JP3386657B2 - High strength cold rolled steel sheet - Google Patents
High strength cold rolled steel sheetInfo
- Publication number
- JP3386657B2 JP3386657B2 JP12459696A JP12459696A JP3386657B2 JP 3386657 B2 JP3386657 B2 JP 3386657B2 JP 12459696 A JP12459696 A JP 12459696A JP 12459696 A JP12459696 A JP 12459696A JP 3386657 B2 JP3386657 B2 JP 3386657B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- rolled steel
- plating
- sio
- strength cold
- 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 - Fee Related
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高強度冷延鋼板に
関し、特に、自動車車体などに用いられ、且つ必要に応
じて、電気めっき、化成処理、クロメート処理などが施
される高強度冷延鋼板に係わる。The present invention relates to relates to a high strength cold rolled steel sheet, high strength, especially, are used in an automobile or the like vehicle, and if necessary, electric plating, Kasei treatment, chromate treatment is applied Related to cold rolled steel sheet.
【０００２】[0002]
【従来の技術】近年、排気ガス規制の観点から、自動車
車体の軽量化が叫ばれている。そして、この車体軽量化
の有効な手段の一つとして板厚を薄くする方法がある
が、この方法を用いる場合には、安全性確保の面から板
厚を薄くした分に見合うよう板自体の強度を高める必要
がある。そこで、従来は、鋼中にＳｉ、Ｍｎ、Ｃｒ、Ｐ
等の所謂固溶強化元素を複合添加したり、あるいはＣ、
Ｍｎを主に添加して、鋼板の高強度化が図られている。2. Description of the Related Art In recent years, weight reduction of automobile bodies has been demanded from the viewpoint of exhaust gas regulation. There is a method of reducing the plate thickness as one of the effective means for reducing the weight of the vehicle body.However, when using this method, the thickness of the plate itself is adjusted so as to be commensurate with the reduced thickness in terms of ensuring safety. It is necessary to increase strength. Therefore, conventionally, in steel, Si, Mn, Cr, P
Or so-called solid solution strengthening elements such as C,
Mn is mainly added to increase the strength of the steel sheet.
【０００３】ところで、上記のような高強度鋼板は、優
れた材質を確保するため、製造過程において、冷間圧延
後８００℃以上の高温で焼鈍される。また、耐食性を付
与するため、上記焼鈍後に、めっきや化成処理などが施
されることがある。その焼鈍は、通常、Ｎ2 −Ｈ2 の雰
囲気下で行うが、この雰囲気はＦｅに関しては還元性雰
囲気であるが、Ｓｉ、Ｍｎ、Ｃｒ、Ｐなどに関しては酸
化性の雰囲気であり、これら元素は、選択的に酸化され
て酸化物となり鋼板表面に濃化する。そして、この鋼板
に例えば溶融亜鉛めっきを施した場合、上記酸化物が溶
融亜鉛と鋼板との濡れ性を低下させ、鋼板表面で所謂
「不めっき」現象をしばしば引き起こす。さらに、焼鈍
後に脱脂や酸洗を施しても、これら酸化物は鋼板から完
全には除去できないので、電気めっきや化成処理などを
施すに際しては、「不めっき」現象や化成処理液の「は
じき」などを引起こすことが多い。つまり、めっき性、
化成処理性などに優れた高強度冷延鋼板は、得がたいも
のであった。By the way, the above high strength steel sheet is annealed at a high temperature of 800 ° C. or more after cold rolling in the manufacturing process in order to secure an excellent material. Further, in order to impart corrosion resistance, plating or chemical conversion treatment may be performed after the annealing. The annealing is usually performed in an N 2 —H 2 atmosphere. This atmosphere is a reducing atmosphere for Fe, but an oxidizing atmosphere for Si, Mn, Cr, P, etc. Is selectively oxidized to form an oxide and is concentrated on the surface of the steel sheet. When this steel sheet is subjected to, for example, hot dip galvanizing, the above oxide reduces the wettability between the hot dip zinc and the steel sheet, often causing a so-called "non-plating" phenomenon on the steel sheet surface. Furthermore, even if degreasing or pickling is performed after annealing, these oxides cannot be completely removed from the steel sheet, so when performing electroplating or chemical conversion treatment, the "non-plating" phenomenon or "repellency" of chemical conversion treatment liquid Often causes. That is, platability,
It was difficult to obtain a high-strength cold-rolled steel sheet excellent in chemical conversion treatability.
【０００４】これらの問題点のうち、溶融めっき性の改
善のため、特公昭６１−９３８６号公報は、溶融めっき
に先立って鋼板の表面にＮｉによる下地めっきを施す方
法を提案した。しかしながら、この方法では、Ｓｉを
０．１ｗｔ％以上３．０ｗｔ％以下含有する鋼板、もし
くはＣを０．０３〜０．１０ｗｔ％、Ｓｉを０．００１
〜０．１０ｗｔ％未満、Ｍｎを０．５〜２．０ｗｔ％、
Ｐを０．０１〜０．１０ｗｔ％、Ｍｏを０．５０ｗｔ％
以下をそれぞれ含有する鋼板を対象とした場合、付着量
が１０ｇ／ｍ2 以上のＮｉめっきを施すことが必要にな
り、製造コストの大幅上昇を招いた。そして、このよう
な大量のＮｉめっきを施すと、溶融亜鉛めっきと鋼板と
の濡れ性は確かに改善されるが、合金化過程においてめ
っき表面にＳｉ、Ｎｉに起因する欠陥が多発するという
別の問題が生じた。Among these problems, in order to improve the hot-dip galvanizing property, Japanese Examined Patent Publication No. 61-9386 proposes a method of subjecting the surface of a steel sheet to undercoating with Ni prior to hot-dip coating. However, in this method, a steel sheet containing 0.1 wt% or more and 3.0 wt% or less of Si, or 0.03 to 0.10 wt% of C and 0.001 of Si.
~ 0.10 wt%, Mn 0.5-2.0 wt%,
0.01 to 0.10 wt% P, 0.50 wt% Mo
In the case of targeting a steel sheet containing each of the following, it is necessary to perform Ni plating with an adhesion amount of 10 g / m 2 or more, which causes a large increase in manufacturing cost. When such a large amount of Ni plating is applied, the wettability between the hot dip galvanized steel sheet and the steel sheet is certainly improved, but another problem is that defects caused by Si and Ni frequently occur on the plating surface during the alloying process. There was a problem.
【０００５】また、特開昭５７−７０２６８号公報は、
上記Ｎｉめっきに代え、鋼板の表面にＦｅの下地めっき
を施す方法を開示した。しかしながら、この方法では、
Ｓｉ添加鋼の「不めっき」を防止することはできたが、
そのために５ｇ／ｍ 2 以上のＦｅをめっきする必要があ
り、Ｎｉの場合と同様極めて不経済であった。さらに、
特開昭５５−１２２８６５号公報や特開平４−２５４５
３１号公報は、冷延後にあらかじめ鋼板を酸化して表層
に鉄酸化膜を形成させ、その後還元焼鈍することによっ
て、合金元素の酸化物被膜の形成を抑制してから所望の
めっきを施す方法を開示した。しかしながら、この方法
は、還元焼鈍でめっき前に残存する鉄酸化膜の厚みを一
定値以下に制御する方法であるため、還元焼鈍で還元さ
れすぎてしまい、合金元素が表面に濃化してかえってめ
っき性が不良となる問題、つまり酸化膜と還元量のバラ
ンスが崩れるという問題があった。加えて、この過還元
を防ぐには、鉄酸化物の膨大量が必要になるため、圧延
時にロールなどによって鉄酸化物皮膜が剥離してしま
い、その後の還元焼鈍時に合金元素の選択酸化が起って
めっき性が阻害されたり、剥離した鉄酸化物の皮膜が焼
鈍炉内に散乱して、操業に悪影響を及ぼすという問題も
あった。Further, Japanese Patent Laid-Open No. 57-70268 discloses that
The method of performing the base plating of Fe on the surface of the steel sheet is disclosed instead of the above Ni plating. However, with this method,
Although it was possible to prevent "non-plating" of Si-added steel,
Therefore, it is necessary to plate Fe of 5 g / m 2 or more, which is extremely uneconomical as in the case of Ni. further,
JP-A-55-122865 and JP-A-4-2545
Japanese Patent No. 31 discloses a method in which after cold rolling, a steel sheet is previously oxidized to form an iron oxide film on the surface layer, and then reduction annealing is performed to suppress the formation of an oxide film of an alloy element and then perform desired plating. Disclosed. However, since this method is a method of controlling the thickness of the iron oxide film remaining before plating by reduction annealing to be a certain value or less, it is excessively reduced by reduction annealing, and the alloying elements are concentrated on the surface and rather plated. There is a problem that the property becomes poor, that is, the balance between the oxide film and the reduction amount is lost. In addition, in order to prevent this over-reduction, an enormous amount of iron oxide is required, so the iron oxide film is peeled off by rolls during rolling, and selective oxidation of alloy elements occurs during subsequent reduction annealing. Therefore, there is a problem that the plating property is hindered or the peeled iron oxide film is scattered in the annealing furnace, which adversely affects the operation.
【０００６】一方、自動車用鋼板について特に要求され
る特性に、塗装前処理、すなわち化成処理性がある。こ
の化成処理性が良好でないと、その後の焼付け塗装がう
まくいかないという問題がある。しかしながら、鋼板の
高強度化を目的に、前記したようにＣ、Ｓｉ、Ｍｎ、Ｐ
等の強化成分を多量に含有させると、前述した表面での
酸化物発生により化成処理性が著しく低下する。また、
その他の用途、主として家電用鋼板として用いられる場
合には、クロメート処理が施されることがある。しかし
ながら、この場合も、化成処理性の場合と同様に、鋼板
の高強度化を目的にＣ、Ｓｉ、Ｍｎ、Ｐ等の強化成分を
多量に含有しているので、クロメート処理性が巧くいか
ないという問題があった。On the other hand, one of the properties particularly required for steel sheets for automobiles is pretreatment for coating, that is, chemical conversion treatment. If the chemical conversion treatment is not good, there is a problem that the subsequent baking coating will not be successful. However, in order to increase the strength of the steel sheet, as described above, C, Si, Mn, P
If a large amount of such a strengthening component as described above is contained, chemical conversion treatability is markedly deteriorated due to the generation of oxides on the surface described above. Also,
When it is used for other purposes, mainly as a steel sheet for home appliances, it may be subjected to chromate treatment. However, also in this case, as in the case of the chemical conversion treatability, since a large amount of reinforcing components such as C, Si, Mn, and P are contained for the purpose of increasing the strength of the steel sheet, the chromate treatability does not work well. There was a problem.
【０００７】以上述べたように、自動車用高強度材料と
して現在魅力のある高強度鋼板であっても、これを、電
気めっき、化成処理、クロメート処理などを施した後に
耐食性の良好な表面処理鋼板として使用するためには、
まだまだ改良の余地が残されているのが実状である。[0007] As described above, even in high-strength steel sheet with a currently attractive as a high strength material for automobile, which, electrostatic <br/> vapor plating, chemical conversion treatment, the corrosion resistance after performing chromate treatment In order to use it as a good surface-treated steel sheet,
The reality is that there is still room for improvement.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、かかる事情
を鑑み、鋼板の母材に工夫をこらして、電気めっき性、
化成処理性、クロメート処理性に優れた高強度冷延鋼板
を提供することを目的としている。[0008] The present invention has been made in view of such circumstances, and ingenuity to the base material of the steel plate, electrical plating properties,
It is an object of the present invention to provide a high-strength cold-rolled steel sheet having excellent chemical conversion treatability and chromate treatability.
【０００９】[0009]
【課題を解決するための手段】前記したように、Ｓｉ、
Ｍｎ等の固溶強化元素が複合添加されている高強度冷延
鋼板に、各種表面処理、例えばめっき、化成処理、クロ
メート処理などを施すと、これら元素が表面に濃化して
皮膜を形成し、溶融亜鉛や化成処理液と鋼板との濡れ性
を阻害するため「不めっき」が発生する。また、表面濃
化量とめっき性、合金化速度には相関があり、表面濃化
量の少ない方がめっき性が良くなるし、合金化速度は速
くなることは、既に知られている。As mentioned above, Si,
When various surface treatments such as plating, chemical conversion treatment, and chromate treatment are performed on a high-strength cold-rolled steel sheet to which a solid solution strengthening element such as Mn is added, these elements are concentrated on the surface to form a film, "Non-plating" occurs because it impedes the wettability of molten steel and the chemical conversion treatment liquid with the steel sheet. Further, it is already known that there is a correlation between the amount of surface concentration, the plating property, and the alloying speed, and the smaller the amount of surface concentration, the better the plating property and the faster the alloying speed.
【００１０】そこで、発明者は、表面濃化を抑制するた
めの鋼板の表層構造の詳細な検討を鋭意行った。その結
果、ある特定した成分を含有する高強度冷延鋼板表層の
結晶粒界、あるいは粒内、あるいは結晶粒界及び粒内
に、予めＳｉＯ2 ，ＭｎＯ，ＦｅＳｉＯ3，Ｆｅ2 Ｓｉ
Ｏ4 ，ＭｎＳｉＯ3 ，Ｍｎ2 ＳｉＯ4 ，Ｐ2 Ｏ5 等の酸
化物を生成させておくと、該高強度鋼板の電気めっき
性、化成処理性、クロメート処理性を飛躍的に向上させ
ることを見いだし、本発明を完成させた。Therefore, the inventor diligently studied in detail the surface layer structure of the steel sheet for suppressing the surface thickening. As a result, SiO 2 , MnO, FeSiO 3 , Fe 2 Si is previously formed in the crystal grain boundary of the high-strength cold-rolled steel sheet surface containing a specified component, or in the grain boundary, or in the crystal grain boundary and the grain.
When O 4, MnSiO 3, Mn 2 SiO 4, allowed to produce a P 2 O 5 oxide such, electric plating of the high-strength steel sheet, Kasei processability, drastically improve the chromate treatment of Then, they have completed the present invention.
【００１１】すなわち、本発明は、電気めっき、あるい
は化成処理、あるいはクロメート処理に供される冷延鋼
板であって、Ｓｉを０．１ｗｔ％以上３．０ｗｔ％以下
含有する高強度冷延鋼板の、鋼板表層から０．１〜１０
０μｍの深さまでの結晶粒界及び／又は結晶粒内に、電
気めっき性、化成処理性及びクロメート処理性の改良に
有効な酸化物、ＳｉＯ2，ＭｎＯ，ＦｅＳｉＯ3，Ｆｅ2
ＳｉＯ4，ＭｎＳｉＯ3、Ｍｎ2ＳｉＯ4及びＰ2Ｏ5から選
ばれた１種以上を形成させてなることを特徴とする高強
度冷延鋼板である。また、本発明は、電気めっき、ある
いは化成処理、あるいはクロメート処理に供される冷延
鋼板であって、鋼板の組成元素として、
Ｃ：０．０３〜０．１０ｗｔ％
Ｓｉ：０．００１〜０．１０ｗｔ％未満
Ｍｎ：０．５〜２．０ｗｔ％
Ｐ：０．０１〜０．１０ｗｔ％
Ｍｏ：０．５０ｗｔ％以下
を含有する高強度冷延鋼板の、鋼板表層から０．１〜１
００μｍの深さまでの結晶粒界及び／又は結晶粒内に、
電気めっき性、化成処理性及びクロメート処理性の改良
に有効な酸化物、ＳｉＯ2，ＭｎＯ，ＦｅＳｉＯ3，Ｆｅ
2ＳｉＯ4，ＭｎＳｉＯ3、Ｍｎ2ＳｉＯ4及びＰ2Ｏ5から
選ばれた１種以上を形成させてなることを特徴とする高
強度冷延鋼板である。That is, the present invention relates to electroplating or
Cold rolled steel for chemical conversion treatment or chromate treatment
A plate, high strength cold rolled steel sheet containing Si less 0.1 wt% or more 3.0 wt%, a steel plate surface of 0.1 to 10
Grain boundaries to a depth of 0μm and / or within the grain, electrostatic
Vapor plating resistance, reduction conversion treatment and effectiveness oxide to improve the chromate treatment of, SiO 2, MnO, FeSiO 3 , Fe 2
It is a high-strength cold-rolled steel sheet characterized by being formed of one or more selected from SiO 4 , MnSiO 3 , Mn 2 SiO 4, and P 2 O 5 . The present invention also has electroplating
Cold rolling for chemical conversion or chromate treatment
A steel sheet , wherein C: 0.03 to 0.10 wt% Si: 0.001 to less than 0.10 wt% Mn: 0.5 to 2.0 wt% P: 0.01 to 0. 10 wt% Mo: containing less 0.50 wt% of high-strength cold-rolled steel sheet, 0.1 to 1 from the steel sheet surface layer
Within a grain boundary and / or grain to a depth of 00 μm ,
Electroplating resistance, reduction conversion treatment and effectiveness oxide to improve the chromate treatment of, SiO 2, MnO, FeSiO 3 , Fe
A high-strength cold-rolled steel sheet, characterized in that it is formed by forming at least one selected from 2 SiO 4 , MnSiO 3 , Mn 2 SiO 4 and P 2 O 5 .
【００１２】[0012]
【００１３】[0013]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明に係る高強度冷延鋼板の表層内の結晶粒
界、あるいは粒内、あるいは結晶粒界及び粒内に存在す
る酸化物は、該鋼板を冷間圧延する前段階の熱間圧延時
に生成させておく。特に、熱延後のコイル巻取温度が高
く、その後の冷却速度が遅い場合に、それら酸化物が成
長する。粒界に形成された酸化物の様子を図１に示す
が、所謂黒皮の直下にそれが観察される。この酸化物を
ＥＰＭＡで分析した結果を図２に示す。図２より、Ｓ
ｉ、Ｍｎ、Ｐ、Ｏのピークが見られることから、これら
元素の酸化物が生成していることがわかる。また、熱延
鋼板の表層のレプリカを取りＴＥＭ（透過型電子顕微
鏡）により観察した結果を図３に示す。図３より、粒界
だけでなく、表層の結晶粒内にも析出物が確認される。
これをＥＤＸにより元素の成分分析した結果を表１に示
す。表１より、粒界については、Ｆｅ、Ｍｎ、Ｓｉな
ど、粒内については、Ｍｎ、Ｓｉなどが確認できる。ま
た、レプリカにより剥離可能であること及びこれらの元
素の鋼中における存在形態を鑑みるに、これらの元素は
酸化物を形成しているものと考えられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The crystal grain boundaries in the surface layer of the high-strength cold-rolled steel sheet according to the present invention, or in the grains, or the oxides present in the grain boundaries and grains are generated during the hot rolling in the previous stage of cold rolling the steel sheet. I will let you. In particular, when the coil winding temperature after hot rolling is high and the subsequent cooling rate is slow, these oxides grow. The appearance of the oxide formed at the grain boundaries is shown in FIG. 1, and it is observed just below the so-called black skin. The results of EPMA analysis of this oxide are shown in FIG. From FIG. 2, S
Since peaks of i, Mn, P, and O are seen, it is understood that oxides of these elements are generated. Further, FIG. 3 shows the results of observing a replica of the surface layer of the hot rolled steel sheet with a TEM (transmission electron microscope). From FIG. 3, not only the grain boundaries but also the precipitates are confirmed in the crystal grains of the surface layer.
Table 1 shows the result of elemental analysis of this by EDX. From Table 1, it is possible to confirm Fe, Mn, Si, etc. in the grain boundaries, and Mn, Si, etc. in the grains. Further, in view of the fact that they can be exfoliated by a replica and the existence form of these elements in steel, it is considered that these elements form an oxide.
【００１４】[0014]
【表１】 [Table 1]
【００１５】さらに、これら鋼板表層直下に存在する酸
化物は、熱間圧延段階で形成した黒皮直下の酸化物が、
その後の酸洗、冷延、焼鈍などの工程を経ても残存する
ものである。図４には、冷延及び焼鈍後の本発明に係る
鋼板をグロー放電（ＧＤＳ）による発光分析法で、表層
から１０μｍ程度の深さまで元素分析した結果を示す。
それによれば、表層からの深さ０．５〜３μｍ程度にみ
えるＳｉ、Ｍｎ、Ｐのピークが上記の酸化物に相当す
る。Further, the oxides present immediately below the surface layer of the steel sheet are the oxides immediately below the black skin formed in the hot rolling stage.
It remains even after the subsequent steps such as pickling, cold rolling and annealing. FIG. 4 shows the results of elemental analysis of the steel sheet according to the present invention after cold rolling and annealing by an emission analysis method by glow discharge (GDS) from the surface layer to a depth of about 10 μm.
According to this, the peaks of Si, Mn, and P that appear at a depth of about 0.5 to 3 μm from the surface layer correspond to the above oxides.
【００１６】通常、ＣＧＬでの還元焼鈍では、Ｓｉ，Ｍ
ｎなどは選択酸化されて表面濃化するが、これら元素が
鋼板表面近傍のバルクから表面へ移動しにくくなり、逆
に酸素の内部への移動が促進されるため、内部酸化層が
生成し、最表面での表面濃化が抑制される。言い換える
と、表層酸化物層により、金属元素の外方向拡散（表面
濃化）から酸素の内方向拡散（内部酸化）に変化する。
そのため、鋼板表面にはめっき密着性や化成処理性を悪
くするＳｉ，Ｍｎなどの酸化物被膜が存在せず、該鋼板
の性能は良好となる。従って、本発明によれば、Ｓｉ，
Ｍｎ等の合金元素が複合添加されている高強度鋼板の各
種表面処理性、具体的には、電気めっき性、化成処理
性、クロメート処理などが飛躍的に向上するのである。Usually, in reduction annealing with CGL, Si, M
n, etc. are concentrated surface is selectively oxidized, but since these elements are less likely to move from the bulk of the steel sheet surface near to the surface, the movement of oxygen into the interior of is promoted conversely, generates an internal oxide layer However, surface concentration on the outermost surface is suppressed. In other words, the surface oxide layer changes the outward diffusion of metal elements (surface concentration) to the inward diffusion of oxygen (internal oxidation).
Therefore, the surface of the steel sheet does not have an oxide coating such as Si or Mn that deteriorates the plating adhesion and the chemical conversion treatment property, and the performance of the steel sheet is good. Therefore, according to the present invention, Si,
Various surface treatment of high-strength steel sheet alloying elements such as Mn are added in combination, specifically, electric plating resistance, Kasei processability, such as chromate treatment is to dramatically improved.
【００１７】[0017]
【００１８】[0018]
【００１９】また、本発明に係る高強度冷延鋼板は、電
気めっき、化成処理、クロメート処理を行っても、上記
と同様な理由で「不めっき」、「付着量むら」などを起
さない。この場合、Ｓｉを０．１ｗｔ％以上もしくはＭ
ｎを０．５ｗｔ％以上含有する鋼板であってもよい。さ
らに、本発明に係る高強度冷延鋼板は、処理対象が電気
亜鉛めっき、電気亜鉛−ニッケルめっき、電気亜鉛−鉄
めっきなどでも優れた性能を示す。これは、ＳｉやＭｎ
などの酸化物の表面への濃化が抑制されるため、鋼板表
面上の鉄と電気めっき浴中の金属イオンとの電析反応性
の低下が抑制されることにより「不めっき」、「めっき
むら」などが生じなくなるためである。化成処理、クロ
メート処理性が向上するのも同様の理由による。Further, the high-strength cold-rolled steel sheet according to the present invention does not cause "non-plating", "uneven amount of adhesion", etc. for the same reason as described above even if it is subjected to electroplating, chemical conversion treatment and chromate treatment. . In this case, Si is 0.1 wt% or more or M
A steel plate containing 0.5 wt% or more of n may be used. Furthermore, the high-strength cold-rolled steel sheet according to the present invention exhibits excellent performance even when the treatment target is electrogalvanizing, electrogalvanizing-nickel plating, electrogalvanizing-iron plating, or the like. This is Si or Mn
Since the concentration of oxides such as iron on the surface is suppressed, the decrease in the electrodeposition reactivity between the iron on the steel plate surface and the metal ions in the electroplating bath is suppressed. This is because "unevenness" does not occur. The chemical conversion treatment and the chromate treatment are improved for the same reason.
【００２０】従って、Ｓｉ、Ｍｎ、Ｃｒ、Ｐなどの強化
元素が添加された高強度冷延鋼板の電気めっき性、化成
処理性、クロメート処理性を飛躍的に向上させるために
は結局のところＳｉ、Ｍｎなどの表面濃化を顕著に抑制
することが最も効果的かつ適切である。[0020] it follows, Si, Mn, Cr, in order to dramatically improve electrical plating of reinforced high-strength cold-rolled steel sheet element is added, of forming processability, a chromate treatment of such as P, After all, it is most effective and appropriate to remarkably suppress the surface concentration of Si, Mn and the like.
【００２１】次に、本発明で採用した成分や他の条件の
限定理由を説明する。第１発明でＳｉ量の下限を０．１
ｗｔ％，第２発明でＭｎ量の下限を０．５ｗｔ％とした
のは、鋼板表層の酸化物は、Ｓｉの含有量が０．１ｗｔ
％未満である鋼板、もしくはＭｎの含有量が０．５ｗｔ
％未満である鋼板では、焼鈍後の鋼板の脱脂、酸洗時に
十分除去可能であるため、通常のめっき槽を用いて基本
的な硫酸浴、あるいは塩酸浴法にて電気めっきが可能で
あるからである。さらに、化成処理性やクロメート処理
性についても同様で、特に従来設備や従来法を変えなく
ても、同様に化成処理やクロメート処理が可能であるか
らである。 Next, the reasons for limiting the components used in the present invention and other conditions will be described. In the first invention, the lower limit of the Si amount is set to 0.1.
wt%, to that of the lower limit of the Mn content and 0.5 wt% in the second invention, an oxide of the steel plate surface layer, 0.1 wt content of Si
% Less than Der Ru steel plate, or the content of Mn 0.5 wt
The% less than Der Ru steel plate, degreasing of the steel sheet after annealing, because it can be removed sufficiently during pickling, basic sulfate bath using conventional plating tank, or can be electroplated with hydrochloric acid bath method Because there is. Furthermore, the same applies to the chemical conversion treatment and the chromate treatment, and the chemical conversion treatment and the chromate treatment can be similarly performed without changing the conventional equipment or the conventional method .
【００２２】第１発明でＳｉ量の上限を３．０ｗｔ％，
第２発明でＭｎ量の上限を２．０ｗｔ％としたのは、Ｓ
ｉ量が３．０ｗｔ％を超える、もしくはＭｎ量が２．０
ｗｔ％を超えると、鋼板表面に酸化膜を形成し、めっき
浴や化成処理液、クロメート処理液との密着性を著しく
低下させるためである。第２の発明は、Ｓｉが０．１ｗ
ｔ％未満の場合でも、上述のようにＭｎを２．０〜０．
５ｗｔ％に限定することのみで、本願の特性を有する高
強度冷延鋼板を得るものであり、Ｓｉの下限値０．００
１ｗｔ％は不可避的な含有量である。In the first invention, the upper limit of the amount of Si is 3.0 wt%,
In the second invention, the upper limit of the amount of Mn is set to 2.0 wt% is that S
i amount exceeds 3.0 wt% or Mn amount is 2.0
This is because if it exceeds wt%, an oxide film is formed on the surface of the steel sheet, and the adhesion to the plating bath, the chemical conversion treatment liquid, and the chromate treatment liquid is significantly reduced. In the second invention, Si is 0.1 w
Even when it is less than t%, Mn is 2.0 to 0.
A high-strength cold-rolled steel sheet having the characteristics of the present application is obtained only by limiting the content to 5 wt%, and the lower limit of Si is 0.00
1 wt% is an unavoidable content.
【００２３】同様に、鋼中にＣｒを０．１ｗｔ％以上、
２．０ｗｔ％以下含有する高強度鋼板においても、鋼中
のＣｒが焼鈍過程において鋼板表面の加熱によって選択
的に酸化され、鋼板表面に拡散されるため、これらの酸
化物が濃化し、鋼板表面で皮膜を形成する。また、この
酸化物層は、酸洗によっても充分には除去されず、鋼板
の電気めっきや化成処理、クロメート処理を著しく阻害
し、「不めっき」や「はじき」、「付着量むら」が起こ
る。しかしながら、本発明では、高強度鋼板の表層の結
晶粒界、あるいは粒内、あるいは結晶粒界及び粒内に、
酸化物を生成させると、Ｓｉ、Ｍｎ、Ｐ、Ｃｒなどの表
面濃化が抑制され、これらの酸化物が鋼板表面に形成し
ないため、これら「不めっき」や「はじき」、「付着量
むら」がおこらない。そのため、鋼中にＣｒを０．１ｗ
ｔ％以上２．０ｗｔ％以下含有する高強度冷延鋼板に対
しても、本発明は効果がある。Similarly, 0.1 wt% or more of Cr in steel,
Even in a high-strength steel sheet containing 2.0 wt% or less, Cr in the steel is selectively oxidized by heating the steel sheet surface in the annealing process and diffused to the steel sheet surface, so these oxides are concentrated and the steel sheet surface To form a film. Further, this oxide layer is sufficiently will not be removed by pickling, the steel sheet
Electroplating, chemical conversion treatment, and chromate treatment are markedly inhibited, and " non-plating", "repelling", and "uneven amount of adhesion" occur. However, in the present invention, the crystal grain boundaries of the surface layer of the high-strength steel sheet, or within the grains, or within the crystal grain boundaries and grains,
When oxides are generated, surface enrichment of Si, Mn, P, Cr, etc. is suppressed, and these oxides do not form on the surface of the steel sheet, so these "non-plating", "repelling", and "uneven amount of adhesion" Does not happen. Therefore, 0.1 w of Cr in steel
The present invention is also effective for a high-strength cold-rolled steel sheet containing t% or more and 2.0 wt% or less.
【００２４】Ｐは、深絞り性の劣化が少なく鋼板を硬化
できること、Ｂは、鋼の二次加工脆性に絶大な効果を有
することから、高強度鋼板には必須の元素である。これ
らは、焼鈍過程において鋼板表面の加熱によって選択的
に酸化され、鋼板表層に拡散されるが、溶融亜鉛との濡
れ性を著しく阻害することはない。また、焼鈍後の脱脂
酸洗が充分でなく表層に残存したとしても「不めっき」
や「はじき」、「化成処理むら」などの原因にもなりに
くい。しかし、Ｐについては多量に含有すると、合金化
遅延を引き起こす恐れがあることから、０．１０ｗｔ％
以下とするが、Ｂについては特に含有量の限定はしな
い。P is an essential element for high-strength steel sheets because P has a large degree of deterioration in deep drawability and can harden steel sheets and B has a great effect on the secondary work embrittlement of steel. These are selectively oxidized by heating the surface of the steel sheet in the annealing process and diffused into the surface layer of the steel sheet, but do not significantly impair the wettability with molten zinc. In addition, even if degreasing and pickling after annealing is not sufficient and remains on the surface layer, "non-plating"
It is also unlikely to cause "repellent" or "uneven chemical conversion treatment". However, if P is contained in a large amount, alloying delay may occur, so 0.10 wt%
The content is as follows, but the content of B is not particularly limited.
【００２５】加えて、Ｍｏの添加は、鋼板の機械的特性
を向上させる効果がある。そのため、本発明ではその含
有量を０．５ｗｔ％以下とする。一方、酸化物層の厚み
を０．１以上、１００μｍ以下に限定したのは、０．１
μｍ以下であると、本発明に係る酸化物の生成量そのも
のが少ないため、表面濃化を抑制することができなくな
るからであり、１００μｍ以上であると、酸化物は脆の
で、鋼板自身の機械的特性が低下する恐れがあるからで
ある。In addition, the addition of Mo has the effect of improving the mechanical properties of the steel sheet. Therefore, in the present invention, the content is 0.5 wt% or less. On the other hand, the reason why the thickness of the oxide layer is limited to 0.1 or more and 100 μm or less is 0.1
This is because if the thickness is less than or equal to μm, the amount of oxide itself according to the present invention is too small to suppress the surface thickening, and if the thickness is greater than or equal to 100 μm, the oxide is brittle, and the machine of the steel sheet itself is poor. This is because there is a possibility that the physical characteristics may deteriorate.
【００２６】[0026]
【実施例】以下に、実施例に基づき本発明の内容を補足
する。表２に示す組成の高強度鋼板を熱間圧延後、酸洗
し冷間圧延を行った。その後、前記した各種表面処理を
施し、表３及び４に挙げたような表面処理鋼板を製造し
た。その条件は、１２００から１２５０℃でスラブ加熱
を実施してから熱間圧延を行った後、８６０〜９１０℃
にて仕上圧延し、巻取温度４５０〜７４０℃でコイル状
に巻き取りを行った。ついで、該熱延鋼板の黒皮を酸洗
で除去し、その後、冷間圧延、還元焼鈍、各種表面処理
を施した。還元焼鈍は、表２の鋼種でＮｏ．１が８５０
℃、Ｎｏ．２が８６０℃で行った。また、表３及び４中
で「厚み」とは、鋼板表層から酸化物が分布する範囲の
厚みを表す。 EXAMPLES The contents of the present invention will be supplemented below with reference to examples. The high-strength steel sheets having the compositions shown in Table 2 were hot-rolled, then pickled and cold-rolled. Then, the above-mentioned various surface treatments were performed to manufacture surface-treated steel sheets as listed in Tables 3 and 4. The condition is 860 to 910 ° C. after performing slab heating at 1200 to 1250 ° C. and then hot rolling.
Then, it was finish-rolled and wound into a coil at a winding temperature of 450 to 740 ° C. Next, the black skin of the hot rolled steel sheet was removed by pickling, and then cold rolling, reduction annealing and various surface treatments were performed. No. No. 1 is 850
° C , No. 2 was performed at 860 ° C. Moreover, in Tables 3 and 4, "thickness" represents the thickness of the range in which the oxide is distributed from the steel plate surface layer .
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】[0029]
【表４】 [Table 4]
【００３０】表面処理方法としては、電気めっきや化成
処理性など各種表面処理方法を施した鋼板の外観性につ
いては、目視で観察した上で良好か否か、「不めっき」
発生があるか否か、「付着量むら」があるか等を判断し
た。なお、鋼板表層直下の酸化物の有無観察は、断面研
磨後１％ナイタール液によりエッチングして行った。[0030] The surface treatment method, the appearance of the steel sheet subjected to various surface treatment method such as electroplating or chemical convertibility, whether good in terms of the visually observed, "non-coating"
It was judged whether or not there was any occurrence, and whether there was "uneven amount of adhesion" . Na us, the presence observation of the oxide immediately below the steel sheet surface layer was performed etched by 1% nital solution after cross polishing.
【００３１】上記のようにして製造した各種表面処理の
結果を前記表３、表４及び表５に示す。本発明の請求範
囲外の場合（比較例）、「不めっき」や「付着量む
ら」、また酸化物層が１５０μｍと厚い場合は鋼板自身
の機械的特性が劣化するなど、様々な不具合が発生し
た。しかし、本発明の請求範囲内の場合（実施例）、
「不めっき」、「付着量むら」はおろか、鋼板自身の機
械的特性の劣化などいかなる不具合も生じなかった。The results of various surface treatments produced as described above are shown in Tables 3, 4, and 5 above. Various defects such as "non-plating" and "uneven amount of adhesion" when the outside of the claims of the present invention (comparative example) and deterioration of mechanical properties of the steel sheet itself when the oxide layer is as thick as 150 μm occur. did. However, within the scope of the claims of the present invention (Example),
Not to mention "non-plating" and "uneven amount of adhesion", there were no problems such as deterioration of mechanical properties of the steel sheet itself.
【００３２】[0032]
【表５】 [Table 5]
【００３３】[0033]
【発明の効果】以上述べたように、本発明に係る鋼板表
層の結晶粒界、あるいは結晶粒内、あるいは結晶粒界及
び粒内に酸化物が生成せしめられている高強度冷延鋼板
は、Ｓｉ、Ｍｎ、Ｃｒなどを含有していても、普通鋼と
同様に効率的に従来困難であった各種表面処理を施すこ
とが可能であり、高機能表面処理鋼板の製造に対し極め
て効果的である。As described above, the high-strength cold-rolled steel sheet according to the present invention has a crystal grain boundary of the steel sheet surface layer, or within the crystal grain, or an oxide is formed at the crystal grain boundary and within the grain. Even if it contains Si, Mn, Cr, etc., it is possible to perform various surface treatments that were difficult in the past as efficiently as ordinary steel, and it is extremely effective for the production of highly functional surface-treated steel sheets. is there.
【図１】熱延鋼板表層の結晶粒界にある酸化物層を示す
図である。FIG. 1 is a diagram showing an oxide layer at a crystal grain boundary of a surface layer of a hot rolled steel sheet.
【図２】上記酸化物層のＥＰＭＡによる断面分析結果を
示す図である。FIG. 2 is a diagram showing a sectional analysis result of the oxide layer by EPMA.
【図３】本発明に係る高強度冷延鋼板の電子顕微鏡によ
る断面を示す図である。FIG. 3 is a view showing a cross section of a high-strength cold-rolled steel sheet according to the present invention, taken by an electron microscope.
【図４】グロー放電による鋼板断面の深さ方向分析結果
を示す図である。FIG. 4 is a diagram showing a result of a depth direction analysis of a steel plate cross section by glow discharge.
１ 粒界 ２ 粒内 ３ 黒皮 ４ 鋼板表面 ５ 酸化物層 1 grain boundary Within 2 grains 3 black skin 4 Steel plate surface 5 Oxide layer
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−276060（ＪＰ，Ａ) 特開 平８−291367（ＪＰ，Ａ) 特開 平５−125485（ＪＰ，Ａ) 特開 平７−118796（ＪＰ，Ａ) 特許2978096（ＪＰ，Ｂ２) 特許3126911（ＪＰ，Ｂ２) 特許2972124（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 38/00 - 38/60 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-276060 (JP, A) JP-A-8-291367 (JP, A) JP-A-5-125485 (JP, A) JP-A-7- 118796 (JP, A) Patent 2978096 (JP, B2) Patent 3126911 (JP, B2) Patent 2972124 (JP, B2) (58) Fields investigated (Int.Cl. 7 , DB name) C22C 38/00-38 / 60
Claims (2)
はクロメート処理に供される冷延鋼板であって、 Ｓｉを０．１ｗｔ％以上３．０ｗｔ％以下含有する高強
度冷延鋼板の、鋼板表層から０．１〜１００μｍの深さ
までの結晶粒界及び／又は結晶粒内に、電気めっき性、
化成処理性及びクロメート処理性の改良に有効な酸化
物、ＳｉＯ2，ＭｎＯ，ＦｅＳｉＯ3，Ｆｅ2ＳｉＯ4，Ｍ
ｎＳｉＯ3、Ｍｎ2ＳｉＯ4及びＰ2Ｏ5から選ばれた１種
以上を形成させてなることを特徴とする高強度冷延鋼
板。1. Electroplating or chemical conversion treatment, or
Is a cold-rolled steel sheet to be subjected to chromate treatment, and is a grain boundary of a high-strength cold-rolled steel sheet containing Si in an amount of 0.1 wt% to 3.0 wt% inclusive, from the steel plate surface layer to a depth of 0.1 to 100 μm. and / or in the crystal grains, electroplating properties,
Kasei process and effectiveness oxide to improved chromate treatment resistance, SiO 2, MnO, FeSiO 3 , Fe 2 SiO 4, M
A high-strength cold-rolled steel sheet, which is formed by forming at least one selected from nSiO 3 , Mn 2 SiO 4, and P 2 O 5 .
はクロメート処理に供される冷延鋼板であって、 鋼板の組成元素として、 Ｃ：０．０３〜０．１０ｗｔ％ Ｓｉ：０．００１〜０．１０ｗｔ％未満 Ｍｎ：０．５〜２．０ｗｔ％ Ｐ：０．０１〜０．１０ｗｔ％ Ｍｏ：０．５０ｗｔ％以下 を含有する高強度冷延鋼板の、鋼板表層から０．１〜１
００μｍの深さまでの結晶粒界及び／又は結晶粒内に、
電気めっき性、化成処理性及びクロメート処理性の改良
に有効な酸化物、ＳｉＯ2，ＭｎＯ，ＦｅＳｉＯ3，Ｆｅ
2ＳｉＯ4，ＭｎＳｉＯ3、Ｍｎ2ＳｉＯ4及びＰ2Ｏ5から
選ばれた１種以上を形成させてなることを特徴とする高
強度冷延鋼板。2. Electroplating or chemical conversion treatment, or
Is a cold-rolled steel sheet subjected to chromate treatment, and as a composition element of the steel sheet, C: 0.03 to 0.10 wt% Si: 0.001 to less than 0.10 wt% Mn: 0.5 to 2.0 wt % P: 0.01-0.10 wt% Mo: 0.50 wt% 0.1-1 from the steel plate surface layer of the high-strength cold-rolled steel plate
Within a grain boundary and / or grain to a depth of 00 μm ,
Electroplating resistance, reduction conversion treatment and effectiveness oxide to improve the chromate treatment of, SiO 2, MnO, FeSiO 3 , Fe
A high-strength cold-rolled steel sheet formed by forming at least one selected from 2 SiO 4 , MnSiO 3 , Mn 2 SiO 4, and P 2 O 5 .
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011078412A1 (en) | 2009-12-25 | 2011-06-30 | Ｊｆｅスチール株式会社 | High-strength cold rolled steel sheet and method for producing same |
| WO2011122694A1 (en) | 2010-03-29 | 2011-10-06 | Ｊｆｅスチール株式会社 | METHOD FOR PRODUCING HIGH-Si COLD ROLLED STEEL SHEET HAVING EXCELLENT CHEMICAL CONVERSION TREATABILITY |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018193614A (en) * | 2013-07-12 | 2018-12-06 | 株式会社神戸製鋼所 | High strength plating steel sheet excellent in plating property, processability and delayed fracture resistance, and manufacturing method therefor |
| JP2015034334A (en) * | 2013-07-12 | 2015-02-19 | 株式会社神戸製鋼所 | High-strength plated steel sheet excellent in platability, processability and delayed fracture resistance characteristics and production method thereof |
| KR20230126728A (en) * | 2021-02-02 | 2023-08-30 | 닛폰세이테츠 가부시키가이샤 | sheet steel |
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1996
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011078412A1 (en) | 2009-12-25 | 2011-06-30 | Ｊｆｅスチール株式会社 | High-strength cold rolled steel sheet and method for producing same |
| WO2011122694A1 (en) | 2010-03-29 | 2011-10-06 | Ｊｆｅスチール株式会社 | METHOD FOR PRODUCING HIGH-Si COLD ROLLED STEEL SHEET HAVING EXCELLENT CHEMICAL CONVERSION TREATABILITY |
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| Publication number | Publication date |
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| JPH09310148A (en) | 1997-12-02 |
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