JPH0734210A - Production of high tensile strength hot-dip galvanized or galvannealed steel sheet - Google Patents
Production of high tensile strength hot-dip galvanized or galvannealed steel sheetInfo
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- JPH0734210A JPH0734210A JP17409393A JP17409393A JPH0734210A JP H0734210 A JPH0734210 A JP H0734210A JP 17409393 A JP17409393 A JP 17409393A JP 17409393 A JP17409393 A JP 17409393A JP H0734210 A JPH0734210 A JP H0734210A
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- Prior art keywords
- steel sheet
- oxidation
- hot
- dip galvanized
- atmosphere
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は主として自動車材料用の
溶融亜鉛めっき高張力鋼板、合金化溶融亜鉛めっき高張
力鋼板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a hot dip galvanized high-strength steel sheet for automobile materials and a method for producing an alloyed hot dip galvanized high-strength steel sheet.
【０００２】[0002]
【従来の技術】合金化溶融亜鉛めっき鋼板は優れた塗装
後耐食性を有しているために、自動車車体の内板、外
板、構造部品などの自動車材料に広く使用されている。
合金化溶融亜鉛めっきの製法としては各種あるが、コス
ト、生産能率のためにライン内焼鈍方式（材質を得るた
めの焼鈍と表面のＦｅ酸化物を還元する焼鈍を兼ねて焼
鈍し、その後溶融亜鉛めっきし、加熱により合金化処理
する）が主流である（鉄鋼便覧第３版第６巻４２１ｐ
（１９８２）丸善）。ライン内焼鈍方式の中でも初期の
ゼンジミア方式ではバーナーのフレームの直火による酸
化により油などのクリーニングを行い、その後還元焼鈍
するもの（いわゆる酸化炉）であったが、Ｆｅが酸化さ
れること、昇温速度が遅くライン長さが長大化するなど
の問題があった。そのため、現在ではゼンジミア方式は
廃れ、無酸化炉方式、さらには電解脱脂方式が主流とな
っている。すなわち油などの除去の表面清浄化を工夫
し、鋼板表面のＦｅを酸化させない方式となっている。
これらの方法で通常の鋼板を何の問題もなく、溶融亜鉛
めっき、合金化溶融亜鉛めっきしている。2. Description of the Related Art Alloyed hot-dip galvanized steel sheets are widely used for automobile materials such as inner plates, outer plates and structural parts of automobile bodies because of their excellent corrosion resistance after painting.
There are various methods for galvannealing, but for cost and production efficiency, in-line annealing method (annealing to obtain the material and annealing to reduce Fe oxide on the surface is also performed, and then hot dip galvanizing The mainstream is plating and alloying by heating (Steel Handbook, 3rd Edition, Vol. 6, 421p).
(1982) Maruzen). Among the in-line annealing methods, the initial Sendzimir method was one in which oil and other materials were cleaned by direct flame oxidation of the burner, and then reduction annealing was performed (so-called oxidation furnace). There was a problem that the temperature was slow and the line length was lengthened. Therefore, the Sendzimir method is now obsolete, and the non-oxidizing furnace method and the electrolytic degreasing method are in the mainstream. That is, it is a system that does not oxidize Fe on the surface of the steel sheet by devising surface cleaning for removing oil and the like.
With these methods, normal steel sheets are hot dip galvanized and alloyed hot dip galvanized without any problems.
【０００３】一方、自動車車体の軽量化のために、鉄鋼
材料の高張力化が要求されている。特にＣＡＦＥで自動
車の燃費の向上が要求されたため、そのニーズは強いも
のがある。従って合金化溶融亜鉛めっき高張力鋼板が必
要となった。高張力化する場合、固溶強化や組織強化な
どの方法があるが、いずれにしろ、Ｆｅ以外の添加元素
が必要である。On the other hand, in order to reduce the weight of automobile bodies, it is required to increase the tensile strength of steel materials. In particular, CAFE is required to improve the fuel efficiency of automobiles, and there is a strong need for it. Therefore, alloyed hot-dip galvanized high-strength steel sheets were needed. In order to increase the tensile strength, there are methods such as solid solution strengthening and structure strengthening, but in any case, an additive element other than Fe is necessary.
【０００４】[0004]
【発明が解決しようとする課題】強化元素としては、
Ｃ，Ｓｉ，Ｍｎ，Ｐ，Ｃｒ，Ｎｉ，Ｍｏ，Ｔｉ，Ｎｂな
どがあるが、これらの内Ｓｉ，Ｍｎ，Ｃｒは著しくめっ
き性を阻害することを知見した。すなわち、Ｓｉ，Ｍ
ｎ，Ｃｒを１種以上を合計で１．０％以上添加した４５
ｋｇ／ｍ2 以上の高張力鋼板の合金化溶融Ｚｎめっき鋼
板を製造しようとした場合、溶融亜鉛めっき時に亜鉛め
っきが全面を覆わず、不めっきが発生した。[Problems to be Solved by the Invention] As the strengthening element,
Although there are C, Si, Mn, P, Cr, Ni, Mo, Ti, Nb, etc., it was found that Si, Mn, Cr of these significantly hinder the plating property. That is, Si, M
One or more kinds of n and Cr added in total of 1.0% or more 45
When an alloyed hot-dip galvanized steel sheet of a high-strength steel sheet of kg / m 2 or more was to be produced, galvanization did not cover the entire surface during hot dip galvanizing, resulting in non-plating.
【０００５】本発明は上記の不めっきを抑制した特にＳ
ｉ，Ｍｎ，Ｃｒなどの添加元素を１種以上合計で１．０
ｗｔ％以上含有する４５ｋｇ／ｍ2 以上の溶融亜鉛めっ
き鋼板または合金化溶融亜鉛めっき高張力鋼板の製造方
法を提供することを目的とするものである。The present invention suppresses the above non-plating, especially S
1.0 or more in total of one or more additive elements such as i, Mn, and Cr
it is an object to provide a method for producing 45 kg / m 2 or more galvanized steel sheet or galvannealed high-strength steel sheets containing more wt%.
【０００６】[0006]
【課題を解決するための手段】上記の問題を解決するた
めの従来技術としては、特開昭５５−１２２８６５号
（無酸化炉方式（ＮＯＦ）において鋼板表面酸化膜を４
００−１００００Åとする）がある。しかしながらこの
方法では見体的方法としてＮＯＦを使用しているため
に、効果が安定しないという致命的な欠陥があった。こ
の技術をさらに発展させたものとして特開平４−２０２
６３０号、同２０２６３２号、同２０２６３３号、同２
０２６３１号、同２５４５３１号、同２５４５３２号な
ど多数の改良技術がある。これらの技術は特開昭５５−
１２２８６５号では効果が安定して得られないことか
ら、例えば、酸化速度や還元量を規定したり、酸化帯で
の酸化膜厚を実測し、これから酸化条件や還元条件を制
御して効果を安定化させようとしたものである。しか
し、我々の検討結果からはこれら技術でもなお効果は不
安定であった。これらの従来技術はいずれもＮＯＦ型の
加熱方式によるものである。As a conventional technique for solving the above problems, Japanese Patent Application Laid-Open No. 55-122865 (a non-oxidizing furnace system (NOF) uses a steel sheet surface oxide film of
00-10000Å). However, this method has a fatal defect that the effect is not stable because NOF is used as an apparent method. As a further development of this technology, JP-A-4-202
No. 630, No. 202632, No. 202633, No. 2
There are many improved technologies such as 02631, No. 254531, and No. 254532. These techniques are disclosed in JP-A-55-
Since the effect cannot be stably obtained with No. 122865, for example, the oxidation rate and the reduction amount are regulated, the oxide film thickness in the oxidation zone is actually measured, and then the oxidation condition and the reduction condition are controlled to stabilize the effect. I tried to make it happen. However, from the results of our study, the effect was still unstable even with these technologies. All of these conventional techniques are based on the NOF type heating method.
【０００７】加熱方式としてＮＯＦでなくオールラジア
ント方式の炉を有するＣＧＬが近年開発されており、そ
の場合、ＮＯＦでは無く、別の酸化方法が必要となる。
そこで、本発明者らは、ＮＯＦを使用した酸化方式では
何故に効果が安定しないかの原因追求を行い、ＮＯＦ以
外の安定した効果を得られる酸化方法を検討した結果、
本発明に至ったものである。In recent years, CGL having an all-radiant furnace instead of NOF as a heating system has been developed. In that case, another oxidation method is required instead of NOF.
Therefore, the inventors of the present invention have investigated the cause of why the effect is not stable in the oxidation method using NOF, and as a result of studying an oxidation method that can obtain a stable effect other than NOF,
The present invention has been achieved.
【０００８】すなわち、本発明は、焼鈍炉を有する連続
溶融亜鉛めっき設備を用いて、溶融亜鉛めっき鋼板また
は合金化溶融亜鉛めっき鋼板を製造するに際し、焼鈍炉
の予熱帯（プリヒートセクション）にてＯ2 濃度０．１
〜１００％の雰囲気で板温４００〜６５０℃に加熱して
Ｆｅを酸化させた後、通常の還元焼鈍、溶融Ｚｎめっ
き、合金化処理を行うことを特徴とする高張力溶融また
は合金化溶融亜鉛めっき鋼板の製造方法を提供するもの
である。That is, according to the present invention, when a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet is produced by using a continuous hot-dip galvanizing equipment having an annealing furnace, the O 2 concentration 0.1
High-strength molten or alloyed molten zinc characterized by performing normal reduction annealing, hot dip Zn plating, and alloying treatment after heating at a plate temperature of 400 to 650 ° C in an atmosphere of -100% to oxidize Fe. A method for manufacturing a plated steel sheet is provided.
【０００９】ここで、鋼板表面のＦｅを酸化させる予熱
帯の雰囲気は実質的にＯ2 −Ｎ2 系のみのガスのがよい
が、高張力鋼板に対しては特にＨ2 Ｏおよび／またはＣ
Ｏ2を含有していてもよい。酸化のための加熱方式は、
オールラジアント式、誘導加熱式、ガスジェット式、通
電加熱式、電気炉式のいずれかが好ましい。Here, the pretropical atmosphere for oxidizing Fe on the surface of the steel sheet is preferably a gas of only O 2 -N 2 system, but especially for high strength steel sheet, H 2 O and / or C
It may contain O 2 . The heating method for oxidation is
Any of the all radiant type, induction heating type, gas jet type, electric heating type, and electric furnace type is preferable.
【００１０】[0010]
【作用】以下に本発明をさらに詳細に説明する。ＮＯＦ
においてめっき性の改善効果が不安定であるのは、酸化
量が変動してしまうためである。そのため、酸化量不足
や過多、また、その後の還元焼鈍時の還元不足によるＦ
ｅ酸化物による不めっきや還元過多によるＳｉ，Ｍｎな
どの添加元素の表面濃化による不めっきが発生する。The present invention will be described in more detail below. NOF
The effect of improving the plating property is unstable because the amount of oxidation varies. Therefore, the amount of oxidation is insufficient or excessive, and the reduction is insufficient during subsequent reduction annealing.
Non-plating due to e oxide or non-plating due to surface concentration of additional elements such as Si and Mn due to excessive reduction occurs.
【００１１】そこで、雰囲気中の組成が酸化量に及ぼす
影響を調査した。その結果を図１に示す。図１から明ら
かなように、Ｏ2 濃度０．１％以下では、Ｏ2 濃度によ
り酸化量の変動が著しく大きいことがわかる。ＮＯＦの
操業条件である空気比（空気／燃料の理論比率）が１．
０未満ではＯ2 濃度は理論上０％であるが、実際には
０．０１〜０．０８％程度のＯ2 濃度が測定される。ま
た空気比１．０〜１．１では０．０１〜０．５％程度の
Ｏ2 濃度が測定される。すなわち、ＮＯＦによる酸化で
は、空気比が通常０．９０〜０．９９で操業され、前述
の従来技術０．９〜１．１の範囲では酸化量が本質的に
変動しやすい。Therefore, the influence of the composition in the atmosphere on the amount of oxidation was investigated. The result is shown in FIG. As is clear from FIG. 1, when the O 2 concentration is 0.1% or less, the variation of the oxidation amount is significantly large depending on the O 2 concentration. The air ratio (air / fuel theoretical ratio), which is the operating condition of NOF, is 1.
If it is less than 0, the O 2 concentration is theoretically 0%, but actually, an O 2 concentration of about 0.01 to 0.08% is measured. When the air ratio is 1.0 to 1.1, an O 2 concentration of about 0.01 to 0.5% is measured. That is, in the oxidation by NOF, the air ratio is usually operated at 0.90 to 0.99, and the oxidation amount is essentially variable in the range of 0.9 to 1.1 of the related art.
【００１２】ＮＯＦはバーナーの炎やその排ガスにより
加熱するものであり、鋼板表面の巾方向、長手方向とも
雰囲気的に均一でなく、このことも酸化量変動を大きく
し、効果の不安定化の原因となる。さらに、供給される
燃料ガス中のＯ2 濃度も０．１％程度の変動は十分おこ
りうることであり、これも酸化量変動を招く。そもそも
０．１％以下のＯ2 量を正確に測定することすら容易と
は言えない。NOF is heated by the flame of the burner and its exhaust gas, and is not atmospherically uniform in the width direction and the longitudinal direction of the steel plate surface. This also causes a large fluctuation in the amount of oxidation and destabilization of the effect. Cause. Further, the O 2 concentration in the supplied fuel gas can also fluctuate by about 0.1%, which also causes a fluctuation in the amount of oxidation. In the first place, it is not easy to accurately measure the O 2 amount of 0.1% or less.
【００１３】一方、Ｏ2 濃度０．１％以上であれば、Ｏ
2 濃度により酸化量はほとんど変化しない。この理由
は、Ｏ2 濃度０．１％以下ではＯ2 供給律速であるが、
０．１％以上であれば十分にＯ2 が供給されるために、
Ｏ2 濃度が酸化速度に影響を与えなくなるためである。
従ってＯ2 濃度０．１〜１００％が本発明の雰囲気の範
囲となる。On the other hand, if the O 2 concentration is 0.1% or more, O
2 The amount of oxidation hardly changes depending on the concentration. The reason for this is that the O 2 supply is rate-determining when the O 2 concentration is 0.1% or less,
If it is 0.1% or more, O 2 is sufficiently supplied,
This is because the O 2 concentration does not affect the oxidation rate.
Therefore, the O 2 concentration of 0.1 to 100% falls within the range of the atmosphere of the present invention.
【００１４】酸素濃度が低い場合には、焼鈍される鋼板
の種類により、元々表面に存在する水や酸化膜の影響を
受けたり、あるいはラインスピードの変動によりＯ2 の
供給律速になることがあるので、好ましくはＯ2 濃度
０．５％以上が良い。さらに、好ましくは１．０％〜２
１％が良い。２１％以下では無料の空気が使用できる
が、２１％以上では安いけれども相対的には高価なＯ2
を供給しなでればならないためである。When the oxygen concentration is low, depending on the type of the steel sheet to be annealed, it may be affected by water or an oxide film originally existing on the surface, or the line speed may be changed to control the supply of O 2. Therefore, the O 2 concentration is preferably 0.5% or more. Furthermore, preferably 1.0% to 2
1% is good. Free air can be used below 21%, but above 21% it is cheap but relatively expensive O 2
This is because it must be supplied.
【００１５】もちろん、ＮＯＦを使用することは前述し
たように不適当であり、本発明においてはオールラジア
ントチューブ方式の焼鈍炉のプリヒートセクション（予
熱帯）にて雰囲気制御して酸化する。その温度は４００
〜６５０℃が適当であり、６５０℃を超えるとＦｅＯが
生成し、酸化膜の密着性が著しく劣化する。４００℃未
満では、連続炉方式では十分な酸化膜量が得られない。
好ましくは５００〜６００℃が良い。Of course, the use of NOF is unsuitable as described above, and in the present invention, the atmosphere is controlled and oxidized in the preheat section (pre-tropical zone) of the all-radiant tube type annealing furnace. Its temperature is 400
A temperature of up to 650 ° C. is suitable, and if it exceeds 650 ° C., FeO is generated and the adhesion of the oxide film is significantly deteriorated. If the temperature is lower than 400 ° C., a sufficient amount of oxide film cannot be obtained by the continuous furnace method.
It is preferably 500 to 600 ° C.
【００１６】その後の還元焼鈍溶融亜鉛めっき、合金化
は通常の条件でよく、還元焼鈍は例えばＨ2 濃度２〜５
０％、露点−１０〜−５０℃、焼鈍温度７００〜９５０
℃である。溶融亜鉛めっき条件は例えばＡｌ濃度０．１
２〜０．２％、浴温４５０〜５００℃、侵入板温４００
〜６００℃である。合金化条件は例えば温度４００℃〜
６００℃である。[0016] subsequent reduction annealing galvanizing, alloying may under normal conditions, the reduction annealing such as H 2 concentration 2-5
0%, dew point -10 to -50 ° C, annealing temperature 700 to 950
℃. The hot dip galvanizing condition is, for example, Al concentration of 0.1.
2 to 0.2%, bath temperature 450 to 500 ° C, penetration plate temperature 400
~ 600 ° C. The alloying conditions are, for example, a temperature of 400 ° C.
It is 600 ° C.
【００１７】上述のプリヒートセクションにてＯ2 存在
下で酸化処理を行う場合、バーナーを使用したり、燃焼
廃ガスを使用することが考えられる。しかし、その場
合、ＮＯＦと同じような不安定化がおこる。これはＯ2
を供給してＯ2 濃度を０．１％以上に高くしてもＮＯＦ
よりは改善されるがおこることがあり、その原因として
燃料中の不純物（ＮやＳ）とＣＯ，Ｈ2 などの還元性ガ
スの影響がある。ＣＯやＨ2 などの還元性ガスはＯ2 と
反応することにより、Ｏ2 とＦｅとの反応のバランスを
くずすためと思われる。When performing the oxidation treatment in the presence of O 2 in the above-mentioned preheat section, it is possible to use a burner or use combustion waste gas. However, in that case, destabilization similar to NOF occurs. This is O 2
Is supplied to increase the O 2 concentration to 0.1% or more, NOF
It may be improved, but it may be caused by the influence of impurities (N and S) in the fuel and reducing gases such as CO and H 2 . Reducing gas such as CO or H 2 by reacting with O 2, it is believed to be due to imbalance of the reaction between O 2 and Fe.
【００１８】図２にＯ2 １％存在下での露点とＣＯの影
響を示す。露点が低い場合にはＣＯの影響を受け、酸化
量が著しく少なくなっている。露点が高い場合にはＣＯ
の影響を受けない。またＣＯが無い場合には露点の影響
を受けない。従来の酸化炉やＮＯＦの雰囲気中にはＣ
Ｏ，Ｈ2 ，露点（Ｈ2 Ｏ），ＣＯ2 ，Ｏ2 が含有されて
いるため、Ｏ2 濃度だけでなく、ＣＯ，Ｈ2 ，Ｈ2 Ｏ，
ＣＯ2 の影響まで受けるため酸化量が極めて制御しにく
くなっていると言える。FIG. 2 shows the effects of dew point and CO in the presence of 1% O 2 . When the dew point is low, the amount of oxidation is significantly reduced due to the influence of CO. CO when the dew point is high
Not affected by. When CO is absent, it is not affected by the dew point. C in the atmosphere of a conventional oxidation furnace or NOF
Since O, H 2 , dew point (H 2 O), CO 2 and O 2 are contained, not only the O 2 concentration but also CO, H 2 , H 2 O,
It can be said that the amount of oxidation is extremely difficult to control because it is affected by CO 2 .
【００１９】そこで本発明では、バーナー、ＮＯＦやそ
の排ガスは使用せず、ＣＯ，Ｈ2 Ｏを含まない雰囲気と
することが好ましい。また、燃料ガス中に含有される不
純物の窒素化合物やイオウ化合物は解媒作用とその被毒
作用があり、Ｆｅの酸化を阻害したり、著しく促進した
りする作用があるため、制御不能となるので不適当であ
る。Therefore, in the present invention, it is preferable to use an atmosphere containing no CO or H 2 O without using the burner, NOF or its exhaust gas. In addition, impurities such as nitrogen compounds and sulfur compounds contained in the fuel gas have a desolving action and a poisoning action, and have an action of inhibiting or significantly promoting the oxidation of Fe, so that they cannot be controlled. So inappropriate.
【００２０】ゼンジミアタイプの酸化炉ではバーナーの
フレームによる油の燃焼除去であるため、上記のＣＯ，
Ｈ2 あるいはＮ化合物，Ｓ化合物の影響があり、酸化量
は制御できない。実際、酸化量問題で駆遂された方法で
ある。実際、バーナーを使用した場合、酸化量の再現性
は著しく不良であった。In a Sendzimir type oxidation furnace, since the combustion and removal of oil is performed by the flame of the burner, the CO,
The amount of oxidation cannot be controlled due to the influence of H 2 or N compounds and S compounds. In fact, this is a method that has been tried to solve the problem of the amount of oxidation. In fact, when the burner was used, the reproducibility of the amount of oxidation was extremely poor.
【００２１】従って雰囲気はＯ2 −Ｎ2 系のみのガスと
することが好ましい。ただし不活性ガスであるＡｒ，大
気中に含まれる程度の微量のＣＯ2 やＨ2 Ｏは無関係で
あり、含んでいでもさしつかえない。Therefore, the atmosphere is preferably a gas of O 2 —N 2 system only. However, Ar, which is an inert gas, and trace amounts of CO 2 and H 2 O contained in the atmosphere are irrelevant and may be contained.
【００２２】このように、本発明の酸化処理は従来の酸
化と異なり、バーナーやフレーム、廃ガスを使用しない
のでＣＯ，Ｈ2 ，Ｎ化合物，Ｓ化合物の影響を受けない
ため、安定した酸化量が得られる。As described above, unlike the conventional oxidation, the oxidation treatment of the present invention does not use a burner, a flame, or a waste gas, and is not affected by CO, H 2 , N compounds, and S compounds, so that a stable oxidation amount is obtained. Is obtained.
【００２３】一方ではバーナーやフレームを使用しない
ため、揮発成分は蒸発し、ある程度熱分解もするが、酸
化炉の技術思想である油の燃焼除去作用は無い。従っ
て、前処理として電解脱脂などの脱脂が必要であり、ま
た酸洗による活性化も酸化の安定化のために好ましい。On the other hand, since no burner or flame is used, the volatile components evaporate and also undergo thermal decomposition to some extent, but there is no oil combustion removal action which is the technical idea of the oxidation furnace. Therefore, degreasing such as electrolytic degreasing is necessary as pretreatment, and activation by pickling is also preferable for stabilizing oxidation.
【００２４】雰囲気としては実質的にＯ2 −Ｎ2 系が必
要であるので、従来のようなバーナーやフレーム、廃ガ
スは使用しない方が良い。従ってオールラジアント型の
加熱方式、通電加熱方式、誘導加熱方式、電気炉方式の
いずれかが適切である。特に、加熱速度が早い点から誘
導加熱方式が最も優れ、コストの点からはオールラジア
ント型が優れている。Since an O 2 --N 2 system is substantially required as the atmosphere, it is better not to use the conventional burner, flame or waste gas. Therefore, any of the all radiant type heating method, electric heating method, induction heating method, and electric furnace method is suitable. In particular, the induction heating method is the best in terms of high heating rate, and the all radiant type is superior in terms of cost.
【００２５】また、Ｏ2 −Ｎ2 系の雰囲気中にＨ2 Ｏや
ＣＯ2 を少量添加すると、酸化量はほとんど変わらない
が、酸化膜の密着性が向上する傾向があるため、Ｈ2 Ｏ
２％以上、好ましくは５％以上含んでいても良い。ＣＯ
2 の場合、０．１％以上好ましくは２％以上含んでいて
も良い。Further, when the O 2 -N 2 system by adding a small amount of H 2 O and CO 2 in the atmosphere, but the oxidation amount hardly changes, since there is a tendency to improve the adhesion of the oxide film, H 2 O
The content may be 2% or more, preferably 5% or more. CO
In the case of 2 , 0.1% or more, preferably 2% or more may be contained.
【００２６】本法による酸化により、通常は酸化膜の密
着性は問題無いが、Ｓｉ，Ｍｎ添加量ががなり多いハイ
ラン材の場合、酸化膜の密着性劣化による表面濃化防止
能力の低下、酸化物の剥離によるラインでの欠陥発生が
問題になることがある。この場合には酸化温度の低減や
Ｈ2 Ｏ，ＣＯ2 の添加が有効である。Oxidation according to this method usually causes no problem in the adhesion of the oxide film, but in the case of a high lanthanum material in which the amounts of Si and Mn added are large, the ability to prevent surface thickening is deteriorated due to the deterioration of the adhesion of the oxide film. Occurrence of defects in the line due to peeling of the oxide may be a problem. In this case, reduction of the oxidation temperature and addition of H 2 O and CO 2 are effective.
【００２７】本法の酸化は雰囲気中にてただ単に板温を
保持すれば良く、保持時間としては瞬時〜５秒程度が適
当である。なお、酸化量は温度によってほぼ決定され、
時間の影響は上記範囲では誤差範囲である。これは酸化
膜を経由する拡散律速になっているためである。In the oxidation of this method, the plate temperature may be simply maintained in the atmosphere, and the suitable holding time is from instant to about 5 seconds. The amount of oxidation is almost determined by the temperature,
The influence of time is an error range in the above range. This is because the diffusion rate is controlled via the oxide film.
【００２８】酸化量は鋼種によっても影響されるが４０
０〜６５０℃ではほぼＯとして２００〜７００ｍｇ／ｍ
2 である。Ｓｉ，Ｍｎ添加量が多い場合には酸化温度を
高くし、酸化量を多くして表面濃化防止能力を強くする
必要があり、鋼成分により設定すれば良い。Ｓｉ，Ｍｎ
などの合金元素が多いほど酸化されにくく還元されやす
い傾向があるため、還元条件はほとんど変更する必要が
無く、その後の還元焼鈍は通常のＮ2 −Ｈ2 雰囲気下で
行えば良い。The amount of oxidation depends on the type of steel, but is 40
At 0 to 650 ° C, almost O as 200 to 700 mg / m
Is 2 . When the amounts of Si and Mn added are large, it is necessary to raise the oxidation temperature and increase the amount of oxidation to strengthen the surface thickening prevention ability, which may be set according to the steel composition. Si, Mn
Since the more alloying elements such as the above are less likely to be oxidized and more likely to be reduced, there is no need to change the reducing conditions, and the subsequent reduction annealing may be performed in a normal N 2 —H 2 atmosphere.
【００２９】上述したように、本発明は、酸化温度を変
更して酸化量を変えることのみによりほぼ全ての鋼種に
対応することができ、酸化温度を管理すれば安定した効
果が得られる。なお、Ｓｉ，Ｍｎの添加量が合計で２．
７％以上、Ｓｉ０．７％以上となると大きな表面濃化抑
制効果を有してはいるが、完全には表面濃化を抑制でき
なくなる。その場合には亜鉛浴温の高温化やＡｌ濃度の
低下、侵入板温の上昇を併用すると不めっき抑制には効
果的である。As described above, the present invention can be applied to almost all kinds of steel only by changing the oxidation temperature to change the oxidation amount, and stable effects can be obtained by controlling the oxidation temperature. The total amount of Si and Mn added was 2.
If it is 7% or more and Si is 0.7% or more, it has a great effect of suppressing the surface enrichment, but cannot completely suppress the surface enrichment. In that case, it is effective to suppress non-plating if the zinc bath temperature is increased, the Al concentration is decreased, and the penetration plate temperature is increased.
【００３０】なお、本発明における酸化量（ｍｇ／
ｍ2 ）は蛍光Ｘ線にてＯを定量化したものであり、Ｆｅ
酸化物皮膜量は約３．６倍になる。In the present invention, the amount of oxidation (mg /
m 2 ) is a quantification of O by fluorescent X-ray, and Fe
The amount of oxide film is about 3.6 times.
【００３１】[0031]
【実施例】以下に本発明を実施例に基づいて具体的に説
明する。 （実施例）表１に示す成分の高張力鋼板に、同じく表１
に示す酸化処理を施し、次いで還元焼鈍、溶融亜鉛めっ
き、合金化処理を行った。その結果を表面濃化およびめ
っき性で評価し、あわせて表１に示す。 （１）表面濃化 めっき性に特に有害なＳｉとＭｎの表面濃化はＧＤＳに
より下記の通り評価した。 ○＝表面濃化なし〜著しく抑制 △＝表面濃化抑制効果あり ×＝表面濃化抑制効果なし （２）めっき性 めっき性は目視により下記のとおり評価した。 ○＝不めっきなし △＝不めっきわずかにあり（侵入板温、浴温などにより
改善可能） ×＝不めっき（めっき条件では改善不可）EXAMPLES The present invention will be specifically described below based on examples. (Example) A high-strength steel sheet having the components shown in Table 1 was also used.
The oxidation treatment shown in 1 was performed, and then reduction annealing, hot dip galvanizing, and alloying treatment were performed. The results are evaluated by the surface concentration and the plating property, and also shown in Table 1. (1) Surface Concentration The surface concentration of Si and Mn, which are particularly harmful to the plating property, was evaluated by GDS as follows. ◯ = No surface thickening-remarkably suppressed △ = Surface thickening suppressed effect X = No surface thickening suppressed effect (2) Plating property The plating property was visually evaluated as follows. ○ = no plating △ = no plating slightly (can be improved by penetration plate temperature, bath temperature, etc.) × = non-plating (cannot be improved under plating conditions)
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【発明の効果】従来のＮＯＦや酸化炉では酸化量制御が
困難である。その原因であるＯ2 濃度を特定し、また酸
化量の著しい変動原因であるＣＯ，Ｈ2 などの還元性ガ
スと燃料ガス中のイオウ化合物と窒素化合物を排除する
ことにより、安定した酸化量が得られる。その結果、そ
の後の還元焼鈍時のＳｉやＭｎの表面濃化を抑制でき、
安定しためっき性を確保できる。EFFECT OF THE INVENTION It is difficult to control the amount of oxidation in the conventional NOF and oxidation furnace. By specifying the O 2 concentration which is the cause of this, and by eliminating the reducing compounds such as CO and H 2 which cause the remarkable fluctuation of the oxidation amount and the sulfur compounds and nitrogen compounds in the fuel gas, a stable oxidation amount can be obtained. can get. As a result, the surface concentration of Si and Mn during the subsequent reduction annealing can be suppressed,
A stable plating property can be secured.
【図１】 酸化量に及ぼす雰囲気中酸素濃度の影響を示
す図である。FIG. 1 is a diagram showing the effect of oxygen concentration in the atmosphere on the amount of oxidation.
【図２】 酸化量に及ぼす雰囲気中露点とＣＯ濃度の影
響を示す図である。FIG. 2 is a diagram showing the influence of the atmospheric dew point and CO concentration on the amount of oxidation.
Claims (4)
用いて、溶融亜鉛めっき鋼板または合金化溶融亜鉛めっ
き鋼板を製造するに際し、焼鈍炉の予熱帯（プリヒート
セクション）にてＯ2 濃度０．１〜１００％の雰囲気で
板温４００〜６５０℃に加熱してＦｅを酸化させた後、
通常の還元焼鈍、溶融亜鉛めっき、必要に応じ合金化処
理を行うことを特徴とする高張力溶融または合金化溶融
亜鉛めっき鋼板の製造方法。1. When producing a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet using a continuous hot-dip galvanizing equipment having an annealing furnace, an O 2 concentration of 0. After heating at a plate temperature of 400 to 650 ° C. in an atmosphere of 1 to 100% to oxidize Fe,
A method for producing a high-strength hot-dip galvanized or galvannealed steel sheet, which comprises performing ordinary reduction annealing, hot dip galvanizing, and optionally alloying treatment.
にＯ2 −Ｎ2 系のみのガスとする請求項１に記載の高張
力溶融または合金化溶融亜鉛めっき鋼板の製造方法。2. The method for producing a high-strength hot-dip galvanized or galvannealed steel sheet according to claim 1, wherein the pre-tropical atmosphere for oxidizing Fe is substantially an O 2 —N 2 -based gas.
はＣＯ2 を含有するＯ2 −Ｎ2 系ガスである請求項２に
記載の高張力溶融または合金化溶融亜鉛めっき鋼板の製
造方法。3. The method for producing a high-strength hot-dip galvanized or galvanized steel sheet according to claim 2, wherein the pretropical atmosphere is an O 2 —N 2 -based gas containing H 2 O and / or CO 2. .
式、誘導加熱式、ガスジェット式、通電加熱式、電気炉
式のいずれかである請求項１〜３のいずれかに記載の高
張力溶融または合金化溶融亜鉛めっき鋼板の製造方法。4. The high-tensile melting method according to claim 1, wherein the heating method for oxidation is any one of all radiant type, induction heating type, gas jet type, electric heating type and electric furnace type. Or the manufacturing method of a galvannealed steel sheet.
Priority Applications (1)
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|---|---|---|---|
| JP17409393A JP3255765B2 (en) | 1993-07-14 | 1993-07-14 | Method for producing high-strength hot-dip or alloyed hot-dip galvanized steel sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17409393A JP3255765B2 (en) | 1993-07-14 | 1993-07-14 | Method for producing high-strength hot-dip or alloyed hot-dip galvanized steel sheet |
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| Publication Number | Publication Date |
|---|---|
| JPH0734210A true JPH0734210A (en) | 1995-02-03 |
| JP3255765B2 JP3255765B2 (en) | 2002-02-12 |
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ID=15972536
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|---|---|---|---|
| JP17409393A Expired - Lifetime JP3255765B2 (en) | 1993-07-14 | 1993-07-14 | Method for producing high-strength hot-dip or alloyed hot-dip galvanized steel sheet |
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