやすくなる。Ａｌ含有量は、好ましくは１０質量％以下である。 The Al content in the plating layer of the Zn-Al-Mg alloy plated steel sheet of the present invention is preferably 1.0 to 15% by mass. When the Al content is 1.0% by mass or more, the amount of Al oxide formed on the outermost layer of the plating layer increases, so that the slidability and the resistance to peeling of the plating can be improved more easily. The Al content is preferably 4.0% by mass or more. On the other hand, when the Al content is 15% by mass or less, it is possible to suppress the increase in the ratio of the Zn/Al binary eutectic on the surface of the plating layer, and the ternary eutectic structure of Zn/Al/ MgZn2 can be suppressed. Since it becomes easier to secure the area ratio, it becomes easier to improve corrosion resistance, slidability, and resistance to peeling of plating. The Al content is preferably 10% by mass or less.
また、上記Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板は耐黒変性を向上させる目的でＮｉを含有してもよい。Ｎｉを含有する場合は０．００５～０．１質量％とする。Ｎｉ含有量が０．００５質量％未満では、優れた耐黒変性が得られにくい。一方で、Ｎｉ含有量が０．１質量％を超えると、後述するが、ＭｇまたはＭｇ－Ｚｎ層を形成する前のＺｎ－Ａｌ系合金めっき鋼板を製造する際に、めっき浴にＮｉを含有するＡｌ－Ｍｇ系ドロスが発生し、ドロス付着によってめっき外観が損なわれてしまうおそれがあるので、好ましくない。 In addition, the Zn-Al-Mg alloy plated steel sheet may contain Ni for the purpose of improving blackening resistance. When Ni is contained, it is 0.005 to 0.1% by mass. If the Ni content is less than 0.005% by mass, it is difficult to obtain excellent blackening resistance. On the other hand, if the Ni content exceeds 0.1% by mass, as will be described later, Ni is added to the plating bath when producing a Zn-Al alloy plated steel sheet before forming the Mg or Mg-Zn layer. Al--Mg-based dross is produced, and the adhesion of the dross may impair the appearance of the plating.
本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板は、Ｚｎ－Ａｌ系合金めっき層を有するＺｎ－Ａｌ系合金めっき鋼板のめっき層上に、ＭｇまたはＭｇ－Ｚｎ層を形成し、前記Ｚｎ－Ａｌ系合金めっき層の融点以上の加熱温度で加熱したのち、平均冷却速度１０℃／秒以下で冷却することにより製造されることが好ましい。 The Zn-Al-Mg alloy plated steel sheet of the present invention is obtained by forming a Mg or Mg-Zn layer on the plating layer of a Zn-Al alloy plated steel sheet having a Zn-Al alloy plating layer, and forming the Zn-Al It is preferable to manufacture by heating at a heating temperature equal to or higher than the melting point of the base alloy plating layer and then cooling at an average cooling rate of 10° C./sec or less.
本発明の鋼板に関しては特に限定されず、冷延鋼板や熱延鋼板を用いることができる。 The steel sheet of the present invention is not particularly limited, and cold-rolled steel sheets and hot-rolled steel sheets can be used.
ＭｇまたＭｇ－Ｚｎ層を形成する前のＺｎ－Ａｌ系合金めっき層は、Ａｌ：１．０～１５質量％、Ｍｇ：０～１０質量％を含有することが好ましい。また、前記成分以外の残部がＺｎおよび不可避的不純物からなることが好ましい。Ｚｎ－Ａｌ系合金めっき鋼板のめっき層は、Ｚｎ相、Ｚｎ／Ａｌ共晶を含有する。また、Ｚｎ－Ａｌ系合金めっき鋼板のめっき層がＭｇを含む場合、該めっき層は、Ｚｎ相、Ｚｎ／Ａｌ共晶、Ｚｎ／Ａｌ／Ｚｎ２Ｍｇ三元共晶を含有する。 The Zn--Al alloy plated layer before forming the Mg or Mg--Zn layer preferably contains Al: 1.0 to 15% by mass and Mg: 0 to 10% by mass. Moreover, it is preferable that the balance other than the above components consists of Zn and unavoidable impurities. The plating layer of the Zn-Al alloy plated steel sheet contains a Zn phase and a Zn/Al eutectic. Further, when the plating layer of the Zn—Al alloy-plated steel sheet contains Mg, the plating layer contains a Zn phase, a Zn/Al eutectic, and a ternary eutectic of Zn/Al/Zn 2 Mg.
ＭｇまたＭｇ－Ｚｎ層を形成する前のＺｎ－Ａｌ系合金めっき層のＡｌ含有量は１．０～１５質量％であることが好ましい。Ａｌ含有量の上下限の限定理由については上述の通りである。さらに、Ａｌが１５質量％を超えると、めっき浴中にＡｌを主体としたトップドロスが発生しやすくなり、めっき外観を損なうおそれも生じるため、上限は１５質量％が好ましい。 The Al content of the Zn--Al alloy plating layer before forming the Mg or Mg--Zn layer is preferably 1.0 to 15% by mass. The reasons for limiting the upper and lower limits of the Al content are as described above. Furthermore, when Al exceeds 15% by mass, top dross mainly composed of Al tends to occur in the plating bath, which may impair the appearance of the plating. Therefore, the upper limit is preferably 15% by mass.
上記Ｚｎ－Ａｌ系合金めっき層のＭｇ含有量は、０～１０質量％とすることが好ましい。１０質量％を超えると、ドロスの発生が顕著であり、めっき外観が劣化するおそれが生じるため、１０質量％を上限とすることが好ましい。 The Mg content of the Zn—Al alloy plating layer is preferably 0 to 10% by mass. If the amount exceeds 10% by mass, dross is generated significantly, and the appearance of the plating may deteriorate. Therefore, the upper limit is preferably 10% by mass.
また、上記Ｚｎ－Ａｌ系合金めっき層は耐黒変性を向上させる目的でＮｉを含有してもよい。Ｎｉを含有する場合は０．００５～０．１質量％とする。Ｎｉ含有量の上下限の設定理由については上述の通りである。 In addition, the Zn—Al alloy plated layer may contain Ni for the purpose of improving blackening resistance. When Ni is contained, it is 0.005 to 0.1% by mass. The reasons for setting the upper and lower limits of the Ni content are as described above.
本発明において、Ｚｎ－Ａｌ系合金めっき層上にＭｇまたはＭｇ－Ｚｎ層を形成するにあたり、真空蒸着法、熱蒸発法、電磁浮揚誘導加熱蒸発法、スパッタリング法、電子ビーム蒸発法、イオンプレーティング法、または電磁浮揚物理気相蒸着法などいずれの方法をも選択できる。 In the present invention, in forming the Mg or Mg-Zn layer on the Zn-Al alloy plated layer, a vacuum deposition method, a thermal evaporation method, an electromagnetic levitation induction heating evaporation method, a sputtering method, an electron beam evaporation method, and an ion plating method are used. method, or electromagnetic levitation physical vapor deposition method can be selected.
本発明ではＺｎ－Ａｌ系合金めっき層上にＭｇ層を形成する場合は片面当たりの付着量が０．１～１０ｇ／ｍ２であるのが好ましい。付着量が０．１ｇ／ｍ２以上であればめっき層の表面にＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織を面積率で８０％以上としやすくなる。好ましくは０．５ｇ／ｍ２以上である。 In the present invention, when the Mg layer is formed on the Zn--Al alloy plating layer, it is preferable that the deposition amount per side is 0.1 to 10 g/m 2 . If the coating amount is 0.1 g/m 2 or more, the ternary eutectic structure of Zn/Al/MgZn 2 tends to be 80% or more in area ratio on the surface of the plating layer. It is preferably 0.5 g/m 2 or more.
めっき層上にＭｇ－Ｚｎ層を形成する場合は、組成の制御が容易であるように、Ｍｇ－Ｚｎ層中のＭｇ組成が１０質量％以上であることが好ましく、またＭｇ量が０．１ｇ／ｍ２以上となるように、Ｍｇ組成に応じてＭｇ－Ｚｎ層の付着量を決定するのが好ましい。 When the Mg--Zn layer is formed on the plated layer, the Mg composition in the Mg--Zn layer is preferably 10% by mass or more so that the composition can be easily controlled, and the Mg amount is 0.1 g. /m 2 or more.
本発明のＺｎ－Ａｌ－Ｍｇ系合金めっき鋼板は、Ｚｎ－Ａｌ系合金めっき層上に、ＭｇまたはＭｇ－Ｚｎ層を形成し、前記Ｚｎ－Ａｌ系合金めっき層の融点以上の温度で加熱したのち、冷却することにより製造される。Ｚｎ－Ａｌ系合金めっき層の融点（℃）は、Ｚｎ－Ａｌ－Ｍｇ状態図から読み取るのが好ましい。Ｚｎ－Ａｌ系合金めっき層の融点以上の加熱温度（℃）で加熱し、Ｚｎ－Ａｌ系合金めっき層およびＭｇまたはＭｇ－Ｚｎ層全体が溶融した後、前記加熱温度から、（Ｚｎ－Ａｌ系合金めっき層の融点－１０℃）までの温度域を、平均冷却速度を１０℃／秒以下と比較的遅く冷却することで、初晶がめっき内部でゆっくりと成長、肥大化するとともに、未凝固の融液はめっき層の表層に流れ、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶として最終凝固するために、めっき層の表面においてＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率が高いめっき組織を形成することができる。前記平均冷却速度は好ましくは５℃／秒以下である。ここで、ＭｇまたはＭｇ－Ｚｎ層を形成することにより、めっき層全体が溶融した際にめっき層の表層のＭｇ濃度が高められるため、めっき層の表面全体に対するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率が８０％以上となり、溶融めっき法によって製造した場合に比べ、めっき層の表面全体に対するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率が高いめっき組織が得られる。また、ＭｇまたはＭｇ－Ｚｎ層を形成することにより、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相が、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率で３５％以上とすることができる。 The Zn-Al-Mg-based alloy plated steel sheet of the present invention is obtained by forming an Mg or Mg-Zn layer on the Zn-Al-based alloy plated layer and heating at a temperature equal to or higher than the melting point of the Zn-Al-based alloy plated layer. After that, it is manufactured by cooling. The melting point (° C.) of the Zn—Al alloy plating layer is preferably read from the Zn—Al—Mg phase diagram. After heating at a heating temperature (° C.) above the melting point of the Zn-Al alloy plating layer, the Zn-Al alloy plating layer and the entire Mg or Mg-Zn layer are melted, from the heating temperature, (Zn-Al system By cooling the temperature range up to the melting point of the alloy plating layer -10 ° C) at a relatively slow average cooling rate of 10 ° C / sec or less, the primary crystals slowly grow and enlarge inside the plating, and the unsolidified The melt flows to the surface layer of the plating layer and finally solidifies as a ternary eutectic of Zn/Al/ MgZn2 , so that the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 A high plating structure can be formed. The average cooling rate is preferably 5° C./sec or less. Here, by forming the Mg or Mg-Zn layer, the Mg concentration in the surface layer of the plating layer is increased when the entire plating layer melts, so the ternary Zn/Al/MgZn2 over the entire surface of the plating layer The area ratio of the eutectic structure is 80% or more, and a plating structure with a high area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 with respect to the entire surface of the plating layer can be obtained compared to the case of manufacturing by the hot dip plating method. . In addition, by forming the Mg or Mg—Zn layer, the MgZn 2 phase in the ternary eutectic structure of Zn/Al/MgZn 2 has an area of the ternary eutectic structure of Zn/Al/MgZn 2 with respect to the entire surface. The ratio can be 35% or more.
なお、一般にはＡｌ：１．０～１５質量％、Ｍｇ：０～１０質量％の組成のＺｎ－Ａｌ系合金めっきの融点は３４０℃～４２０℃である。 In general, the melting point of Zn-Al alloy plating with a composition of Al: 1.0 to 15% by mass and Mg: 0 to 10% by mass is 340°C to 420°C.
熱処理における加熱方法は、特に限定されず、加熱炉および通電加熱を用いることができるが、めっき層および蒸着膜を十分に溶融させることが有効なため、炉加熱を用いるのが好ましい。炉加熱の場合、熱処理時間に関しては特に限定されないが、鋼板が設定温度に到達し、所定温度に保持される時間も考慮すると、炉に投入してから取り出すまでの時間を１５分以上とするのが好ましい。長時間加熱を行うと、母材鋼板とめっき層との間のＦｅ２Ａｌ５などの形成が促進され、めっき層の表面におけるＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率が低下してしまうため、前記加熱温度での加熱時間の上限は１時間とする。通電加熱を行う場合は、めっき層およびＭｇまたはＭｇ－Ｚｎ層を十分に溶融させるため、炉加熱の場合よりも到達温度を高めに設定するのが好ましい。なお、めっき層中のＭｇ、Ａｌの酸化を抑制するために、Ｎ２、Ａｒ等の不活性ガス雰囲気下で加熱を行うこともできる。
また、熱処理における冷却方法も特に限定されないが、空冷やミスト冷却、ガス冷却などを適用することができる。
A heating method in the heat treatment is not particularly limited, and a heating furnace and electric heating can be used. However, since it is effective to sufficiently melt the plated layer and the deposited film, it is preferable to use furnace heating. In the case of furnace heating, the heat treatment time is not particularly limited, but considering the time it takes for the steel plate to reach the set temperature and to be held at the predetermined temperature, the time from putting it in the furnace to taking it out should be 15 minutes or more. is preferred. When heated for a long time, the formation of Fe 2 Al 5 and the like between the base steel sheet and the coating layer is promoted, and the area ratio of the ternary eutectic structure of Zn/Al/MgZn 2 on the surface of the coating layer decreases. Therefore, the upper limit of the heating time at the heating temperature is set to 1 hour. In the case of electric heating, it is preferable to set the reaching temperature higher than in the case of furnace heating in order to sufficiently melt the plating layer and the Mg or Mg--Zn layer. In addition, in order to suppress the oxidation of Mg and Al in the plating layer, heating may be performed in an atmosphere of an inert gas such as N 2 or Ar.
Also, the cooling method in the heat treatment is not particularly limited, but air cooling, mist cooling, gas cooling, or the like can be applied.
以下、本発明を実施例に基づいて具体的に説明する。下記の実施例は本発明を限定するものではなく、要旨構成の範囲内で適宜変更することは、本発明の範囲に含まれるものとする。 EXAMPLES The present invention will be specifically described below based on examples. The following examples are not intended to limit the present invention, and appropriate modifications within the scope of the gist and configuration are included in the scope of the present invention.
鋼板表面に表１に示す組成、付着量となるように溶融Ｚｎ－Ａｌ系合金めっき層（ただし、Ｎｏ．１２は、Ａｌを含有しない溶融Ｚｎ系合金めっき層）を形成した。真空蒸着法によって表１に示す量のＭｇまたはＭｇ－Ｚｎ層を形成し、加熱炉を用いて表１に示す加熱温度、時間で加熱した後、所定の冷却速度で冷却し、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板を作製した（ただし、Ｎｏ．１２は、Ａｌを含有しないＺｎ－Ｍｇ系合金めっき鋼板）。なお、表１中の付着量は、鋼板片面当たりの付着量を示す。また、表１中の平均冷却速度は、加熱温度から、（Ｚｎ－Ａｌ系合金めっき層の融点－１０℃）までの温度域における平均冷却速度を示す。 A hot-dip Zn-Al alloy plating layer (No. 12 is a hot-dip Zn-based alloy plating layer containing no Al) was formed on the surface of the steel sheet so as to have the composition and coating amount shown in Table 1. A Mg or Mg—Zn layer of the amount shown in Table 1 is formed by a vacuum deposition method, heated at the heating temperature and time shown in Table 1 using a heating furnace, cooled at a predetermined cooling rate, and Zn—Al— Mg-based alloy-plated steel sheets were produced (No. 12 is a Zn--Mg-based alloy-plated steel sheet containing no Al). In addition, the adhesion amount in Table 1 indicates the adhesion amount per one side of the steel plate. The average cooling rate in Table 1 indicates the average cooling rate in the temperature range from the heating temperature to (the melting point of the Zn--Al alloy plating layer -10°C).
作製しためっき鋼板の任意の位置から２０ｍｍｘ２０ｍｍのサイズで１０サンプルを採取し、薄膜Ｘ線回折法でＺｎ－Ｍｇ金属間化合物相を同定した。次に、各サンプル表面について、走査型電子顕微鏡（ＳＥＭ）を用い、加速電圧１５ｋＶで、１２５μｍｘ９５μｍの視野の二次電子像（ＳＥＭ像）を１０００倍の倍率で取得するとともに、同エリアについてＳＥＭ－ＥＤＸ面分析を行い、ＳＥＭ像内のＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織を識別した。次に、画像解析ソフトを用いて、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率（めっき層の表面全体に対する面積率）を算出し、３視野×１０サンプルの平均値を、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の面積率とした。また、加速電圧１５ｋＶで、１３μｍｘ１０μｍの視野のＳＥＭ像を１００００倍の倍率で取得するとともに、同エリアについてＳＥＭ－ＥＤＸ面分析を行い、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中におけるＭｇＺｎ２相の、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の表面全体に対する面積率を算出し、３視野×１０サンプルの平均値をＭｇＺｎ２の面積率とした。 Ten samples with a size of 20 mm×20 mm were taken from arbitrary positions of the produced plated steel sheet, and the Zn—Mg intermetallic compound phase was identified by the thin film X-ray diffraction method. Next, for each sample surface, using a scanning electron microscope (SEM), at an acceleration voltage of 15 kV, a secondary electron image (SEM image) of a field of view of 125 μm×95 μm is obtained at a magnification of 1000 times, and the same area is SEM- EDX surface analysis was performed to identify the ternary eutectic structure of Zn/Al/ MgZn2 in the SEM images. Next, using image analysis software, the area ratio of the ternary eutectic structure of Zn / Al / MgZn 2 (area ratio with respect to the entire surface of the plating layer) is calculated, and the average value of 3 fields of view × 10 samples is The area ratio of the ternary eutectic structure of /Al/ MgZn2 . In addition, at an acceleration voltage of 15 kV, an SEM image of a field of view of 13 μm × 10 μm was acquired at a magnification of 10000 times, and SEM-EDX surface analysis was performed on the same area . The area ratio of the Zn/Al/ MgZn2 ternary eutectic structure of the phase to the entire surface was calculated, and the average value of 3 fields of view×10 samples was taken as the area ratio of MgZn2 .
続いて、表面観察した１０サンプルについて、樹脂断面埋め込み研磨を行い、加速電圧１５ｋＶで、幅５０μｍのＳＥＭ像を２５００倍の倍率で取得するとともに、同エリアについてＳＥＭ－ＥＤＸ面分析を行い、ＳＥＭ像内のＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織を識別し、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の厚み（めっき層の厚み方向断面における厚み）を１０点測り、３視野×１０サンプルの平均値をＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の平均厚みとした。 Subsequently, 10 samples whose surface was observed were subjected to resin cross-section embedding polishing, and an SEM image with a width of 50 μm was obtained at a magnification of 2500 times at an acceleration voltage of 15 kV. Identify the ternary eutectic structure of Zn / Al / MgZn 2 inside, measure the thickness of the ternary eutectic structure of Zn / Al / MgZn 2 (thickness in the thickness direction cross section of the plating layer) at 10 points, 3 fields of view × The average value of 10 samples was taken as the average thickness of the ternary eutectic structure of Zn/Al/ MgZn2 .
（１）平板部耐食性
作製しためっき鋼板から１５０ｍｍ×５０ｍｍサイズのサンプルを切り出し、端面および裏面をテープシールしたのち、ＪＩＳ Ｚ ２３７１規格に従って塩水噴霧試験を行い、表面に赤錆が発生した時間を以下の判定基準で評価した。
＜判定基準＞
◎：赤錆発生時間４０００時間以上
〇：赤錆発生時間３５００時間以上４０００時間未満
〇-：赤錆発生時間３０００時間以上３５００時間未満
△：赤錆発生時間２０００時間以上３０００時間未満
×：赤錆発生時間２０００時間未満
(1) Corrosion resistance of flat plate portion A sample of 150 mm x 50 mm size was cut out from the produced plated steel sheet, the end surface and the back surface were tape-sealed, and then a salt spray test was performed according to JIS Z 2371 standard. Evaluated according to the criteria.
<Judgment Criteria>
◎: Red rust generation time 4000 hours or more ○: Red rust generation time 3500 hours or more and less than 4000 hours ○-: Red rust generation time 3000 hours or more and less than 3500 hours △: Red rust generation time 2000 hours or more and less than 3000 hours ×: Red rust generation time less than 2000 hours
（２）加工部耐食性
作製しためっき鋼板から１５０ｍｍ×５０ｍｍサイズのサンプルを切り出し、９０℃曲げを行い、端面および裏面をテープシールしたのち、ＪＩＳ Ｚ ２３７１規格に従って、塩水噴霧試験を２０００時間行い、曲げ部に赤錆が発生した時間によって耐食性を評価した。
＜判定基準＞
◎：赤錆発生時間３０００時間以上
〇：赤錆発生時間２５００時間以上３０００時間未満
〇-：赤錆発生時間２０００時間以上２５００時間未満
△：赤錆発生時間１０００時間以上２０００時間未満
×：赤錆発生時間１０００時間未満
(2) Corrosion resistance of processed part Cut out a 150 mm × 50 mm size sample from the produced plated steel sheet, bend it at 90 ° C., seal the end face and back surface with tape, and then perform a salt spray test for 2000 hours according to the JIS Z 2371 standard. Corrosion resistance was evaluated by the time for red rust to occur on the part.
<Judgment Criteria>
◎: Red rust generation time 3000 hours or more ○: Red rust generation time 2500 hours or more and less than 3000 hours ○-: Red rust generation time 2000 hours or more and less than 2500 hours △: Red rust generation time 1000 hours or more and less than 2000 hours ×: Red rust generation time less than 1000 hours
（３）摺動性
潤滑油を塗布したサンプルを取り付け、金型を一定荷重Ｎで試験片に押付けながら、以下に示す条件で、一定速度で試験片を引抜くときの引抜き荷重Ｆを測定し，Ｆ／Ｎより摩擦係数を求め、摺動性を評価した。潤滑油は、粘度が４０℃において２．０ｃＳｔの市販の一般洗浄油を用いた。同一サンプルで３回連続摩擦係数測定を行い、２回目と３回目の摩擦係数の平均値を算出した。
金型形状：ビード（先端４．５Ｒ）
金型材質：ＳＫＤ１１（ＪＩＳ）
接触面積：３×１０ｍｍ
摺動長さ：１００ｍｍ
面圧：１３０．４ＭＰａ
摺動速度：１ｍ／ｍｉｎ
＜判定基準＞
◎：摩擦係数０．１未満
〇：０．１以上０．２未満
〇-：０．２以上０．２５未満
△：０．２５以上０．３未満
×：０．３以上
(3) Sliding property Attach a sample coated with lubricating oil, press the mold against the test piece with a constant load N, and measure the pull-out load F when pulling out the test piece at a constant speed under the conditions shown below. , F/N to determine the coefficient of friction, and evaluated the slidability. A commercially available general cleaning oil having a viscosity of 2.0 cSt at 40° C. was used as the lubricating oil. The same sample was continuously measured for the coefficient of friction three times, and the average value of the second and third coefficients of friction was calculated.
Mold shape: bead (tip 4.5R)
Mold material: SKD11 (JIS)
Contact area: 3x10mm
Sliding length: 100mm
Surface pressure: 130.4 MPa
Sliding speed: 1m/min
<Judgment Criteria>
◎: less than 0.1 coefficient of friction ○: 0.1 or more and less than 0.2 ○ -: 0.2 or more and less than 0.25 △: 0.25 or more and less than 0.3 ×: 0.3 or more
（４）耐めっき剥離性
非摺動面のめっき層を剥離した後に、上記の条件で摺動試験を行い、摺動前後での重量変化を求めた。さらに摺動後の摺動部に対し、テープ剥離を行い、剥離前後の重量変化を求めた。摺動前後、およびテープ剥離前後での重量変化の合計値をめっき剥離量とし、耐めっき剥離性を評価した。なお試験は、異なるサンプルを用いて３回試験を行い、平均値を算出した。
＜判定基準＞
◎：めっき剥離量０．５ｇ／ｍ２未満
〇：０．５ｇ／ｍ２以上１．０ｇ／ｍ２未満
〇-：１．０ｇ／ｍ２以上１．５ｇ／ｍ２未満
△：１．５ｇ／ｍ２以上２．０ｇ／ｍ２未満
×：２．０ｇ／ｍ２以上
(4) Resistance to peeling of plating After peeling off the plating layer on the non-sliding surface, a sliding test was performed under the above conditions to determine the weight change before and after sliding. Further, the tape was peeled off from the sliding portion after sliding, and the change in weight before and after the peeling was determined. The total weight change before and after sliding and before and after tape peeling was taken as the amount of peeled plating, and resistance to peeling of plating was evaluated. The test was performed three times using different samples, and the average value was calculated.
<Judgment Criteria>
◎: Less than 0.5 g/m 2 of plating peeling ○: 0.5 g/m 2 or more and less than 1.0 g/m 2 ○ -: 1.0 g/m 2 or more and less than 1.5 g/m 2 △: 1.5 g /m 2 or more and less than 2.0 g/m 2 ×: 2.0 g/m 2 or more
（５）耐黒変性
作製しためっき鋼板から５０×５０ｍｍサイズのサンプルを切り出し、温度：８０℃、相対湿度：９８％の雰囲気に制御された恒温恒湿機に２４時間静置した際の明度（Ｌ値）の変化（ΔＬ＝試験後のＬ値－試験前のＬ値）で算出した。評価基準は以下のとおりである。Ｌ値は、日本電色工業（株）製のＳＲ２０００を使用し、ＳＣＩモード（正反射光込み）で測定した。
＜判定基準＞
○：－１０＜△Ｌ、かつ、ムラが無い均一な外観
○-：－１４＜△Ｌ≦－１０、かつ、ムラが無い均一な外観
△：－１４＜△Ｌ≦－１０、かつ、軽微なムラのある外観
×：△Ｌ≦－１４、または、顕著にムラのある外観
(5) Blackening resistance A 50 × 50 mm size sample was cut from the prepared plated steel sheet, and the brightness when left for 24 hours in a constant temperature and humidity machine controlled at a temperature of 80 ° C. and a relative humidity of 98% ( L value)) (ΔL = L value after test - L value before test). Evaluation criteria are as follows. The L value was measured using SR2000 manufactured by Nippon Denshoku Industries Co., Ltd. in SCI mode (including specular reflection light).
<Judgment Criteria>
○: -10 < △L, and uniform appearance without unevenness ○-: -14 < △L ≤ -10, and uniform appearance without unevenness △: -14 < △L ≤ -10, and slight Appearance with slight unevenness ×: △L ≤ -14, or appearance with noticeable unevenness
（６）外観
２３０×３５０ｍｍサイズのサンプルに対し、目視により、不めっき、めっき剥離、亀裂などの欠陥部の数を評価することで、外観評価を行った。
＜判定基準＞
○：欠陥部なし
○-：欠陥部１～２か所
△：欠陥部３～１０か所
×：欠陥部１１か所以上
(6) Appearance Appearance was evaluated by visually evaluating the number of defects such as non-plating, peeling of plating, and cracks on a sample of 230×350 mm.
<Judgment Criteria>
○: No defects ○-: 1 to 2 defects △: 3 to 10 defects ×: 11 or more defects
Ｚｎ－Ａｌ－Ｍｇ系合金めっき層の表面において、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が表面面積率８０％以上で存在していると、優れた平板部耐食性、加工部耐食性、摺動性および耐めっき剥離性を示す。さらに、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織中のＭｇＺｎ２相が三元共晶組織全体に対する面積率で３５％以上であると、平板部耐食性、加工部耐食性、摺動性および耐めっき剥離性はさらに向上する。また、Ｚｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織が厚み方向断面において、平均厚み０．１０μｍ以上であると、平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性がさらに向上する。 If the ternary eutectic structure of Zn/Al/ MgZn2 exists at a surface area ratio of 80% or more on the surface of the Zn-Al-Mg-based alloy plating layer, excellent corrosion resistance of the plate part, corrosion resistance of the processed part, and abrasion resistance can be obtained. It exhibits kinetics and resistance to plating peeling. Furthermore, when the area ratio of the MgZn2 phase in the ternary eutectic structure of Zn/Al/ MgZn2 to the entire ternary eutectic structure is 35% or more, the corrosion resistance of the plate part, the corrosion resistance of the processed part, the slidability and the resistance are improved. Plating releasability is further improved. In addition, when the ternary eutectic structure of Zn/Al/ MgZn2 has an average thickness of 0.10 μm or more in the cross section in the thickness direction, the corrosion resistance of the flat plate portion, the corrosion resistance of the processed portion, the slidability, and the resistance to plating peeling are further improved. do.
本発明のＺｎ－Ａｌ－Ｍｇ系めっき鋼板は、平板部耐食性、加工部耐食性、摺動性、および耐めっき剥離性に優れ、自動車、電機、建材など幅広い分野に適用可能である。 INDUSTRIAL APPLICABILITY The Zn-Al-Mg-based plated steel sheet of the present invention is excellent in corrosion resistance of flat parts, corrosion resistance of worked parts, slidability, and resistance to plating peeling, and can be applied to a wide range of fields such as automobiles, electrical machinery, and building materials.
Claims (9)
前記Ｚｎ－Ａｌ－Ｍｇ系合金めっき層の表面に存在するＺｎ／Ａｌ／ＭｇＺｎ２の三元共晶組織の前記めっき層の表面全体に対する面積率が８０％以上であることを特徴とする、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板。 A Zn-Al-Mg alloy plated steel sheet having a Zn-Al-Mg alloy plating layer on at least one surface of the steel sheet,
Zn, characterized in that the area ratio of the ternary eutectic structure of Zn/Al/ MgZn2 present on the surface of the Zn-Al-Mg-based alloy plating layer to the entire surface of the plating layer is 80% or more. - Al-Mg alloy plated steel sheet.
前記加熱温度から、前記Ｚｎ－Ａｌ系合金めっき層の融点－１０℃まで温度域を、平均冷却速度１０℃／秒以下で冷却することを特徴とする、Ｚｎ－Ａｌ－Ｍｇ系合金めっき鋼板の製造方法。 A Mg or Mg-Zn layer is formed on the Zn-Al alloy plated layer of a Zn-Al alloy plated steel sheet having a Zn-Al alloy plated layer, and the temperature is higher than the melting point of the Zn-Al alloy plated layer. After performing heat treatment to heat at the heating temperature,
A Zn-Al-Mg alloy-plated steel sheet characterized by cooling the temperature range from the heating temperature to the melting point of the Zn-Al-based alloy plating layer -10 ° C. at an average cooling rate of 10 ° C./sec or less. Production method.
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