JP2010090463A - Plated steel sheet to be hot-press-formed, and method for manufacturing the same - Google Patents
Plated steel sheet to be hot-press-formed, and method for manufacturing the same Download PDFInfo
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本発明は、耐酸化性に優れた熱間プレス成形用めっき鋼板およびその製造方法に関するものである。 The present invention relates to a plated steel sheet for hot press forming excellent in oxidation resistance and a method for producing the same.
近年、自動車車体の軽量化のため、鋼板の高強度化（例えば、780Mpa級）を図り、使用する鋼板の厚みを減ずる努力が行われている。しかし、鋼板をプレス加工する場合、例えば、絞り加工を行う場合、鋼板の強度が高くなると、絞り加工時に金型との接触圧力が高まることに起因して、鋼板のかじりや破断が発生する。また、そのような問題を少しでも軽減するために、鋼板の絞り加工時の材料の金型内への流入を高めるためのブランク押さえ圧を下げた場合、成形後の形状がばらつく等の問題点がある。
また、形状安定性いわゆるスプリングバックの問題も発生する。これに対しては潤滑剤を使用することにより改善する方法があるが、780Mpa級の高強度鋼板ではその効果は小さい。
In recent years, efforts have been made to increase the strength of steel sheets (for example, 780 MPa class) and reduce the thickness of the steel sheets used in order to reduce the weight of automobile bodies. However, when press-working a steel plate, for example, when drawing is performed, if the strength of the steel plate is increased, the contact pressure with the mold is increased during drawing, and the steel plate is galvanized or broken. In addition, in order to alleviate such problems as much as possible, when the blank pressing pressure for increasing the inflow of the material into the mold during drawing of the steel sheet is lowered, the shape after forming varies. There is.
In addition, the problem of shape stability, so-called spring back, also occurs. There is a method to improve this by using a lubricant, but the effect is small with a high strength steel plate of 780 Mpa grade.
このような現状に対して、780Mpa以上の高強度鋼板のような難プレス成形材料をプレス成形する技術として、成形すべき材料を予め加熱して成形する方法が考えられる。いわゆる熱間プレス成形および温間プレス成形である（以下、熱間プレス成形および温間プレス成形をまとめて熱間プレス成形と称する）。 In view of such a current situation, as a technique for press-forming a difficult-to-press material such as a high-strength steel plate of 780 Mpa or higher, a method in which the material to be formed is heated and formed in advance can be considered. These are so-called hot press forming and warm press forming (hereinafter, hot press forming and warm press forming are collectively referred to as hot press forming).
しかしながら、熱間プレス成形は、加熱した鋼板を加工する成形方法であるため、表面酸化は避けられず、たとえ鋼板を非酸化性雰囲気中で加熱しても、例えば、加熱炉からプレス成形のために取り出すときに大気にふれると表面に鉄系酸化物が形成される。この鉄系酸化物はプレス時に脱落して金型に付着して生産性を低下させる。あるいは、プレス後の製品に残存して外観不良の原因となる。さらには、次工程で塗装する場合に鋼板と塗膜との密着性が劣ることになる。 However, since hot press forming is a forming method for processing a heated steel sheet, surface oxidation is unavoidable. Even if the steel sheet is heated in a non-oxidizing atmosphere, for example, for press forming from a heating furnace. When exposed to the atmosphere, iron oxide is formed on the surface. This iron-based oxide falls off at the time of pressing and adheres to the mold, reducing productivity. Or it remains in the product after pressing and causes the appearance defect. Furthermore, when it coats at the next process, the adhesiveness of a steel plate and a coating film will be inferior.
そこで、熱間プレス成形後は、ショットブラストを行ってそのような鉄系酸化物から成るスケールを除去することが必要になる。しかし、これはコスト増を免れない。 Therefore, after hot press molding, it is necessary to perform shot blasting to remove scales made of such iron-based oxides. However, this is subject to an increase in cost.
このような問題を解決するべく、特許文献１では熱間成形時に母材鋼板の耐酸化抵抗性を持たせるためにアルミニウムを被覆し、所定の組成および組織とした鋼板を提案している。しかしながら、このような鋼板は普通鋼と比較した場合、大幅なコスト増となる。
以上のように、高強度の鋼板に熱間プレス成形を行った場合、生成した鉄系酸化物を除去する工程が必要であり、大幅なコスト増なしに該酸化物を除去する工程を省略できないこと、そして、たとえ該酸化物を除去してもめっき層などの表面処理層を有しない鋼板では防錆性に劣るのが現状である。
As described above, when hot press forming is performed on a high-strength steel sheet, a step of removing the produced iron-based oxide is necessary, and the step of removing the oxide cannot be omitted without a significant increase in cost. In addition, even if the oxide is removed, a steel sheet having no surface treatment layer such as a plating layer is inferior in rust prevention.
本発明は、かかる事情に鑑み、優れた耐酸化性を有する熱間プレス成形用めっき鋼板およびその製造方法を大幅なコスト増を伴うことなく提供することを目的とする。 In view of such circumstances, an object of the present invention is to provide a hot press-formed plated steel sheet having excellent oxidation resistance and a method for producing the same without significantly increasing costs.
本発明者らは、上記の課題を解決すべく、鋭意研究を重ねた。その結果、以下の知見を得た。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, the following knowledge was obtained.
熱間プレス成形前にＺｒイオンを含有する酸性溶液に鋼板（亜鉛系めっき層）を接触させ、めっき層の表面にＺｎおよびＺｒを必須成分として含む酸化物層を形成させることで、熱間プレス成形後に外観を損ねることなく、また大幅なコスト増を伴うことなく、耐酸化性に顕著な改善が見られることを見出した。 A hot press is performed by bringing a steel plate (zinc-based plating layer) into contact with an acidic solution containing Zr ions before hot press forming, and forming an oxide layer containing Zn and Zr as essential components on the surface of the plating layer. It has been found that the oxidation resistance can be remarkably improved without deteriorating the appearance after molding and without significantly increasing the cost.
本発明は、以上の知見に基づきなされたものであり、その要旨は以下の通りである。
[1] 亜鉛系めっき鋼板を酸性溶液に接触させ、接触処理終了後1〜90秒間保持した後、水洗及び乾燥を行うことにより前記めっき鋼板表面に平均厚さ10nm以上の酸化物層を形成するめっき鋼板の製造方法において、前記酸性溶液は、Ｚｒイオンを含有することを特徴とする熱間プレス成形用めっき鋼板の製造方法。
［２］前記［１］において、前記酸性溶液中に、Ｚｒの硫酸塩、硝酸塩、塩化物、リン酸塩のうち、少なくとも1種類以上を、Ｚｒイオン濃度として0.1〜100ｇ／ｌの範囲で含有することを特徴とする熱間プレス成形用めっき鋼板の製造方法。
［３］前記［１］または［２］において、前記酸性溶液は、pH緩衝作用を有し、かつ1リットルの該酸性溶液のpHを2.0から5.0まで上昇させるのに必要な1.0mol/l水酸化ナトリウム溶液の量（l）で定義するpH上昇度が0.05〜0.5の範囲にあることを特徴とする熱間プレス成形用めっき鋼板の製造方法。
［４］前記［１］〜［３］のいずれかにおいて、前記酸性溶液は、酢酸塩、フタル酸塩、クエン酸塩、コハク酸塩、乳酸塩、酒石酸塩、ホウ酸塩、リン酸塩のうち少なくとも1種類以上を、前記成分含有量5〜50g/lの範囲で含有し、pHが0.5〜2.0、液温が20〜70℃の範囲にあることを特徴とする熱間プレス成形用めっき鋼板の製造方法。
［５］前記［１］〜［４］のいずれかにおいて、前記酸性溶液に接触させた後のめっき鋼板表面に形成する酸性溶液膜が２０g/m2以下であり、かつ、前記酸性溶液膜がめっき鋼板表面に形成された状態での保持時間が1〜90秒の範囲であることを特徴とする熱間プレス成形用めっき鋼板の製造方法。
［６］前記［１］〜［５］のいずれかに記載の熱間プレス成形用めっき鋼板の製造方法により製造され、ＺｎおよびＺｒを含む酸化物層を鋼板表面に平均厚さが10nm以上形成したことを特徴とする熱間プレス成形用めっき鋼板。
The present invention has been made based on the above findings, and the gist thereof is as follows.
[1] A zinc-based plated steel sheet is brought into contact with an acidic solution, held for 1 to 90 seconds after completion of the contact treatment, and then washed with water and dried to form an oxide layer having an average thickness of 10 nm or more on the surface of the plated steel sheet. In the manufacturing method of a plated steel plate, the said acidic solution contains Zr ion, The manufacturing method of the plated steel plate for hot press forming characterized by the above-mentioned.
[2] In the above [1], the acidic solution contains at least one of Zr sulfate, nitrate, chloride, and phosphate in a range of 0.1 to 100 g / l as a Zr ion concentration. A method for producing a hot-pressed plated steel sheet, comprising:
[3] In the above [1] or [2], the acidic solution has a pH buffering action, and 1.0 mol / l water necessary to raise the pH of 1 liter of the acidic solution from 2.0 to 5.0. A method for producing a hot-pressed plated steel sheet, characterized in that the pH increase defined by the amount (l) of sodium oxide solution is in the range of 0.05 to 0.5.
[4] In any one of the above [1] to [3], the acidic solution is composed of acetate, phthalate, citrate, succinate, lactate, tartrate, borate, phosphate. Hot press-forming plating, characterized in that at least one of them is contained in the range of the component content of 5 to 50 g / l, the pH is in the range of 0.5 to 2.0, and the liquid temperature is in the range of 20 to 70 ° C. Manufacturing method of steel sheet.
[5] In any one of the above [1] to [4], the acidic solution film formed on the surface of the plated steel sheet after contact with the acidic solution is 20 g / m 2 or less, and the acidic solution film is A method for producing a hot-pressed plated steel sheet, characterized in that the retention time in the state of being formed on the surface of the plated steel sheet is in the range of 1 to 90 seconds.
[6] Manufactured by the method for producing a hot press-formed plated steel sheet according to any one of [1] to [5] above, an oxide layer containing Zn and Zr is formed on the steel sheet surface with an average thickness of 10 nm or more A plated steel sheet for hot press forming characterized by the above.
なお、本発明においては、亜鉛を含有するめっき層を有する鋼板を総称して亜鉛系めっき鋼板と呼称する。したがって、めっき処理後に合金化処理を施す、施さないにかかわらず、亜鉛を含有するめっき層を有していれば本発明の亜鉛系めっき鋼板である。すなわち、本発明における亜鉛系めっき鋼板とは、合金化処理を施していない溶融亜鉛めっき鋼板、合金化処理を施した合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板、溶融亜鉛−アルミニウムめっき鋼板など、いずれも含むものである。 In the present invention, steel plates having a plating layer containing zinc are collectively referred to as zinc-based plated steel plates. Therefore, it is the zinc-based plated steel sheet of the present invention as long as it has a plating layer containing zinc, regardless of whether or not the alloying treatment is performed after the plating treatment. That is, the galvanized steel sheet in the present invention is a hot dip galvanized steel sheet not subjected to alloying treatment, an alloyed hot dip galvanized steel sheet subjected to alloying treatment, an electrogalvanized steel sheet, a hot dip galvanized steel sheet, etc. Both are included.
本発明によれば、優れた耐酸化性を有する熱間プレス成形用めっき鋼板が得られる。そして、本発明の熱間プレス成形用めっき鋼板を用いて熱間プレス成形を行うことにより、鋼板のかじりや破断が発生することなく加工が可能となり、ショットブラストなどのスケール除去を行う必要がないためコスト低減が可能となる。 According to the present invention, a hot press-formed plated steel sheet having excellent oxidation resistance can be obtained. And, by performing hot press forming using the hot-press-formed plated steel sheet of the present invention, processing can be performed without causing galling or breakage of the steel sheet, and there is no need to remove scale such as shot blasting. Therefore, the cost can be reduced.
熱間プレス成形時には鋼板はA3変態点以上（約900℃以上）の加熱を受ける。この場合、Znの融点は418℃、沸点は907℃であることから、亜鉛系めっき鋼板の場合は、鋼板上のZnめっきが蒸発することが予想され、その結果、鋼板素地が酸化されることになる。このため、めっき鋼板の表面には、硬質かつ高融点の物質が存在することが鋼板素地の酸化防止の点から非常に有効であると考えられる。 During hot press forming, the steel plate is heated above the A3 transformation point (about 900 ° C or higher). In this case, since the melting point of Zn is 418 ° C and the boiling point is 907 ° C, in the case of zinc-based plated steel sheet, it is expected that the Zn plating on the steel sheet will evaporate, resulting in oxidation of the steel sheet substrate become. For this reason, it is considered that the presence of a hard and high melting point substance on the surface of the plated steel sheet is very effective from the viewpoint of preventing oxidation of the steel sheet substrate.
そこで、硬質かつ高融点の物質をめっき表面に形成させる検討を進めた。その結果、亜鉛系めっき鋼板表面に高融点で所定の厚さの酸化物層を形成させることが優れた耐酸化性を付与する手法として非常に有効であることを見出した。さらに、この酸化物層に高融点のＺｒを含有させることで、より高融点の酸化物層とすることでき、耐酸化性を飛躍的に向上させることが可能となることも見出した。 Therefore, studies were made to form a hard and high melting point material on the plating surface. As a result, it has been found that forming an oxide layer having a high melting point and a predetermined thickness on the surface of a zinc-based plated steel sheet is very effective as a method for imparting excellent oxidation resistance. Furthermore, it has also been found that by containing Zr having a high melting point in this oxide layer, it is possible to obtain a higher melting point oxide layer, and to dramatically improve the oxidation resistance.
以上より、本発明においては、めっき鋼板表面には、ＺｎおよびＺｒを含む酸化物層を有することとする。 From the above, in the present invention, the plated steel sheet surface has an oxide layer containing Zn and Zr.
そして、めっき鋼板表面に形成する酸化物層の平均厚さは１０nm以上とする。１０nm以上とすることにより、熱間プレス成形時の加熱温度（Ac3変態点以上の温度）においてもこの酸化物層がバリア層となり、スケールの発生を抑制することができる。一方、厚さを２００ｎｍ以下とすると、熱間プレス成形性の効果が得られる上に、この厚さを有する酸化物層をめっき層表面に形成するためのライン長さをとくに考慮する必要がなく、設備上の問題も生じない。よって、上限は、好ましくは２００ｎｍ以下である。 And the average thickness of the oxide layer formed in a plated steel plate surface shall be 10 nm or more. By setting the thickness to 10 nm or more, the oxide layer becomes a barrier layer even at the heating temperature (temperature above the Ac3 transformation point) during hot press molding, and scale generation can be suppressed. On the other hand, if the thickness is 200 nm or less, the effect of hot press formability can be obtained, and there is no need to particularly consider the line length for forming the oxide layer having this thickness on the surface of the plating layer. There will be no problems with the equipment. Therefore, the upper limit is preferably 200 nm or less.
なお、本発明における酸化物層の平均厚さは、膜厚が既知のシリカ皮膜のO（酸素）のＫα蛍光Ｘ線強度により作成した検量線を用いて求めたシリカ換算の膜厚である。 In addition, the average thickness of the oxide layer in this invention is the film thickness of the silica conversion calculated | required using the analytical curve created with the K (alpha) fluorescence X-ray intensity of O (oxygen) of a silica membrane | film | coat with a known film thickness.
以上から、本発明では、熱間プレス成形用のめっき鋼板表面には、ＺｎおよびＺｒを含み、平均厚さが10nm以上の酸化物層が形成されていることとする。これらは本発明の特徴であり、このような酸化物層が鋼板表面に存在することで鋼板素地の酸化を防止し、優れた耐酸化性を有することになる。 From the above, in the present invention, an oxide layer containing Zn and Zr and having an average thickness of 10 nm or more is formed on the surface of the hot-press-formed plated steel sheet. These are the features of the present invention, and the presence of such an oxide layer on the surface of the steel sheet prevents oxidation of the steel sheet substrate and has excellent oxidation resistance.
めっき鋼板の表面に上記酸化物層を形成させる方法としては、めっき層の水溶液による反応を利用する方法が最も効果的である。例えば、亜鉛系めっき鋼板をＺｒイオンを含有する酸性溶液に接触させ、接触処理終了後1〜90秒間保持した後、水洗及び乾燥を行うことによりめっき鋼板表面に平均厚さ10nm以上の酸化物層を形成することができる。 As a method for forming the oxide layer on the surface of the plated steel sheet, a method using a reaction of the plating layer with an aqueous solution is most effective. For example, an oxide layer having an average thickness of 10 nm or more is formed on the surface of the plated steel sheet by bringing the zinc-based plated steel sheet into contact with an acidic solution containing Zr ions, holding it for 1 to 90 seconds after completion of the contact treatment, and then washing and drying. Can be formed.
この酸化物層形成メカニズムについては明確ではないが、次のように考えることができる。亜鉛系めっき鋼板を酸性溶液に接触させると、鋼板側からは亜鉛の溶解が生じる。この亜鉛の溶解は、同時に水素発生を生じるため、亜鉛の溶解が進行すると、酸性溶液中の水素イオン濃度が減少し、その結果、酸性溶液のpHが上昇し、酸化物（水酸化物）が安定となるpH領域に達すると、亜鉛系めっき鋼板表面にＺｎ系酸化物層が形成すると考えられる。この際にＺｒイオンを含有する酸性溶液を使用すると、Ｚｒ系酸化物の形成反応がＺｎ系酸化物の形成反応よりも低いpH領域において生じ、その後さらにpHが上昇するとＺｎ系酸化物の形成反応が生じるため、Ｚｎ系酸化物のみの形成時と比較して酸化物層の形成反応が容易に起こることが考えられる。
酸性溶液にＺｒイオンを含有させるためには、Ｚｒの硫酸塩、硝酸塩、塩化物、リン酸塩のうち、少なくとも1種類以上をＺｒイオン濃度として0.1〜100g/lの範囲で含有することが好ましい。Ｚｒイオン濃度が0.1g/l以上では、形成されるＺｎ系酸化物量が少量でありＺｒが主体となる酸化物層となるため、高温加熱時の耐酸化性効果が十分得られるので、熱間プレス成形性改善効果が十分に得られる。一方、100g/l以下とすると、形成されるＺｒ系酸化物の割合が適度であり、亜鉛系めっき鋼板を対象に設計された接着剤との適合性を劣化させることもない。また、形成される酸化物が粗大とならず、かつ量も多くないため、プレス金型等へ付着することがなく、生産性の低下を招くこともない。
使用する酸性溶液は、pH＝0.5〜5.0の領域においてpH緩衝作用を有するものが好ましい。これは、前記pH範囲でpH緩衝作用を有する酸性溶液を使用すると、酸性溶液に接触後、所定時間保持することで、酸性溶液とめっき層の反応によりＺｎの溶解とＺｒ系酸化物およびＺｎ系酸化物の形成反応が十分に生じ、鋼板表面に本発明の目的とする酸化物層を安定して得ることができるためである。
Although the oxide layer formation mechanism is not clear, it can be considered as follows. When the galvanized steel sheet is brought into contact with an acidic solution, dissolution of zinc occurs from the steel sheet side. This dissolution of zinc causes hydrogen generation at the same time. As the dissolution of zinc proceeds, the hydrogen ion concentration in the acidic solution decreases, and as a result, the pH of the acidic solution increases and oxides (hydroxides) are formed. When reaching a stable pH range, it is considered that a Zn-based oxide layer is formed on the surface of the galvanized steel sheet. In this case, when an acidic solution containing Zr ions is used, a Zr-based oxide formation reaction occurs in a pH range lower than that of the Zn-based oxide formation reaction. Therefore, it can be considered that the formation reaction of the oxide layer easily occurs as compared with the formation of only the Zn-based oxide.
In order to contain Zr ions in the acidic solution, it is preferable to contain at least one of Zr sulfate, nitrate, chloride, and phosphate in the range of 0.1 to 100 g / l as the Zr ion concentration. . When the Zr ion concentration is 0.1 g / l or more, the amount of Zn-based oxide formed is small, and an oxide layer mainly composed of Zr is obtained, so that a sufficient oxidation resistance effect at high temperature heating can be obtained. A sufficient effect of improving press formability can be obtained. On the other hand, when the amount is 100 g / l or less, the proportion of the Zr-based oxide formed is moderate, and compatibility with an adhesive designed for a zinc-based plated steel sheet is not deteriorated. Further, since the oxide formed is not coarse and the amount is not large, it does not adhere to a press die or the like, and the productivity is not reduced.
The acidic solution used preferably has a pH buffering action in the range of pH = 0.5 to 5.0. This is because, when an acidic solution having a pH buffering action in the above pH range is used, the Zn solution is dissolved and Zr-based oxides and Zn-based oxides are reacted by the reaction between the acidic solution and the plating layer by holding the acidic solution for a predetermined time. This is because the oxide formation reaction occurs sufficiently, and the target oxide layer of the present invention can be stably obtained on the steel sheet surface.
また、このようなpH緩衝作用の指標として、1リットルの酸性溶液のpHを2.0〜5.0まで上昇させるのに要する1.0mol/l水酸化ナトリウム水溶液の量（l）で定義するpH上昇度で評価でき、この値が0.05〜0.5の範囲にあるとよい。pH上昇度を0.05以上とすると、pHの上昇が速やかに起こって酸化物層の形成に十分な亜鉛の溶解が得られないことがないため、十分な酸化物層の形成が生じる。一方で、0.5以下とすると、亜鉛の溶解が促進されすぎることがなく、酸化物層の形成に長時間を有することがないだけでなく、めっき層の損傷も激しくなく、本来のＺｎの鋼に対する犠牲防食の役割も失うことがないと考えられるためである。ここで、pHが2.0を超える酸性溶液のpH上昇度は、酸性溶液に硫酸などのpH=2.0〜5.0の範囲でほとんど緩衝性を有しない無機酸を添加してpHを一旦2.0に低下させて評価することとする。 In addition, as an index of such pH buffering action, evaluated by the degree of pH increase defined by the amount (l) of 1.0 mol / l sodium hydroxide aqueous solution required to raise the pH of a 1 liter acidic solution from 2.0 to 5.0 This value is preferably in the range of 0.05 to 0.5. If the degree of pH increase is 0.05 or more, the pH will increase rapidly, and sufficient zinc dissolution for forming the oxide layer will not be obtained, so that a sufficient oxide layer will be formed. On the other hand, if it is 0.5 or less, the dissolution of zinc is not promoted too much, and not only does it take a long time to form the oxide layer, but also the plating layer is not severely damaged. It is because it is thought that the role of sacrificial protection will not be lost. Here, the pH increase degree of an acidic solution having a pH exceeding 2.0 is obtained by adding an inorganic acid having almost no buffering property in the pH range of 2.0 to 5.0 such as sulfuric acid to the acidic solution, and once reducing the pH to 2.0. We will evaluate it.
このようなpH緩衝性を有する酸性溶液としては、酢酸ナトリウム（CH3COONa）などの酢酸塩やフタル酸水素カリウム（(KOOC)2C6H4）などのフタル酸塩、クエン酸ナトリウム（Na3C6H5O7）やクエン酸二水素カリウム（KH2C6H5O7）などのクエン酸塩、コハク酸ナトリウム（Na2C4H4O4）などのコハク酸塩、乳酸ナトリウム（NaCH3CHOHCO2）などの乳酸塩、酒石酸ナトリウム（Na2C4H4O6）などの酒石酸塩、ホウ酸塩、リン酸塩のうち少なくとも1種類以上を、前記各成分含有量を5〜50g/lの範囲で含有する水溶液を使用することができる。前記濃度を5g/l以上とすると、亜鉛の溶解とともに溶液のpH上昇が比較的すばやく生じることがないため、耐酸化性の向上に十分な酸化物層を形成することができる。また、50g/l以下とすると、亜鉛の溶解が促進されすぎることがなく、酸化物層の形成に長時間を有することがないだけでなく、めっき層の損傷も激しくなく、本来のＺｎの鋼に対する犠牲防食の役割も失うことがないと考えられるためである。 As such an acidic solution having a pH-buffering, phthalates such as acetates or potassium hydrogen phthalate, sodium acetate (CH 3 COONa) ((KOOC ) 2 C 6 H 4), sodium citrate (Na Citrates such as 3 C 6 H 5 O 7 ) and potassium dihydrogen citrate (KH 2 C 6 H 5 O 7 ), succinates such as sodium succinate (Na 2 C 4 H 4 O 4 ), and lactic acid At least one of lactate such as sodium (NaCH 3 CHOHCO 2 ), tartrate such as sodium tartrate (Na 2 C 4 H 4 O 6 ), borate and phosphate, An aqueous solution containing 5 to 50 g / l can be used. When the concentration is 5 g / l or more, since the pH of the solution does not rise relatively quickly with the dissolution of zinc, an oxide layer sufficient for improving the oxidation resistance can be formed. Moreover, if it is 50 g / l or less, the dissolution of zinc is not promoted too much, the oxide layer is not formed for a long time, and the plating layer is not severely damaged. It is because it is thought that the role of sacrificial protection against losing is never lost.
酸性溶液のpHは0.5〜2.0の範囲にあることが望ましい。pHを2.0以下とすると、溶液中でＺｒイオンの沈殿（水酸化物の形成）が生じず、酸化物層中にＺｒ系酸化物が十分に取り込まれる。一方、pHを0.5以上とすると、亜鉛の溶解が促進されすぎることがなく、めっき付着量の減少がないだけでなく、めっき皮膜に亀裂が生じることがなく加工時に剥離が生じやすくならないので、望ましい。なお、酸性溶液のpHが0.5〜2.0の範囲より高い場合は硫酸等のpH緩衝性のない無機酸でpH調製することができる。 The pH of the acidic solution is desirably in the range of 0.5 to 2.0. When the pH is 2.0 or less, Zr ion precipitation (hydroxide formation) does not occur in the solution, and the Zr-based oxide is sufficiently taken into the oxide layer. On the other hand, when the pH is 0.5 or more, the dissolution of zinc is not promoted too much, and not only the plating adhesion amount is not reduced, but also the plating film is not cracked and is not easily peeled off during processing. . When the pH of the acidic solution is higher than the range of 0.5 to 2.0, the pH can be adjusted with an inorganic acid having no pH buffering property such as sulfuric acid.
酸性溶液の温度については、20〜70℃の範囲であることが好ましい。20℃以上とすると、酸化物層の生成反応に長時間を有することがなく、生産性の低下を招くことがない。一方、70℃以下とすると、鋼板表面に処理ムラを発生することがなく、反応を比較的すばやく進行させることができる。 About the temperature of an acidic solution, it is preferable that it is the range of 20-70 degreeC. If it is 20 ° C. or higher, the production reaction of the oxide layer does not take a long time, and the productivity is not lowered. On the other hand, when the temperature is 70 ° C. or lower, there is no processing unevenness on the surface of the steel sheet, and the reaction can proceed relatively quickly.
めっき鋼板を酸性溶液に接触させる方法には特に制限はなく、めっき鋼板を酸性溶液に浸漬する方法、めっき鋼板に酸性溶液をスプレーする方法、塗布ロールを介して酸性溶液をめっき鋼板に塗布する方法等がある。 The method for bringing the plated steel sheet into contact with the acidic solution is not particularly limited, the method of immersing the plated steel sheet in the acidic solution, the method of spraying the acidic solution onto the plated steel sheet, and the method of applying the acidic solution to the plated steel sheet through the coating roll Etc.
めっき鋼板を以上からなる酸性溶液に接触させた後に、その溶液が薄い液膜状で鋼板表面に存在することが望ましい。これは、鋼板表面に存在する溶液の量が多すぎると、亜鉛の溶解が生じても溶液のpHが上昇しにくく、次々と亜鉛の溶解が生じるのみであり、目的とする酸化物層を形成するまでに長時間を有するためである。また、めっき層の損傷も激しく、本来の防錆鋼板としての役割を失うことも考えられるためである。この観点から、鋼板表面に形成する溶液膜量は、２０ｇ/ｍ２以下に調整することが好ましい。より好ましくは、液膜の乾燥を防ぐ目的で３g/m2以上の液膜量が適している。なお、溶液膜量の調整は、絞りロール、エアワイピング等で行うことができる。
また、酸性溶液に接触後、水洗までの時間（水洗までの保持時間）は、1〜90秒間必要である。これは水洗までの時間が1秒未満であると、溶液のpHが上昇しＺｒ系酸化物層およびＺｎ系酸化物層が形成される前に酸性溶液が洗い流されるために、耐酸化性の向上効果が得られない。一方、90秒を超えても、酸化物層の形成量に変化が見られないためである。
After the plated steel sheet is brought into contact with the acidic solution composed of the above, it is desirable that the solution exists in the form of a thin liquid film on the steel sheet surface. This is because if the amount of the solution present on the steel plate surface is too large, the pH of the solution will hardly rise even if zinc dissolution occurs, and only zinc dissolution will occur one after another, forming the desired oxide layer. This is because it takes a long time to complete. In addition, the plating layer is severely damaged, and it may be possible to lose its original role as a rust-proof steel plate. From this viewpoint, the amount of the solution film formed on the steel sheet surface is preferably adjusted to 20 g / m 2 or less. More preferably, a liquid film amount of 3 g / m 2 or more is suitable for the purpose of preventing the liquid film from drying. The amount of the solution film can be adjusted by a squeeze roll, air wiping or the like.
Moreover, after contact with an acidic solution, the time to water washing (holding time to water washing) is required for 1 to 90 seconds. If the time until washing with water is less than 1 second, the pH of the solution rises and the acidic solution is washed away before the Zr-based oxide layer and Zn-based oxide layer are formed. The effect is not obtained. On the other hand, even if it exceeds 90 seconds, no change is observed in the amount of oxide layer formed.
なお、酸性溶液に接触させる前に、表面活性化処理を施してもよく、表面活性化処理に用いる薬液はｐＨ１１以上であるアルカリ性溶液であることが好ましい。この処理の目的は、例えば、溶融亜鉛めっき鋼板の場合では、表面に形成したZn系酸化物を除去し、表面に新生面を露出させることにより、新生面が露出された部分で反応を活性化させ、新たに酸化物層の形成を容易にするためである。 In addition, before making it contact with an acidic solution, you may perform a surface activation process, and it is preferable that the chemical | medical solution used for a surface activation process is an alkaline solution which is pH11 or more. The purpose of this treatment is, for example, in the case of a hot-dip galvanized steel sheet, removing the Zn-based oxide formed on the surface, exposing the new surface to the surface, and activating the reaction at the exposed part of the new surface, This is to facilitate the formation of a new oxide layer.
また、この表面活性化処理の前に調質圧延を行ってもよい。さらに、めっき処理後表面活性化処理を行い、調質圧延を行い、その後、酸性溶液に接触させるようにしてもよい。これは、調質圧延の際に使用する調圧ロールなどにより、めっき鋼板表面に存在するZn系酸化物層の一部を破壊することもでき、表面活性化処理を組み合わせることによりZn系酸化物層を効果的に除去できる。 Moreover, you may perform temper rolling before this surface activation process. Furthermore, after the plating treatment, surface activation treatment may be performed, temper rolling may be performed, and then contacted with an acidic solution. It is possible to destroy part of the Zn-based oxide layer present on the surface of the plated steel sheet with a pressure-control roll used during temper rolling, and by combining surface activation treatment with a Zn-based oxide. The layer can be removed effectively.
表面活性化処理に用いる水溶液はｐＨが１１以上、浴温を３０℃以上とし、該液との接触時間を１〜３０秒とすることが好ましい。１秒以下の場合はZn系酸化物を十分溶解できない為、その後に引き続く酸性溶液との反応性を高めることが出来ず、酸化物層が十分に形成しない。一方、３０秒より多くても構わないが、長時間処理することは生産性を低下するため好ましくない。より好ましくはｐＨ１１以上、浴温５０℃以上である。上記範囲内のｐＨであれば溶液の種類に制限はなく、水酸化ナトリウムや水酸化ナトリウム系の脱脂剤などを用いることができる。
表面活性化処理は酸性溶液に接触する前に実施することが好ましいが、必要に応じて行われるめっき処理後に行われる調質圧延の前、後いずれで実施しても良い。ただし、調質圧延の後、表面活性化処理を施すと、圧延ロールにより押しつぶされ凸部となった部分でZn系酸化物が機械的に破壊されるため、凸部以外の凹部とZn系酸化物の除去量が異なる傾向がある。このため、表面活性化処理後のZn系酸化物量が、面内で不均一となり、引き続き行われる酸化処理が不均一となり十分な特性を得られない場合がある。このため、より好ましくはめっき処理後、表面活性化処理を施し、面内で均一にZn系酸化物を適正量除去した後、調質圧延を実施し、引き続き酸性溶液に接触させる処理とするプロセスが好ましい。
表面活性化処理の方法については、特に限定しない。浸漬法、スプレー法、ロール塗布法などが挙げられる。
以上により、めっき鋼板表面には、平均厚さ10nm以上の酸化物層が形成される。
The aqueous solution used for the surface activation treatment preferably has a pH of 11 or more, a bath temperature of 30 ° C. or more, and a contact time with the solution of 1 to 30 seconds. In the case of less than 1 second, the Zn-based oxide cannot be sufficiently dissolved, so that the reactivity with the subsequent acidic solution cannot be increased, and the oxide layer is not sufficiently formed. On the other hand, it may be longer than 30 seconds, but it is not preferable to perform the treatment for a long time because the productivity is lowered. More preferably, the pH is 11 or more and the bath temperature is 50 ° C. or more. If it is pH in the said range, there will be no restriction | limiting in the kind of solution, Sodium hydroxide, a sodium hydroxide type | system | group degreasing agent, etc. can be used.
The surface activation treatment is preferably performed before contact with the acidic solution, but may be performed either before or after the temper rolling performed after the plating treatment performed as necessary. However, if the surface activation treatment is performed after temper rolling, the Zn-based oxide is mechanically destroyed at the portion that has been crushed by the rolling roll to become a convex portion. There is a tendency that the amount of removal of objects is different. For this reason, the amount of Zn-based oxide after the surface activation treatment becomes non-uniform in the surface, and the subsequent oxidation treatment becomes non-uniform, so that sufficient characteristics may not be obtained. For this reason, more preferably, after the plating treatment, the surface activation treatment is performed, and after removing an appropriate amount of the Zn-based oxide uniformly in the surface, the temper rolling is performed, and the treatment is subsequently brought into contact with the acidic solution. Is preferred.
The method for the surface activation treatment is not particularly limited. Examples of the method include a dipping method, a spray method, and a roll coating method.
As a result, an oxide layer having an average thickness of 10 nm or more is formed on the surface of the plated steel sheet.
なお、本発明における酸化物層とは、ＺｎとＺｒを含んだ酸化物及び／又は水酸化物などからなる層のことである。このようなＺｎおよびＺｒを含む酸化物層の平均厚さは10nm以上であることが必要である。酸化物層の平均厚さが、10nm未満と薄くなると耐酸化性に対する効果が不十分となる。一方、ZnおよびＺｒを含む酸化物層の平均厚さを200nm以下とすると、熱間プレス成形中に皮膜が破壊することがないので摺動抵抗が上昇しない。また溶接性が低下することもないので好ましい。さらに、形成される酸化物が粗大とはならず、かつ量も多くないため、プレス金型等へ付着せず、生産性を低下させることがないので好ましい。 The oxide layer in the present invention is a layer made of an oxide and / or hydroxide containing Zn and Zr. The average thickness of such an oxide layer containing Zn and Zr needs to be 10 nm or more. If the average thickness of the oxide layer is reduced to less than 10 nm, the effect on the oxidation resistance becomes insufficient. On the other hand, if the average thickness of the oxide layer containing Zn and Zr is 200 nm or less, the coating does not break during hot press molding, so the sliding resistance does not increase. Moreover, since weldability does not fall, it is preferable. Furthermore, since the formed oxide does not become coarse and does not have a large amount, it does not adhere to a press die or the like and productivity is not lowered, which is preferable.
なお、本発明では、使用する酸性溶液中にＺｒイオンを含有していれば、耐酸化性に優れた、つまり熱間プレス成形性に優れた酸化物層を安定して形成できるため、酸性溶液中にその他の金属イオンや無機化合物などを不純物として、あるいは故意に含有していても本発明の効果が損なわれるものではない。特にＺｎイオンは、めっき層と酸性溶液が接触する際に溶出するイオンであるため、操業中に酸性溶液中Ｚｎ濃度の増加が認められるが、このZnイオンの濃度の大小は本発明の効果には特に影響を及ぼさない。 In the present invention, if the acidic solution to be used contains Zr ions, an oxide layer excellent in oxidation resistance, that is, excellent in hot press formability can be stably formed. Even if other metal ions or inorganic compounds are contained as impurities or intentionally contained therein, the effect of the present invention is not impaired. In particular, since Zn ions are ions that elute when the plating layer and the acidic solution come into contact with each other, an increase in the Zn concentration in the acidic solution is observed during operation. The magnitude of this Zn ion concentration is effective for the effect of the present invention. Has no particular effect.
また、本発明にかかる素地鋼材は、特に限定はしないが、めっき処理時のめっき濡れ性、めっき後のめっき密着性が良好となる鋼組成とすることが好ましい。また、熱間プレス成形を行う場合を考慮して、その特性として、熱間プレス成形後に急冷して高強度、高硬度となる焼入れ鋼、例えば高張力鋼板が実用上は特に好ましい。 Moreover, although the base steel material concerning this invention is not specifically limited, It is preferable to set it as the steel composition from which the plating wettability at the time of a plating process and the plating adhesiveness after plating become favorable. In consideration of the case where hot press forming is performed, a hardened steel, such as a high-tensile steel plate, which is rapidly cooled after hot press forming to become high strength and high hardness, such as a high-strength steel plate, is particularly preferable.
また、本発明において、めっき法に特に限定はないが、溶融亜鉛めっき法がコストの点で好ましい。もちろん、所定のＺｎとＺｒを含有する酸化物層をめっき表面に得られるのであれば、例えば、電気めっき、溶射めっき、蒸着めっき等その他いずれの方法でめっき層を設けても良い。 In the present invention, the plating method is not particularly limited, but the hot dip galvanizing method is preferable in terms of cost. Of course, as long as an oxide layer containing predetermined Zn and Zr can be obtained on the plating surface, the plating layer may be provided by any other method such as electroplating, thermal spray plating, vapor deposition plating or the like.
また、熱間プレス成形の方法については特に限定しない。例えば、本発明の熱間プレス成形用亜鉛系めっき鋼板に対して、1〜100℃/秒の加熱速度にてAc3変態点以上に加熱し、5〜6000秒間の保持後、400〜800℃の温度域で熱間プレス成形することにより、本発明の耐酸化性の効果を最大限に得ることができる。
また、熱間プレス成形中に、ダイとパンチを用いて10〜200℃/sの冷却速度にて部材を冷却したり、熱間プレス成形後に、熱間プレス成形した部材を金型より取り出し、液体または気体を用いて冷却することも可能である。
Moreover, it does not specifically limit about the method of hot press molding. For example, with respect to the zinc-based plated steel sheet for hot press forming of the present invention, it is heated to the Ac3 transformation point or higher at a heating rate of 1 to 100 ° C./second, and after holding for 5 to 6000 seconds, it is 400 to 800 ° C. By performing hot press molding in the temperature range, the effect of oxidation resistance of the present invention can be maximized.
In addition, during hot press molding, the member is cooled at a cooling rate of 10 to 200 ° C./s using a die and a punch, or after hot press molding, the hot press molded member is taken out from the mold, It is also possible to cool using liquid or gas.
次に、本発明を実施例により詳細に説明する。 Next, the present invention will be described in detail with reference to examples.
鋼成分として、C：0.23mass％、Si：0.12mass％、Mn：1.5mass％、Cr：0.50mass％、B：0.0020mass％を含有する鋼板に対して、溶融亜鉛めっき処理、合金化溶融亜鉛めっき処理、電気亜鉛めっき処理および溶融亜鉛−アルミニウムめっき処理を各々行い、板厚1.2mmの溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板および溶融亜鉛−アルミニウムめっき鋼板を作製した。なお、溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板および溶融亜鉛−アルミニウムめっき鋼板のめっき付着量はいずれも45g/m2である。 For steel sheets containing C: 0.23 mass%, Si: 0.12 mass%, Mn: 1.5 mass%, Cr: 0.50 mass%, B: 0.0020 mass% as steel components Plating treatment, electrogalvanizing treatment, and hot dip galvanized aluminum plating treatment were performed, respectively, to produce a hot dip galvanized steel sheet having a thickness of 1.2 mm, an alloyed hot dip galvanized steel sheet, an electrogalvanized steel sheet, and a hot dip galvanized steel sheet. In addition, the plating adhesion amount of the hot dip galvanized steel sheet, the alloyed hot dip galvanized steel sheet, the electrogalvanized steel sheet and the hot dip galvanized steel sheet is 45 g / m 2 .
次いで、溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板、電気亜鉛めっき鋼板および溶融亜鉛−アルミニウムめっき鋼板に対して、酸性溶液接触処理を行った。なお、酸性溶液処理は、緩衝性を持つ酢酸ナトリウム40g/lの酸性水溶液を作成し、次いで、ｐHを硫酸で調整した酸性溶液に3秒浸漬した。その後、ロール絞りを行い、液量を調整した後、1〜90秒間大気中、室温にて放置し、十分水洗を行った後、乾燥を実施し、めっき鋼板表面に、Ｚｎ及びＺｒを含む酸化物層を形成した。形成した酸化物層の断面をエネルギー分散型蛍光X線分析装置により分析することにより、ＺｎとＺｒの存在を確認した。なお、詳細な条件は、表1〜表４に示す。また、比較例として、上記酸性溶液処理を行わないもの、及びＺｒイオンを含有しない酸性溶液処理を行ったものも作製した。 Next, an acidic solution contact treatment was performed on the hot dip galvanized steel sheet, the alloyed hot dip galvanized steel sheet, the electrogalvanized steel sheet, and the hot dip galvanized steel sheet. In the acidic solution treatment, an acidic aqueous solution of 40 g / l sodium acetate having buffering properties was prepared, and then immersed in an acidic solution prepared by adjusting pH with sulfuric acid for 3 seconds. Then, after squeezing the roll and adjusting the amount of liquid, it is allowed to stand in the atmosphere at room temperature for 1 to 90 seconds, sufficiently washed with water, and then dried, and the surface of the plated steel sheet is oxidized with Zn and Zr. A physical layer was formed. The presence of Zn and Zr was confirmed by analyzing the cross section of the formed oxide layer with an energy dispersive X-ray fluorescence analyzer. Detailed conditions are shown in Tables 1 to 4. In addition, as a comparative example, a sample not subjected to the acidic solution treatment and a sample subjected to an acidic solution treatment not containing Zr ions were also produced.
以上により作製した鋼板について、自動車用外板として十分な熱間プレス成形性（成形後の外観）を有するか判定するとともに、めっき表面の酸化物層の平均厚さを測定した。熱間プレス成形性の評価方法及び酸化物層厚さの測定方法の詳細は以下の通りである。
・ 熱間プレス成形性（外観評価）
加熱炉内で、大気雰囲気下で加熱速度：15℃/ｓにて900℃まで加熱し、900℃で60秒間保持後加熱炉より取り出し、円筒絞りの熱間プレス成形を行った。熱間プレス成形は、絞り高さ：25mm、肩R：5mm、ブランク直径：90mm、パンチ直径：50mm、ダイ直径：53mmの条件の下で実施した。成形後の試験片のめっき層密着状態として、めっき層の剥離の有無を目視で観察して、熱間プレス成形性として2段階で評価した。
◎：剥離なし、×剥離あり
・ 酸化物層厚さ測定
膜厚が９６nmの熱酸化ＳｉＯ2膜が形成されたＳｉウエハを参照物質として用い、蛍光Ｘ線分析装置でＯ・Ｋα Ｘ線を測定することで、ＳｉＯ2換算の酸化物層の平均厚さを求めた。分析面積は３０ｍｍφである。
About the steel plate produced by the above, while determining whether it had sufficient hot press formability (appearance after shaping | molding) as a motor vehicle outer plate, the average thickness of the oxide layer of the plating surface was measured. Details of the hot press formability evaluation method and the oxide layer thickness measurement method are as follows.
・ Hot press formability (appearance evaluation)
In a heating furnace, it was heated to 900 ° C. at a heating rate of 15 ° C./s in an air atmosphere, held at 900 ° C. for 60 seconds, taken out from the heating furnace, and subjected to hot press molding of a cylindrical drawing. Hot press molding was performed under the conditions of drawing height: 25 mm, shoulder R: 5 mm, blank diameter: 90 mm, punch diameter: 50 mm, and die diameter: 53 mm. As the plating layer adhesion state of the test piece after molding, the presence or absence of peeling of the plating layer was visually observed, and the hot press formability was evaluated in two stages.
◎: No exfoliation, x exfoliation ・ Measurement of oxide layer thickness Using a Si wafer on which a thermally oxidized SiO 2 film with a film thickness of 96 nm is formed as a reference material, measure O / Kα X-rays with a fluorescent X-ray analyzer Thus, the average thickness of the oxide layer in terms of SiO 2 was determined. The analysis area is 30 mmφ.
以上により得られた結果を条件と併せて表1〜表４に示す。 The results obtained as described above are shown in Tables 1 to 4 together with the conditions.
本発明例では、熱間プレス成形時のめっきの蒸発抑制およびスケール発生防止により外観不良が抑制され、めっき層剥離は観察されず、耐酸化性に優れるため、熱間プレス成形性が良好であった。 In the example of the present invention, the appearance defect is suppressed by suppressing the evaporation of plating and the prevention of scale generation during hot press forming, and the plating layer peeling is not observed and the oxidation resistance is excellent, so the hot press formability is good. It was.
一方で、酸性溶液処理を行っていない比較例では、本発明の酸化物層が形成されず、熱間プレス成形後にスケール発生に起因するめっき層剥離が観察された。 On the other hand, in the comparative example in which the acidic solution treatment was not performed, the oxide layer of the present invention was not formed, and plating layer peeling due to scale generation was observed after hot press molding.
本発明の熱間プレス成形用めっき鋼板は、耐酸化性に優れることから、自動車用の足回り、シャーシ、補強部品などの自動車車体用途を中心に広範な分野で適用できる。 The plated steel sheet for hot press forming according to the present invention is excellent in oxidation resistance, and therefore can be applied in a wide range of fields mainly for automobile body applications such as automobile undercarriages, chassis and reinforcing parts.
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