JPH04276060A - Cold rolled steel sheet and its manufacture - Google Patents
Cold rolled steel sheet and its manufactureInfo
- Publication number
- JPH04276060A JPH04276060A JP5783691A JP5783691A JPH04276060A JP H04276060 A JPH04276060 A JP H04276060A JP 5783691 A JP5783691 A JP 5783691A JP 5783691 A JP5783691 A JP 5783691A JP H04276060 A JPH04276060 A JP H04276060A
- Authority
- JP
- Japan
- Prior art keywords
- rolled steel
- steel sheet
- chemical conversion
- cold
- cold rolled
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010960 cold rolled steel Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 49
- 238000000137 annealing Methods 0.000 abstract description 22
- 229910018643 Mn—Si Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 50
- 239000000463 material Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010953 base metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、化成処理性の良好な
冷延鋼板並びにその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold-rolled steel sheet with good chemical conversion treatment properties and a method for producing the same.
【０００２】0002
【従来技術とその課題】従来から冷延鋼板の化成処理性
改善に係わる様々な研究が行われていて、例えば低合金
冷延鋼板に関し「鋼板表層部にＰ（リン）を濃化させる
処理を施す方法（特公昭５６−２５２５３号）」や「鋼
板の表面にＭｎ，Ｃｒを含有する酸化皮膜を形成させる
方法（特公昭５６−９２７１号）」等、これまでにも化
成処理性向上のための数多くの提案がなされてきた。[Prior art and its problems] Various studies have been conducted to improve the chemical conversion properties of cold-rolled steel sheets. There have been several methods for improving chemical conversion properties, such as "method of forming an oxide film containing Mn and Cr on the surface of a steel sheet (Japanese Patent Publication No. 56-9271)". Many proposals have been made.
【０００３】しかしながら、Ｍｎ及びＳｉを含有する高
張力冷延鋼板等では未だに良好な化成処理性を示す製品
を安定して製造することは難しく、化成処理性に優れた
低合金高張力冷延鋼板等の安定製造は長年の大きな課題
となっていた。なぜなら、一般的な“Ｍｎ，Ｓｉをそれ
ぞれ ０．１〜３．０ ％，０．０１〜３．０ ％（以
降、 成分割合を表す％は重量％とする）の割合で含有
する高張力冷延鋼板”では成分組成の微妙な差異によっ
て化成処理性に変化が生じがちであり、また同一成分組
成の場合でも“バッチ焼鈍”， ”連続焼鈍”と言った
焼鈍法の相違により化成処理性が異なる現象が見られる
など、化成処理性の安定化が極めて困難だったからであ
る。However, it is still difficult to stably produce products that exhibit good chemical conversion treatment properties with high-strength cold-rolled steel sheets containing Mn and Si, and low-alloy high-strength cold-rolled steel sheets with excellent chemical conversion treatment properties are still difficult to manufacture. Stable production of such products has been a major challenge for many years. This is because common high-tension cooling materials containing Mn and Si in proportions of 0.1 to 3.0% and 0.01 to 3.0%, respectively (hereinafter, % representing component proportions are expressed as weight %) Subtle differences in chemical composition of "rolled steel sheets" tend to cause changes in chemical conversion treatability, and even in the case of the same composition, chemical conversion treatability may vary due to differences in annealing methods such as "batch annealing" and "continuous annealing." This is because different phenomena were observed, making it extremely difficult to stabilize chemical conversion treatment properties.
【０００４】このようなことから、本発明が目的とした
のは、需要が多いにもかかわらず上記化成処理性に係わ
る問題が大きい“Ｍｎ，Ｓｉをそれぞれ ０．１〜３．
０ ％，０．０１〜３．０ ％含有する冷延鋼板”に関
し、鋼板の成分組成や履歴に影響されることなく良好な
化成処理性を安定して付与する手段を確立することであ
った。[0004] For this reason, the purpose of the present invention is to reduce the amount of Mn and Si, each of which is in the range of 0.1 to 3.
The objective was to establish a means to stably impart good chemical conversion treatability to cold-rolled steel sheets containing 0.0%, 0.01 to 3.0%, without being affected by the composition or history of the steel sheet. .
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記目的
を達成すべく様々な観点から詳細な検討を行ったが、そ
の過程でまず「Ｍｎ，Ｓｉをそれぞれ０．１〜 ３．０
％，０．０１〜 ３．０％含有する冷延鋼板では、 母
材Ｓｉ含有量が多くなると化成処理性が劣化し、 母材
Ｍｎ量が多くなると化成処理性は良好になる傾向がある
点」に着目することとなり、Ｍｎ，Ｓｉ含有量調整によ
って化成処理性の改善を図ることも考えた。しかし、実
際に製造される高張力冷延鋼板では、所定の性質を保持
させるため種別毎に母材のＭｎ及びＳｉ含有量は特定値
に規定されており、化成処理性改善のためにのみ母材成
分値を変更できるものでないことは言うまでもなかった
。[Means for Solving the Problems] In order to achieve the above object, the present inventors conducted detailed studies from various viewpoints, and in the process, they first determined that Mn and Si were each 0.1 to 3.0.
%, 0.01 to 3.0%, the chemical conversion treatability tends to deteriorate as the base metal Si content increases, and the chemical conversion treatability tends to improve as the base metal Mn content increases. '' and considered improving chemical conversion treatment properties by adjusting the Mn and Si contents. However, in the high-strength cold-rolled steel sheets that are actually manufactured, the Mn and Si contents of the base metal are specified to specific values for each type in order to maintain predetermined properties, and the Mn and Si contents of the base metal are specified to specific values for each type. Needless to say, it is not possible to change the material component values.
【０００６】このため、“Ｍｎ，Ｓｉを含む冷延鋼板の
化成処理性”に関する基礎的な研究を更に続けた本発明
者等は、新たに、「通常の“焼鈍された冷延鋼板”では
ＭｎやＳｉが選択酸化して濃縮した表層の存在が認めら
れるが、 その化成処理性は母材の成分組成と言うより
も前記表層中のＭｎ酸化物とＳｉ酸化物の濃度比に依存
して決まる」ことを見付け出すに至った。[0006] For this reason, the present inventors, who continued basic research on ``chemical conversion treatability of cold-rolled steel sheets containing Mn and Si'', newly discovered that ``ordinary ``annealed cold-rolled steel sheets'' The presence of a surface layer in which Mn and Si are selectively oxidized and concentrated is observed, but the chemical conversion treatment properties depend on the concentration ratio of Mn oxide and Si oxide in the surface layer rather than the component composition of the base material. I came to find out that it is decided.
【０００７】そこで、表層のＭｎ酸化物とＳｉ酸化物の
濃度比を幅広く変化させるべく、Ｍｎ，Ｓｉ量の異なっ
た冷延鋼板に雰囲気や温度等の条件を種々変化させた焼
鈍を施し、得られた鋼板表層の状態と化成処理性との関
連について更に検討を重ねた結果、次のような知見が得
られたのである。[0007] Therefore, in order to vary the concentration ratio of Mn oxide and Si oxide in the surface layer over a wide range, cold rolled steel sheets with different amounts of Mn and Si were annealed under various conditions such as atmosphere and temperature. As a result of further investigation into the relationship between the condition of the steel plate surface layer and chemical conversion treatability, the following knowledge was obtained.
【０００８】（ａ） Ｍｎ，Ｓｉを含む冷延鋼板の化
成処理性は、冷延鋼板表層に形成されたＭｎ，Ｓｉ酸化
物の濃縮層におけるこれら酸化物の濃度比に依存して決
まるものであるが、特に該表層のＳｉとＭｎの原子比〔
Ｓｉ／Ｍｎ〕が１以下であれば化成処理性は良好となり
、１を超えると劣化する。(a) The chemical conversion treatment property of a cold rolled steel sheet containing Mn and Si is determined depending on the concentration ratio of these oxides in the concentrated layer of Mn and Si oxides formed on the surface layer of the cold rolled steel sheet. However, the atomic ratio of Si and Mn in the surface layer [
When Si/Mn] is 1 or less, chemical conversion treatment properties are good, and when it exceeds 1, it deteriorates.
【０００９】（ｂ） また、前記表層におけるＳｉと
Ｍｎの原子比〔Ｓｉ／Ｍｎ〕は、経験的に次の式から算
出できる。
即ち、この （１）式は「冷延鋼板表層におけるＳ
ｉとＭｎの原子比〔Ｓｉ／Ｍｎ〕は母材におけるＳｉと
Ｍｎの成分比（Ｓｉ／Ｍｎ），焼鈍雰囲気中の水素と水
分の比，焼鈍温度の関係で求めることができる」ことを
意味している訳である。(b) Furthermore, the atomic ratio of Si to Mn [Si/Mn] in the surface layer can be calculated empirically from the following formula. In other words, this equation (1) is ``S in the surface layer of cold rolled steel sheet''
The atomic ratio of i and Mn [Si/Mn] can be determined from the relationship between the component ratio of Si and Mn in the base material (Si/Mn), the ratio of hydrogen to moisture in the annealing atmosphere, and the annealing temperature. That is why we are doing so.
【００１０】（ｃ） 前記の各知見事項からすれば、
良好な化成処理性が確保されるためには上記 （１）式
の両辺が「１以下」でなければならないから、「１以下
」に条件設定して （１）式の右辺を誘導するとが導か
れる。そして、還元性雰囲気中にて、特定の温度で、か
つ上記 （２）式を満たす条件で“Ｍｎ，Ｓｉを含む冷
延鋼板”の焼鈍を実施すると、実際、冷延鋼板表層にお
けるＳｉとＭｎの原子比〔Ｓｉ／Ｍｎ〕が安定して１以
下となり、非常に良好な化成処理性が確保される。(c) Based on the above findings,
In order to ensure good chemical conversion properties, both sides of equation (1) above must be ``1 or less,'' so setting the condition to ``1 or less'' to derive the right side of equation (1) leads to It will be destroyed. When a "cold rolled steel sheet containing Mn and Si" is annealed in a reducing atmosphere at a specific temperature and under conditions that satisfy equation (2) above, Si and Mn in the surface layer of the cold rolled steel sheet are actually annealed. The atomic ratio [Si/Mn] is stably 1 or less, and very good chemical conversion treatment properties are ensured.
【００１１】本発明は、上記知見事項等を基に完成され
たものであり、「合金成分としてＭｎ：０．１ 〜３．
０ ％，Ｓｉ：０．０１〜３．０ ％を含む冷延鋼板を
、 表面にＭｎ，Ｓｉの酸化物を含有する層が形成され
、 かつ該表層中に酸化物として存在するＳｉとＭｎと
の原子比〔Ｓｉ／Ｍｎ〕が１以下に調整されて成る構成
とすることにより、 良好な化成処理性を確保した点」
に大きな特徴を有し、更には「合金成分としてＭｎ：０
．１ 〜３．０ ％，Ｓｉ：０．０１〜３．０ ％を含
む冷延鋼板を、 ５５０〜９００℃の焼鈍温度（Ｔ℃）
にて、 雰囲気の水素と水分の分圧比（Ｐ）が式
を満たす還元性雰囲気中で焼鈍することにより、 良好
な化成処理性を示すＭｎ，Ｓｉ含有冷延鋼板を安定して
製造し得るようにした点」をも特徴としている。The present invention has been completed based on the above-mentioned findings and the like.
0%, Si: 0.01-3.0%, a layer containing oxides of Mn and Si is formed on the surface, and Si and Mn present as oxides in the surface layer are formed. By adjusting the atomic ratio [Si/Mn] to 1 or less, we have ensured good chemical conversion treatment properties.
It has a major feature of ``Mn:0 as an alloy component.
．． 1 to 3.0%, Si: 0.01 to 3.0%, annealing temperature of 550 to 900°C (T°C)
By annealing in a reducing atmosphere where the partial pressure ratio (P) of hydrogen and moisture in the atmosphere satisfies the formula, it is possible to stably produce Mn and Si-containing cold-rolled steel sheets that exhibit good chemical conversion properties. It is also characterized by the fact that
【００１２】なお、本発明において冷延鋼板のＭｎ含有
量，Ｓｉ含有量を前記の如き範囲に限定したのは、該Ｍ
ｎ，Ｓｉ量範囲の冷延鋼板が化成処理性の点で特に問題
となっている上、その需要も非常に多いことによる。[0012] In the present invention, the Mn content and Si content of the cold rolled steel sheet are limited to the above ranges.
This is because cold-rolled steel sheets in the n, Si content range are particularly problematic in terms of chemical conversion treatability, and are also in great demand.
【００１３】続いて、本発明をその作用と共により詳細
に説明する。Next, the present invention will be explained in more detail along with its operation.
【作用】上述したように、“Ｍｎ，Ｓｉをそれぞれ ０
．１〜３．０ ％，０．０１〜３．０ ％含有する冷延
鋼板”において化成処理性を良好とするためには、表層
に酸化物として存在するＳｉとＭｎの原子比を１以下に
すれば良く、そのためには焼鈍雰囲気が前記 （１）式
を満足するようにコントロ−ルすることが肝要である。[Operation] As mentioned above, “Mn and Si are each 0
．． In order to improve the chemical conversion properties of cold-rolled steel sheets containing 1 to 3.0% and 0.01 to 3.0%, the atomic ratio of Si and Mn, which are present as oxides in the surface layer, should be 1 or less. For this purpose, it is important to control the annealing atmosphere so that it satisfies the above formula (1).
【００１４】Ｍｎ，Ｓｉ含有冷延鋼板の化成処理性が表
層の酸化物組成比によって決まる理由は次のように推定
できる。つまり、鋼板面での化成処理反応としては「Ｆ
ｅ→Ｆｅ２＋＋２ｅ− 」なるアノ−ド反応と「２Ｈ＋
＋２ｅ− →Ｈ２ ↑」なるカソ−ド反応が基本とな
っており、カソ−ド部での水素イオン濃度の低下が化成
結晶の析出をもたらすと言われている。ただ、本発明が
対象母材とする“Ｍｎ，Ｓｉを比較的多く含有した冷延
鋼板”の場合には、焼鈍後の表層はＭｎ，Ｓｉの酸化物
が主となっていてＦｅが少量なため、化成処理反応は次
に示す状況となる。The reason why the chemical conversion treatability of cold-rolled steel sheets containing Mn and Si is determined by the oxide composition ratio of the surface layer can be estimated as follows. In other words, the chemical conversion reaction on the steel sheet surface is "F
e→Fe2++2e-” and the anodic reaction “2H+
The basic cathode reaction is ``+2e- → H2 ↑'', and it is said that a decrease in the hydrogen ion concentration at the cathode causes the precipitation of chemical crystals. However, in the case of "cold-rolled steel sheets containing relatively large amounts of Mn and Si", which is the target base material of the present invention, the surface layer after annealing consists mainly of Mn and Si oxides, with a small amount of Fe. Therefore, the chemical conversion reaction results in the following situation.
【００１５】即ち、冷延鋼板表層のＭｎ酸化物は化成処
理液中へ容易に溶解し、この反応は次の （３）式で示
すように、水素イオン濃度を低下させて化成処理析出反
応を促進する。
ＭｎＯ＋２Ｈ＋ → Ｍｎ２＋＋Ｈ２
Ｏ ……（３
）しかしながら、Ｓｉ酸化物（ＳｉＯ２ ）は化成処理
液程度のＰＨでは溶解しない。そのため、冷延鋼板表層
においてＳｉ酸化物がＭｎ酸化物より多いと化成結晶の
析出が起こり難いが、Ｍｎ酸化物がＳｉ酸化物より多い
場合には化成結晶の析出が容易になり、良好な化成処理
性を示すと考えられる。That is, the Mn oxide on the surface layer of the cold-rolled steel sheet easily dissolves in the chemical conversion treatment solution, and this reaction reduces the hydrogen ion concentration and promotes the chemical conversion precipitation reaction, as shown in the following equation (3). Facilitate. MnO+2H+ → Mn2++H2
O...(3
) However, Si oxide (SiO2) does not dissolve at a pH comparable to that of the chemical conversion treatment solution. Therefore, if the Si oxide is more than the Mn oxide in the surface layer of a cold rolled steel sheet, precipitation of chemical crystals is difficult to occur, but if the Mn oxide is more than the Si oxide, the precipitation of chemical crystals becomes easy, and good chemical conversion is achieved. This is considered to indicate processability.
【００１６】ところで、化成処理性が良好な冷延鋼板を
安定に製造するには、水素と水分の分圧比（Ｐ＝ＰＨ２
／ＰＨ２Ｏ ） が前記 （１）式から導かれる （２
）式の条件を満たす還元性雰囲気中にて５５０〜９００
℃で焼鈍する必要があることは前述した通りである。こ
こで、冷延鋼板表層中に酸化物として存在するＳｉとＭ
ｎとの原子比〔Ｓｉ／Ｍｎ〕が前記 （１）式で表され
る要因は、母材中のＭｎ，Ｓｉが共に還元雰囲気中焼鈍
により選択酸化されるのが５５０℃（８３３Ｋ）以上で
あることに加え、雰囲気における〔Ｈ２ ／Ｈ２ Ｏ〕
の比が２５前後でＭｎ，Ｓｉの選択酸化速度が変わるた
めであると考えられる。なお、 （１）式中の定数「
１．２ 」 は実験値と理論値を合わせるための補正項
であり、酸化速度のパラメ−タも入っていると推測され
るものである。そして、還元焼鈍雰囲気における〔Ｈ２
／Ｈ２ Ｏ〕の比が大きく、また焼鈍温度が高いほど
冷延鋼板表層でＳｉがＭｎより多くなる理由は、酸化ポ
テンシャルが小さいほどＭｎより酸化されやすいＳｉの
酸化が顕著になるためと考えられる。By the way, in order to stably produce cold-rolled steel sheets with good chemical conversion treatability, the partial pressure ratio of hydrogen and water (P=PH2
/PH2O) is derived from equation (1) above (2
) 550 to 900 in a reducing atmosphere that satisfies the conditions of the formula.
As mentioned above, it is necessary to anneal at ℃. Here, Si and M present as oxides in the surface layer of the cold rolled steel sheet
The reason why the atomic ratio [Si/Mn] with n is expressed by the above formula (1) is that both Mn and Si in the base material are selectively oxidized by annealing in a reducing atmosphere at 550°C (833K) or higher. In addition to that, [H2 /H2 O] in the atmosphere
It is thought that this is because the selective oxidation rate of Mn and Si changes when the ratio is around 25. Note that the constant in formula (1) “
1.2'' is a correction term for matching the experimental value with the theoretical value, and is presumed to include the oxidation rate parameter. Then, [H2
/H2O] ratio is larger and the annealing temperature is higher, the reason why Si becomes more abundant than Mn in the surface layer of the cold rolled steel sheet is thought to be that the smaller the oxidation potential, the more pronounced the oxidation of Si, which is easier to oxidize than Mn. .
【００１７】また、焼鈍温度を５５０〜９００℃と限定
した理由は、焼鈍温度が５５０℃未満であると上述した
ように母材中Ｍｎ，Ｓｉの選択酸化が起きないため、冷
延鋼板表層中に酸化物として存在するＳｉとＭｎの原子
比の調整を行うことができず、一方、焼鈍温度が９００
℃を超えると相変態（α→γ）を起こし、通常の冷延鋼
板の焼鈍では適用されないからである。[0017] Furthermore, the reason why the annealing temperature is limited to 550 to 900°C is that when the annealing temperature is less than 550°C, selective oxidation of Mn and Si in the base material does not occur. The atomic ratio of Si and Mn, which exist as oxides, cannot be adjusted; on the other hand, when the annealing temperature is 900
This is because phase transformation (α→γ) occurs when the temperature exceeds °C, and this is not applicable to normal annealing of cold-rolled steel sheets.
【００１８】なお、ＳｉとＭｎの原子比〔Ｓｉ／Ｍｎ〕
を１以下に調整する必要のある冷延鋼板表層厚さは数十
Å程度で良い。なぜなら、化成処理の反応層厚さは数百
Åに及ぶものの、反応初期段階に起きる“化成処理性を
決定する結晶核生成反応”は全体反応が数十Å程度の深
さに達するまでの間に生じてしまうからである。[0018] The atomic ratio of Si and Mn [Si/Mn]
The surface layer thickness of the cold-rolled steel sheet, which needs to be adjusted to 1 or less, may be about several tens of angstroms. This is because, although the reaction layer thickness in chemical conversion treatment is several hundred Å thick, the “crystal nucleation reaction that determines chemical conversion treatment properties” that occurs in the initial stage of the reaction takes place until the entire reaction reaches a depth of several tens of Å. This is because it will occur.
【００１９】続いて、本発明を実施例によって更に具体
的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
【実施例】実施例 １
まず、真空溶製に続く熱間圧延及び冷間圧延によって表
１に示される成分組成の冷延鋼板（板厚：１ｍｍ）とし
た。[Examples] Example 1 First, a cold rolled steel plate (thickness: 1 mm) having the composition shown in Table 1 was obtained by vacuum melting followed by hot rolling and cold rolling.
【００２０】[0020]
【００２１】下記に示す冷延鋼板を種々の条件で焼鈍し
、その表層のＳｉ／Ｍｎ原子比及び化成処理性を調査し
た。次に、前記各鋼板を表２に示す焼鈍条件で焼鈍して
（焼鈍時間は何れも３０分とした）製品冷延鋼板を得た
後、それらの表層組成をＸＰＳ（Ｘ線励起光電子分光法
）で分析し表層中に酸化物として存在するＳｉとＭｎと
の原子比〔Ｓｉ／Ｍｎ〕を測定すると共に、化成処理性
の調査を実施した。化成処理性は、リン酸亜鉛処理液（
日本ペイント製の商品名ＳＤ２５００）に２分間浸漬し
て調査した。これらの結果を表２に併せて示す。The cold rolled steel sheets shown below were annealed under various conditions, and the Si/Mn atomic ratio and chemical conversion treatability of the surface layer were investigated. Next, each steel plate was annealed under the annealing conditions shown in Table 2 (the annealing time was 30 minutes) to obtain a product cold-rolled steel plate. ) to measure the atomic ratio of Si and Mn present as oxides in the surface layer [Si/Mn], and to investigate chemical conversion treatment properties. Chemical conversion treatment property is determined by zinc phosphate treatment solution (
The test was conducted by immersing the sample in Nippon Paint (trade name: SD2500) for 2 minutes. These results are also shown in Table 2.
【００２２】[0022]
【表２】[Table 2]
【００２３】なお、表２中の「表層〔Ｓｉ／Ｍｎ〕経験
式値」は前記（１）式を用いて算出した値であり、「化
成処理性」の評価結果については
○：リン酸亜鉛の結晶が微細でかつ緻密なもの，×：リ
ン酸亜鉛の結晶が粗大であるか、結晶の未析出部が存在
したもの，で表示した。[0023] The "surface layer [Si/Mn] empirical formula value" in Table 2 is a value calculated using the above formula (1), and the evaluation results for "chemical conversion treatment" are: ○: zinc phosphate; The results were shown as follows: The crystals of zinc phosphate were fine and dense; ×: The zinc phosphate crystals were coarse or there were unprecipitated portions of crystals.
【００２４】表２に示される結果からも明らかなように
、本発明の規定を満足する冷延鋼板は良好な化成処理性
を示すのに対して、表層〔Ｓｉ／Ｍｎ〕比の実測値が１
を超えるものでは化成処理性の劣化することが確認でき
る。また、前記 （１）式を用いて算出した「表層〔Ｓ
ｉ／Ｍｎ〕経験式」の値が実測値と非常に良く一致して
いることも分かる。As is clear from the results shown in Table 2, the cold-rolled steel sheet that satisfies the specifications of the present invention exhibits good chemical conversion treatment properties, whereas the actual value of the surface layer [Si/Mn] ratio is 1
It can be confirmed that the chemical conversion treatment property deteriorates when the amount exceeds 100%. In addition, the “surface layer [S
It can also be seen that the value of "i/Mn] empirical formula" agrees very well with the measured value.
【００２５】実施例 ２
表１に示した成分組成の冷延鋼板供試材Ｂ，Ｃ，Ｄ
，Ｅを準備し、これらを表３に示す種々条件で焼鈍して
表層のＳｉ／Ｍｎ原子比及び化成処理性を調査した。な
お、焼鈍雰囲気は水素を１０％含むＮ２ 雰囲気であっ
た。これらの調査結果を表３に併せて示す。Example 2 Cold-rolled steel sheet specimens B, C, and D having the composition shown in Table 1
, E were prepared and annealed under various conditions shown in Table 3, and the Si/Mn atomic ratio and chemical conversion treatability of the surface layer were investigated. Note that the annealing atmosphere was a N2 atmosphere containing 10% hydrogen. These survey results are also shown in Table 3.
【００２６】[0026]
【表３】[Table 3]
【００２７】表２に示される結果からも、本発明の規定
を満足する冷延鋼板は良好な化成処理性を示すことが明
らかである。[0027] From the results shown in Table 2, it is clear that the cold-rolled steel sheet satisfying the provisions of the present invention exhibits good chemical conversion treatability.
【００２８】ところで、図１は、経験式たる前記 （１
）式を“焼鈍温度”， ”焼鈍雰囲気（露点：Ｈ２ 割
合は１０％一定）”及び“表層〔Ｓｉ／Ｍｎ 〕／母材
（Ｓｉ／Ｍｎ） 比率（＝Ｒ）”との関係で表したグラ
フである。そして、図１中の破線で示したレベルは供試
材Ｂ，Ｃ，Ｄ，Ｅで表層〔Ｓｉ／Ｍｎ〕が１となる条件
を示している。従って、この線以下の領域に条件を決め
ると化成処理性の良好な鋼板が得られることとなる。By the way, FIG. 1 shows the empirical formula (1
) was expressed in relation to "annealing temperature", "annealing atmosphere (dew point: H2 ratio constant 10%)", and "surface layer [Si/Mn]/base material (Si/Mn) ratio (=R)". It is a graph. The levels indicated by broken lines in FIG. 1 indicate the conditions under which the surface layer [Si/Mn] is 1 in the test materials B, C, D, and E. Therefore, if conditions are set in the region below this line, a steel plate with good chemical conversion treatment property will be obtained.
【００２９】[0029]
【効果の総括】以上に説明した如く、この発明によれば
、Ｍｎ及びＳｉをそれぞれ ０．１〜３．０ ％，０．
０１〜３．０ ％含有する鋼板であって、しかも良好な
化成処理性を示す冷延鋼板を安定して提供することが可
能となるなど、産業上極めて有用な効果がもたらされる
。[Summary of Effects] As explained above, according to the present invention, Mn and Si are contained in amounts of 0.1 to 3.0% and 0.0%, respectively.
It is possible to stably provide a cold-rolled steel sheet containing 0.01 to 3.0% and exhibiting good chemical conversion treatment properties, resulting in extremely useful effects industrially.
【図１】良好な化成処理性が確保できる冷延鋼板の焼鈍
条件を示すグラフである。FIG. 1 is a graph showing annealing conditions for a cold-rolled steel sheet that can ensure good chemical conversion treatment properties.
Claims (2)
０ ％，Ｓｉ：０．０１〜３．０ ％（何れも重量％）
を含有すると共に、表面にＭｎ，Ｓｉの酸化物を含有す
る層が形成された冷延鋼板であって、前記表層中に酸化
物として存在するＳｉとＭｎとの原子比〔Ｓｉ／Ｍｎ〕
が１以下に調整されて成ることを特徴とする冷延鋼板。Claim 1: Mn as an alloy component: 0.1 to 3.
0%, Si: 0.01-3.0% (all percentages by weight)
and a layer containing oxides of Mn and Si is formed on the surface, the atomic ratio of Si and Mn existing as oxides in the surface layer [Si/Mn]
A cold-rolled steel sheet, characterized in that: is adjusted to 1 or less.
０ ％，Ｓｉ：０．０１〜３．０ ％（何れも重量％）
を含有する冷延鋼板を、５５０〜９００℃の焼鈍温度（
Ｔ℃）にて、雰囲気の水素と水分の分圧比（Ｐ＝ＰＨ２
／ＰＨ２Ｏ ） が下記式を満たす還元性雰囲気中で焼
鈍することを特徴とする冷延鋼板の製造方法。2. Mn as an alloy component: 0.1 to 3.
0%, Si: 0.01-3.0% (all percentages by weight)
A cold-rolled steel plate containing
The partial pressure ratio of hydrogen and moisture in the atmosphere (P=PH2
/PH2O) is annealed in a reducing atmosphere satisfying the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5783691A JPH04276060A (en) | 1991-02-28 | 1991-02-28 | Cold rolled steel sheet and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5783691A JPH04276060A (en) | 1991-02-28 | 1991-02-28 | Cold rolled steel sheet and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04276060A true JPH04276060A (en) | 1992-10-01 |
Family
ID=13067041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5783691A Pending JPH04276060A (en) | 1991-02-28 | 1991-02-28 | Cold rolled steel sheet and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04276060A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1548142A1 (en) * | 2003-12-25 | 2005-06-29 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold-rolled steel sheet excellent in coating film adhesion |
| WO2006109489A1 (en) | 2005-03-31 | 2006-10-19 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold-rolled steel sheet excellent in coating adhesion, workability and hydrogen embrittlement resistance, and steel component for automobile |
| JP2007092134A (en) * | 2005-09-29 | 2007-04-12 | Jfe Steel Kk | Cold-rolled steel sheet excellent in chemical conversion treatment, and manufacturing method therefor |
| JP2010047808A (en) * | 2008-08-22 | 2010-03-04 | Jfe Steel Corp | High-strength cold-rolled steel sheet and method for producing the same |
| KR20140106676A (en) | 2011-12-27 | 2014-09-03 | 제이에프이 스틸 가부시키가이샤 | Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating |
| WO2014132637A1 (en) | 2013-02-28 | 2014-09-04 | Ｊｆｅスチール株式会社 | Process for producing high-strength cold-rolled steel sheet |
| WO2020095682A1 (en) * | 2018-11-09 | 2020-05-14 | Ｊｆｅスチール株式会社 | Cold rolled steel sheet for zirconium-based chemical conversion treatment, method for producing same, zirconium-based chemical conversion-treated steel sheet, and method for producing same |
| CN111647733A (en) * | 2020-05-11 | 2020-09-11 | 首钢集团有限公司 | Method for improving phosphating performance of low-carbon aluminum killed steel automobile plate and automobile plate |
-
1991
- 1991-02-28 JP JP5783691A patent/JPH04276060A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1548142A1 (en) * | 2003-12-25 | 2005-06-29 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold-rolled steel sheet excellent in coating film adhesion |
| US8986468B2 (en) | 2005-03-31 | 2015-03-24 | Kobe Steel, Ltd. | High-strength cold-rolled steel sheet excellent in coating adhesion, workability and hydrogen embrittlement resistance, and steel component for automobile |
| WO2006109489A1 (en) | 2005-03-31 | 2006-10-19 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold-rolled steel sheet excellent in coating adhesion, workability and hydrogen embrittlement resistance, and steel component for automobile |
| EP1865085A1 (en) * | 2005-03-31 | 2007-12-12 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold-rolled steel sheet excellent in coating adhesion, workability and hydrogen embrittlement resistance, and steel component for automobile |
| EP1865085A4 (en) * | 2005-03-31 | 2010-07-28 | Kobe Steel Ltd | High-strength cold-rolled steel sheet excellent in coating adhesion, workability and hydrogen embrittlement resistance, and steel component for automobile |
| EP2671961A1 (en) | 2005-03-31 | 2013-12-11 | Kabushiki Kaisha Kobe Seiko Sho | High strength cold-rolled steel sheet and automobile components of steel having excellent properties in coating film adhesion, workability, and hydrogen embrittlement resistivity |
| EP2671960A1 (en) | 2005-03-31 | 2013-12-11 | Kabushiki Kaisha Kobe Seiko Sho | High strength cold-rolled steel sheet and automobile components of steel having excellent properties in coating film adhesion, workability, and hydrogen embrittlement resistivity |
| EP2679699A2 (en) | 2005-03-31 | 2014-01-01 | Kabushiki Kaisha Kobe Seiko Sho | High strength cold-rolled steel sheet and automobile components of steel having excellent properties in coating film adhesion, workability, and hydrogen embrittlement resistivity |
| JP2007092134A (en) * | 2005-09-29 | 2007-04-12 | Jfe Steel Kk | Cold-rolled steel sheet excellent in chemical conversion treatment, and manufacturing method therefor |
| JP2010047808A (en) * | 2008-08-22 | 2010-03-04 | Jfe Steel Corp | High-strength cold-rolled steel sheet and method for producing the same |
| KR20140106676A (en) | 2011-12-27 | 2014-09-03 | 제이에프이 스틸 가부시키가이샤 | Method for producing cold-rolled steel sheet having excellent chemical conversion properties and excellent corrosion resistance after coating |
| WO2014132637A1 (en) | 2013-02-28 | 2014-09-04 | Ｊｆｅスチール株式会社 | Process for producing high-strength cold-rolled steel sheet |
| WO2020095682A1 (en) * | 2018-11-09 | 2020-05-14 | Ｊｆｅスチール株式会社 | Cold rolled steel sheet for zirconium-based chemical conversion treatment, method for producing same, zirconium-based chemical conversion-treated steel sheet, and method for producing same |
| JPWO2020095682A1 (en) * | 2018-11-09 | 2021-02-15 | Ｊｆｅスチール株式会社 | Cold-rolled steel sheet for zirconium-based chemical conversion treatment and its manufacturing method, and zirconium-based chemical conversion-treated steel sheet and its manufacturing method |
| CN111647733A (en) * | 2020-05-11 | 2020-09-11 | 首钢集团有限公司 | Method for improving phosphating performance of low-carbon aluminum killed steel automobile plate and automobile plate |
| CN111647733B (en) * | 2020-05-11 | 2022-03-22 | 首钢集团有限公司 | Method for improving phosphating performance of low-carbon aluminum killed steel automobile plate and automobile plate |
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