TW201213550A - High strength steel sheet and method for preparing the same - Google Patents
High strength steel sheet and method for preparing the same Download PDFInfo
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201213550 六、發明說明: 【發明所屬之技術領域】 .本發明係關於即便在Si含有量多之情況,仍具有優異之 化成處理性及電著塗裝後之耐钱性的高強度鋼板及其製造 方法。 【先前技術】 近年來,從汽車之燃料費提高及提升汽車之衝突安全性的 觀點而言,係利用車體材料之高強度化而尋求薄壁化,車體 本身之輕量化且高強度化的需求日漸提高。因此,高強度鋼 板對汽車之應用正被提倡中。 一般而言,汽車用鋼板係經塗裝而使用,作為該塗裝之前 處理,係施行稱作磷酸鹽處理的化成處理。鋼板之化成處理 係用以確保塗裝後之耐姓性的重要處理之一。 為了提南鋼板之強度、延展性,Si之添加係為有效。然 而,於連續退火時’即便在Fe之氧化不會發生(將Fe氧化 物還原)的還原性N2+H2氣體環境中進行退火之情況,si仍 會氧化,而於鋼板最表層形成Si氧化物(Si〇2)。由於該si〇2 會阻礙化成處理中化成皮瞑的生成反應,故會形成化成皮膜 未生成之微小區威(以下亦稱為空孔),而降低化成處理性。 作為改善含高Si鋼板之化成處理性的 習知技術,專利文 獻1中揭示有使用電艘法於鋼板上形成20〜1500mg/m2之鐵 被覆層的方法。然而 ^方去需要另外增設電锻設備,而有 099133254 3 201213550 步驟增加且成本亦增高之問題。 又’專利文獻2中係規定Mn/Si比率、專利文獻3中則藉 由添加Ni而提升磷酸處理性。然而,其效果係依存於鋼板 中之Si含有量,對於Si含有量高的鋼板,需要更進一步的 改善。 此外,專利文獻4中揭示一種方法,其藉由將退火時之露 點定為-25〜(TC,在鋼板基板表面起深1μπι以内,形成由 含Si氧化物所構成之内部氧化層,俾使鋼板表面長度 中所佔之含Si氧化物的比例為80%以下。然而,專利文獻 1 所記載之方法的情況,係以控制露點的區域為爐内整體為 前提,因此露點之控制性困難,而難以進行穩定操作。又, 在不安定的露师歡基射進行退火m形成於鋼板 之内部氧化物的分佈狀態會觀察到偏差’會有在鋼板長度方 向或寬度方向發生化成處理性之W整體或-部分有空孔) 虞此外,在提升化成處理性之情況,因為化成處理皮膜 在有έ Si氧化物,故有電著塗裝後之耐钱性 佳的問題。 專利文獻5中,係記載在氧化性環境中使鋼板溫度到 、 〇◦,於鋼板表面形成氧化膜,之後再於還原怡 s兄中力…、至再結晶溫度並冷卻之方法。然而,該方法中, 因為氧化之方法’形成於鋼板表面之氧化皮膜的厚度發生差 異,會有無法充分進行氧化,或者氧化皮膜變得過厚,在之 099133254 201213550 性環境中,於退火中發錢化膜之前或剝離,而 生狀惡化之情況。其實施例中雖記載在大氣中進行氧 =技術,但具有大氣中之氧化生成厚的氧化物岐得其後. '之還原困難,或者需要高氫漠度之還原環境等問題。 此外,專利文獻6中記載—種方法,其係對以質量%計含 有&0.1%以上及/或Mnl._上之冷札鋼板,以鋼板溫度 / 〇CΜ上且鐵的氧化環境下,於鋼板表面形成氧化膜,其 後’於鐵的縣環境下將上述鋼板表面之氧化膜予以還原之 方法。具體而言,係於40(TC以上,使用空氣比〇 93以上且 I·10以下之直火爐將鋼板表面之Fe氧化後,在將Fe氧化物 還原之①儀氣體環境下退火,#此抑制會使化成處理性 劣化之Si〇2於最表面之氧化,並於最表面形成Fe之氧化層 的方法。專利文獻6中並未具體記載直火爐的加熱溫度,但 在含有較多Si(大約0.6%以上)之情況,較Fe更容易氧化之 &之氧化量變多,Fe之氧化會受到抑制,或者以之氧化本 身會變得過少。其結果,會有還原後之表面Fe還原層的形 -成不充分,或還原後之鋼板表面存在Si〇2而發生化成皮膜 的空孔之情況。 [先前技術文獻] [專利文獻] (專利文獻1)曰本專利特開平5-320952號公報 (專利文獻2)曰本專利特開2004-323969號公報 099133254 5 201213550 (專利文獻3)曰本專利特開平6-10096號公報 (專利文獻4)曰本專利特開2003-113441號公報 (專利文獻5)曰本專利特開昭55-145122號公報 (專利文獻6)曰本專利特開2〇〇6-45615號公報 【發明内容】 (發明所欲解決之問題) 本發明係有鑑於上述情況,目的在於提供即便在Si含有 里夕之情況’仍具有優異之化成處理性及電著塗裝後之耐名虫 性的高強度鋼板及其製造方法。 (解決問題之手段) 習知技術中,針對含有Si、Μη等易氧化性元素之鋼板, 係在改善化成處理性之目的下積極地使鋼板之内部氧化。然 而電著塗裝後之耐钱性亦同時會劣化。因此,本發明人等 以習知技術之概念中未被採用之嶄新方法,檢討解決問題之 方法。結果發現,藉由適當控制退火步驟之環境與溫度,可 抑制鋼板表層部之内部氧化物的形成,而可獲得優異之化成 處理性及更高之耐純。具體而言,係將退火爐内溫度: 750 C以上之溫度區域以環境中之露點:·4〇^以下之方式進 节控制並退火,進行化成處理。藉由使退火爐内溫度:750Ϊ ^上之溫度區域為環境中之露點:書c以下,使鋼板與環 兄之>界面的氧位能降低,可不形成内部氧化物地控制^、 n等之選擇性表面擴散、氧化(以下稱為表面漠化)。 099133254 201213550 文獻 1 (7th International Conference on Zinc and Zinc Alloy Coated Steel Sheet Galvatech 2007, Proceedings p404)中揭 示,若從Si、Μη之氧化反應的熱力學數據,將氧位能換算 為露點’則在800°C、N2-5%H2存在下,若Si不在未滿-80°C、 Μη不在未滿-60 C之露點’則無法防止氧化。因此,當對含 有Si、Μη之高強度鋼板進行退火之情況,向來認為即便提 高氫濃度’若不在至少未滿-80°C之露點,則無法防止表面 濃化。因此,習知技術中從未嘗試在進行_4〇〜-7〇°C之露點 的退火後進行化成處理。 圖1係文獻2(金屬物理化學p72〜73,平成8年5月20曰 fs_4亍’曰本金屬學會發行)所揭不’從Si、Μη之氧化反應的 熱力學數據如下述般算出Si、Mn之氧化還原平衡與露點的 關係,並顯示該關係之圖。201213550 6. OBJECT OF THE INVENTION: The present invention relates to a high-strength steel sheet having excellent chemical conversion treatability and durability after electrocoating even when Si content is large. Production method. [Prior Art] In recent years, from the viewpoint of improving the fuel cost of automobiles and improving the safety of conflicts between automobiles, the use of the strength of the vehicle body material has been sought to reduce the thickness of the vehicle body, and the weight of the vehicle body itself has been increased. The demand is increasing. Therefore, the application of high-strength steel sheets to automobiles is being promoted. In general, a steel sheet for automobiles is used for coating, and as a treatment before the coating, a chemical conversion treatment called phosphate treatment is performed. The formation of steel sheets is one of the important treatments to ensure the resistance to surnames after painting. In order to increase the strength and ductility of the steel plate, the addition of Si is effective. However, in the case of continuous annealing, even in the case where the oxidation of Fe does not occur (reduction of Fe oxide) in a reductive N2+H2 gas atmosphere, si is oxidized, and Si oxide is formed on the outermost layer of the steel sheet. (Si〇2). Since the si 〇 2 hinders the formation reaction of the skin sputum in the chemical conversion treatment, micro-dipoles (hereinafter also referred to as pores) which are not formed into the film are formed, and the chemical conversion treatment property is lowered. As a conventional technique for improving the chemical conversion treatment property of a high-Si steel sheet, Patent Document 1 discloses a method of forming an iron coating layer of 20 to 1500 mg/m2 on a steel sheet by an electric boat method. However, there is a need to add additional electric forging equipment, and there are 099133254 3 201213550 steps to increase and the cost is also increased. Further, in Patent Document 2, the Mn/Si ratio is specified, and in Patent Document 3, the addition of Ni improves the phosphoric acid treatability. However, the effect depends on the Si content in the steel sheet, and further improvement is required for a steel sheet having a high Si content. Further, Patent Document 4 discloses a method of forming an internal oxide layer composed of a Si-containing oxide by setting a dew point during annealing to -25 to (TC, within a depth of 1 μm from the surface of the steel sheet substrate. The ratio of the Si-containing oxide in the surface length of the steel sheet is 80% or less. However, in the case of the method described in Patent Document 1, the area where the dew point is controlled is assumed to be the entire furnace, and therefore the controllability of the dew point is difficult. It is difficult to carry out stable operation. Moreover, in the distribution state of the internal oxide formed in the steel sheet by the annealing of the unstable Lu Shihuan base, it is observed that the deviation 'will be processed in the longitudinal direction or the width direction of the steel sheet. In addition, in the case of the improvement of the processability, since the chemical conversion treatment film has yttrium oxide, it has a problem of good durability after electrocoating. Patent Document 5 describes a method of forming an oxide film on the surface of a steel sheet in an oxidizing atmosphere, and then reducing the temperature of the steel sheet to a temperature of recrystallization and cooling. However, in this method, the oxidation method is different in the thickness of the oxide film formed on the surface of the steel sheet, and the oxidation may not be sufficiently performed, or the oxide film may become too thick, and it may be in the annealing in the environment of 099133254 201213550. Before the film is peeled off or peeled off, the condition deteriorates. In the examples, although it is described that oxygen = technology is carried out in the atmosphere, there is a problem that the oxidation in the atmosphere is thick to form a thick oxide, and the reduction is difficult, or the reduction environment of high hydrogen inversion is required. Further, Patent Document 6 describes a method in which a cold-coated steel sheet containing & 0.1% or more and/or Mnl._ is contained in a mass%, and the steel sheet temperature / 〇CΜ is in an oxidizing atmosphere of iron. An oxide film is formed on the surface of the steel sheet, and then the oxide film on the surface of the steel sheet is reduced in a county environment of iron. Specifically, it is 40 (TC or more, and the Fe on the surface of the steel sheet is oxidized by a direct-fired furnace having an air ratio of 〇93 or more and I·10 or less, and then annealed in a gas atmosphere in which the Fe oxide is reduced. A method of forming an oxide layer of Fe on the outermost surface by oxidizing Si〇2 which deteriorates the processability to the outermost surface. Patent Document 6 does not specifically describe the heating temperature of the direct fire furnace, but contains a large amount of Si (about In the case of 0.6% or more, the amount of oxidation of the oxide which is more easily oxidized than Fe is increased, the oxidation of Fe is suppressed, or the oxidation itself becomes too small. As a result, there is a surface Fe reduced layer after reduction. In the case where the shape of the steel sheet is insufficient, or the surface of the steel sheet after the reduction is present, Si 2 is formed, and the pores of the film are formed. [Prior Art] [Patent Document 1] Patent Document 1 (Japanese Patent Application Laid-Open No. Hei 5-320952) (Patent Document 2) Japanese Patent Laid-Open No. Hei. No. 2004-323969 (Patent Document 3) Japanese Patent Laid-Open No. Hei 6-10096 (Patent Document 4). Document 5) 曰本专利专开昭55-1451 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a lithium even in the case of Si. In the case of 'high-strength steel sheet having excellent chemical conversion treatment and insect-repellent resistance after electrocoating, and a method for producing the same. (Means for solving the problem) In the prior art, oxidizing properties such as Si and Μ are contained. The steel sheet of the element actively oxidizes the inside of the steel sheet for the purpose of improving the processability. However, the durability of the steel sheet after electroforming is also deteriorated. Therefore, the present inventors have not adopted the concept of the prior art. A new method was adopted to review the method for solving the problem. As a result, it was found that by appropriately controlling the environment and temperature of the annealing step, the formation of internal oxides in the surface portion of the steel sheet can be suppressed, and excellent chemical processing properties and higher can be obtained. Specifically, the temperature in the annealing furnace is 750 C or more, and the temperature is controlled by the dew point in the environment: 4 〇 ^ or less. The temperature region in the annealing furnace is 750 Ϊ ^ is the dew point in the environment: book c or less, the oxygen potential of the interface between the steel plate and the ring brother is lowered, and the internal oxide can be controlled without forming an internal oxide. Selective surface diffusion, oxidation (hereinafter referred to as surface desertification). 099133254 201213550 Document 1 (7th International Conference on Zinc and Zinc Alloy Coated Steel Sheet Galvatech 2007, Proceedings p404) reveals the thermodynamics of oxidation reaction from Si and Μη In the data, the oxygen level energy is converted to the dew point, and in the presence of 800 ° C and N 2 -5% H 2 , oxidation is not prevented if Si is not below -80 ° C and Μη is not below the dew point of -60 C. Therefore, when the high-strength steel sheet containing Si or Μη is annealed, it is considered that even if the hydrogen concentration is increased, if the dew point is at least less than -80 °C, the surface concentration cannot be prevented. Therefore, conventional techniques have never attempted to carry out a chemical conversion treatment after annealing at a dew point of _4 〇 to -7 °C. Fig. 1 is a literature 2 (metal physical chemistry p72~73, May 20, 曰fs_4亍's published by the Institute of Metals). The thermodynamic data of the oxidation reaction from Si and Μη is calculated as follows. The relationship between the redox balance and the dew point and shows a graph of the relationship.
Si在氫-氮環境下之氧化還原平衡係以下式表示。 Si02(solid)+2H2(gas)=Si+2H20(gas) ⑴ 5亥反應之平衡常數K係以Si之活動(activity)作為1,如 下所述。 K=(H2〇分壓之平方)/(¾分壓之平方)⑺ 又’標準自由能量AG(1)係以R:氣體常數、T:溫度, 如下所示。 AG(l)=-RTlnK (3) 其中, 099133254 7 201213550 H2(gas)=l/202(gas)=H2〇(gas) (4)The redox balance of Si in a hydrogen-nitrogen environment is represented by the following formula. Si02(solid)+2H2(gas)=Si+2H20(gas) (1) The equilibrium constant K of the 5 hai reaction is 1 as the activity of Si, as described below. K = (square of H2 〇 partial pressure) / (square of partial pressure of 3⁄4) (7) Further, the standard free energy AG (1) is R: gas constant, T: temperature, as shown below. AG(l)=-RTlnK (3) where, 099133254 7 201213550 H2(gas)=l/202(gas)=H2〇(gas) (4)
Si(solid)+02(gas)=Si〇2(solid) (5) 之各反應式的標準自由能量AG(4)、AG(5)係作為τ之函數 而以下述表示。The standard free energy AG(4) and AG(5) of each reaction formula of Si(solid)+02(gas)=Si〇2(solid)(5) are expressed as follows as a function of τ.
AG(4)=-246000+54.8TAG(4)=-246000+54.8T
AG(5)=-902100+174T 因此,由 2χ(4)-(5),成為 AG(l)=4l0100-64.4T (6),由 (3)=(6),成為 K=exp{(l/R)(64.4-410100/T)} (7)。 此外,由(2)=(7)、Η?分壓=0.1氣壓(10%之情況),求出各 溫度T下之Ηβ分壓,將其換算為露點,則可獲得圖1。 對於Μη亦同樣,Μη在氫-氮環境下之氧化還原平衡係以 下式表示。AG(5)=-902100+174T Therefore, from 2χ(4)-(5), it becomes AG(l)=4l0100-64.4T (6), and by (3)=(6), it becomes K=exp{( l/R) (64.4-410100/T)} (7). Further, from (2) = (7), Η? partial pressure = 0.1 air pressure (in the case of 10%), the Ηβ partial pressure at each temperature T is obtained, and this is converted into a dew point, and Fig. 1 can be obtained. Similarly, for Μη, the redox balance of Μη in a hydrogen-nitrogen environment is expressed by the following formula.
MnO(solid)+H2(gas)=Mn+H20(gas) (8) 該反應之平衡常數K係如下所述。 Κ=(Η20 分壓)/(H2 分壓) (9) 又’標準自由能量AG(8)係以R :氣體常數、τ :溫度 如下所示。 △G(8)=-RTlnK (10) 其中, H2(gas)=l/202(gas)=H20(gas) (11)MnO(solid)+H2(gas)=Mn+H20(gas) (8) The equilibrium constant K of the reaction is as follows. Κ=(Η20 partial pressure)/(H2 partial pressure) (9) Further, the standard free energy AG(8) is R: gas constant, τ: temperature is as follows. △G(8)=-RTlnK (10) where H2(gas)=l/202(gas)=H20(gas) (11)
Mn(solid)+l/2〇2(gas)=MnO(solid), (12) 之各反應式的標準自由能量ΔΟ(11)、AG(12)係作為τ之; 099133254 8 201213550 數而以下述表示。Mn(solid)+l/2〇2(gas)=MnO(solid), (12) The standard free energy ΔΟ(11) and AG(12) of each reaction formula are as τ; 099133254 8 201213550 and below Said.
△G(l 1)=-246000+54.8T AG(12)=-384700+72.8T 因此’由(11)-(12),成為 ag(8)=138700-18.0T (13), 由(10)=(13) ’ 成為 K=exp{(i/R)(i8.0-138700/T)} (14)。 此外’由(9)=(14)、Η:分壓=〇·ι氣壓(1〇%之情況),求出 各溫度T下之HA分壓,將其換算為露點’則可獲得圖i。 由圖1,在標準退火溫度之8〇〇aC下,Si在露點_8(rc以上 係為氧化狀態,為了使其為還原狀態,必須為未滿_8(rc。 Μη亦同樣地,可理解若不是未滿則不會成為還原狀 態。此結果與文獻1之結果一致。 此外,於退火時必須從室溫加熱至8〇〇<t以上。另外,從 圖1與文獻1所示之結果,顯示越低溫則用以使Si、成 為還原狀態之露點越低,從室溫至8〇(rc之間,需要未滿 -l〇〇°C之極低露點,強烈暗示了以工業上而言,一邊防止△G(l 1)=-246000+54.8T AG(12)=-384700+72.8T Therefore 'from (11)-(12), becomes ag(8)=138700-18.0T (13), by (10) )=(13) ' Become K=exp{(i/R)(i8.0-138700/T)} (14). In addition, '(9)=(14), Η: partial pressure = 〇·ι pressure (in the case of 1〇%), the HA partial pressure at each temperature T is obtained, and it is converted into the dew point' to obtain the graph i. . From Fig. 1, at 8 〇〇 aC of the standard annealing temperature, Si is in the dew point _8 (the above rc is in an oxidized state, and in order to make it a reduced state, it must be less than _8 (rc. Μη is also the same, It is understood that it will not be in a reduced state unless it is not full. This result is consistent with the result of Document 1. In addition, it is necessary to heat from room temperature to 8 〇〇 < t at the time of annealing. Further, as shown in Fig. 1 and Document 1 As a result, the lower the temperature is, the lower the dew point of Si is in the reduced state. From room temperature to 8 〇 (between rc, a very low dew point of less than -10 °C is required, strongly suggesting that the industry On the one hand, while preventing
Si、Μη之氧化,一邊實現加熱至退火溫度之退火環境係不 可能的。 上述係相關技術者所周知的從熱力學數據可容易導出之 技術常識’亦為阻礙了嘗試以S i、Μ η應會被選擇氧化之露 點-40〜-7G°C進行退火之技術常識。㉟,本發明丨等認為, 即便在原本被認為會發生Si、Μη之表面濃化的_4〇〜_7〇ΐ 之露點,以平衡論而言雖係為氧化會發生之露點區域,但當 099133254 9 201213550 如連續退火般之短時間減理之情况^速度論而言應該有 不致達到大幅損害化成處理性之表面濃化的可能。因而進行 其檢討。其結果完成了以下特徵之本發明。 本發明之特徵在於,在對鋼板施行退火時,使退火爐内溫 度:750°C以上之溫度區域為環境中之露點:_4〇<3c以下。 通常,鋼板之退火環境的露點係_3〇ΐ以上,因此為了成 為-40C以下之露點,必須除去退火環境中之水分,欲使退 火爐^體之%境成為_4GC ’需要龐大的設備費與操作成 本。然而,本發明中係僅於退火爐内溫度:75〇。〇以上之限 疋區域中使露點HC:以下,故具有可降低設備費與操作 成本之特徵。此外’僅利用7贼以上之限定區域中的控 制,即可充分獲得所需之特性。 此外,若以使_。(:以上之溫度區域成為環境中之露點: 4(TC以下之方式予以㈣並進行退火、化成處理,可獲得 更良好的化成處理性。若使75〇〇c以上或 600°C以上之溫度 區域成為環i兄中的露點:_45。〇以下,則可獲得更良好之化 成處理性。 藉由僅於如此限定之區域中控制環境中之露點,不會形成 内部氧化物’可極力抑制表面濃化,可獲得沒有空孔、不均 之化成處理性及f著塗錢之_性優異之高強度鋼板。另 外。化成處理性優異係指有不具减處理後之空孔、不均外 觀0 099133254 201213550 另外,藉由以上方法所得之高強度鋼板,係於從鋼板表面 起ΙΟΟμηι以内之鋼板表層部中’抑制選自 P、進而 B、Nb、Ti、Cr、Mo、Cu、Ni 中之 1 種以上(僅 Fe 除外)的氧化物之形成,其形成量係抑制為合計每單面在 0.060g/m以下。藉此,化成處理性優異,可明顯提升電著 塗裝後之耐蝕性。 本發明係根據上述發現,特徵如下。 [1 ] 一種尚強度鋼板之製造方法,係在對以質量%含有c : 0.01 〜0.18%、Si:0.4〜2.0%、Μικί.ο〜3.0%、AliO.OOl〜1.0%、 P:0.005〜0.060%、SS0.01%,其餘部分為Fe及不可避免之 雜質所構成的鋼板施行連續退火時, 使退火爐内溫度:750°C以上之溫度區域的環境中之露 點:-40°C以下。 [2] 如上述[1]之高強度鋼板之製造方法,其中,上述鋼板 之成分組成係以質量%進一步含有從以下元素中所選擇之 1 種以上的元素;Β:0·〇〇ΐ〜0.005%、Nb:〇.〇〇5〜0.05%、 Ti:0.005-0.05% 、CnO.OOl 〜ι.〇〇/0 、、The oxidation of Si and Μη is not possible in an annealing environment where heating to the annealing temperature is achieved. The technical common sense that can be easily derived from thermodynamic data well known to those skilled in the art is also a technical common sense that attempts to anneal the dew point of -40 to -7 G °C which should be selectively oxidized by S i and η η. 35. According to the present invention, the dew point of _4〇~_7〇ΐ which is originally thought to occur on the surface of Si and Μη is concentrated, although it is a dew point region where oxidation occurs, but when 099133254 9 201213550 Short-term reduction in the case of continuous annealing. ^In terms of speed theory, there should be no possibility of greatly reducing the surface concentration of the treatment. Therefore, its review was carried out. As a result, the present invention of the following features was completed. The present invention is characterized in that, in the annealing of the steel sheet, the temperature in the annealing furnace: 750 ° C or higher is the dew point in the environment: _4 〇 < 3 c or less. Usually, the dew point of the annealing environment of the steel sheet is _3〇ΐ or more. Therefore, in order to become the dew point of -40C or less, it is necessary to remove the moisture in the annealing environment, and it is necessary to make the equipment cost of the annealing furnace become _4GC'. And operating costs. However, in the present invention, the temperature in the annealing furnace is only 75 Torr. 〇The above limits The dew point HC is below the 疋 area, so it has the feature of reducing equipment costs and operating costs. In addition, the control in a limited area of 7 or more thieves can be used to fully obtain the desired characteristics. In addition, if you want to make _. (: The above temperature range becomes the dew point in the environment: 4 (The method of TC or less is given (4), and annealing and chemical conversion treatment are performed, and better chemical conversion treatment property can be obtained. If the temperature is 75 〇〇c or more or 600 ° C or higher, The area becomes the dew point in the ring brother: _45. 〇 below, better processing properties can be obtained. By controlling the dew point in the environment only in the thus defined area, no internal oxide is formed, which can suppress the surface as much as possible. When it is concentrated, it is possible to obtain a high-strength steel sheet which has no voids, is not uniform in processing property, and is excellent in chemical properties. Moreover, it is excellent in chemical conversion property, and it means that there is no void after treatment, and the uneven appearance is 0. 099133254 201213550 In addition, the high-strength steel sheet obtained by the above method is used to suppress one of P, B, Nb, Ti, Cr, Mo, Cu, and Ni selected from the surface of the steel sheet from the surface of the steel sheet. In the formation of the above-mentioned oxides (except for Fe), the amount of formation is suppressed to 0.060 g/m or less per one surface in total, whereby the chemical conversion property is excellent, and the corrosion resistance after electrocoating can be remarkably improved.The present invention is characterized by the above findings, and is characterized as follows: [1] A method for producing a strength-strength steel sheet, which comprises c: 0.01 to 0.18% by mass, Si: 0.4 to 2.0%, Μικί.ο~3.0%, and AliO. .OOl~1.0%, P: 0.005~0.060%, SS0.01%, and the rest of the steel sheet composed of Fe and unavoidable impurities is subjected to continuous annealing, and the temperature in the annealing furnace is 750 ° C or higher. The dew point in the environment: -40 ° C or less. [2] The method of producing a high-strength steel sheet according to the above [1], wherein the component composition of the steel sheet further contains one or more selected from the following elements in mass% Element; Β: 0·〇〇ΐ~0.005%, Nb: 〇.〇〇5~0.05%, Ti: 0.005-0.05%, CnO.OOl~ι.〇〇/0,
Cu:0.05〜1.0%、Ni:0.05〜1.0% 〇 [3] 如上述[1]或[2]之高強度鋼板之製造方法,其中,在進 行上述連續退火後,在含有硫酸之水溶液中進行電解酸洗。 [4] 一種向強度鋼板,係利用上述[1]至[3]中任—項之製造 方法所製造,從鋼板表面起1〇〇^m以内之鋼板表層部所生 099133254 201213550 成之從 Fe、Si、Μη、A1、P、B、Nb、Ti、Cr、Mo、Cu、 Ni中所選擇之1種以上的氧化物,每單面係0.060g/m2以下。 另外,本發明中,高強度係指拉伸強度TS在340MPa以 上。 (發明效果) 根據本發明’即便在Si含有量多之情況,仍可獲得具有 優異化成處理性及電著塗裝後耐蝕性之高強度鋼板。 【實施方式】 以下’針對本發明具體進行說明。另外,以下說明中,鋼 成分組成之各元素的含有量單位係「質量妬」,以下只要未 特別限制’均以「%」表示。 首先’針對屬於本發明最重要之要件的決定鋼板表面構造 之退火環境條件進行說明。 在鋼中添加有大量Si及Mn之高強度鋼板中,為了滿足 ⑻生’係要求極力減少可能成為腐#起點之鋼板表層的内 部氧化。 、 方面,雖可藉由促進Si與Μη之内部氧化而提升化Cu: 0.05 to 1.0%, Ni: 0.05 to 1.0% 〇 [3] The method for producing a high-strength steel sheet according to the above [1] or [2], wherein the continuous annealing is performed in an aqueous solution containing sulfuric acid Electrolytic pickling. [4] A strength-strength steel plate manufactured by the method of the above-mentioned item [1] to [3], which is produced from the surface layer of the steel sheet from the surface of the steel sheet to 099133254 201213550. One or more oxides selected from the group consisting of Si, Μη, A1, P, B, Nb, Ti, Cr, Mo, Cu, and Ni are 0.060 g/m 2 or less per one side. Further, in the present invention, high strength means that the tensile strength TS is 340 MPa or more. (Effect of the Invention) According to the present invention, even when the Si content is large, a high-strength steel sheet having excellent chemical conversion treatment properties and corrosion resistance after electrocoating can be obtained. [Embodiment] Hereinafter, the present invention will be specifically described. In the following description, the content unit of each element of the steel component composition is "mass 妒", and unless otherwise specified, it is expressed by "%". First, the annealing environment conditions for determining the surface structure of the steel sheet, which are the most important requirements of the present invention, will be described. In the high-strength steel sheet in which a large amount of Si and Mn are added to the steel, the internal oxidation of the surface layer of the steel sheet which may become the starting point of the rot # is extremely reduced in order to satisfy the requirement of (8). And, in terms of promoting the internal oxidation of Si and Μη,
成處理It ’但此方法相對地會帶來耐齡之劣化 了促進 S 理性並且内部氧化之外’必須維持良好的化成處 内部乳化而提升耐蝕性。經檢討結果,本發明 俾使^1確保化成處雜而在退火步财使氧位能降低, 、易乳化性元素之Si與Μη等在基底鐵表層部之活 099133254 12 201213550 動降低。另外,抑制該等元素 而 處理性。此外,形成於鋼板表^部氧化,結果改善了化成 可改善電著塗裝後之耐做/奴内部氧化亦被抑制,— 此種效果係可藉由在施行退 職以上之溫度區域的環境中:以使退火爐内溫度·· 進行控制而獲得。藉由將退切=成為_4G。⑶下之方式 ^ 人壚内溫度:750。(:以上之溫度 匕兑杈制為%境中之露點為_ 之界面的氧位能,可降低鋼板與環境 ^ ’ 。卩氧化地控制Si、Μη等之選擇 性表面擴散、表面濃化。另外 化赤卢田 獲付無空孔或不均之良好 化成處理性與電著塗裝後之耐蝕性。 將控制露點之溫度區域 7 〇 Λ疋马750 C以上之理由如下。在 〇c以上之溫度區域中’容易料會導致空孔與不均之發It is treated as It', but this method relatively brings about deterioration of age resistance, promotes S rationality, and does not require internal oxidization to maintain good internal emulsification and improve corrosion resistance. As a result of the review, the present invention ensures that the formation of impurities is reduced, and the oxygen level energy is lowered in the annealing step, and the Si and 易η of the easily emulsifiable element are reduced in the surface layer of the base iron by 099133254 12 201213550. In addition, these elements are suppressed and handled. In addition, it is formed in the surface of the steel sheet to be oxidized, and as a result, the chemical conversion can be improved, and the internal oxidation of the slave/slave after the electrocoating is also suppressed, and the effect can be suppressed by the environment in the temperature region above the resignation. : It is obtained by controlling the temperature in the annealing furnace. By turning back = _4G. (3) The way below ^ The temperature inside the person: 750. (The above temperature is controlled by the oxygen potential energy at the interface where the dew point in the % is _, which can reduce the steel plate and the environment ^ '. Selective surface diffusion and surface concentration of Si, Μ, etc. In addition, the red radish is treated with no porosity or unevenness, and the corrosion resistance after electrocoating is improved. The reason for controlling the dew point temperature region 7 〇Λ疋 750 C or more is as follows. In the temperature zone, 'easy to cause holes and uneven hair
、耐=性之劣化等問題的程度之表面濃化與内部氧化。因 係疋為可表現本發明效果之溫度區域的75(rc以上。此 若將抆制硌點之溫度區域定為6〇〇〇c以上,則可進一步 安定表面濃化與内部氧化並進行控制。 控制露點為_4(TC以下之溫度區域的上限並無特別設定。 …、而’ §超過之情況’雖本發明之效果不會有問題, 從成本牦加之觀點而言係為不利。因此,較佳為9⑻。〇以 下。 將露點定為-4(TC以下之理由如下。可確認到表面濃化之Surface concentration and internal oxidation to the extent of problems such as deterioration of resistance. Since the temperature is 75 (rc or more) in the temperature range in which the effect of the present invention can be exhibited, if the temperature region of the tantalum defect is set to 6 〇〇〇c or more, the surface concentration and internal oxidation can be further stabilized and controlled. The control dew point is _4 (the upper limit of the temperature range below TC is not specifically set. ..., and ' § exceeds the case'. Although the effect of the present invention is not problematic, it is disadvantageous from the viewpoint of cost increase. Preferably, it is 9 (8). The following is given. The dew point is set to -4 (the reason for the TC or less is as follows. It can be confirmed that the surface is concentrated.
抑制效果者健點H町。露點之下限並無特別設定, 099133254 S 201213550 但未滿-70 C則效果飽和,以成本而言不利,因此較佳係 -70°C以上。 其次,針對本發明對象之高強度鋼板的鋼成分組成進行說 明0 C : 0.01 〜0.18% C係作為鋼組織而形成麻田散鐵等,藉此使加工性提升。 因此,需要0.01%以上。另一方面,若超過0.18%,則延伸 度降低,材質劣化,甚至使熔接性劣化。因此,C量係定為 0.01%以上且0.18%以下。The effect of the suppression effect is H Hachi. The lower limit of the dew point is not specifically set. 099133254 S 201213550 However, the effect is saturated with less than -70 C, which is disadvantageous in terms of cost, so it is preferably -70 ° C or higher. Next, the steel composition of the high-strength steel sheet according to the present invention is described as 0 C : 0.01 to 0.18%. C is a steel structure to form a granulated iron or the like, thereby improving workability. Therefore, 0.01% or more is required. On the other hand, when it exceeds 0.18%, the elongation is lowered, the material is deteriorated, and the weldability is deteriorated. Therefore, the amount of C is set to be 0.01% or more and 0.18% or less.
Si : 0.4-2.0%Si : 0.4-2.0%
Si係使鋼強化並提高延伸度,係用以獲得良好材質之有 效元素,而為了獲得本發明目的之強度,需要0.4%以上。 若Si未滿0,4%,則無法獲得本發明適用範圍之強度,化成 處理性則不成問題。另一方面,若超過2.0%,則鋼之強化 能力與延伸度提升效果飽和。因此,Si量係定為0.4%以上 且2.0%以下。 Μη : 1.0〜3.0% Μη係鋼高強度化之有效元素。為了確保機械特性與強 度,必須含有1.0%以上。另一方面,若超過3.0%,則難以 確保溶接性或鑛敷密著性,或難以確保強度與延展性之平 衡。因此,Μη量係定為1.0%以上且3.0%以下。 Α1 : 0.001 〜1.0% 099133254 14 201213550 A1係以嫁鋼之脫酸作為目的而添加。其含有量未滿〇 〇〇 1 %之情況,無法達成該目的。0.001%以上可獲得熔鋼之脫 酸效果。另/方面,若超過1.0%,則會導致成本增加。此 外,Α1之表面》辰化會變多,化成處理性之改善變得困難。 因此,Α1量係疋為0.001%以上且1.0%以下。 Ρ : 0.005〜〇.06〇% 以下 Ρ係不可避免地含有之元素之一,若欲使其未滿0005 % ’則有成本增加之顧慮,因此定為0.005%以上。另一方 面,若Ρ含有超過0.060%,則熔接性會劣化。此外,化成 處理性之劣化變得激烈,即便利用本發明,仍難以提昇化成 處理性。因此,ρ量係定為0.005%以上且0.060%以下。 S^O.Ol% S係不可避免地含有之元素之一。下限並無規定,若大量 地含有’則熔接性與耐蝕性會劣化,因此定為〇·〇1%以了。 另外’為了控制強度與延展性之平衡’亦可視需要添加從 Β··0.001 〜0.005%、Nb:〇.〇〇5 〜0.05%、Ti:〇.〇〇5 〜0 05〇/〇、 Cr:0.001〜1.0%、Mo:0.05〜1.0%、Cu:0.05~1.0%、Ni:0.05〜10% 中所選擇之1種以上的元素。 添加該等元素之情況的適當添加量之限定理由如下。 B : 0.001 〜0.005% B若未滿0.001%則難以獲得淬火促進效果。另一方面, 若含有超過0.005%,則化成處理性會劣化,因此,在含有 099133254 ,c 201213550 之情況,B量係定為0.001%以上且0.005%以下。The Si system strengthens the steel and increases the elongation, and is used to obtain an effective element of a good material, and 0.4% or more is required in order to obtain the strength of the object of the present invention. If Si is less than 0, 4%, the strength of the application range of the present invention cannot be obtained, and the chemical conversion process is not a problem. On the other hand, if it exceeds 2.0%, the steel strengthening ability and the elongation improving effect are saturated. Therefore, the amount of Si is set to be 0.4% or more and 2.0% or less. Μη : 1.0~3.0% 有效η steel is an effective element for high strength. In order to ensure mechanical properties and strength, it must be 1.0% or more. On the other hand, when it exceeds 3.0%, it is difficult to ensure the weldability or the mineral adhesion, or it is difficult to ensure the balance between strength and ductility. Therefore, the amount of Μη is set to be 1.0% or more and 3.0% or less. Α1 : 0.001 ~1.0% 099133254 14 201213550 A1 is added for the purpose of deacidification of marrying steel. If the content is less than 〇〇 1%, this cannot be achieved. The deacidification effect of the molten steel can be obtained by 0.001% or more. On the other hand, if it exceeds 1.0%, it will lead to an increase in cost. In addition, the surface of the crucible 1 will become more and more difficult to be processed. Therefore, the amount of Α1 is 0.001% or more and 1.0% or less. Ρ : 0.005~〇.06〇% The following is one of the elements that are inevitably contained in the system. If you want to make it less than 0005%, there is a concern that the cost increases. Therefore, it is set to 0.005% or more. On the other hand, if the niobium content exceeds 0.060%, the weldability may deteriorate. Further, deterioration in chemical conversion treatability is fierce, and even with the present invention, it is difficult to improve the processability. Therefore, the amount of ρ is set to be 0.005% or more and 0.060% or less. S^O.Ol% S is one of the elements inevitably contained. The lower limit is not specified, and if it is contained in a large amount, the weldability and corrosion resistance are deteriorated, so it is determined to be 1%. In addition, 'in order to control the balance between strength and ductility' can also be added from Β··0.001 to 0.005%, Nb:〇.〇〇5 to 0.05%, Ti:〇.〇〇5 to 0 05〇/〇, Cr One or more elements selected from the group consisting of 0.001 to 1.0%, Mo: 0.05 to 1.0%, Cu: 0.05 to 1.0%, and Ni: 0.05 to 10%. The reason for the appropriate addition amount in the case of adding these elements is as follows. B : 0.001 to 0.005% B If it is less than 0.001%, it is difficult to obtain a quenching promoting effect. On the other hand, when the content is more than 0.005%, the chemical conversion property is deteriorated. Therefore, when the content is 099133254 or c 201213550, the amount of B is 0.001% or more and 0.005% or less.
Nb : 0.005〜0.05%Nb : 0.005~0.05%
Nb若未滿0.005%,則難以獲得強度調整之效果。另一方 面,若超過0.05%,則會導致成本增加。因此,在含有之情 況,Nb量係定為0.005%以上且0.05%以下。If Nb is less than 0.005%, it is difficult to obtain the effect of strength adjustment. On the other hand, if it exceeds 0.05%, it will lead to an increase in cost. Therefore, in the case of inclusion, the amount of Nb is set to be 0.005% or more and 0.05% or less.
Ti : 0.005〜0.05%Ti : 0.005~0.05%
Ti若未滿0.005%,則難以獲得強度調整之效果。另一方 面,若超過0.05%,則會導致化成處理性劣化。因此,在含 有之情況,Ti量係定為0.005%以上且0.05%以下。If Ti is less than 0.005%, it is difficult to obtain the effect of strength adjustment. On the other hand, if it exceeds 0.05%, the chemical conversion treatment property is deteriorated. Therefore, in the case of inclusion, the amount of Ti is set to be 0.005% or more and 0.05% or less.
Cr : 0.001 〜1.0%Cr : 0.001 to 1.0%
Cr若未滿0.001%,則難以獲得淬火促進效果。另一方面, 若超過1.0%,則Cr會發生表面濃化,因而使熔接性劣化。 因此,在含有之情況,Cr量係定為0.001%以上且1.0%以 下。If Cr is less than 0.001%, it is difficult to obtain a quenching promoting effect. On the other hand, when it exceeds 1.0%, surface-concentration of Cr will occur, and the weldability will deteriorate. Therefore, in the case of being contained, the amount of Cr is set to be 0.001% or more and 1.0% or less.
Mo :0.05〜1.0%Mo: 0.05~1.0%
Mo若未滿0.05%,則難以獲得強度調整之效果。另一方 面,若超過1.0%,則會導致成本增加。因此,在含有之情 況,Mo量係定為0.05%以上且1.0%以下。If Mo is less than 0.05%, it is difficult to obtain the effect of strength adjustment. On the other hand, if it exceeds 1.0%, it will lead to an increase in cost. Therefore, in the case of inclusion, the amount of Mo is set to be 0.05% or more and 1.0% or less.
Cu : 0.05〜1.0%Cu : 0.05~1.0%
Cu若未滿0.05%,則難以獲得殘留γ相形成促進效果。 另一方面,若超過1.0%,則會導致成本增加。因此,在含 有之情況,Cu量係定為0.05%以上且1.0%以下。 099133254 16 201213550When Cu is less than 0.05%, it is difficult to obtain a residual γ phase formation promoting effect. On the other hand, if it exceeds 1.0%, the cost will increase. Therefore, in the case of inclusion, the amount of Cu is set to be 0.05% or more and 1.0% or less. 099133254 16 201213550
Ni : 0.05〜l.o%Ni : 0.05~l.o%
Ni若未滿〇 〇5%,則難以獲得殘留γ相形成促進效果。 另一方面,若超過1.0%,則會導致成本增加。因此,在含 有之情況,Ni量係定為0 05%以上立1.0%以下。 上述以外之其餘部分係Fe及不玎避免之雜質。 其次’針對本發明之高強度鋼板之製造方法與其限定理由 進行說明。 例如,在將具有上述化學成分之鋼予以熱軋後,進行^ 軋’接著於連續式退火設備中進行退火。另外,返火時,本 發明中係將退火爐内溫度:750。(:以上之溫度區域定為環产 中之露點:-40°C以下。此係於本發明中最重要的要件。此 外,若將控制露點之溫度區域定為600°C以上,則可+ 安定上述表面濃化或與内部氧化並進行控制。又,L丄 八上述中, 亦有於熱軋結束後不施行冷軋而直接進行退火之情況。 [熱軋] 可以一般進行之條件進行。 [酸洗] 較佳係於熱軋後進行酸洗處理。利用酸洗步驟, 邱,將表面所 生成之黑皮鏽去除’接著進行冷軋。另外’酸洗條件並無特 別限定。 [冷軋] 若軋縮率 較佳係以40%以上且80%以下之軋縮率進行 099133254 17 201213550 未滿40%,則再結晶溫度會低溫化,因此機械特性容易劣 化。另一方面,若軋縮率超過80%,則屬於高強度鋼板, 故不僅會提高輥軋成本,退火時之表面濃化情形亦會增加, 因此有化成處理性劣化之情況。 對於經冷軋之鋼板或經熱軋之鋼板進行退火,接著施行化 成處理。 在退火爐中係進行以前段之加熱帶將鋼板加熱至既定溫 度之加熱步驟,並進行以後段之均熱帶於既定溫度下保持既 定時間之均熱步驟。 另外,如上所述,以使退火爐内溫度:750°C以上之溫度 區域的環境中露點成為-40°C以下之方式進行控制,進行退 火、化成處理。通常之露點係.高於-40°C,因此以除濕裝置 或吸收劑將爐内之水分吸收除去,藉此成為-40°C以下之露 點。 退火爐内之氣體成分係由氮、氫及不可避免之雜質所構 成。只要為不損及本發明效果者,亦可含有其他氣體成分。 另外,若氫濃度未滿1體積%,則無法獲得還原所帶來之活 性化效果,化成處理性劣化。上限並無特別規定,若超過 50體積%則會增加成本,且效果飽和。因此,氫濃度以1 體積%以上且50體積%以下為佳。進一步係以5體積%以 上且30體積%以下為佳。 從750°C以上之溫度區域冷卻後,亦可視需要進行淬火、 099133254 18 201213550 回火。其條件並無特別限定,但回火較佳係於150〜400°C 之溫度下進行。因若未滿15〇t:會有延伸度劣化之傾向,若 超過400°C,則有硬度降低之傾向。 本發明中,即便未實施電解酸洗,仍可確保良好的化成處 理1·生’但較佳係將退火時不可避免地產生之微量表面濃化物 去除,而為了確保更良好的化成處理性之目的,較佳係進行 電解酸洗。 電解酸洗之條件並無特別限定,為了有效率地將退火後形 成之不可避免地發生表㈣化之Si與的氧化物去除, 較佳係為電流密度1A/dm2以上之交流電。交流電之理由在 於’若將鋼_持保持紐極,騎洗效果小,反之,若將 鋼板維持保持為陽極,則電解時溶出之Fe會累積於酸洗液 中,酸洗Μ之Fe敍增大,若崎於鋼板表面則會發生 乾燥污垢等之問題。 此外,使用於電解酸洗之酸洗液並無特別限定,石肖酸愈氫 氣酸對設備之腐純強,於操作上必須特別注意,因此較不 佳。又,鹽酸可能從陰極產生氣氣,料佳。因此,若考虎 腐錄與環境’較祕使用_。硫㈣度較佳為5質量^ ::且2〇質量%以下。〜度未滿職,則導電 率降低,因此電解時之__師滅㈣上升 源負荷增大之情況。另一方而 因帶出效應(―所造成:於超過20質量%之情況, X之知失大,成本上會有問題。 099133254 19 201213550 電解液之溫度較佳為40t:以上 解所造成之發熱會使浴溫上升,因j°C以下。由於連續電 未滿机之情況,從電解槽^有難以將溫度維持在 言,溫度超過70。(:較為不佳。久性之觀點而 由上可獲得本發明之高強度鋼板。 另外,如下所述,鋼板表面之構造係具有特徵。 從鋼板表面起100,m以内之鋼板 成之從Fe、Si、Mn、A1、p、1 ° 母早面所形If Ni is less than 5%, it is difficult to obtain a residual γ phase formation promoting effect. On the other hand, if it exceeds 1.0%, the cost will increase. Therefore, in the case of inclusion, the amount of Ni is set to be 0.5% or more and 1.0% or less. The rest of the above is Fe and impurities that are not avoided. Next, the method for producing the high-strength steel sheet according to the present invention and the reason for the limitation will be described. For example, after the steel having the above chemical composition is hot rolled, it is subjected to annealing and then annealing is performed in a continuous annealing apparatus. Further, in the case of re-ignition, the temperature in the annealing furnace is 750 in the present invention. (: The above temperature range is defined as the dew point in the ring production: -40 ° C or less. This is the most important requirement in the present invention. In addition, if the temperature range for controlling the dew point is set to 600 ° C or more, then + The above surface is concentrated or controlled by internal oxidation. Further, in the above, there is a case where the cold rolling is performed without performing cold rolling after completion of hot rolling. [Hot rolling] It can be carried out under normal conditions. [Pickling] It is preferable to carry out pickling treatment after hot rolling. The pickling step is used to remove black rust generated on the surface by the pickling step, followed by cold rolling. Further, the pickling conditions are not particularly limited. Rolling] If the rolling reduction ratio is preferably 40% or more and 80% or less, the 099133254 17 201213550 is less than 40%, the recrystallization temperature is lowered, so the mechanical properties are easily deteriorated. When the shrinkage ratio exceeds 80%, it is a high-strength steel sheet, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the chemical treatment property is deteriorated. For cold-rolled steel sheets or hot rolled The steel plate is annealed and connected In the annealing furnace, a heating step of heating the steel sheet to a predetermined temperature is performed in a heating belt of the preceding stage, and a soaking step of maintaining the tempering zone at a predetermined temperature for a predetermined time in the subsequent stage is performed. It is controlled so that the dew point in the temperature range of the annealing furnace temperature: 750 ° C or higher is -40 ° C or less, and annealing and chemical conversion treatment are performed. Usually, the dew point is higher than -40 ° C, so The dehumidifying device or the absorbent absorbs and removes moisture in the furnace, thereby forming a dew point of -40 ° C or lower. The gas component in the annealing furnace is composed of nitrogen, hydrogen, and unavoidable impurities, as long as the present invention is not impaired. In addition, when the hydrogen concentration is less than 1% by volume, the activation effect by reduction cannot be obtained, and the chemical conversion treatment property is deteriorated. The upper limit is not particularly specified, and if it exceeds 50% by volume, The cost is increased and the effect is saturated. Therefore, the hydrogen concentration is preferably 1% by volume or more and 50% by volume or less, and more preferably 5% by volume or more and 30% by volume or less. After cooling in a temperature range of 750 ° C or higher, quenching and 099133254 18 201213550 tempering may be carried out as needed. The conditions are not particularly limited, but the tempering is preferably carried out at a temperature of 150 to 400 ° C. 15〇t: There is a tendency for the elongation to deteriorate, and if it exceeds 400 °C, the hardness tends to decrease. In the present invention, even if electrolytic pickling is not performed, a good chemical conversion treatment can be ensured. In order to ensure better chemical conversion treatment, electrolytic pickling is preferably performed for the purpose of ensuring better chemical conversion treatment. The conditions of electrolytic pickling are not particularly limited, in order to efficiently It is inevitable that the Si and the oxide are removed after the annealing, and it is preferably an alternating current having a current density of 1 A/dm 2 or more. The reason for the alternating current is that if the steel is kept at the new pole, the riding effect is small. On the contrary, if the steel plate is maintained as the anode, the Fe dissolved during the electrolysis will accumulate in the pickling liquid, and the Fe of the pickling is increased. Large, if the surface of the steel plate on the surface of the steel plate, there will be problems such as drying dirt. Further, the pickling liquid used for the electrolytic pickling is not particularly limited, and the sulphuric acid is more pure to the equipment, and must be paid attention to in handling, and thus is not preferable. Also, hydrochloric acid may generate gas from the cathode, which is preferred. Therefore, if the test is rotted and the environment is used more secretly. The sulfur (tetra) degree is preferably 5 masses ^:: and 2% by mass or less. When the degree is not full, the conductivity is lowered, so the __ division is extinguished during electrolysis (4). The other side is brought about by the effect (": caused by more than 20% by mass, the knowledge of X is too large, there will be problems in cost. 099133254 19 201213550 The temperature of the electrolyte is preferably 40t: the heat caused by the above solution The bath temperature will rise, because it is below j ° C. Since the continuous power is not full, it is difficult to maintain the temperature from the electrolytic cell, and the temperature exceeds 70. (: It is not good. From the viewpoint of longness The high-strength steel sheet of the present invention can be obtained. Further, as described below, the structure of the surface of the steel sheet has characteristics. From the surface of the steel sheet, the steel sheet of 100, m or less is formed from Fe, Si, Mn, A1, p, 1 ° Face shape
Cu、Ni中所選擇之1種以B HG'Mo、 0.060W以下。 的氧化物,合計係抑制於 於鋼中添加有大量Si及Mn 顺性,必須極力地減少缝鋼板中,為了滿足 部氧化。 麵鱗點之鋼板表層的内 本發日种,首先係為了確保化成處雜 财使氧位能降低,藉此降低屬於易氧化元素之 =表層部之活動。另外,抑制該等元素之外部氧化:η 改善了化成處理性。 、〜果 匕卜开/成於表層奴内部氧化Μ到抑制,而改 性。此種效果係由從鋼板表面起動㈣以内之鋼板 中,從One of Cu and Ni selected is B HG'Mo and 0.060 W or less. The total amount of oxides is suppressed by adding a large amount of Si and Mn to the steel, and it is necessary to reduce the amount of the steel in the steel sheet to meet the oxidation. The inner surface of the surface of the steel plate with the surface of the scale is firstly used to ensure the reduction of the oxygen level in order to ensure the formation of impurities, thereby reducing the activity of the surface layer which is an easily oxidized element. In addition, inhibition of external oxidation of these elements: η improves chemical conversion treatability. , ~ fruit 匕 开 open / into the surface of the slave internal oxidative Μ to inhibition, and change. This effect is made from the steel plate that is started from the surface of the steel plate (4).
Cu、Nl中所選擇之至少1種以上的氧化物之形成量合計俾 抑制於o‘_gW以下而確認。若氧化物形成量之合她下、 099133254 20 201213550 稱為内部氧化量)超過0.060g/m2,則而性劣化。又,即便 將内部氧化量抑制為未滿0.0 001 g / m2,耐蝕性提升效果仍飽 和,因此内部氧化量之下限以0.0001 g/m2以上為佳。 [實施例1] 以下,根據實施例具體說明本發明。 將表1所示之鋼組成所構成的熱軋鋼板予以酸洗,去除黑 皮鏽後,進行冷軋,獲得厚度1.0mm之冷軋鋼板。另外, 一部分係未實施冷軋,亦準備去除黑皮鏽後之熱軋鋼板(厚 度 2.0mm)。 099133254 21 201213550The total amount of formation of at least one type of oxide selected in Cu and N1 is suppressed by o'_gW or less. If the amount of oxide formation is equal to 099133254 20 201213550, the internal oxidation amount exceeds 0.060 g/m 2 , and the properties are deteriorated. Further, even if the internal oxidation amount is suppressed to less than 0.0001 g / m2, the corrosion resistance improving effect is still sufficient, so the lower limit of the internal oxidation amount is preferably 0.0001 g/m2 or more. [Example 1] Hereinafter, the present invention will be specifically described based on examples. The hot-rolled steel sheet having the steel composition shown in Table 1 was pickled to remove black rust, and then cold-rolled to obtain a cold-rolled steel sheet having a thickness of 1.0 mm. Further, some of them were not subjected to cold rolling, and were also prepared to remove hot-rolled steel sheets (thickness 2.0 mm) after black rust. 099133254 21 201213550
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PM ¾ ο d ΊΚ Η Τ Η Η KZS660 201213550 備之冷軋鋼缺祕顺裝人連續退火設 上之溫度區域的露1如tr示’控制退火爐内之7肌以 3帆⑽秒之;^ 讀,料淬火後進行 w人。接者,於40〇C、5皙旦〇/ 士 —政> — 液中,以表2所示夕+ + 質里^之硫g夂水洛 ,丨百皮 々 电流密度條件,將樣品以陽極、陰極之 順序,以各3秒之交流電進行電解酸洗,獲得樣品。另外, 本。又,環产^ 退火爐之露點係以_35。0為基 -骑讲之氣體成分係由氣氣與氫氣及不可避免的雜質 耽體所構成,f點係將環境中之水分予以除濕核收去除而 進灯控制叫中之氫濃度係以體積%為基本。 二' π之樣叩,根據JIS Z 2241金屬材料拉伸試驗方法 、 又,對所得之樣品調查化成處理性及耐餘性。 測定存在於鋼板表層正下方至削㈣為止之鋼板表層部的 氧化物之置(内部氧化量)。測定方法及評估基準如下所示。 (化成處理性) 化成處理性之評估方法記載如下。 化成處理液係使用曰本PARKERIZING(股)製之化成處理 液(ParbondL3080(註冊商標)),以下述方法施行化成處理。 以日本PARKERIZING(股)製之脫脂液Fine Cleaner(註冊 商標)脫脂後,進行水洗,接著以日本PARKERIZING(股) 製之表面調整液Prepan Z(註冊商標)進行30秒之表面調 整,於43°C之化成處理液(ParbondL3080)中浸潰120秒後, 099133254 23 201213550 進行水洗並以溫風乾燥。 將化成處理後<樣品利用掃瞒型電子顯微鏡(SEM)以倍 率500倍_觀察5視野,利用影像處理測定化成處理皮膜 之空孔面積率’利用空孔面積率進行以下之評估。〇係合格 等級。 〇:10%以下 X :超過10% (電著塗裝後之耐蝕性) 從上述方法所得之經化成處理的樣品中切出尺寸 70inmXl50mm 之試驗片,以 Nippon Paint(股)製之 PN-150G(註冊商標)進行陽離子電著塗裝(硬化條件: 170 C 20刀鐘’獏厚25#m)。其後,將端部與不進行評估 之侧的面UAi膠帶進行密封’以切刀橫切至到達基底鐵(橫 切角度60。),作為樣品。 其次’將樣品於5質量%NaC1水溶液(55。〇中浸潰⑽ 小時後取A ’水洗並錢後’將橫㈣進行膠帶_,測定 剝離寬度,進行以下之評估。〇為合格等級。 〇:剝離寬度係單側未滿2.5mm •剝離寬度係單側2.5mm以上 (加工性) 加工性係在相對於輥軋方向9〇。之方向,從試料採取JIS5 號拉伸試驗片,依據JISZ2241之規定,以十字頭㈣灿㈣ 099133254 24 201213550 速度固定l〇mm/min,進行拉伸試驗,測定拉伸強度(TS/MPa) 與延伸度(El%) ’當TS未滿650MPa之情況,TSxElk22000 者為良好’ TSxEl < 22000者為不良。當ts為650MPa以上 且 900MPa 之情況 ’ TSXE12 20000 者為良好,tsxEI< 20000 者為不良。當TS為900MPa以上之情況,TSxElg 18000者 為良好,TSxElC 18000者為不良。 (鋼板表層ΙΟΟμιη為止之區域中的内部氧化量) 内部氧化量係利用「脈衝爐溶融-紅外線吸收法」測定。 惟,由於必須扣除素材(亦即實施退火前之高強度鋼板)中所 含之氧量,故本發明中,係將連續退火後之高強度鋼板的兩 面之表層部研磨100μιη以上,測定鋼中氧濃度,以該測定 值作為素材所含之氧量0Η,並且測定連續退火後之高強度 鋼板的板厚方向整體之鋼中氧濃度,將該測定值作為内部氧 化後之氧量〇1。使用如此所得之高強度鋼板之内部氧化後 的氧里01與素材中所含之氧量ΟΗ,算出01與ΟΗ之差 (=〇Ι-〇Η),進一步以換算為單面單位面積(亦即lm2)之量的 值(g/m2)作為内部氧化量。 將以上所得之結果與製造條件一起示於表2。 099133254 25 201213550 【(Nl 1 好1發明例1 良好發明例 良好發明例 良好發明例 良好發明例 良好發明例 良妤1發明例1 1良好發明例 良好發明例 不良 比較例 1 £ s 1 κ* •^srr •g £ $ s ί % £ -C& fSxEl |加工性丨備註| 1 I $ I 1 i 索 良好丨發明例丨 良好發明例 良好發明例1 良好發明例 良好發明例 良好發明例 良好發明例 良好發明例 良好發明例 不良1比皋交例 良好丨發明例 良好發明例 良好發明例 Φ 良好發明例 φ $ 21960 20620 20060 20502 21280 20804 20683 20338 21058 20754 20800 20547 20577 21025 19087 21269 22506 23288 ,20208 I 21213 22069 1 23681 I 21216 20902 19969 21796 21910 1 22186 I 21226 1 21165 17443 .19800 1 16464 5 22079 6 21167 7 \ 22273 m 20.6 : 20.0 : 19.4 20.1 20.6 S 20.1 19.9 21.4 20.9 17.9 19.7 19.9 20.1 26.4 (N 22.0 22.5 1 19.6 19.9 20.8 1 20.7 20.4 〇 〇\ (N 20.4 20.6 26.4 20.1 13.8 in vg )14; οό vr> 〇0 MPa 1066 : 1031 : 1034 1020 1033 1035 1029 1022 Os m s 1162 1043 1034 1046 3 1008 1023 1035 〇 1066 1061 1 1144 1040 1061 1051 1033 1074 1077 s 00 1053 1264 1200 U2C δ t—^ ΓΟ B T—^ 電著塗裝1 唆对触性】 X X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Ο X 〇 X 化成處丨. 理性h X X X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 X X 〇 ㈣ 1 1 1 1 1 1 1 1 1 1 1 1 〇 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I I 1 1 電解酸洗1 之有無 4: m 4ί 4: m m 碟 41 φΗ I 命 i 0.221 0.143 0.074 0.056 I 0.016 1 0.042 0.009 1 0.005 1 0.010 1 0.012 I 1 0.025 1 丨 0.013 I 0.012 I 0.012 I 0.005 0.009 I 0.011 0-030 丨 0.039 | | 0.021 1 0.051 I 0.022 0.015 0.016 0.013 I 0.014 I 0.016 1 0.015 1 0.013 I 0.017 0.019 0.052 0.016 0.051 i 0.033 0.020 ! np ss ο «/ί 00 o in 00 o in 00 00 ο 00 ο IT) 00 ο 00 00 8 1 § o \n 00 ο 00 〇 ΙΛ 00 00 〇 00 〇 00 〇〇 00 00 00 I 850 〇 »〇 00 〇 〇 yn 00 00 00 00 00 〇 〇 ο v-) 00 Ο \Τί 00 Ο \η 00 ο ID 00 00 I yn m 00 CO 1 ? (S 卜 卜 卜 卜 卜 守 守 絲 750〇C ^ΜΚ°0 in in m 1 \n in 9 in 1 in f? IT) 1 in in yn yn 1 in U-) m m m 9 1 9 1 κη V) V) cn 1 冷軋 ML 冷軋1 冷軋 冷軋1 冷軋 冷軋Τ Μ· 戚 冷軋1 冷軋 1 冷幸n 冷 冷軋 丨冷軋i 丨冷乱; 丨冷軋1 冷軋 冷軋 冷軋 |冷軋 冷軋 冷軋 冷軋 冷軋 冷幸L 1 冷軋 冷札 冷軋 冷軋 冷軋 冷軋 l冷軋 ^ m ^1¾ S s 〇\ Cs Η 〇〇 Η 〇\ η Os σ\ Η C\ 2 眾 <ξ mm g CO cn rO ro ΓΟ Γ〇 cn cn ΓΟ ro CO CO CO 〇\ 卜 fO ΓΟ cn ro ΓΟ ΓΛ ΓΟ ΓΛ ΓΟ rn η ρη ΓΛ ro rn mm Q Q Q Q Q Q o Q o o o Q Q Q < U W Ρη ο ffi HH »—> Ο α, 〇 Oil 001 Η PI >1 — (S m 寸 Ό 卜 00 Os o cs 2 2 v〇 〇〇 〇\ <N <N m (N CN a CN m in 201213550 由表2可知’本發明法所製造之高強度鋼板,雖係大量含 有Si、Mn等之易氧化性元素的高強度鋼扳,但化成處理性、 電著塗裝後之财#性、加工性優異。 另一方面,比較例中,化成處理性、電著塗裝後之耐蝕性、 加工性係有任一者以上不佳。 (產業上之可利用性) 本發明之高強度顺係化成處理性m加 異,可利用作為用以使⑦車車體本身輕量高強度憂 面處理鋼板。又,除了气車之外,亦可做 表 防鏽性之表面處理鋼板,應㈣ =鋼板賦予 域。 糾領料之廣泛領 【 圖式簡單說明】 圖1為表示Si、Μη之氧化還原平衡與露點 關係之圖 099133254 27PM 3⁄4 ο d ΊΚ Η Τ Η Η KZS660 201213550 The cold-rolled steel is short-lived and smoothed. The continuous annealing zone is set to the temperature of the exposed area as shown in the figure. 'Control the 7 muscles in the annealing furnace to 3 sails (10) seconds; ^ Read After the quenching, the material is carried out. Receiver, in the 40 〇C, 5 皙 〇 〇 / 士 政 政 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Electrolytic pickling was carried out in the order of the anode and the cathode in alternating current of 3 seconds to obtain a sample. In addition, this. In addition, the dew point of the ring furnace is based on _35. 0 - the gas component of the ride is composed of gas and hydrogen and inevitable impurities, and the point f is to dehumidify the water in the environment. The concentration of hydrogen removed in the control of the incoming light is based on volume %. The sample of the two 'π' was sampled according to JIS Z 2241 metal material tensile test method, and the obtained sample was investigated for processability and durability. The oxide (internal oxidation amount) of the surface layer portion of the steel sheet which was present immediately below the surface layer of the steel sheet and cut (4) was measured. The measurement method and evaluation criteria are as follows. (Chemical Processing Property) The evaluation method of the chemical conversion property is described below. In the chemical conversion treatment liquid (Parbond L3080 (registered trademark)) manufactured by PAR本 PARKERIZING Co., Ltd., the chemical conversion treatment was carried out in the following manner. After degreasing with the degreasing liquid Fine Cleaner (registered trademark) manufactured by Japan PARKERIZING Co., Ltd., it was washed with water, and then subjected to surface conditioning of Prepan Z (registered trademark) manufactured by Japan PARKERIZING Co., Ltd. for 30 seconds at 43°. After being immersed in the chemical conversion solution of C (Parbond L3080) for 120 seconds, 099133254 23 201213550 was washed with water and dried with warm air. After the chemical conversion treatment, the sample was evaluated by a broom-type electron microscope (SEM) at a magnification of 500 times - 5 fields of view were observed, and the cell area ratio of the chemical conversion film was measured by image processing. The following evaluation was performed using the cell area ratio. 〇 is a qualified grade. 〇: 10% or less X: more than 10% (corrosion resistance after electrocoating) A test piece having a size of 70 inm×150 mm was cut out from the chemically treated sample obtained by the above method, and PN-150G manufactured by Nippon Paint Co., Ltd. (registered trademark) Conductive electrocoating (hardening conditions: 170 C 20 knives '貘25#m). Thereafter, the end portion was sealed with the surface UAI tape on the side where the evaluation was not performed, and the cutter was transversely cut to reach the base iron (cross-cut angle 60) as a sample. Next, the sample was subjected to a tape _ in a 5 mass% NaC1 aqueous solution (55 immersed in a crucible for 10 hours, and then taken a 'water-washed and then money'), and the tape width was measured. The peeling width was measured, and the following evaluation was carried out. : The peeling width is less than 2.5 mm on one side. • The peeling width is 2.5 mm or more on one side (processability). The workability is JIS No. 5 tensile test piece from the sample in the direction of 9 相对 with respect to the rolling direction, according to JIS Z2241. The stipulation is to carry out the tensile test by measuring the tensile strength (TS/MPa) and the elongation (El%) by the crosshead (four) can (four) 099133254 24 201213550 fixed l〇mm/min, when the TS is less than 650MPa, TSxElk22000 is good for 'TSxEl < 22000. When ts is 650 MPa or more and 900 MPa, 'TSXE12 20000 is good, tsxEI < 20000 is bad. When TS is 900 MPa or more, TSxElg 18000 is good. The TSxElC 18000 is defective. (The amount of internal oxidation in the area of the steel sheet surface ΙΟΟμιη) The internal oxidation amount is measured by the "pulse furnace melting-infrared absorption method". In the present invention, the surface layer portions of both surfaces of the high-strength steel sheet after continuous annealing are polished to 100 μm or more, and the oxygen concentration in the steel is measured, and the measured value is used as the measured value. The amount of oxygen contained in the material was 0 Η, and the oxygen concentration in the steel in the thickness direction of the high-strength steel sheet after continuous annealing was measured, and the measured value was taken as the amount of oxygen 内部1 after internal oxidation. The high-strength steel sheet thus obtained was used. The amount of oxygen contained in the oxygen oxidized 01 and the material after the internal oxidation is calculated as the difference between 01 and ( (=〇Ι-〇Η), and further converted into a value of a single-sided unit area (that is, lm2) ( g/m2) as the internal oxidation amount. The results obtained above are shown in Table 2 together with the production conditions. 099133254 25 201213550 [(Nl 1 good 1 invention example 1 good invention example good invention example good invention example good invention example good invention example) Liangzhu 1 invention example 1 1 good invention example good invention example poor comparison example 1 £ s 1 κ* •^srr •g £ $ s ί % £ -C& fSxEl |Processability 丨Remarks | 1 I $ I 1 i Good invention example good invention example GENERAL EMBODIMENT EXAMPLES GENERAL EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT EMBODIMENT 1 皋 皋 丨 丨 丨 丨 丨 良好 良好 良好 良好 良好 良好 Φ Φ 21 21 21 21 20683 20338 21058 20754 20800 20547 20577 21025 19087 21269 22506 23288 , 20208 I 21213 22069 1 23681 I 21216 20902 19969 21796 21910 1 22186 I 21226 1 21165 17443 .19800 1 16464 5 22079 6 21167 7 \ 22273 m 20.6 : 20.0 : 19.4 20.1 20.6 S 20.1 19.9 21.4 20.9 17.9 19.7 19.9 20.1 26.4 (N 22.0 22.5 1 19.6 19.9 20.8 1 20.7 20.4 〇〇\ (N 20.4 20.6 26.4 20.1 13.8 in vg ) 14; οό vr> 〇0 MPa 1066 : 1031 : 1034 1020 1033 1035 1029 1022 Os ms 1162 1043 1034 1046 3 1008 1023 1035 〇1066 1061 1 1144 1040 1061 1051 1033 1074 1077 s 00 1053 1264 1200 U2C δ t—^ ΓΟ BT—^ Electro-coating 1 唆Tactile XX 〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 X 〇X turns into a 丨. Rational h XXX 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇X 〇XX 〇(4) 1 1 1 1 1 1 1 1 1 1 1 1 〇1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 II 1 1 Electrolytic pickling 1 with or without 4: m 4ί 4: mm Disc 41 φΗ I Life i 0.221 0.143 0.074 0.056 I 0.016 1 0.042 0.009 1 0.005 1 0.010 1 0.012 I 1 0.025 1 丨0.013 I 0.012 I 0.012 I 0.005 0.009 I 0.011 0-030 丨0.039 | | 0.021 1 0.051 I 0.022 0.015 0.016 0.013 I 0.014 I 0.016 1 0.015 1 0.013 I 0.017 0.019 0.052 0.016 0.051 i 0.033 0.020 ! np ss ο «/ί 00 o in 00 o in 00 00 ο 00 ο IT) 00 ο 00 00 8 1 § o \n 00 ο 00 〇ΙΛ 00 00 〇00 〇00 〇 〇00 00 00 I 850 〇»〇00 〇〇yn 00 00 00 00 00 〇〇ο v-) 00 Ο \Τί 00 Ο \η 00 ο ID 00 00 I yn m 00 CO 1 ? (S 卜卜卜卜守守丝750 〇C ^ΜΚ°0 in in m 1 \n in 9 in 1 in f? IT) 1 in in yn yn 1 in U-) mmm 9 1 9 1 κη V) V) cn 1 cold-rolled ML cold-rolled 1 cold-rolled cold-rolled 1 cold-rolled cold-rolled Τ Μ · 戚 cold-rolled 1 cold-rolled 1 cold lucky n cold-rolled cold-rolled cold-rolled i 丨 cold mess;丨Cold rolling 1 cold rolling cold rolling cold rolling|cold rolling cold rolling cold rolling cold rolling cold rolling cold rolling cold L 1 cold rolling cold cold rolling cold rolling cold rolling cold rolling cold rolling l cold rolling ^ m ^13⁄4 S s 〇 \ Cs Η 〇〇Η 〇\ η Os σ\ Η C\ 2 众<ξ mm g CO cn rO ro ΓΟ Γ〇cn cn ΓΟ ro CO CO CO 〇\ 卜 fO ΓΟ cn ro ΓΟ ΓΟ ΓΟ ΓΛ ΓΟ rn η ρη ΓΛ ro Rm mm QQQQQQ o Q ooo QQQ < UW Ρη ο ffi HH »—> Ο α, 〇Oil 001 Η PI >1 — (S m Ό 卜 00 Os o cs 2 2 v〇〇〇〇\ < N <N m (N CN a CN m in 201213550) It can be seen from Table 2 that the high-strength steel sheet produced by the method of the present invention is a high-strength steel sheet containing a large amount of easily oxidizable elements such as Si or Mn, but is chemically processed. Sexuality, electric painting, and good fortune. On the other hand, in the comparative example, the chemical conversion treatment property, the corrosion resistance after the electrocoating, and the workability are not preferable. (Industrial Applicability) The high-strength system of the present invention can be used to treat the steel sheet in a lightweight and high-strength manner for the 7-vehicle body itself. In addition to the air car, it can also be used as a surface-treated steel plate with rust-proof properties. A broad understanding of the materials [Simplified diagram] Figure 1 is a graph showing the relationship between the redox balance of Si and Μη and the dew point. 099133254 27
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JPH0919775A (en) * | 1995-07-06 | 1997-01-21 | Yamaki Kogyo Kk | Lead composite steel and its manufacture |
JPH10110300A (en) * | 1996-10-03 | 1998-04-28 | Hitachi Metals Ltd | Surface cleaning method for steel and steel |
CA2625790C (en) * | 2005-10-14 | 2010-10-12 | Nippon Steel Corporation | Continuous annealing and hot dip plating method and continuous annealing and hot dip plating system of steel sheet containing si |
JP5256936B2 (en) * | 2008-08-26 | 2013-08-07 | Jfeスチール株式会社 | Manufacturing method of high strength cold-rolled steel sheet |
JP5663833B2 (en) * | 2008-11-27 | 2015-02-04 | Jfeスチール株式会社 | Method for producing high-strength hot-dip galvanized steel sheet |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111954727A (en) * | 2018-03-30 | 2020-11-17 | 杰富意钢铁株式会社 | Cold-rolled steel sheet, method for producing same, and cold-rolled steel sheet for annealing |
CN111954727B (en) * | 2018-03-30 | 2022-06-03 | 杰富意钢铁株式会社 | Cold-rolled steel sheet, method for producing same, and cold-rolled steel sheet for annealing |
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