JPS59129781A - Plated steel material with superior corrosion resistance - Google Patents
Plated steel material with superior corrosion resistanceInfo
- Publication number
- JPS59129781A JPS59129781A JP369583A JP369583A JPS59129781A JP S59129781 A JPS59129781 A JP S59129781A JP 369583 A JP369583 A JP 369583A JP 369583 A JP369583 A JP 369583A JP S59129781 A JPS59129781 A JP S59129781A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- chemical conversion
- plating
- corrosion resistance
- conversion treatment
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Abstract
Description
【発明の詳細な説明】
本発明は、自動車用鋼板等のメッキ鋼材に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to plated steel materials such as steel plates for automobiles.
従来から、耐食用鋼材として、ＺｎメッキずたはＺｎを
主体とする合金メッキ鋼材が汎く用いられている。これ
は、素地鋼に対する電気化学的保護作用をもつとともに
、一般腐食項境において表面に不働態皮膜を形成すると
いうＺｎのもつ優れた防食機能に着目したもので、自動
車または家電等の分野で広く用いられている。BACKGROUND ART Conventionally, Zn-plated steel materials have been widely used as corrosion-resistant steel materials. This technology focuses on the excellent anti-corrosion function of Zn, which not only has an electrochemical protective effect on base steel but also forms a passive film on the surface under general corrosion conditions, and is widely used in fields such as automobiles and home appliances. It is used.
しかし、ｚｎまたはＺｎを主体とする合金表面は、一般
に塗装耐食性に難があシ、塗膜の防食機能が千金でない
。特に、最近では、自動車用鋼板においてはカチオン電
着塗装が主流になシつつあり、そのだめの下地処理とし
て、リン酸亜鉛、−鉄系化成処理が用いられているが、
との化成処理は亜鉛系表面に対しで殆んど効果がないこ
とが明らかとなった。However, the surface of Zn or an alloy mainly composed of Zn generally has poor coating corrosion resistance, and the anticorrosion function of the coating film is insufficient. In particular, recently, cationic electrodeposition coating has become less mainstream for automotive steel sheets, and zinc phosphate and iron-based chemical conversion treatments are used as base treatments.
It has become clear that chemical conversion treatment with zinc has almost no effect on zinc-based surfaces.
そこで、リン酸亜鉛−鉄系化成処理性の向上のため、し
いては塗装後の耐食性向上のため、Ｆｅ−Ｚｎ合金メッ
キまたはＦｅ系メッキを最表層とすることが提案されて
いる。たとえば、特開昭５６．１４２８８５号公報にお
いては、内層を防食金属とし、その上にＦｅ系メッキを
施すことが、特開昭５６−１３３４８８号、特開昭５５
−７３８８８号、特開昭５４−１０７８３８号の各公報
においては、最表層をＦｅ−Ｚｎ合金メッキとすること
がそれぞれ開示されている。Therefore, it has been proposed to use Fe-Zn alloy plating or Fe-based plating as the outermost layer in order to improve the zinc-iron phosphate chemical conversion treatment properties and also to improve the corrosion resistance after painting. For example, in JP-A-56-142885, it is proposed that the inner layer be made of anti-corrosion metal and Fe-based plating applied thereon.
73888 and JP-A-54-107838 each disclose that the outermost layer is plated with Fe-Zn alloy.
かかる技術に共通する現象的な根底思想は、リン酸塩化
成処理に当って、ホスホフィライト（Ｐｈｏｓｐｈｏｐ
ｈｙｌｌｉｔｅ ） ＣＺｎ２Ｆｅ（ＰＯ４）２．：ｌ
型の結晶を、ホーバイト（Ｈｏｐｅｊｔｅ ） （’
Ｚｎ５（ＰＯ４）２）型の結晶よシも優先的に析出させ
んとすることにあシ、もって化成処理性の向上を企図す
るものである。The basic idea common to these technologies is that phosphophyllite (Phosphophyllite) is used in phosphate chemical treatment.
hyllite) CZn2Fe(PO4)2. :l
The crystal of the type, Hopejte ('
The purpose is to preferentially precipitate Zn5(PO4)2) type crystals, thereby improving chemical conversion treatment properties.
しかし、本発明者らの幾多の実験によれば、Ｆｅ系また
はＦｅ−Ｚｎ合金系メッキを最表層とすることによって
化成処理性は、Ｚｎ系またはＺｎを主体とする合金メッ
キ系のものよシ格段と向上するけれども、そしてＰ値、
すなわちホスホフィライト結晶とホー・（イト結晶との
比ＣＰ／Ｐ十Ｈ］は高くなるけれども、リン酸塩結晶の
結晶核が少ない場合には、時々大きな結晶がみられ、塗
装後の総合的な耐食性という点で問題があることが判っ
た。However, according to numerous experiments conducted by the present inventors, by using Fe-based or Fe-Zn alloy-based plating as the outermost layer, chemical conversion treatment properties are improved compared to Zn-based or Zn-based alloy plating. Although it improves significantly, and the P value,
In other words, although the ratio of phosphophyllite crystals to phosphorite crystals (CP/P0H) becomes high, when there are few crystal nuclei of phosphate crystals, large crystals are sometimes seen, and the overall It was found that there was a problem in terms of corrosion resistance.
この問題点を一挙に解決したのが本発明で、その要旨は
、少くとも表層がＦｅ系またはＦｅ−Ｚｎ合金系のメッ
キ層を有する鋼材の表面に、Ｉ’７＋＋Ｍｎ＋Ｃｏ＋Ｃ
ｕ＋Ｍｏ、ＳｎおよびＣｒ０群の中から選ばれた金属の
１種まだは２種以上がＺｎとの合金として０．００５〜
０１ｇ／／ｍ２の微量付着量をもって析出していること
を特徴とする耐食性にすぐれたメッキ鋼材、にある。The present invention solves this problem all at once, and its gist is that I'7++ Mn + Co + C
u+One or more metals selected from the group of Mo, Sn and Cr0 as an alloy with Zn from 0.005
The present invention is a plated steel material with excellent corrosion resistance, which is characterized in that the deposit is deposited in a trace amount of 0.1 g//m2.
すなわち、本発明は、Ｆｅ系またはＦｅ−Ｚｎｎ全金糸
メッキ層上、Ｎｉ等とのＺｎ合金金属が微量付着したも
のである。That is, in the present invention, a small amount of Zn alloy metal with Ni or the like is deposited on an Fe-based or Fe-Znn all-gold thread plating layer.
一方、Ｎ１等の金属を鋼板の裸面に直接的に微量付着さ
せることは、たとえば特開昭５６−１１６８８３号公報
、特開昭５７−２８８９号公報または特開昭５６−１１
６８８８号公報によって公知である。しかるに、特開昭
５６−１４２８８５号公報３頁下段左欄１８行〜２０行
に記載され、その発明者が推測しているように、Ｆｅメ
ッキを施した場合、たとえ表面がＦｅであっても、冷延
鋼板の裸面つま９２０面と比較して、化成処理性が異な
るのである。実際、本発明者らもこのことは確認済であ
る。このように、前記各公報には、冷延鋼板の裸面にＮ
ｉ等を微量付着させることを開示しているけれども、化
成処理性が異なる、本発明に係る、Ｆｅ系またはＦｅ−
Ｚｎ合金系メッキ層の表面にＮｉ等を微量付着させるこ
とは教示していないし、また前述の従来技術では、Ｆｅ
系またはＦｅ−Ｚｎ合金系メッキ表面その捷まで化成処
理性お ゛よび塗装後の耐食性が十分であるとしてい
る。On the other hand, direct attachment of a small amount of metal such as N1 to the bare surface of a steel plate is disclosed in, for example, JP-A-56-116883, JP-A-57-2889, or JP-A-56-11.
It is known from the publication No. 6888. However, as stated in JP-A-56-142885, page 3, bottom left column, lines 18 to 20, and as the inventor speculates, when Fe plating is applied, even if the surface is Fe, Compared to the bare toe 920 surface of a cold-rolled steel sheet, chemical conversion treatment properties are different. In fact, the present inventors have also confirmed this fact. In this way, each of the above-mentioned publications states that N
Although it is disclosed that a small amount of Fe-based or Fe-
There is no teaching on attaching a small amount of Ni etc. to the surface of the Zn alloy plating layer, and the above-mentioned prior art does not teach that Fe
It is said that the chemical conversion treatment properties of the plating surface and the corrosion resistance after coating are sufficient.
本発明は、その種のメッキ表面をもって化成処理性、特
に塗装後の耐食性を十分とするのではなく、実際後述の
実施例で明らかにするように、十分でないことに鑑み、
さらにメッキ表面にＮｉ等とのＺｎ合金層を微量付着さ
せる構成を採るものである。The present invention does not aim to provide sufficient chemical conversion treatment properties, especially corrosion resistance after coating, with this type of plated surface, but in view of the fact that, as will be made clear in the Examples described later, this is not sufficient.
Furthermore, a structure is adopted in which a small amount of a Zn alloy layer with Ni or the like is deposited on the plated surface.
本発明に従うメッキ鋼材は、第１図に示すように、鋼材
素地１に、メッキ層２、好適には防食を主眼とする下層
２Ａと化成処理性改善のだめの上層２Ｂとからなるメッ
キ層に、Ｎ１等とのＺｎ合金フラッシュ金属３が微量、
よって一般には故点状形態をもって付着させた構造を有
する。As shown in FIG. 1, the plated steel material according to the present invention includes a steel material base 1, a plating layer 2, preferably a plating layer consisting of a lower layer 2A mainly for corrosion prevention and an upper layer 2B for improving chemical conversion properties. Small amount of Zn alloy flash metal 3 with N1 etc.
Therefore, it generally has a structure in which it is attached in a dot-like form.
そして、′この上に、後に塗装前処理としての化成処理
、たとえば自動車用にあってはリン酸亜鉛〜鉄系処理剤
が施される。Then, a chemical conversion treatment is then applied as a pre-painting treatment, such as a zinc phosphate to iron treatment agent for automobiles.
フラッシュ金属としては、Ｎｒ ｒ Ｍｎ ｐ Ｃｏ
ｓ Ｃｕ ＋ Ｍｏ ＋ Ｓ ｎおよびＣｒ０群の中か
ら選ばれた金属の１種または２種以上とのＺｎ合金金属
が選ばれる。As a flash metal, Nr r Mn p Co
A Zn alloy metal with one or more metals selected from the group s Cu + Mo + S n and Cr0 is selected.
またその付着量としては、０．００５〜０．１７９７ｍ
２とされる。Ｏ’、 ＯＯ５７７７ｍ２未満では、化成
処理性の向上に効果がみられず、また０、 １９７ｍ２
を超えてもかえって化成処理性が低下するからである。In addition, the amount of adhesion is 0.005 to 0.1797 m
2. If O', OO is less than 5777 m2, no effect is seen in improving the chemical conversion treatment property, and if it is 0, 197 m2
This is because, even if it exceeds the above range, the chemical conversion treatment properties will deteriorate.
なお、０．００５ ｊｊ／ｍ２という数値は、現在の計
量器の極出精度から測定が困難であるけれども、付着後
の外観および蛍光Ｘ線によるカウント数、電気メッキの
場合には通電量、電流効率等から推測できるものである
。Although it is difficult to measure the value of 0.005 jj/m2 due to the extreme accuracy of current measuring instruments, it is determined by the appearance after adhesion, the number of counts determined by fluorescent X-rays, the amount of current applied in the case of electroplating, and the current This can be inferred from efficiency etc.
フラッシュ金属の付着または析出の方法としては、電気
メッキ方法、置換メッキまたは蒸着メッキ等を用いるこ
とができる。特に置換メッキとする場合には、フラ、ン
ユメ、キ液槽に鋼帯を通すことによって、本発明が対象
とする成品面のみならず、裸面にもフラッ／ユ金属を析
出させることができるので、裸面の化成処理性をも改善
でき好適である。As a method for attaching or depositing flash metal, electroplating, displacement plating, vapor deposition plating, or the like can be used. Particularly in the case of displacement plating, by passing the steel strip through a liquid tank, the metal can be deposited not only on the surface of the finished product, which is the object of the present invention, but also on the bare surface. Therefore, it is suitable because it can also improve the chemical conversion treatment properties of bare surfaces.
本発明は、従来技術にない、総合的に化成処理性および
塗装後の耐食性に優れたメッキ鋼材を提供するものであ
る。このだめに、フラッシュ金属との関係で、その下面
のメッキ層の組成は重要な要素である。すなわち、フラ
ッシュ金属を析出させるメッキ表層は少くともＦｅ系ま
たはＦｅ−Ｚｎ合金系メッキ層であることが必要とされ
る。Ｚｎ系メッキ層では、特に自動車用鋼板としたとき
、カチオン電着塗装後、黒錆および塗膜の外観欠陥を示
す。The present invention provides a plated steel material that has excellent overall chemical conversion treatment properties and corrosion resistance after painting, which is not available in the prior art. To this end, the composition of the plating layer on the lower surface is an important factor in relation to the flash metal. That is, the plating surface layer on which the flash metal is deposited is required to be at least an Fe-based or Fe-Zn alloy-based plating layer. The Zn-based plating layer shows black rust and defects in the appearance of the coating film after cationic electrodeposition coating, especially when applied to steel sheets for automobiles.
よシ好ましいのは、黒錆等の原因となる亜鉛量が少い、
つｔｐＺｎ≦４０％のものである。Ｚｎ量が少いと、鋼
材の素地に対する電気化学的な保護作用に劣る。しかし
、メッキ層自体の防食性よシも、塗装後の耐食性は、化
成処理性および塗膜の密着性に大きく依存するとの本発
明者らの知見に従って、Ｆｅ系まだはＦ’ｅ −Ｚ ｎ
合金系メッキとする必要があるのである。It is preferable that the amount of zinc, which causes black rust etc., is small.
and tpZn≦40%. If the amount of Zn is small, the electrochemical protective effect on the base steel material will be inferior. However, in accordance with the inventors' knowledge that the corrosion resistance after painting, as well as the corrosion resistance of the plating layer itself, greatly depends on the chemical conversion treatment properties and the adhesion of the coating film, Fe-based materials are F'e-Zn.
It is necessary to use alloy plating.
メッキ層は、Ｆｅ系まだはＦｅ−Ｚｎ合金系の単層メッ
キでもよいが、複層メッキは総合的特性に優れたものを
与えてくれる。The plating layer may be a single layer plating of Fe type or Fe-Zn alloy type, but multilayer plating provides excellent overall properties.
すなわち、下層を耐食性を目的としてＦｅ含有量が２０
〜３０％のＦｅ−Ｚｎ系のものまたはＮｉ含有量が１０
〜１３ｔ１６のＮｉ−Ｚｎ系のもの、上層をＦｅ含有量
が８０〜９５％のＦｅ−Ｚｎ系のものがとシわけ好適で
ある。下層を、Ｚｎ含有量を高めてＺｎのもつ防食機能
を十分に発揮させ、上層においてはＺｎ含有量を少くし
逆にＦｅ含有量を高めて化成処理性および塗装後の耐食
性を向上させる狙いである。That is, the lower layer has an Fe content of 20% for the purpose of corrosion resistance.
~30% Fe-Zn type or Ni content 10
-13t16 Ni-Zn type and Fe-Zn upper layer with Fe content of 80 to 95% are suitable. The aim is to increase the Zn content in the lower layer to fully demonstrate the anti-corrosion function of Zn, and to reduce the Zn content and increase the Fe content in the upper layer to improve chemical conversion treatment properties and corrosion resistance after painting. be.
一般に自動車用鋼板におけるカチオン電着塗装に対する
リン酸塩処理としては、ホー・ｐイト型よシもホスホフ
ィライト（Ｐｈｏｓｐｈｏｐｈｙｌｌｉｔｅ ）〔ｚｎ
２Ｆｅ（ＰＯ２）２〕型が好ましいことが知られている
。このホスホフィライトはホーバイトか析出した後に、
Ｚｎの一部がＦｅに置換することによって生成すると云
われている。したかって、リン酸塩処理に当って、ホー
バイトをいかに析出させ、これをいかにホスホフィライ
トに置換するようになすことが重要である。In general, as a phosphate treatment for cationic electrodeposition coating on automotive steel sheets, phosphophyllite (phosphophyllite) [zn
2Fe(PO2)2] type is known to be preferable. After this phosphophyllite is precipitated as hovite,
It is said that Zn is produced by partially replacing Zn with Fe. Therefore, in the phosphate treatment, it is important to determine how to precipitate hovite and how to replace it with phosphophyllite.
一方、ホー・やイトの析出する核は、鋼材表面上のカソ
ード部であり、この核を起点として結晶が生長する。そ
のために、リン酸塩処理の反応としては、アノード律速
型の反応を生じさせることが重要である。On the other hand, the nucleus where HO/YITE precipitates is the cathode portion on the surface of the steel material, and crystals grow from this nucleus as a starting point. For this reason, it is important to cause an anode rate-limited reaction in the phosphate treatment reaction.
そこで、本発明では、Ｎ１等とのＺｎ合金を表面に
゛微量析出させることによシ、カソード部の核を生成
させ、アノード律速型の反応をもってリン酸塩処理性を
向上させるものである。また、Ｎ１等とのＺｎ合金の微
量析出によって、リン酸塩結晶を微細化し、リン酸塩皮
膜のポロシティ−を低減させ、もって塗装後の耐食性を
向上させるものである。Therefore, in the present invention, a Zn alloy with N1 etc. is used on the surface.
By precipitating a small amount, a nucleus is generated in the cathode region, and the anode rate-limiting reaction improves the phosphate treatment properties. In addition, the minute precipitation of the Zn alloy with N1 etc. makes the phosphate crystals finer, reduces the porosity of the phosphate film, and improves the corrosion resistance after painting.
Ｎ１等とのＺｎ合金の場合、Ｎｉ単独を微量析出させる
のに比較し、付着量のコントロールに容易である。In the case of a Zn alloy with N1 or the like, it is easier to control the adhesion amount compared to depositing a small amount of Ni alone.
リン酸塩結晶を微細化させるに当って、メッキ皮膜のＦ
ｅ％が高いとある程度微細化したものが得られるが、そ
こには限度がある。ちなみに、冷延鋼板の化成処理性は
、冷延鋼板の製造過程、特に焼鈍過程で鋼板表面にＭｎ
＋ Ｐの炭化層が形成され、またＣの付着量が生じる
ことから、化成処理性に大きな影響を及ぼすととが知ら
れている。特に、Ｍｎ濃化層はリン酸塩処理反応のカソ
ード部の核に寄与する為、リン酸塩結晶の微細化や反応
性に効果がある。このように冷延鋼板表面は均一なＦｅ
表面ではない。In making the phosphate crystals finer, the F of the plating film is
If e% is high, a certain degree of fineness can be obtained, but there is a limit to this. By the way, the chemical conversion treatment properties of cold-rolled steel sheets are determined by the presence of Mn on the steel sheet surface during the manufacturing process of cold-rolled steel sheets, especially during the annealing process.
It is known that since a carbonized layer of + P is formed and an amount of C is deposited, it has a large effect on chemical conversion treatment properties. In particular, since the Mn-enriched layer contributes to the nucleus of the cathode portion of the phosphate treatment reaction, it is effective in reducing the size and reactivity of phosphate crystals. In this way, the surface of the cold-rolled steel sheet has uniform Fe.
Not on the surface.
一方、Ｆｅ系メッキ層を表層に有する鋼板の化成処理性
は、表層の組成等が比較的均一である為、冷延鋼板のＭ
ｎ濃化層に相当するものがないことから、リン酸塩処理
に於いて粗大な結晶が成長することにな９、必ずしも良
好な結果が得られない。On the other hand, the chemical conversion treatment properties of steel sheets with Fe-based plating layer on the surface layer are relatively uniform, so the M
Since there is no equivalent to the n-enriched layer, coarse crystals grow during phosphate treatment9, and good results are not necessarily obtained.
そこで、Ｆｅ系メ、上層の表面にＮｉ等のＺｎ合金を析
出させることによシ化成処理性、特に結晶の微細化をは
かる。図面で見られるように、Ｚｎ−Ｎ１フラッシュの
前後でリン酸塩結晶の微細化が見られる。すなわち、第
２図および第３図は、走査型電子顕微鏡（ＳＥＭ ）の
写真（倍率１４６０倍）で、第２図は下層および上層に
Ｆｅ−Ｚｎ合金層をそれぞれ形成し、第３図はそれにさ
らにＺｎ−Ｎｉフラッシュメッキを１ ’ＯＯｍ９７ｍ
２施した後、化成処理を行ったときのリン酸塩結晶状態
を示している。Therefore, by precipitating a Zn alloy such as Ni on the surface of the Fe-based upper layer, chemical conversion treatment properties, particularly crystal refinement, are attempted. As seen in the drawings, refinement of phosphate crystals can be seen before and after the Zn-N1 flash. That is, Fig. 2 and Fig. 3 are scanning electron microscope (SEM) photographs (magnification: 1460x). Furthermore, Zn-Ni flash plating was applied to 1'OOm97m.
2 shows the state of phosphate crystals when chemical conversion treatment is performed.
以上の通り、本発明によれば、化成処理性を著しく改善
できるばかりでなく、特に塗装後の耐食性を含めた総合
的特性に優れたメッキ鋼材が提供される。As described above, according to the present invention, it is possible to provide a plated steel material that not only can significantly improve chemical conversion treatment properties but also has excellent overall characteristics, including particularly corrosion resistance after painting.
以下、実施例を示し、本発明による効果について説明す
る。Hereinafter, the effects of the present invention will be explained with reference to Examples.
実施例１
板厚０．７ｔの冷延鋼板（アルミキルド鋼）を素材とし
て、第１表に示す条件で、亜鉛−鉄系合金メッキの２層
電気メツキを形成した。Example 1 Using a cold-rolled steel plate (aluminum killed steel) with a thickness of 0.7 t as a raw material, two-layer electroplating of zinc-iron alloy plating was formed under the conditions shown in Table 1.
このようにして得られたメッキ鋼板表面上に、第２表に
示すメッキ条件によりてＮ ］ ｔ Ｃｒ ｐ Ｍｎ
ｒ Ｃｕ ｒＣｏ、Ｍｏの１種とＺｎとの合金及びＮ
＋ ＋ ’Ｍｎ ｒ Ｚ ｎとの合金のフラッシュメッ
キを施した。その後、これらの鋼板に第３表に示す条件
でリン酸塩処理及びカチオン電着塗装を施し、化成処理
性及び塗装耐食性を調査した。化成処理性は、化成皮膜
のＸ線回折によＩ） Ｐｈｏｓｐｈｏｐｈｙｌｌｅｉｔ
ｅとＨｏｐｅｉｔｅとの比、即ちＰ／Ｐ＋Ｈの比率およ
び化成皮膜付着量、走査型電子顕微鏡による結晶の観察
を行った。On the surface of the plated steel sheet thus obtained, N ] t Cr p Mn was applied under the plating conditions shown in Table 2.
rCu rCo, alloy of one type of Mo and Zn and N
+ + 'Flash plating of alloy with Mn r Z n was performed. Thereafter, these steel plates were subjected to phosphate treatment and cationic electrodeposition coating under the conditions shown in Table 3, and chemical conversion treatment properties and coating corrosion resistance were investigated. Chemical conversion treatment properties are determined by X-ray diffraction of the chemical conversion film.I) Phosphophylleit
The ratio of e to Hopeite, that is, the ratio of P/P+H, the amount of chemical conversion film attached, and the crystals were observed using a scanning electron microscope.
また、塗装耐食性は電着塗膜のクロス力、ト部の塩水噴
霧試験９６０時間後のテープ剥離中で評価した。The corrosion resistance of the coating was evaluated by cross force of the electrodeposited coating and tape peeling after 960 hours of salt spray test on the top part.
その一覧表を第４表に示す。The list is shown in Table 4.
第３表
実施例２
板厚０．７ｔの冷延鋼板（アルミキルド鋼）を素材とし
て、第５表に示す条件で、内層としてニッケルー亜鉛合
金メッキ、表層として鉄−亜鉛系合金メッキを形成せし
め、その後第２表に示すメッキ条件によシ、メッキ鋼板
表面上にＮｉ、ＣｒｔＭｎ、Ｃｕ。Table 3 Example 2 Using a cold-rolled steel plate (aluminum killed steel) with a thickness of 0.7 t as a material, nickel-zinc alloy plating was formed as an inner layer and iron-zinc alloy plating was formed as a surface layer under the conditions shown in Table 5. Thereafter, under the plating conditions shown in Table 2, Ni, CrtMn, and Cu were deposited on the surface of the plated steel sheet.
ｃｏ２ＭＯの１種とＺｎとの合金及びＮｉ、Ｍｎ、Ｚｎ
との合金のフラッシュメッキを施した。Alloy of one type of co2MO and Zn and Ni, Mn, Zn
Alloy flash plated.
その後、これら鋼板に実施例１と同様にリン酸塩処理、
カチオン電着塗装を施し、化成処理性、塗装耐食性を調
査した。その結果の一覧表を第６表に示した。Thereafter, these steel plates were subjected to phosphate treatment in the same manner as in Example 1.
Cationic electrodeposition coating was applied, and chemical conversion treatment properties and coating corrosion resistance were investigated. A list of the results is shown in Table 6.
第１図は本発明に係るメッキ鋼材の概要図９、第２図お
よび第３図はそれぞれ比較例および本発明例の、走査型
電子顕微鏡による倍率１４６０倍の、リン酸塩結晶状態
を示す写真である。
■・・・鋼材素地、２・・・メッキ層、３・・・フラッ
シュ金属。
第１図Figure 1 is a schematic diagram of the plated steel material according to the present invention; Figures 2 and 3 are photographs showing the state of phosphate crystals of a comparative example and an example of the present invention, respectively, taken with a scanning electron microscope at a magnification of 1460 times. It is. ■...Steel material material, 2...Plating layer, 3...Flash metal. Figure 1
Claims (1)
系のメッキ層を有する鋼材の表面に、Ｎｉ＋ＭｎｙＣｏ
ｔＣｕ＋Ｍｏ＋ＳｎおよびＣｒの群の中から選ばれた金
属の１種または２種以上がＺｎとの合金として０．００
５〜０１仏２の微量付着量をもって析出していることを
特徴とする耐食性にすぐれたメッキ鋼材。(1) Ni+MnyCo is applied to the surface of a steel material that has at least a Fe-based or Fe-Zn alloy-based plating layer.
0.00 as an alloy of one or more metals selected from the group of tCu+Mo+Sn and Cr with Zn.
A plated steel material with excellent corrosion resistance characterized by depositing with a trace amount of deposits of 5 to 01 French.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP369583A JPS59129781A (en) | 1983-01-13 | 1983-01-13 | Plated steel material with superior corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP369583A JPS59129781A (en) | 1983-01-13 | 1983-01-13 | Plated steel material with superior corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59129781A true JPS59129781A (en) | 1984-07-26 |
Family
ID=11564517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP369583A Pending JPS59129781A (en) | 1983-01-13 | 1983-01-13 | Plated steel material with superior corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59129781A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6479393A (en) * | 1987-09-22 | 1989-03-24 | Nippon Steel Corp | Production of zinc-chromium electroplated steel sheet |
| DE3943243A1 (en) * | 1988-12-30 | 1990-07-05 | Po Hang Iron & Steel | STEEL SHEET WITH A COATING FROM AN IRON-MANGANE ALLOY AND METHOD FOR THE PRODUCTION THEREOF |
| US6308544B1 (en) | 1998-01-22 | 2001-10-30 | Emhart Inc. | Vehicle body component with a tin/zinc coating |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51135840A (en) * | 1975-05-21 | 1976-11-25 | Nippon Packaging Kk | Surface treatment process for zinc or zinc alloy |
| JPS54107838A (en) * | 1978-02-13 | 1979-08-24 | Kobe Steel Ltd | Zinc-iron alloy-electroplated steel sheet for spot welding and pressing |
| JPS5565326A (en) * | 1978-11-06 | 1980-05-16 | Kawasaki Steel Corp | Cold rolled steel sheet excellent in painting property and temporary rust preventive property |
| JPS5573888A (en) * | 1978-11-22 | 1980-06-03 | Nippon Kokan Kk <Nkk> | High corrosion resistant zinc-electroplated steel sheet with coating and non-coating |
| JPS5669377A (en) * | 1979-11-12 | 1981-06-10 | Nippon Steel Corp | Surface treatment method of zinc |
| JPS56133488A (en) * | 1980-03-24 | 1981-10-19 | Nippon Steel Corp | Plated steel material |
| JPS56142885A (en) * | 1980-04-08 | 1981-11-07 | Nippon Steel Corp | Steel material with plural plating layers |
| JPS572889A (en) * | 1980-06-07 | 1982-01-08 | Nippon Steel Corp | Steel plate having supepior chemical conversion treatment property |
| JPS5794577A (en) * | 1980-12-05 | 1982-06-12 | Nippon Steel Corp | Zinc type surface treated steel material of superior corrosion resistance |
| JPS57149429A (en) * | 1981-03-11 | 1982-09-16 | Nippon Kokan Kk <Nkk> | Preparation of cold rolled steel plate having excellent corrosion resistance and formation-treatment property |
-
1983
- 1983-01-13 JP JP369583A patent/JPS59129781A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51135840A (en) * | 1975-05-21 | 1976-11-25 | Nippon Packaging Kk | Surface treatment process for zinc or zinc alloy |
| JPS54107838A (en) * | 1978-02-13 | 1979-08-24 | Kobe Steel Ltd | Zinc-iron alloy-electroplated steel sheet for spot welding and pressing |
| JPS5565326A (en) * | 1978-11-06 | 1980-05-16 | Kawasaki Steel Corp | Cold rolled steel sheet excellent in painting property and temporary rust preventive property |
| JPS5573888A (en) * | 1978-11-22 | 1980-06-03 | Nippon Kokan Kk <Nkk> | High corrosion resistant zinc-electroplated steel sheet with coating and non-coating |
| JPS5669377A (en) * | 1979-11-12 | 1981-06-10 | Nippon Steel Corp | Surface treatment method of zinc |
| JPS56133488A (en) * | 1980-03-24 | 1981-10-19 | Nippon Steel Corp | Plated steel material |
| JPS56142885A (en) * | 1980-04-08 | 1981-11-07 | Nippon Steel Corp | Steel material with plural plating layers |
| JPS572889A (en) * | 1980-06-07 | 1982-01-08 | Nippon Steel Corp | Steel plate having supepior chemical conversion treatment property |
| JPS5794577A (en) * | 1980-12-05 | 1982-06-12 | Nippon Steel Corp | Zinc type surface treated steel material of superior corrosion resistance |
| JPS57149429A (en) * | 1981-03-11 | 1982-09-16 | Nippon Kokan Kk <Nkk> | Preparation of cold rolled steel plate having excellent corrosion resistance and formation-treatment property |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6479393A (en) * | 1987-09-22 | 1989-03-24 | Nippon Steel Corp | Production of zinc-chromium electroplated steel sheet |
| DE3943243A1 (en) * | 1988-12-30 | 1990-07-05 | Po Hang Iron & Steel | STEEL SHEET WITH A COATING FROM AN IRON-MANGANE ALLOY AND METHOD FOR THE PRODUCTION THEREOF |
| US6308544B1 (en) | 1998-01-22 | 2001-10-30 | Emhart Inc. | Vehicle body component with a tin/zinc coating |
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