JPH0713308B2 - Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldability - Google Patents
Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldabilityInfo
- Publication number
- JPH0713308B2 JPH0713308B2 JP2088692A JP8869290A JPH0713308B2 JP H0713308 B2 JPH0713308 B2 JP H0713308B2 JP 2088692 A JP2088692 A JP 2088692A JP 8869290 A JP8869290 A JP 8869290A JP H0713308 B2 JPH0713308 B2 JP H0713308B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- film
- chemical conversion
- oxide
- 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.)
- Expired - Lifetime
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- Chemical Treatment Of Metals (AREA)
- Coating With Molten Metal (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、プレス成形性、化成処理性、溶接性に優れた
亜鉛系めっき鋼板に関するものである。TECHNICAL FIELD The present invention relates to a zinc-based plated steel sheet excellent in press formability, chemical conversion treatment property, and weldability.
（従来の技術及び発明が解決しようとする課題） 亜鉛系めっき鋼板のプレス成形性を向上させる方法とし
ては、例えば、特開昭62−185883号公報記載の如く、め
っき鋼板表面に電解クロメート処理を施し、Cr2O3の酸
化物皮膜を生成せしめる方法や、特開昭62−192597号公
報記載の如く、鉄亜鉛合金めっきを施す方法等の亜鉛系
めっき鋼板上に硬い皮膜を形成し、プレス時のめっきと
ダイスのかじりを防止してプレスの潤滑性の向上をはか
ることが開示されている。(Problems to be Solved by the Related Art and Invention) As a method for improving the press formability of a zinc-based plated steel sheet, for example, as described in JP-A-62-185883, electrolytic chromate treatment is applied to the surface of the plated steel sheet. And forming a hard film on a zinc-based plated steel sheet, such as a method of forming an oxide film of Cr 2 O 3 or a method of performing iron-zinc alloy plating, as described in JP-A-62-192597, and pressing It is disclosed to prevent galling of the die and die at the time and improve the lubricity of the press.
又、特開平１−136952号公報記載の如く、めっき鋼板の
表面に有機潤滑皮膜や潤滑油等の有機物を塗布または被
覆し、プレス成形性を向上させることが開示されてい
る。Further, as described in JP-A-1-136952, it is disclosed that an organic lubricating film or an organic substance such as lubricating oil is applied or coated on the surface of a plated steel sheet to improve press formability.
しかしながら、このような製品は自動車ユーザー等の使
用において、以下のような不十分な点がある。However, such products have the following inadequate points when used by automobile users.
自動車ユーザーでの使用工程の概略は、鋼板を油で洗浄
する工程、プレス工程、脱脂工程、化成処理工程、塗装
工程からなっており、電解クロメート処理鋼板の場合
は、化成処理での化成処理皮膜が形成せず、また潤滑油
や潤滑皮膜などを塗布した鋼板の場合は、洗浄工程で油
が落ちるので十分な潤滑性能を発揮せず、さらには、化
成処理前の脱脂工程に負荷がかかりコストが高くなる。
一方、亜鉛系めっき鋼板に鉄亜鉛合金フラッシュめっき
を施したものは、電解クロメート処理に比較して鋼板の
コストが高くなるという問題点があり、低コストで、化
成処理が可能で、脱脂等の工程に負荷をかけず、プレス
成形性に優れる亜鉛系めっき鋼板の開発が望まれてい
る。The outline of the process used by automobile users consists of the process of washing the steel plate with oil, the pressing process, the degreasing process, the chemical conversion treatment process, and the painting process.In the case of electrolytic chromate treated steel plate, the chemical conversion treatment film during chemical conversion treatment. In the case of a steel sheet on which no lubricant is formed and which has been coated with lubricating oil or a lubricating film, the oil does not come out in the cleaning process, so sufficient lubrication performance cannot be exhibited, and further, the degreasing process before chemical conversion treatment puts a load on the cost. Becomes higher.
On the other hand, the zinc-based plated steel sheet subjected to iron-zinc alloy flash plating has a problem that the cost of the steel sheet is higher than that of the electrolytic chromate treatment, and it is possible to perform chemical conversion treatment at low cost and to remove degreasing and the like. It is desired to develop a zinc-based plated steel sheet that does not impose a load on the process and is excellent in press formability.
又、溶接性向上については、従来特にその対策が講ぜら
れたことはなく、プレス成形性、化成処理性と相俟って
溶接性の向上も強く要求されているところである。Further, as to the improvement of the weldability, no particular measures have been taken so far, and there is a strong demand for the improvement of the weldability in combination with the press formability and the chemical conversion treatment property.
本発明はこのような要求を有利に解決し得る亜鉛系めっ
き鋼板を提供しようとするものである。The present invention is intended to provide a zinc-based plated steel sheet that can advantageously solve such requirements.
（発明が解決しようとする課題） 本発明の要旨とするところは、Zn酸化物３〜500mg/m
2（Znとして）、Mn酸化物５〜500mg/m2（Mnとして）、
りん酸とMo酸化物、Ｗ酸化物、Ｖ酸化物の１種又は２種
以上を1000mg/m2以下（P,Mo,W,Vとして）及びその他酸
化物からなる皮膜を表面に被覆してなるプレス成形性、
化成処理性、溶接性に優れた亜鉛系めっき鋼板にある。(Problems to be Solved by the Invention) The gist of the present invention is that Zn oxide is 3 to 500 mg / m 2.
2 (as Zn), Mn oxide 5 to 500 mg / m 2 (as Mn),
The surface is coated with a film consisting of phosphoric acid and one or more of Mo oxide, W oxide, and V oxide of 1000 mg / m 2 or less (as P, Mo, W, V) and other oxides. Press formability,
It is a zinc-based plated steel sheet with excellent chemical conversion treatability and weldability.
本発明が対象とする亜鉛系めっき鋼板とは、例えば溶融
めっき法、電気めっき法、蒸着めっき法、溶射法などの
各種の製造方法によるものがあり、めっき組成としては
純Znの他、ZnとFe,ZnとNi,ZnとAl,ZnとMn,ZnとCr,ZnとT
i,ZnとMgなどZnを主成分として、耐食性など諸機能の向
上のためFe,Ni,Co,Al,Pb,Sn,Sb,Cu,Ti,Si,B,P,N,S,O等
の１種ないし２種以上の合金元素および不純物元素を含
み、また、SiO2,Al2O3などのセラミックス微粒子、Ti
O2,BaCrO4などの酸化物、アクリル樹脂などの有機高分
子をめっき層中に分散させたものがあり、めっき層の厚
み方向で単一組成のもの、連続的あるいは層状に組成が
変化するものがあり、さらに多層めっき鋼板では、最上
層に、めっき組成としては純Znの他、ZnとFe,ZnとNi,Zn
とAl,ZnとMn,ZnとCr,ZnとTi,ZnとMgなどZnを主成分とし
て、耐食性などの諸機能の向上のため１種ないし２種以
上の合金元素および不純物元素を含み、また、SiO2,Al2
O3などのセラミックス微粒子、TiO2,BaCrO4などの酸化
物、アクリル樹脂などの有機高分子をめっき層中に分散
させたものがある。The zinc-based plated steel sheet targeted by the present invention include, for example, hot dipping method, electroplating method, vapor deposition plating method, those by various manufacturing methods such as thermal spraying method, and other than pure Zn as the plating composition, Zn and Fe, Zn and Ni, Zn and Al, Zn and Mn, Zn and Cr, Zn and T
Fe, Ni, Co, Al, Pb, Sn, Sb, Cu, Ti, Si, B, P, N, S, O, etc. are mainly composed of Zn such as i, Zn and Mg to improve various functions such as corrosion resistance. 1 to 2 or more types of alloying elements and impurity elements, fine particles of ceramics such as SiO 2 and Al 2 O 3 , Ti,
Some oxides such as O 2 and BaCrO 4 and organic polymers such as acrylic resin are dispersed in the plating layer.The composition varies in the thickness direction of the plating layer, and the composition changes continuously or in layers. In addition, in the case of multi-layer plated steel sheets, in addition to pure Zn as the plating composition, Zn and Fe, Zn and Ni, Zn are used as the plating composition in the uppermost layer.
And Al, Zn and Mn, Zn and Cr, Zn and Ti, Zn and Mg, such as Zn and Mg, as main components, and contain one or more alloying elements and impurity elements to improve various functions such as corrosion resistance. , SiO 2 , Al 2
There is one in which fine particles of ceramics such as O 3 and the like, oxides such as TiO 2 and BaCrO 4 and organic polymers such as acrylic resin are dispersed in the plating layer.
例えば、溶融亜鉛めっき鋼板、蒸着亜鉛めっき鋼板、鉄
−亜鉛合金化溶融亜鉛めっき鋼板、亜鉛を主とするアル
ミニウム、鉄などの合金溶融亜鉛めっき鋼板、めっき層
断面方向で下層が合金化されている合金化溶融亜鉛めっ
き鋼板（一般にハーフアロイと称する）、片面鉄−亜鉛
合金化溶融亜鉛めっき層、他面溶融亜鉛めっき層からな
るめっき鋼板、これらのめっき層上に電気めっき、蒸着
めっき等により亜鉛、または亜鉛を主成分とし、鉄、ニ
ッケルを含有する金属をめっきした鋼板、あるいは、電
気亜鉛めっき鋼板、亜鉛、ニッケル、クロム等合金電気
めっき鋼板等、更に単一合金層又は多層合金電気めっき
鋼板、亜鉛および亜鉛含有金属の蒸着めっき鋼板等があ
る。その他、SiO2,Al2O3などのセラミックス微粒子、Ti
O2酸化物微粒子及び有機高分子などを亜鉛又は亜鉛合金
めっき中に分散させた分散めっき鋼板がある。For example, hot-dip galvanized steel sheet, vapor-deposited galvanized steel sheet, iron-zinc alloyed hot-dip galvanized steel sheet, aluminum mainly containing zinc, hot-dip galvanized steel sheet of iron or the like, lower layer is alloyed in the plating layer cross-section direction. Alloyed hot-dip galvanized steel sheet (generally referred to as half alloy), single-sided iron-zinc alloyed hot-dip galvanized layer, galvanized steel sheet consisting of other-side hot-dip galvanized layer, zinc on these plated layers by electroplating, vapor deposition plating, etc. , Or a steel sheet containing zinc as a main component and a metal containing iron or nickel, or an electrogalvanized steel sheet, an electroplated steel sheet such as zinc, nickel or chromium alloy, or a single alloy layer or a multilayer alloy electroplated steel sheet. , Zinc and zinc-containing metal vapor-deposited steel sheets. In addition, fine particles of ceramics such as SiO 2 and Al 2 O 3 , Ti
There is a dispersion-plated steel sheet in which fine particles of O 2 oxide and an organic polymer are dispersed in zinc or zinc alloy plating.
このような亜鉛系めっき鋼板表面に、前記の如く、Zn酸
化物、Mn酸化物、りん酸とMo酸化物、Ｗ酸化物、Ｖ酸化
物の１種又は２種以上およびその他酸化物からなる皮膜
を被覆することによりプレス成形性、化成処理性、溶接
性を向上させようとするものである。As described above, a film composed of one or more of Zn oxide, Mn oxide, phosphoric acid and Mo oxide, W oxide, V oxide, and other oxides on the surface of such a zinc-based plated steel sheet. It is intended to improve press formability, chemical conversion treatment property, and weldability by coating with.
（作 用） 前記皮膜がかかる効果を奏する理由は以下の如くであ
る。(Operation) The reason why the above-mentioned film exerts such an effect is as follows.
プレス成形に際しての潤滑性をめっき鋼板に付与するに
は、めっき鋼板表面に硬質の皮膜を形成する方法が有効
である。この点で電解クロメート処理、鉄亜鉛合金めっ
きは有効であるが、前者は化成処理皮膜が形成できず、
後者は処理量が多くコスト高になる。A method of forming a hard film on the surface of the plated steel sheet is effective for imparting lubricity to the plated steel sheet during press forming. In this respect, electrolytic chromate treatment and iron-zinc alloy plating are effective, but the former cannot form a chemical conversion coating,
The latter requires a large amount of processing and is costly.
これらの解決には、めっき鋼板表面の硬質皮膜として
は、酸化物皮膜であって、かつ化成処理液中で溶解し、
化成処理皮膜を形成できるとともに、皮膜成分が化成処
理液に溶け出しても化成処理に悪影響を与えないもので
あることが必要である。To solve these problems, the hard coating on the surface of the plated steel sheet is an oxide coating and dissolves in the chemical conversion treatment liquid.
It is necessary that a chemical conversion treatment film can be formed and that the chemical conversion treatment is not adversely affected even if the film components are dissolved in the chemical conversion treatment liquid.
本発明者らは、このような観点から、亜鉛系めっき鋼板
表面にMn酸化物皮膜を形成すれば良いことを見出した。
Mn酸化物皮膜はクロメート皮膜と同様ガラス状の皮膜と
なり、プレス時にめっきのダイスへのかじりを抑制し、
摺動性を良好とする。さらに、化成処理液には溶解する
ためクロメート皮膜と異なり、化成処理皮膜を形成する
ことができ、また、化成処理液に溶出しても悪影響はな
い。From such a viewpoint, the present inventors have found that it is sufficient to form the Mn oxide film on the surface of the zinc-based plated steel sheet.
The Mn oxide film becomes a glass-like film like the chromate film, and suppresses galling of the plating die during pressing,
Good slidability. Furthermore, since it dissolves in the chemical conversion treatment liquid, unlike the chromate film, a chemical conversion treatment film can be formed, and even if it is eluted into the chemical conversion treatment liquid, there is no adverse effect.
Zn酸化物は、単独では湿式法でプレス摺動性改善皮膜を
形成し難いが、Mn酸化物との混晶状態ではプレス摺動性
を著しく向上できる。またZn酸化物も化成処理皮膜を形
成することができ、化成処理液に溶出しても悪影響はな
い。Zn oxide alone is difficult to form a press slidability improving film by a wet method, but in a mixed crystal state with Mn oxide, press slidability can be significantly improved. Further, Zn oxide can also form a chemical conversion treatment film, and there is no adverse effect even if it is eluted in the chemical conversion treatment liquid.
Mn,Zn,P系酸化物皮膜の構造は明確ではないが、Mn−O,Z
n−O,P−Ｏ結合からなるネットワークが主体で、部分的
に−OH,CO3,PO2基等が結合されているが、さらにはめっ
きから供給される金属が置換したアモルファス状の巨大
分子構造であろうと推定される。The structure of Mn, Zn, P-based oxide film is not clear, but Mn-O, Z
n-O, the network is mainly composed of PO bonds, partially -OH, CO 3, PO is 2 group or the like is attached, more massive like amorphous metal supplied has been substituted from the plating It is presumed to have a molecular structure.
また、この皮膜は酸化物皮膜のため、油による洗浄工程
や脱脂工程でも溶解しないので、潤滑性能が低下した
り、他の工程に負荷をかけたりすることがない。Further, since this film is an oxide film, it does not dissolve even in the oil cleaning process and the degreasing process, so that the lubricating performance is not deteriorated and no load is applied to other processes.
この皮膜の密着性や成膜性を良好にするため、ほう酸、
硫酸、硝酸、塩酸などの無機酸や、それらからなる塩を
添加することは効果的である。In order to improve the adhesion and film formability of this film, boric acid,
It is effective to add an inorganic acid such as sulfuric acid, nitric acid or hydrochloric acid, or a salt thereof.
さらに、この皮膜中には、処理浴中やめっきに含まれる
物質を不純物として含んでいてもよい。これら不純物と
してはZn,Al,Cr,Co,Mn,Pb,Sn,Cu,Ti,Si,B,N,S,P,cl,K,N
a,Mg,Ca,Ba,In,C,Fe,V,W,Niなどがある。Further, this coating may contain substances contained in the treatment bath or plating as impurities. These impurities include Zn, Al, Cr, Co, Mn, Pb, Sn, Cu, Ti, Si, B, N, S, P, cl, K, N.
a, Mg, Ca, Ba, In, C, Fe, V, W, Ni, etc.
次に、本発明の皮膜の皮膜量範囲について述べる。Next, the coating amount range of the coating of the present invention will be described.
この皮膜の皮膜量としては、プレス成形性を良好とする
には、Mn酸化物（Mnとして）5mg/m2以上含有すればよい
が、Mn皮膜量が500mg/m2を越えると化成処理皮膜の形成
が不十分となる。Regarding the coating amount of this coating, in order to improve press moldability, it is sufficient to contain 5 mg / m 2 or more of Mn oxide (as Mn), but if the Mn coating amount exceeds 500 mg / m 2 , the chemical conversion coating Formation is insufficient.
ゆえに、適正なMn酸化物皮膜量は、Mnとして5mg/m2以上
500mg/m2以下である。Therefore, the proper amount of Mn oxide film is 5 mg / m 2 or more as Mn.
It is 500 mg / m 2 or less.
次にこの皮膜の密着性、成膜性等を向上させるため、り
ん酸とMo酸化物、Ｗ酸化物、Ｖ酸化物の１種又は２種以
上を1000mg/m2以下（P,Mo,W,Vとして）混在させるもの
であるが、このようにすることによりMn酸化物皮膜の構
造が均一化し、成膜性が向上して潤滑性を向上し、プレ
ス成形性が一層向上するものと認められる。しかし1000
mg/m2超になると化成処理性が劣化することがあり好ま
しくなく、下限は存在していればよい。Next, in order to improve the adhesion and film-forming property of this film, one or more of phosphoric acid and Mo oxide, W oxide, and V oxide should be 1000 mg / m 2 or less (P, Mo, W , V) are mixed together, but it is recognized that by doing so, the structure of the Mn oxide film becomes uniform, the film formability is improved, the lubricity is improved, and the press formability is further improved. To be But 1000
If it exceeds mg / m 2 , the chemical conversion treatability may deteriorate, which is not preferable, and the lower limit may be present.
又、Zn酸化物の混在により、溶接性が向上するものであ
るが、このような酸化物皮膜の生成量としては、酸化物
皮膜中のZn量（片面当たり）として３〜500mg/m2とする
ものである。3mg/m2未満では効果がなく、又500mg/m2超
になると、電気抵抗が大となり、チップが軟化変形を生
じ易くなり、チップ寿命が短命になるので好ましくな
い。即ち溶接等においては、その加熱により、めっき金
属が溶融状態となり、次いで鋼板との合金化へと進行す
るが、先のめっき金属が溶融状態のとき電極チップと直
接接触すると、チップ組成の銅とめっき組成の亜鉛が選
択的に反応し、硬く脆い銅−亜鉛合金層を形成して、チ
ップが損耗し、電極チップ寿命を短命にすることにな
る。Also, the inclusion of Zn oxide improves weldability, but the amount of such oxide film produced is 3 to 500 mg / m 2 as the Zn amount (per one side) in the oxide film. To do. If it is less than 3 mg / m 2 , there is no effect, and if it exceeds 500 mg / m 2 , it is not preferable because the electrical resistance becomes large, the chip is likely to be softened and deformed, and the chip life becomes short. That is, in welding or the like, the heating causes the plated metal to be in a molten state, and then progresses to alloying with the steel sheet. The zinc of the plating composition selectively reacts to form a hard and brittle copper-zinc alloy layer, which causes wear of the tip and shortens the life of the electrode tip.
この溶融状態のめっき金属は、前記めっき鋼板表面に生
成せしめた酸化物皮膜により、チップとの接触を断た
れ、めっき金属のチップとの直接接触による溶損等を防
止するとともに、さらに、溶融状態のめっき金属が鋼板
の鉄と合金化され、主として鉄−亜鉛合金となり、これ
が酸化物皮膜の亀裂部等を通じて、あるいは酸化物皮膜
と一緒に電極チップ先端部へ付着し、堆積してチップの
保護金属膜となり、理由は明確ではないが、溶接を継続
しても保護膜の厚み、形状等には変化がなく、常時良好
な溶接ができ、かつ、チップの損傷も防止できる。ここ
で、電極保護金属とは、めっき金属と地鉄との合金を主
体とするもので、平均濃度として、Fe:20〜60％、Zn:40
〜80％程度の場合が多いが、一般にFe濃度の高い方が好
ましく、特に、高濃度Zn部分が局部的に存在するような
場合は好ましくない。また、電極保護金属はめっき金属
の成分、Mn,Sなどの鋼板成分、およびCuなどの電極チッ
プの成分を含むことがある。The molten plated metal is cut off from the contact with the chip by the oxide film formed on the surface of the plated steel sheet, preventing melting damage due to direct contact with the chip of the plated metal, and the molten state. The plated metal is alloyed with the iron of the steel sheet to form an iron-zinc alloy, which mainly adheres to the tip of the electrode tip through the cracks in the oxide film or together with the oxide film, deposits and protects the chip. Although it is a metal film and the reason is not clear, the thickness, shape, etc. of the protective film do not change even if welding is continued, and good welding is always possible, and damage to the tip can be prevented. Here, the electrode protection metal is mainly composed of an alloy of plated metal and base iron, and as an average concentration, Fe: 20 to 60%, Zn: 40
Although it is often about 80%, it is generally preferable that the Fe concentration is high, and it is not preferable especially when the high-concentration Zn portion is locally present. In addition, the electrode protection metal may include a plating metal component, a steel plate component such as Mn and S, and an electrode tip component such as Cu.
また、この電極保護金属膜は、チップ先端形状を凸状に
保つ効果を有するので、チップが同程度に軟化損傷した
場合でも、低電流で溶接ができ、チップ保護膜をチップ
先端表面の50％以上の面積に付着させると、電極チップ
寿命を大幅に延長することができる。すなわち、亜鉛め
っき表面に電極保護金属を付着させるZnOを主体とする
酸化物皮膜を生成せしめ、溶接熱によりめっき金属と鋼
板との合金を上記酸化物皮膜を通して、あるいは、酸化
物皮膜と一緒に該電極保護金属を電極チップへ付着させ
つつ溶接するものである。In addition, this electrode protection metal film has the effect of keeping the tip shape convex so that even if the tip is softened and damaged to the same extent, welding can be done at a low current, and the tip protection film is 50% of the tip surface. If it is attached to the above area, the life of the electrode tip can be greatly extended. That is, an oxide film mainly composed of ZnO for adhering an electrode protective metal to the galvanized surface is generated, and an alloy of the plated metal and the steel sheet is passed through the oxide film by welding heat, or together with the oxide film. The electrode protection metal is welded while being attached to the electrode tip.
Mn酸化物がZn酸化物と複合して皮膜形成していても、上
記Zn酸化物と同様に溶接性改善効果が認められる。Mn−
Znの複合酸化物の電気抵抗がそれほど大きくならないこ
とによるものと推察している。Even if the Mn oxide is combined with the Zn oxide to form a film, the effect of improving the weldability is recognized as in the case of the Zn oxide. Mn-
It is speculated that this is because the electric resistance of the Zn composite oxide does not increase so much.
りん酸およびMo,W,V酸化物等は本発明の組成範囲内なら
ば溶接性に影響を及ぼさない。Phosphoric acid and Mo, W, V oxides, etc. do not affect the weldability as long as they are within the composition range of the present invention.
かくして、MnとZnの酸化物およびりん酸、Mo,W,V酸化物
等を主体とする皮膜を亜鉛系めっき鋼板上に同時に形成
させることにより、プレス成形性と溶接性をともに向上
でき、化成処理も可能となる。Thus, by simultaneously forming a film mainly composed of Mn and Zn oxides and phosphoric acid, Mo, W, V oxides, etc. on the zinc-plated steel sheet, both press formability and weldability can be improved, and Processing is also possible.
このような酸化物皮膜の生成方法としては、例えば過マ
ンガン酸カリウム１〜70g/、硝酸亜鉛100〜800g/、
りん酸１〜60g/、Mo酸及びその塩類、Ｗ酸及びその塩
類、Ｖ酸及びその塩類をそれぞれ選択して用いるが、１
〜60g/で十分である。この他エッチング剤としては例
えば、硫酸、硝酸、過塩素酸等の１種又は２種以上を添
加することが有効である。As a method for producing such an oxide film, for example, potassium permanganate 1 to 70 g /, zinc nitrate 100 to 800 g /,
Phosphoric acid 1-60 g /, Mo acid and its salts, W acid and its salts, V acid and its salts are selected and used.
~ 60g / is sufficient. In addition to these, it is effective to add one or more of sulfuric acid, nitric acid, perchloric acid and the like as an etching agent.
このような水溶液にめっき鋼板を浸漬するか、水溶液を
散布するか、又は水溶液中でめっき鋼板を陰極として電
解処理することにより確実に所望の酸化物皮膜を生成さ
せることができる。By dipping the plated steel sheet in such an aqueous solution, spraying the aqueous solution, or electrolytically treating the plated steel sheet as a cathode in the aqueous solution, a desired oxide film can be reliably produced.
このようにして酸化物皮膜を生成させると、酸化物皮膜
中へめっき層及びめっき層中の合金金属の一部等がその
他酸化物として混入する。When the oxide film is generated in this manner, the plating layer, a part of the alloy metal in the plating layer, and the like are mixed into the oxide film as other oxides.
（実施例） 次に本発明の実施例を比較例と共に、第１表に示す。(Example) Next, an example of the present invention is shown in Table 1 together with a comparative example.
注１）めっき鋼板の種類:AS:合金化溶融亜鉛めっき鋼板
（Fe:10％,Al:0.25％，残Zn）,EC:電気亜鉛めっき鋼
板、GI:溶融亜鉛めっき鋼板（Al:0.3％,Fe:0.8％,Pb:0.
1％，残Zn）,HA:半合金化溶融亜鉛めっき鋼板（Fe:5％,
Al:0.3％，残Zn），鋼板厚はいずれも0.8mmの普通鋼。 Note 1) Types of galvanized steel sheets: AS: hot-dip galvanized steel sheet (Fe: 10%, Al: 0.25%, residual Zn), EC: galvanized steel sheet, GI: hot-dip galvanized steel sheet (Al: 0.3%, Fe: 0.8%, Pb: 0.
1%, residual Zn), HA: Semi-alloyed galvanized steel sheet (Fe: 5%,
Al: 0.3%, residual Zn), steel plate thickness is 0.8 mm for all standard steel.
注２）プレス成形性（摩擦係数） サンプルサイズ:17mm×300mm,引張り速度:500mm/min,角
ビード肩R:1.0/3.0mm,摺動長:200mm,塗油：ノックスラ
スト530F40,1g/m2の条件で、面圧を100〜600kgfの間で
数点試験を行い、引き抜き加重を測定し、面圧と引き抜
き加重の傾きから摩擦係数を求めた。Note 2) Press formability (friction coefficient) Sample size: 17mm × 300mm, Peeling speed: 500mm / min, Square bead shoulder R: 1.0 / 3.0mm, Sliding length: 200mm, Oil: Knoxlast 530F40, 1g / m Under the condition of No. 2 , several points of tests were conducted at a surface pressure of 100 to 600 kgf, the pulling load was measured, and the friction coefficient was obtained from the slope of the surface pressure and the pulling load.
注３）化成処理性 化成処理液にはSD5000（日本ペイント社製）を用い、処
方どうり脱脂、表面調整を行った後化成処理を行った。
化成処理皮膜の判定は、SEM（２次電子線像）により、
均一に皮膜が形成されているものは〇、部分的に皮膜形
成されているものは△、皮膜が形成されていないものは
×と判定した。Note 3) Chemical conversion treatment SD5000 (manufactured by Nippon Paint Co., Ltd.) was used as the chemical conversion treatment liquid, and the chemical conversion treatment was performed after degreasing and surface adjustment according to the formulation.
Judgment of chemical conversion treatment film is made by SEM (secondary electron beam image)
A film having a uniform film formation was evaluated as ◯, a film having a partial film formation was evaluated as Δ, and a film without a film formation was evaluated as x.
注４）製造条件は、過マンガン酸カリウム１〜70g/、
硝酸亜鉛100〜800g/、りん酸１〜60g/とMo酸、Ｗ
酸、Ｖ酸の１種又は２種以上を１〜60g/、エッチング
剤として硫酸5g/からなる水溶液中でめっき鋼板を陰
極として電解処理（５〜10A/dm2,1.0〜1.5秒）して酸化
物皮膜を生成させた。Note 4) Manufacturing conditions are potassium permanganate 1-70g /,
Zinc nitrate 100-800g /, phosphoric acid 1-60g / and Mo acid, W
Acid or V acid is electrolyzed (5 to 10 A / dm 2 , 1.0 to 1.5 seconds) using a plated steel sheet as a cathode in an aqueous solution containing 1 to 60 g / of sulfuric acid and 5 g / of sulfuric acid as an etching agent. An oxide film was formed.
注５）溶接条件 溶接条件は下記による。Note 5) Welding conditions Welding conditions are as follows.
１）加圧力:250kgf ２）初期加圧時間:40Hr ３）通電時間:12Hr ４）保持時間:5Hr ５）溶接電流:11kA ６）チップ先端径:5.0φ（円錐台頭型） ７）電極寿命終点判定：溶接電流の85％でのナゲット径
が3.6mmを確保できる打点数 ８）電極材質:Cu−Cr（一般に用いられているもの） 溶接は、めっき鋼板の片面を上、他面を下として、２枚
重ね合わせて連続打点数をとった。1) Pressurizing force: 250kgf 2) Initial pressurizing time: 40Hr 3) Energizing time: 12Hr 4) Holding time: 5Hr 5) Welding current: 11kA 6) Tip diameter of tip: 5.0φ (cone head type) 7) End of electrode life Judgment: Number of dots that can secure a nugget diameter of 3.6 mm at 85% of welding current 8) Electrode material: Cu-Cr (generally used) Welding is performed with one side of the plated steel sheet facing up and the other side facing down. Two sheets were piled up and the number of consecutive points was taken.
注６）酸化物の測定はGDS（グロー放電分光法）、ICAP
（イオンプラズマ発光分析法）により行った。Note 6) Oxides are measured by GDS (Glow Discharge Spectroscopy), ICAP
(Ion plasma emission spectrometry).
（発明の効果） 本発明によれば、プレス成形においては摺動性を冷延鋼
板並以上に向上し、かつ化成処理皮膜も形成可能とする
ことができ、又溶接性をも向上することができる。これ
によって、従来より低コストで、またユーザーの工程に
おける負荷を低減でき、生産性を向上させることができ
るなどの優れた効果が奏せられる。(Effects of the Invention) According to the present invention, in press forming, the slidability can be improved more than that of a cold-rolled steel sheet, a chemical conversion treatment film can be formed, and the weldability can be improved. it can. As a result, it is possible to achieve excellent effects such as a lower cost than before, a load on the user's process can be reduced, and productivity can be improved.
Claims (1)
化物５〜500mg/m2（Mnとして）、りん酸とMo酸化物、Ｗ
酸化物、Ｖ酸化物の１種又は２種以上を1000mg/m2以下
（P,Mo,W,Vとして）及びその他酸化物からなる皮膜を表
面に被覆してなるプレス成形性、化成処理性、溶接性に
優れた亜鉛系めっき鋼板。1. A Zn oxide 3~500mg / m 2 (as Zn), (as Mn) Mn oxide 5 to 500 mg / m 2, phosphate and Mo oxide, W
Press moldability and chemical conversion treatability by coating the surface with one or more oxides, V oxides of 1000 mg / m 2 or less (as P, Mo, W, V) and other oxides. , Zinc-based plated steel sheet with excellent weldability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2088692A JPH0713308B2 (en) | 1990-04-03 | 1990-04-03 | Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2088692A JPH0713308B2 (en) | 1990-04-03 | 1990-04-03 | Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03287784A JPH03287784A (en) | 1991-12-18 |
| JPH0713308B2 true JPH0713308B2 (en) | 1995-02-15 |
Family
ID=13949897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2088692A Expired - Lifetime JPH0713308B2 (en) | 1990-04-03 | 1990-04-03 | Galvanized steel sheet with excellent press formability, chemical conversion treatment and weldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713308B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001042530A1 (en) * | 1999-12-13 | 2001-06-14 | Toyo Kohan Co., Ltd. | Method for producing surface treated steel sheet, surface treated steel sheet and surface treated steel sheet coated with resin |
| KR100707255B1 (en) | 2003-04-18 | 2007-04-13 | 제이에프이 스틸 가부시키가이샤 | Hot-dip galvanized steel sheet having excellent press formability and method for producing the same |
| JP5593601B2 (en) * | 2008-09-24 | 2014-09-24 | Ｊｆｅスチール株式会社 | Alloyed hot-dip galvanized steel sheet and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5867885A (en) * | 1981-10-15 | 1983-04-22 | Nippon Steel Corp | Surface-treated steel sheet excellent in corrosion resistance and phosphatability |
| JPS6063394A (en) * | 1983-09-17 | 1985-04-11 | Nippon Steel Corp | Galvanized steel sheet with superior weldability |
| JPH0247270A (en) * | 1988-08-08 | 1990-02-16 | Kawasaki Steel Corp | Surface treated steel sheet having excellent secondary adhesive property of coated film and production thereof |
-
1990
- 1990-04-03 JP JP2088692A patent/JPH0713308B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5867885A (en) * | 1981-10-15 | 1983-04-22 | Nippon Steel Corp | Surface-treated steel sheet excellent in corrosion resistance and phosphatability |
| JPS6063394A (en) * | 1983-09-17 | 1985-04-11 | Nippon Steel Corp | Galvanized steel sheet with superior weldability |
| JPH0247270A (en) * | 1988-08-08 | 1990-02-16 | Kawasaki Steel Corp | Surface treated steel sheet having excellent secondary adhesive property of coated film and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03287784A (en) | 1991-12-18 |
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