JP2007270341A - Method for producing hot dip galvanized steel sheet - Google Patents

Method for producing hot dip galvanized steel sheet Download PDF

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JP2007270341A
JP2007270341A JP2006207509A JP2006207509A JP2007270341A JP 2007270341 A JP2007270341 A JP 2007270341A JP 2006207509 A JP2006207509 A JP 2006207509A JP 2006207509 A JP2006207509 A JP 2006207509A JP 2007270341 A JP2007270341 A JP 2007270341A
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steel sheet
bath
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plating
austempering
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JP4940813B2 (en
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Yusuke Fushiwaki
祐介 伏脇
Yoshitsugu Suzuki
善継 鈴木
Yoshiharu Sugimoto
芳春 杉本
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Jfe Steel Kk
Jfeスチール株式会社
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<P>PROBLEM TO BE SOLVED: To provide a hot dip galvanized steel sheet having excellent ductility. <P>SOLUTION: Regarding the production method, using a galvanizing bath in which bath temperature is 400 to 450°C, the concentration of Al is 1.0 to 10 mass%, and the concentration of Mg is 0.10 to 10 mass%, hot dip galvanizing treatment and austempering treatment are simultaneously performed. Alternatively, before and after the plating treatment, the steel sheet is held at the above plating bath temperature. The total austempering treatment time of the holding time before and after the plating treatment and the plating treatment time is 50 to 600 s. As a result, the time for which the steel sheet passes through the plating bath can be effectively used for the austempering treatment, thus its ductility is improved. For example, the steel sheet comprises, by mass, 0.05 to 0.20% C, and comprises one or more kinds selected from 0.01 to 3.0% Si, 0.5 to 3.0% Mn and 0.01 to 3.0% Al, and the balance Fe with inevitable impurities. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、延性に優れた溶融亜鉛めっき鋼板を製造する方法に関する。   The present invention relates to a method for producing a hot-dip galvanized steel sheet having excellent ductility.
近年、地球環境保全という観点から、自動車の燃費改善が要求されている。さらに加えて、衝突時に乗員を保護するため、自動車車体の安全性向上も要求されている。このようなことから、自動車車体の軽量化および強化が積極的に進められている。自動車車体の軽量化と強化を同時に満足させるには、部品素材を高強度化することが効果的であると言われており、最近では高張力鋼板が自動車部品に積極的に使用されている。   In recent years, there has been a demand for improving fuel efficiency of automobiles from the viewpoint of global environmental conservation. In addition, in order to protect passengers in the event of a collision, it is also required to improve the safety of automobile bodies. For these reasons, weight reduction and strengthening of automobile bodies are being actively promoted. It is said that it is effective to increase the strength of component materials in order to satisfy the weight reduction and strengthening of the automobile body at the same time. Recently, high-tensile steel plates have been actively used for automobile parts.
鋼板を素材とする自動車部品の多くがプレス加工によって成形されるため、自動車部品用鋼板には優れたプレス成形性が要求される。優れたプレス成形性を実現するには、高い延性を確保することが肝要である。そのため、自動車部品用高張力鋼板には、高い延性を有することが強く求められている。   Since many automobile parts made of steel plates are formed by press working, excellent press formability is required for steel sheets for automobile parts. In order to achieve excellent press formability, it is important to ensure high ductility. Therefore, high tensile strength steel sheets for automobile parts are strongly required to have high ductility.
延性に優れる高張力鋼板としては、フェライトと低温変態相との複合組織からなる組織強化型鋼板が提案されている。この組織強化型鋼板では、フェライトとマルテンサイトの複合組織を有する二相組織鋼板が代表的である。また最近では、残留オーステナイトに起因する変態誘起塑性を利用した高延性鋼板も実用化の段階に至っている。   As a high-strength steel sheet having excellent ductility, a structure-strengthened steel sheet composed of a composite structure of ferrite and a low-temperature transformation phase has been proposed. A typical example of the structure strengthened steel sheet is a duplex steel sheet having a composite structure of ferrite and martensite. Recently, high ductility steel sheets using transformation-induced plasticity due to retained austenite have also been put to practical use.
また、例えば、特許文献1では、溶融亜鉛めっき処理に先立って行う焼鈍の後に、470〜350℃の温度域まで冷却し、この温度域で10〜500秒保持して残留オーステナイトを鋼中に存在させ(以下、オーステンパー処理と称す)、その後に溶融亜鉛めっきを施す製造方法が記載されている。
特開2002-129241号公報
Further, for example, in Patent Document 1, after annealing performed prior to the hot dip galvanizing treatment, the steel is cooled to a temperature range of 470 to 350 ° C. and held in this temperature range for 10 to 500 seconds, and residual austenite is present in the steel. (Hereinafter referred to as austempering), followed by a hot dip galvanizing manufacturing method.
JP 2002-129241 A
しかしながら、特許文献1を通常の溶融亜鉛めっきラインに適用しようとすると、焼鈍炉とめっき浴との間で、470〜350℃の温度域で10〜500秒保持できるような長大な保持帯が必要となり、設備的な制約を受けてしまう。   However, if Patent Document 1 is applied to a normal hot dip galvanizing line, a long holding band that can hold for 10 to 500 seconds in a temperature range of 470 to 350 ° C. is required between the annealing furnace and the plating bath. And is subject to equipment limitations.
本発明はかかる事情に鑑みてなされたものであって、必要最小限の設備でオーステンパー処理を可能とし、かつ、延性に優れた溶融亜鉛めっき鋼鈑を製造する方法を提供することを目的とする。   The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing a hot-dip galvanized steel sheet that enables austempering with the minimum necessary equipment and is excellent in ductility. To do.
鋼板の延性を向上させるには、めっき浴の前後で420〜440℃程度×50〜100s程度保持する加熱処理いわゆるオーステンパー処理を施すことが有効である。しかし、上述のように、めっき浴の前後でオーステンパー処理を施すには、めっき浴の前あるいは後にオーステンパー処理用の設備を新たに設けなくてはならず、かつ設備そのものも長大であるため現実的でない。   In order to improve the ductility of the steel sheet, it is effective to perform a heat treatment so-called austempering treatment that holds about 420 to 440 ° C. for about 50 to 100 seconds before and after the plating bath. However, as described above, in order to perform the austempering treatment before and after the plating bath, a new austempering facility must be provided before or after the plating bath, and the facility itself is long. Not realistic.
そこで、本発明者らは、めっき浴温をオーステンパー処理温度である420〜440℃とすることで、めっき浴中を通過する時間を有効にオーステンパー処理に使い、オーステンパー処理のための設備を簡略化できないかという技術思想を思いつき、この技術思想を基に検討を進めた。その結果、以下の知見を得た。
例えば、780MPa級高張力鋼板に関して、CAL材に比べCGL(1回法)材で延性(El)が劣化(CAL材≧30%、CGL材25%程度)する問題はオーステンパー処理を施すことにより解決する(オーステンパー処理を施すことで延性が向上する)。
一方で、従来から、めっき処理はZn−0.1〜0.2%Al(融点419℃)の溶融Zn浴を用いて浴温460℃程度で実施されている。そのため、めっき浴中でオーステンパー処理しようとすると、浴温を現行の460℃から420〜440℃に低下させなければならない。しかし、融点が419℃であるため420〜440℃での低温操業は安定姓に欠ける。
そこで、浴温を現行460℃から420〜440℃に低下させた場合でも安定操業が可能となる方法を鋭意研究した。浴中成分三元共晶組成での融点低下に着目したところ、Mgをめっき浴に適量含有させることで、めっき浴の融点が低くなり、めっき浴の温度を低下させても安定操業が可能となることを見出した。
Therefore, the present inventors set the plating bath temperature to 420 to 440 ° C. which is the austempering temperature, so that the time for passing through the plating bath is effectively used for the austempering treatment, and the equipment for the austempering treatment is used. I came up with the technical idea of whether or not it could be simplified, and proceeded with a study based on this technical idea. As a result, the following knowledge was obtained.
For example, regarding the 780 MPa class high-tensile steel sheet, the problem that ductility (El) deteriorates (CAL material ≧ 30%, CGL material about 25%) with CGL (single method) material compared to CAL material is due to austempering treatment. Solved (ductility is improved by austempering).
On the other hand, conventionally, the plating treatment is performed at a bath temperature of about 460 ° C. using a Zn-0.1 to 0.2% Al (melting point: 419 ° C.) molten Zn bath. Therefore, when an austemper treatment is performed in the plating bath, the bath temperature must be lowered from the current 460 ° C. to 420 to 440 ° C. However, since the melting point is 419 ° C., low temperature operation at 420 to 440 ° C. is not stable.
Therefore, intensive research was conducted on a method that enables stable operation even when the bath temperature is lowered from the current 460 ° C to 420-440 ° C. Focusing on lowering the melting point of the component ternary eutectic composition in the bath, by adding an appropriate amount of Mg to the plating bath, the melting point of the plating bath is lowered, and stable operation is possible even if the temperature of the plating bath is lowered. I found out that
本発明は、以上の知見に基づきなされたもので、その要旨は以下のとおりである。
[1]鋼板にめっき処理を施し溶融亜鉛めっき鋼板を製造するにあたり、浴温が400〜450℃、浴中Al濃度が1.0〜10mass%、浴中Mg濃度が0.10〜10mass%の亜鉛めっき浴を用いて、鋼板に溶融亜鉛めっき処理と加熱処理を同時に行うことを特徴とする溶融亜鉛めっき鋼板の製造方法。
[2]鋼板にめっき処理を施し溶融亜鉛めっき鋼板を製造するにあたり、400〜450℃まで鋼板を冷却した後に、浴温が400〜450℃、浴中Al濃度が1.0〜10mass%、浴中Mg濃度が0.10〜10mass%の亜鉛めっき浴を用いて、鋼板に溶融亜鉛めっき処理および加熱処理を行い、次いで、400〜450℃にて鋼板を保持し、さらに、冷却時の温度が400〜450℃に到達した時点から保持終了時点までのトータルの処理時間が50s以上600s以下とすることを特徴とする溶融亜鉛めっき鋼板の製造方法。
[3]前記[1]または[2]において、前記鋼板が、mass%で、C:0.05〜0.20%を含有し、Si:0.01〜3.0%、Mn:0.5〜3.0%、Al:0.01〜3.0%の中から1種以上を含み、残部がFe及び不可避的不純物からなることを特徴とする溶融亜鉛めっき鋼板の製造方法。
[4]前記[3]において、さらに、mass%で、Cr:0.01〜2.0%、Mo:0.01〜1.0%、B:0.001〜0.01%の1種または2種以上を含有することを特徴とする溶融亜鉛めっき鋼板の製造方法。
[5]前記[3]または[4]において、さらに、mass%で、V:0.001〜0.1%、Nb:0.001〜0.1%、Ti:0.001〜0.1%の1種または2種以上を含有することを特徴とする溶融亜鉛めっき鋼板の製造方法。
[6]前記[3]〜[5]のいずれかにおいて、さらに、mass%で、Cu:0.01〜2.0%、Ni:0.01〜2.0%、W:0.001〜0.1%の1種または2種以上を含有することを特徴とする溶融亜鉛めっき鋼板の製造方法。
なお、本明細書において、鋼の成分を示す%は、すべてmass%である。
The present invention has been made based on the above findings, and the gist thereof is as follows.
[1] When manufacturing hot-dip galvanized steel sheet by plating the steel sheet, a galvanizing bath with a bath temperature of 400-450 ° C, an Al concentration of 1.0-10 mass% in the bath, and an Mg concentration of 0.10-10 mass% in the bath is used. A method for producing a hot dip galvanized steel sheet, characterized in that a hot dip galvanizing process and a heat treatment are simultaneously performed on the steel sheet.
[2] In manufacturing a hot-dip galvanized steel sheet by plating the steel sheet, after cooling the steel sheet to 400 to 450 ° C, the bath temperature is 400 to 450 ° C, the Al concentration in the bath is 1.0 to 10 mass%, and Mg in the bath Using a galvanizing bath with a concentration of 0.10 to 10 mass%, hot dip galvanizing treatment and heat treatment are performed on the steel plate, then the steel plate is held at 400 to 450 ° C., and the temperature during cooling is 400 to 450 ° C. A method for producing a hot dip galvanized steel sheet, characterized in that the total processing time from the point of reaching to the end of holding is 50 s to 600 s.
[3] In the above [1] or [2], the steel sheet is mass% and contains C: 0.05 to 0.20%, Si: 0.01 to 3.0%, Mn: 0.5 to 3.0%, Al: 0.01 to 3.0. A method for producing a hot-dip galvanized steel sheet, comprising at least one of% and the balance comprising Fe and inevitable impurities.
[4] In the above [3], the composition further comprises one or more of mass: Cr: 0.01 to 2.0%, Mo: 0.01 to 1.0%, B: 0.001 to 0.01%. Manufacturing method of hot dip galvanized steel sheet.
[5] In the above [3] or [4], the material further contains one or more of V: 0.001 to 0.1%, Nb: 0.001 to 0.1%, and Ti: 0.001 to 0.1% in mass%. A method for producing a hot-dip galvanized steel sheet.
[6] In any one of the above [3] to [5], in mass%, Cu: 0.01 to 2.0%, Ni: 0.01 to 2.0%, W: 0.001 to 0.1%, or one or more of A method for producing a hot-dip galvanized steel sheet, comprising:
In addition, in this specification,% which shows the component of steel is all mass%.
本発明によれば、延性に優れた溶融亜鉛めっき鋼板が得られる。従来、溶融亜鉛めっきラインでのオーステンパー処理は不可能であった。しかし、本発明によれば、現行の溶融亜鉛めっきラインで、新たな設備を必要とせずに、オーステンパー処理が可能となる。   According to the present invention, a hot-dip galvanized steel sheet having excellent ductility can be obtained. Conventionally, austempering in a hot dip galvanizing line has been impossible. However, according to the present invention, it is possible to perform austempering on the current hot dip galvanizing line without requiring new equipment.
また、本発明では、浴中にMgを含有させている。そのため、耐食性の向上効果も望める。さらに、一般に、単にめっき浴温を420〜440℃と下げたのでは、浴中で凝固浮遊物が生ずるために表面欠陥が発生するが、本発明では浴の融点そのものを下げているため、420〜440℃℃に制御しても凝固浮遊物が浴内に発生せず、安定操業が可能となる。   In the present invention, Mg is contained in the bath. Therefore, the improvement effect of corrosion resistance can also be expected. Furthermore, in general, when the plating bath temperature is simply lowered to 420 to 440 ° C., surface defects occur due to the formation of solidified suspended matter in the bath, but in the present invention, the melting point of the bath itself is lowered, so 420 Even if the temperature is controlled at ˜440 ° C., solidified suspended matter is not generated in the bath, and stable operation is possible.
以下、本発明について具体的に説明する。
まず、本発明に使用される鋼板について説明する。本発明の鋼板の成分組成は以下の通りである。なお、本発明は以下に示す成分組成に必ずしも限定されないが、高張力溶融亜鉛めっき鋼板を製造する場合は以下に示す成分組成とすることが好ましい。
Hereinafter, the present invention will be specifically described.
First, the steel plate used in the present invention will be described. The composition of the steel sheet of the present invention is as follows. In addition, although this invention is not necessarily limited to the component composition shown below, when manufacturing a high tension hot-dip galvanized steel plate, it is preferable to set it as the component composition shown below.
C:0.05〜0.20%
Cは、鋼板の高強度化に有効な元素であり、さらに残留オーステナイトや低温変態相の生成に効果があり、オーステンパー処理によるTS×Elの向上を確保するために有効な元素である。しかし、C含有量が0.05%未満ではオーステンパー処理による所望の効果を得がたい。一方、0.20%を超えると、溶接性の劣化を招く。以上より、Cは0.05%以上0.20%以下の範囲が好ましい。
さらに、本発明では、オーステンパー処理による強度−伸びバランスの向上を有効に発現させるために、下記の元素のうちの1種または2種以上を含有させることが好ましい。
C: 0.05-0.20%
C is an element effective for increasing the strength of a steel sheet, and further effective for generating retained austenite and a low-temperature transformation phase, and is an element effective for ensuring improvement of TS × El by austempering. However, when the C content is less than 0.05%, it is difficult to obtain a desired effect by the austempering treatment. On the other hand, if it exceeds 0.20%, the weldability is deteriorated. Accordingly, C is preferably in the range of 0.05% or more and 0.20% or less.
Furthermore, in this invention, in order to express the improvement of the strength-elongation balance by an austemper process effectively, it is preferable to contain the 1 type (s) or 2 or more types of the following elements.
Mn:0.5〜3.0%
Mnは、固溶強化により鋼を強化するとともに、鋼の焼入性を向上し、さらに残留オーステナイトや低温変態相の生成を促進する作用を有し、オーステンパー処理による効果を発現させるために有効な元素である。このような作用は、Mn含有量が0.5%以上で認められる。一方、3.0%を超えて含有しても効果が飽和し、含有量に見合う効果が期待できなくなりコストの上昇を招く。以上より、Mnは0.5%以上3.0%以下の範囲が好ましい。
Mn: 0.5-3.0%
Mn strengthens the steel by solid solution strengthening, improves the hardenability of the steel, further promotes the formation of retained austenite and low-temperature transformation phase, and is effective for developing the effects of austempering Element. Such an effect is observed when the Mn content is 0.5% or more. On the other hand, if the content exceeds 3.0%, the effect is saturated, and an effect commensurate with the content cannot be expected, resulting in an increase in cost. From the above, Mn is preferably in the range of 0.5% to 3.0%.
Si:0.01〜3.0%
Siは、固溶強化により鋼を強化するとともに、炭化物の生成を抑制し、オーステナイトを安定化し、残留オーステナイト相の生成を促進する作用を有し、オーステンパー処理による効果を発現させるために有効な元素である。このような作用は、Si含有量が0.01%以上で認められる。一方、3.0%を超えて含有すると、めっき性が顕著に劣化する。以上より、Siは0.01%以上3.0%以下の範囲が好ましい。
Si: 0.01-3.0%
Si strengthens steel by solid solution strengthening, suppresses the formation of carbides, stabilizes austenite, promotes the formation of residual austenite phase, and is effective for expressing the effect of austempering treatment. It is an element. Such an effect is observed when the Si content is 0.01% or more. On the other hand, if the content exceeds 3.0%, the plating property is remarkably deteriorated. Accordingly, Si is preferably in the range of 0.01% to 3.0%.
Al:0.01〜3.0%、
Alは、Siと同様に炭化物の生成を抑制し、残留オーステナイト相の生成を促進する作用を有し、オーステンパー処理による効果を発現させるために有効な元素である。このような作用は、0.01%以上の含有で認められる。一方、3.0%を超える含有は、鋼中の介在物量を増加させ、延性を低下させる。以上より、Alは0.01%以上3.0%以下の範囲が好ましい。
Al: 0.01-3.0%
Al, like Si, suppresses the formation of carbides and promotes the formation of residual austenite phase, and is an effective element for expressing the effect of austempering. Such an effect is recognized when the content is 0.01% or more. On the other hand, the content exceeding 3.0% increases the amount of inclusions in the steel and lowers the ductility. From the above, Al is preferably in the range of 0.01% to 3.0%.
以上の添加元素で、本発明鋼は目的とする特性は得られるが、上記の添加元素に加えて、所望の特性に応じて以下の元素を含有することができる。   With the above additive elements, the steel of the present invention can obtain the desired characteristics, but in addition to the above additive elements, the following elements can be contained according to desired characteristics.
Cr:0.01〜2.0%、Mo:0.01〜1.0%、B:0.001〜0.01%の1種または2種以上
鋼の焼入性を向上し、低温変態相の生成を促進する作用を有する元素である。このような作用は、Cr:0.01%以上、Mo:0.01%以上、B:0.001%以上含有して認められる。一方、Cr:2.0%、Mo:1.0%、B:0.01%を超えて含有しても効果が飽和し、含有量に見合う効果を期待できず、経済的に不利となる。以上より、含有する場合、Crは0.01%以上2.0%以下、Moは0.01%以上1.0%以下、Bは0.001%以上0.01%以下が好ましい。
Cr: 0.01-2.0%, Mo: 0.01-1.0%, B: 0.001-0.01% One or more steels are elements that have the effect of improving the hardenability of steel and promoting the formation of low-temperature transformation phase . Such an effect is observed when Cr: 0.01% or more, Mo: 0.01% or more, and B: 0.001% or more. On the other hand, if the content exceeds Cr: 2.0%, Mo: 1.0%, and B: 0.01%, the effect is saturated, and an effect commensurate with the content cannot be expected, which is economically disadvantageous. Accordingly, when contained, Cr is preferably 0.01% to 2.0%, Mo is 0.01% to 1.0%, and B is preferably 0.001% to 0.01%.
V:0.001〜0.1%、Nb:0.001〜0.1%、Ti:0.001〜0.1%の1種または2種以上
炭窒化物を形成し、鋼を析出効果により高強度化する作用を有する元素であり、必要に応じて添加できる。このような作用は、V、Nb、Tiいずれも0.001%以上含有して認められる。一方、V、Nb、Tiいずれも0.1%を超えて含有する場合、過度に高強度化し、延性が劣化してしまう。以上より、含有する場合、Vは0.001%以上0.1%以下、Nbは0.001%以上0.1%以下、Tiは0.001%以上0.1%以下が好ましい。
V: 0.001 to 0.1%, Nb: 0.001 to 0.1%, Ti: 0.001 to 0.1% one or more carbonitrides are formed, and the element has the effect of increasing the strength of the steel by the precipitation effect, It can be added as necessary. Such an effect is recognized by containing 0.001% or more of V, Nb, and Ti. On the other hand, when V, Nb and Ti are contained in excess of 0.1%, the strength is excessively increased and ductility is deteriorated. Accordingly, when contained, V is preferably 0.001% or more and 0.1% or less, Nb is 0.001% or more and 0.1% or less, and Ti is 0.001% or more and 0.1% or less.
Cu:0.01〜2.0%、Ni:0.01〜2.0%、W:0.001〜0.1%の1種または2種以上
Si、Mnと複合添加する事により、Γ相の生成を抑制し、めっき密着性を向上させる効果がある。このような作用はCu:0.01%以上、Ni:0.01%以上、W:0.001%以上含有して認められる。一方、Cu: 2.0%、Ni:2.0%、W:0.1%を超えて含有しても効果が飽和し、含有量に見合う効果を期待できず、経済的に不利となる。以上より、含有する場合、Cuは0.01%以上2.0%以下、Niは0.01%以上2.0%以下、Wは0.001%以上0.1%以下が好ましい。
Cu: 0.01-2.0%, Ni: 0.01-2.0%, W: 0.001-0.1%
Adding Si and Mn together has the effect of suppressing the formation of the Γ phase and improving the plating adhesion. Such an effect is observed when Cu: 0.01% or more, Ni: 0.01% or more, W: 0.001% or more is contained. On the other hand, if the content exceeds Cu: 2.0%, Ni: 2.0%, W: 0.1%, the effect is saturated, and an effect commensurate with the content cannot be expected, which is economically disadvantageous. Accordingly, when contained, Cu is preferably 0.01% or more and 2.0% or less, Ni is 0.01% or more and 2.0% or less, and W is 0.001% or more and 0.1% or less.
なお、本発明に用いる鋼板は、上記した化学成分以外は、残部Feおよび不可避的不純物からなる。不可避的不純物としては、P:0.05%以下、S:0.02%以下が許容できる。   In addition, the steel plate used for this invention consists of remainder Fe and an unavoidable impurity except the above-mentioned chemical component. As unavoidable impurities, P: 0.05% or less and S: 0.02% or less are acceptable.
次に溶融亜鉛めっき鋼板の製造方法について、説明する。
上記した組成を有する溶鋼を溶製し、通常の公知の方法で鋳造し、通常の公知の方法で熱間圧延、あるいはさらに冷間圧延して、鋼板とする。また、必要に応じて、酸洗あるいは焼鈍等の工程を加えることができる。
次いで、上記により得られた鋼板に溶融亜鉛めっきを施す。なお、この時、本発明においては、浴温が400〜450℃、浴中Al濃度が1.0〜10%、浴中Mg濃度が0.10〜10%の亜鉛めっき浴を用いて溶融亜鉛めっき処理と同時にオーステンパー処理を行うこととする。これは本発明において、重要な要件であり、このようなめっき条件とすることにより、めっき浴を用いて、めっき処理と同時に、オーステンパー処理を行うことが可能となる。そして、このように、オーステンパー処理を行うことで、延性に優れた溶融亜鉛めっき鋼板が得られることになる。以下に詳細に説明する。
Next, the manufacturing method of a hot dip galvanized steel plate is demonstrated.
Molten steel having the above-described composition is melted and cast by a commonly known method, and hot rolled or further cold rolled by a generally known method to obtain a steel plate. Moreover, processes, such as pickling or annealing, can be added as needed.
Next, hot dip galvanizing is performed on the steel sheet obtained as described above. At this time, in the present invention, the bath temperature is 400 to 450 ° C., the Al concentration in the bath is 1.0 to 10%, and the Mg concentration in the bath is 0.10 to 10%. Austempering is performed. This is an important requirement in the present invention. By setting such plating conditions, it becomes possible to perform the austempering treatment simultaneously with the plating treatment using the plating bath. Thus, by performing the austempering treatment, a hot-dip galvanized steel sheet having excellent ductility can be obtained. This will be described in detail below.
通常の溶融亜鉛めっき鋼鈑は、0.1〜0.2%程度のAlを含有させた亜鉛浴を用いて行われている。この場合の溶融亜鉛の融点は419℃であり、浴温は460℃程度で実施されている。そして、上述したように、めっき浴中へ浸漬している間の時間をオーステンパー処理に有効に使おうとした場合、0.1〜0.2%程度のAlを含有させた亜鉛浴では、浴温を420〜440℃程度に制御しようとしても、融点との浴温の差が小さすぎて、全浴内について安定して溶融状態を保つことが困難である。
そこで、発明者らは、めっき浴の温度を下げても安定操業が可能とするために、浴中成分三元共晶組成での融点低下について検討し、Zn浴中にAl、Mgを適量添加することで浴の融点を下げることを発想した。Zn中にMg、Alが存在する場合には、3mass%Mg−4mass%Alである場合に三元共晶により融点は最も低くなり343℃となる。したがって、Mgを3mass%、Alをmass4%近傍とすることで、亜鉛浴の温度は低温化することが可能となる。Mgは、めっき鋼板が腐食環境下に暴露されたとき、めっき表面に安定錆を形成させる作用を有し、めっき鋼板の耐食性を向上させる。この効果を得るためには、Mg:0.10〜10%とする。0.10%未満では、上記効果が得られず、10%を超えると、めっき浴の粘度が増大し、めっき付着量制御が困難となる。
上記思想を基に、Mg、Al量を種々の値とし、浴温度を420〜430℃に制御した溶融亜鉛浴を準備して、溶融亜鉛めっき鋼鈑を製造し、浴中の凝固物発生による欠陥発生有無、および、得られた溶融亜鉛めっき鋼板の耐食性を調査した。なお、上記欠陥とは、浴中に凝固物が発生しこれを巻き込んで疵となったり、付着した場合である。
Ordinary hot-dip galvanized steel sheets are made using a zinc bath containing about 0.1 to 0.2% Al. In this case, the melting point of molten zinc is 419 ° C., and the bath temperature is about 460 ° C. And as mentioned above, when trying to use the time during immersion in the plating bath effectively for the austempering treatment, in the zinc bath containing about 0.1 to 0.2% Al, the bath temperature is 420 to Even if the temperature is controlled to about 440 ° C., the difference in bath temperature from the melting point is too small, and it is difficult to maintain a stable molten state in the entire bath.
Therefore, in order to enable stable operation even when the temperature of the plating bath is lowered, the inventors examined the melting point decrease in the component ternary eutectic composition in the bath, and added appropriate amounts of Al and Mg in the Zn bath. The idea was to lower the melting point of the bath. When Mg and Al are present in Zn, the melting point becomes the lowest at 343 ° C. due to ternary eutectic in the case of 3 mass% Mg-4 mass% Al. Therefore, the temperature of the zinc bath can be lowered by setting Mg to 3 mass% and Al to the mass 4%. Mg has the effect of forming stable rust on the plated surface when the plated steel sheet is exposed to a corrosive environment, and improves the corrosion resistance of the plated steel sheet. In order to obtain this effect, Mg: 0.1 to 10% is set. If it is less than 0.10%, the above-mentioned effect cannot be obtained, and if it exceeds 10%, the viscosity of the plating bath increases, and it becomes difficult to control the amount of plating.
Based on the above idea, a hot dip galvanized steel bath prepared with various values of Mg and Al and a bath temperature controlled at 420 to 430 ° C. is manufactured, and a hot dip galvanized steel sheet is produced. The presence or absence of defects and the corrosion resistance of the obtained hot-dip galvanized steel sheet were investigated. In addition, the said defect is a case where a solidified substance generate | occur | produces in a bath, and this entrains and becomes a wrinkle or adheres.
得られた結果を図1に示す。図1中の○は欠陥発生、耐食性がともに問題ないレベルであることを、図中の●は欠陥または耐食性が問題あるレベルであることを示す(判定基準は後述の実施例のように、凝固物付着あるいは疵発生のいずれかが不良である場合を●とした。耐食性についても、後述の実施例のように評価し不良である場合を●とした。)。
図1から、Zn中のAl濃度が1.0〜10%、Mg濃度が0.10〜10%を満足する場合に、浴温度を420〜430℃程度にまで低温化した場合であっても、凝固物による欠陥発生が問題ないレベルであることがわかる。
The obtained results are shown in FIG. 1 in FIG. 1 indicates that there is no problem with the occurrence of defects and corrosion resistance, and ● in the figure indicates that there is a problem with defects or corrosion resistance (the criterion is solidification as in the examples described later). The case where either object adhesion or wrinkle generation is defective is indicated by ●, and the corrosion resistance is also evaluated as in the examples described later, and the case where it is defective is indicated by ●.
From FIG. 1, when the Al concentration in Zn satisfies 1.0 to 10% and the Mg concentration satisfies 0.10 to 10%, even if the bath temperature is lowered to about 420 to 430 ° C, It can be seen that there is no problem in generating defects.
以上より、本発明ではめっき浴中にAlを1.0%以上10%以下、Mgを0.10%以上10%以下含有するもののとする。   From the above, in the present invention, the plating bath contains Al in the range of 1.0% to 10% and Mg in the range of 0.10% to 10%.
次に最適なオーステンパー処理温度を調査するため、オーステンパー処理温度とTS×Elとの関係を調査した。図2は、C:0.18%、Si:0.45%、Mn:1.8%を含有する板厚1mmの冷延鋼鈑について、770℃あるいは800℃で30秒の焼鈍を行った後、熱処理(図中のオーステンパー処理温度まで30秒で冷却し、次いで、図中のオーステンパー処理温度で50秒保持した後冷却する)を行った場合の、TS×Elに及ぼすオーステンパー処理温度の影響を示す図である。図2より、焼鈍温度が770℃、800℃いずれの場合でも、オーステンパー処理温度が400〜450℃である場合には、TS×Elの値が高い値を示すことがわかる。したがって、本発明においては、オーステンパー処理温度は400〜450℃の範囲とする。すなわち、本発明において、亜鉛めっきの浴温は400℃以上450℃以下とする。このような温度範囲でオーステンパー処理を行うことで、例えば、780MPa級高張力鋼板では、CGLでCAL材並の高El(30%)を確保することができるようになる。   Next, in order to investigate the optimum austempering temperature, the relationship between the austempering temperature and TS × El was investigated. Fig. 2 shows a cold rolled steel sheet with a thickness of 1 mm containing C: 0.18%, Si: 0.45%, Mn: 1.8%, after annealing at 770 ° C or 800 ° C for 30 seconds, followed by heat treatment (in the figure Figure shows the effect of austempering temperature on TS x El when cooling to austempering temperature of 30 seconds and then cooling after holding for 50 seconds at the austempering temperature in the figure) It is. From FIG. 2, it can be seen that the value of TS × El shows a high value when the austempering temperature is 400 to 450 ° C., regardless of whether the annealing temperature is 770 ° C. or 800 ° C. Accordingly, in the present invention, the austempering temperature is in the range of 400 to 450 ° C. That is, in the present invention, the bath temperature of galvanization is set to 400 ° C. or higher and 450 ° C. or lower. By performing the austempering treatment in such a temperature range, for example, with a 780 MPa class high-tensile steel plate, it is possible to ensure a high El (30%) equivalent to that of a CAL material with CGL.
さらに、上記結果に基づき、オーステンパー処理時間について調査した。図3は、C:0.18%、Si:0.45%、Mn:1.8%を含有する板厚1mmの冷延鋼鈑について、770℃あるいは800℃で30秒の焼鈍を行った後、420℃まで30秒で冷却し、その後、420℃でオーステンパー処理を行った場合の、オーステンパー処理時間がTS×Elの値に及ぼす影響を示す図である。図3より、オーステンパー処理時間が50秒以上で、良好なTS×Elの値が得られることがわかる。よって、本発明においてはオーステンパー処理時間の下限値は50秒とする。一方、処理時間が長すぎると生産性が悪くなるので、上限値は600秒以下とする。
なお、本発明においては、めっき浴中を通過する時間を有効にオーステンパー処理に使うことを基本思想としているため、オーステンパー処理はめっき処理と同時に行うことを前提とする。しかし、めっき処理時間が短く、めっき処理時間内にオーステンパー処理が完了せず時間が不足する場合は、めっき処理前後において鋼板をめっき浴温(オーステンパー処理温度)で保持することにより不足時間を補うことができる。すなわち、本発明では、オーステンパー処理時間とは、めっき処理前後でのオーステンパー処理温度(400〜450℃)での保持時間とめっき処理時間を合わせてのトータルの処理時間とする。トータルで50秒以上保持できれば、特性(TS×El)は満足できるため、オーステンパー処理時間としては、めっき処理時間のみでも、めっき処理時間とめっき処理前後の保持時間のトータルであってもよい。
めっき付着量は特に定めないが、耐食性及びめっき付着量制御上10g/m2以上が好ましく、加工性の観点から120g/m2以下が好ましい。
Further, based on the above results, the austempering time was investigated. FIG. 3 shows that a cold rolled steel sheet having a thickness of 1 mm containing C: 0.18%, Si: 0.45%, Mn: 1.8% is annealed at 770 ° C or 800 ° C for 30 seconds, and then up to 420 ° C. It is a figure which shows the influence which the austempering process time has on the value of TSxEl at the time of cooling in second and performing an austempering process at 420 degreeC after that. FIG. 3 shows that a good TS × El value can be obtained when the austempering time is 50 seconds or more. Therefore, in the present invention, the lower limit of the austempering time is 50 seconds. On the other hand, if the processing time is too long, the productivity is deteriorated, so the upper limit is set to 600 seconds or less.
In the present invention, since the basic idea is to use the time for passing through the plating bath effectively for the austempering process, it is assumed that the austempering process is performed simultaneously with the plating process. However, if the plating process time is short and the austempering process is not completed within the plating process time and the time is insufficient, the time is reduced by maintaining the steel plate at the plating bath temperature (austempering temperature) before and after the plating process. Can be supplemented. That is, in the present invention, the austempering time is the total processing time including the holding time at the austempering temperature (400 to 450 ° C.) before and after the plating and the plating time. Since the characteristics (TS × E1) can be satisfied if the total holding time is 50 seconds or longer, the austempering time may be only the plating time or the total of the plating time and the holding time before and after the plating.
The plating adhesion amount is not particularly defined, but is preferably 10 g / m 2 or more from the viewpoint of corrosion resistance and plating adhesion amount, and preferably 120 g / m 2 or less from the viewpoint of workability.
以上により、JIS5号引張試験片を採取し,引張試験を行って測定した引張強さTS(MPa)及び伸びEl(%)において,TS×Elの値が21000MPa・%以上である溶融亜鉛めっき鋼板が得られる。   As mentioned above, hot-dip galvanized steel sheet with a tensile strength TS (MPa) and elongation El (%) measured by taking a JIS No. 5 tensile test piece and having a value of TS x El of 21000 MPa ·% or more. Is obtained.
また、溶融亜鉛めっき処理後、合金化処理を施してもよい。合金化処理は、溶融亜鉛めっき処理後、460℃〜570℃の温度域まで再加熱し溶融亜鉛めっき皮膜の合金化を行う。460℃以下では合金化進行が遅く、570℃以上では過合金により地鉄界面に生成する固くて脆いZn-Fe合金層が生成しすぎてめっき密着性が劣化するだけでなく、残留オーステナイト相が分解するため、強度延性バランスも劣化する。合金化処理後は、5℃/sec以上の冷却速度で300℃まで冷却するのが好ましい。合金化処理後の冷却速度が極端に低い場合には、必要な残留オーステナイトの確保が困難になる。このため、合金化処理後から300℃までの温度範囲における冷却速度を5℃/sec以上に限定するのが好ましい。   Further, an alloying treatment may be performed after the hot dip galvanizing treatment. In the alloying treatment, after the hot dip galvanizing treatment, the hot dip galvanized film is alloyed by reheating to a temperature range of 460 ° C to 570 ° C. Below 460 ° C, alloying progresses slowly, and at 570 ° C and above, a hard and brittle Zn-Fe alloy layer formed on the iron-iron interface due to overalloying is formed not only to deteriorate the plating adhesion but also the residual austenite phase. Since it decomposes, the strength ductility balance also deteriorates. After the alloying treatment, it is preferable to cool to 300 ° C. at a cooling rate of 5 ° C./sec or more. If the cooling rate after the alloying process is extremely low, it becomes difficult to secure the necessary retained austenite. For this reason, it is preferable to limit the cooling rate in the temperature range from 300 degreeC after an alloying process to 5 degrees C / sec or more.
なお、めっき処理後あるいは合金化処理後の鋼板には、形状矯正、表面粗度等の調整のための調質圧延を加えてもよい。また、樹脂あるいは油脂コーティング、各種塗装等の処理を施しても何ら不都合はない。   In addition, you may add the temper rolling for adjustment of shape correction, surface roughness, etc. to the steel plate after a plating process or an alloying process. In addition, there is no inconvenience even if treatments such as resin or oil coating and various paintings are applied.
以下、本発明を実施例に基づいて具体的に説明する。
表1に示す成分組成を有する冷延鋼鈑(板厚1.0mm×幅1000mm)について、800℃×30秒の焼鈍を行った後、めっき浴温と同一となる温度まで冷却した。次いで、表2〜表4に示すAl濃度、Mg濃度、浴温の溶融亜鉛めっき浴を用いて溶融亜鉛めっきおよびオーステンパー処理を施した。さらにめっき浴通過後にめっき浴温と同一温度で保持を行った。鋼鈑温度がめっき浴温となった時点から保持終了までの時間をオーステンパー処理時間として表2〜表4に示す。なお、各条件につき1コイル(10t)について行い、めっき付着量は30〜60g/mとした。
Hereinafter, the present invention will be specifically described based on examples.
Cold-rolled steel sheets having a composition shown in Table 1 (plate thickness 1.0 mm × width 1000 mm) were annealed at 800 ° C. for 30 seconds and then cooled to a temperature equal to the plating bath temperature. Next, hot dip galvanization and austempering treatment were performed using a hot dip galvanizing bath having Al concentration, Mg concentration and bath temperature shown in Tables 2 to 4. Further, after passing through the plating bath, it was held at the same temperature as the plating bath temperature. Tables 2 to 4 show the time from when the steel plate temperature reaches the plating bath temperature to the end of holding as the austempering time. In addition, it performed about 1 coil (10t) for each conditions, and the plating adhesion amount was 30-60 g / m < 2 >.
上記により得られた溶融亜鉛めっき鋼鈑について、下記に示す方法にて機械的特性、凝固浮遊物付着あるいは疵の有無、耐食性の調査を行った。得られた結果を条件と併せて表2〜4に示す。   The hot-dip galvanized steel sheet obtained as described above was investigated for mechanical properties, adhesion of solidified suspended solids, presence or absence of defects, and corrosion resistance by the following methods. The obtained results are shown in Tables 2 to 4 together with the conditions.
機械的特性
JIS5号引張試験片を採取し引張試験を行って引張強さTS(MPa)及び伸びEl(%)を測定した。TS×Elの値が21000MPa・%以上で機械特性○、21000MPa・%未満では×とした。
Mechanical properties
A JIS No. 5 tensile test piece was collected and subjected to a tensile test to measure the tensile strength TS (MPa) and elongation El (%). The mechanical properties were good when the TS x El value was 21000 MPa ·% or more, and x when it was less than 21000 MPa ·%.
凝固浮遊物付着あるいは疵の有無
それぞれ1コイルについて欠陥の有無を目視判定し、欠陥数が1個/m以上を不良(×)、1個/m未満を良好(○)とした。
Coagulated suspended matter adhering or visually determined whether the presence or absence of a defect for each first coil of the flaw, defect one / m 2 or more the number of defects (×), and less than 1 / m 2 and good (○).
耐食性
JIS Z2371に基づく塩水噴霧試験を3日間行い、腐食生成物をクロム酸を用いて洗浄除去し、試験前後のめっき腐食減量(g/m2・日)を重量法にて測定し、下記基準で評価した。
○(良好):20 g/m2・日未満
×(不良):20 g/m2・日以上
Corrosion resistance
A salt spray test based on JIS Z2371 was conducted for 3 days. Corrosion products were washed away with chromic acid, and the plating corrosion weight loss (g / m 2 · day) before and after the test was measured by the gravimetric method. evaluated.
○ (Good): Less than 20 g / m 2 · day × (Bad): 20 g / m 2 · day or more
表2〜4より、本発明例では、機械的特性、凝固浮遊物付着あるいは疵の有無、耐食性のいずれも良好な結果が得られている。   From Tables 2 to 4, in the examples of the present invention, good results were obtained in all of the mechanical properties, adhesion of solidified suspended solids, presence or absence of wrinkles, and corrosion resistance.
本発明のめっき鋼板の製造方法によれば、高張力でありながら、延性にも優れており、かつ、表面欠陥もなく耐食性にも優れた溶融亜鉛めっき鋼板を製造でき、自動車部品を中心に、幅広い用途での使用が見込まれる。   According to the method for producing a plated steel sheet of the present invention, it is possible to produce a hot-dip galvanized steel sheet that is excellent in ductility and excellent in corrosion resistance while having high tension, mainly in automobile parts, Expected to be used in a wide range of applications.
浴中成分三元共晶組成と浴中の凝固物発生による欠陥発生有無および耐食性との関係を示す図である。It is a figure which shows the relationship between the component ternary eutectic composition in a bath, the presence or absence of the defect by the solidified substance generation | occurrence | production in a bath, and corrosion resistance. TS×Elに及ぼすオーステンパー処理温度の影響を示す図である。It is a figure which shows the influence of the austempering process temperature which acts on TSxEl. オーステンパー処理時間がTS×Elの値に及ぼす影響を示す図である。It is a figure which shows the influence which an austemper process time has on the value of TSxEl.

Claims (6)

  1. 鋼板にめっき処理を施し溶融亜鉛めっき鋼板を製造するにあたり、
    浴温が400〜450℃、浴中Al濃度が1.0〜10mass%、浴中Mg濃度が0.10〜10mass%の亜鉛めっき浴を用いて、鋼板に溶融亜鉛めっき処理と加熱処理を同時に行うことを特徴とする溶融亜鉛めっき鋼板の製造方法。
    In producing a hot-dip galvanized steel sheet by plating the steel sheet,
    A hot dip galvanizing treatment and a heat treatment are performed simultaneously on a steel sheet using a galvanizing bath having a bath temperature of 400 to 450 ° C., an Al concentration of 1.0 to 10 mass% in the bath, and an Mg concentration of 0.10 to 10 mass% in the bath. A method for producing a hot-dip galvanized steel sheet.
  2. 鋼板にめっき処理を施し溶融亜鉛めっき鋼板を製造するにあたり、
    400〜450℃まで鋼板を冷却した後に、
    浴温が400〜450℃、浴中Al濃度が1.0〜10mass%、浴中Mg濃度が0.10〜10mass%の亜鉛めっき浴を用いて、鋼板に溶融亜鉛めっき処理および加熱処理を行い、
    次いで、400〜450℃にて鋼板を保持し、
    さらに、冷却時の温度が400〜450℃に到達した時点から保持終了時点までのトータルの処理時間が50s以上600s以下とすることを特徴とする溶融亜鉛めっき鋼板の製造方法。
    In producing a hot-dip galvanized steel sheet by plating the steel sheet,
    After cooling the steel plate to 400-450 ° C,
    Using a galvanizing bath with a bath temperature of 400 to 450 ° C, an Al concentration of 1.0 to 10 mass% in the bath, and an Mg concentration of 0.10 to 10 mass% in the bath, hot dip galvanizing treatment and heat treatment are performed on the steel plate,
    Next, hold the steel plate at 400-450 ° C,
    Furthermore, the manufacturing method of the hot dip galvanized steel sheet characterized by making the total processing time from the time when the temperature at the time of cooling reaches 400 to 450 ° C. to the end of holding to be 50 s or more and 600 s or less.
  3. 前記鋼板が、mass%で、C:0.05〜0.20%を含有し、Si:0.01〜3.0%、Mn:0.5〜3.0%、Al:0.01〜3.0%の中から1種以上を含み、残部がFe及び不可避的不純物からなることを特徴とする請求項1または2に記載の溶融亜鉛めっき鋼板の製造方法。   The steel sheet is mass% and contains C: 0.05 to 0.20%, Si: 0.01 to 3.0%, Mn: 0.5 to 3.0%, Al: 0.01 to 3.0%, and the balance is Fe. The method for producing a hot-dip galvanized steel sheet according to claim 1 or 2, wherein the hot-dip galvanized steel sheet is made of inevitable impurities.
  4. さらに、mass%で、Cr:0.01〜2.0%、Mo:0.01〜1.0%、B:0.001〜0.01%の1種または2種以上を含有することを特徴とする請求項3に記載の溶融亜鉛めっき鋼板の製造方法。   The hot dip galvanizing according to claim 3, further comprising one or more of Cr: 0.01 to 2.0%, Mo: 0.01 to 1.0%, and B: 0.001 to 0.01% in mass%. A method of manufacturing a steel sheet.
  5. さらに、mass%で、V:0.001〜0.1%、Nb:0.001〜0.1%、Ti:0.001〜0.1%の1種または2種以上を含有することを特徴とする請求項3または4に記載の溶融亜鉛めっき鋼板の製造方法。   The melt according to claim 3 or 4, further comprising at least one of V: 0.001 to 0.1%, Nb: 0.001 to 0.1%, and Ti: 0.001 to 0.1% in mass%. Manufacturing method of galvanized steel sheet.
  6. さらに、mass%で、Cu:0.01〜2.0%、Ni:0.01〜2.0%、W:0.001〜0.1%の1種または2種以上を含有することを特徴とする請求項3〜5のいずれかに記載の溶融亜鉛めっき鋼板の製造方法。   Furthermore, in mass%, Cu: 0.01-2.0%, Ni: 0.01-2.0%, W: 0.001-0.1% of 1 type or 2 types or more are contained, In any one of Claims 3-5 characterized by the above-mentioned. The manufacturing method of the hot-dip galvanized steel sheet of description.
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