JP2007254811A - Steel sheet for chemical conversion treatment and its production method - Google Patents
Steel sheet for chemical conversion treatment and its production method Download PDFInfo
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本発明は、表面処理用の鋼板、特に自動車、電機、缶材料等の塗装に先立って行われる化成処理用の鋼板及びその製造方法に関する。 The present invention relates to a steel sheet for surface treatment, in particular, a steel sheet for chemical conversion treatment that is performed prior to coating of automobiles, electric machines, can materials, and the like, and a method for manufacturing the same.
自動車、家電、家具、建材等に利用される鋼板は、耐食性及び装飾性の付与のため、素材鋼板の段階で、あるいはプレス加工の段階で、塗装処理が広く行われている。かかる塗装処理の事前処理として、塗料の鋼板への密着性を高め、塗装欠陥の発生を防止するために、たとえば、燐酸処理、燐酸亜鉛処理等の化成被膜を付与する化成処理が行われる。したがって、化成処理は、いわゆるすけなどの欠陥が発生しないように極力完全に行われる必要がある。 Steel sheets used for automobiles, home appliances, furniture, building materials, and the like are widely subjected to coating treatment at the stage of raw steel sheets or at the stage of press processing in order to impart corrosion resistance and decorativeness. As a pretreatment for such a coating treatment, for example, a chemical conversion treatment such as a phosphoric acid treatment or a zinc phosphate treatment is performed in order to increase the adhesion of the paint to the steel plate and prevent the occurrence of coating defects. Therefore, the chemical conversion treatment needs to be performed as completely as possible so that defects such as so-called soot do not occur.
しかしながら、自動車の軽量化等のために行われる鋼板の高張力化は、種々の合金元素の添加を必要とし、そのため、化成処理性の低下を招いている。たとえば、鋼の高張力化のために添加されるCrは、その添加量にもよるが、化成処理性を大きく劣化させ、化成処理に要する時間を長引かせる。また、鋼の高張力化のために加えられる強化元素の種類・組み合わせは、鋼板の機械的性質や成形性等の要求に応じて極めて多種にのぼり、そのため、たとえば、自動車の組立てに使用される鋼板でも、部品ごとに化成処理性が異なり、化成処理工程の管理を複雑にする。 However, the increase in the tensile strength of the steel sheet, which is carried out for the purpose of reducing the weight of automobiles, requires the addition of various alloy elements, and therefore causes a reduction in the chemical conversion processability. For example, although Cr added for increasing the tensile strength of steel depends on the amount of addition, the chemical conversion property is greatly deteriorated and the time required for the chemical conversion treatment is prolonged. In addition, the types and combinations of strengthening elements added to increase the tensile strength of steel are extremely diverse depending on the requirements of the mechanical properties and formability of the steel sheet, and are therefore used, for example, in the assembly of automobiles. Even with steel plates, the chemical conversion processability differs for each part, complicating the management of the chemical conversion process.
このような問題を解決するために、特許文献1には、Siを0.1mass%以上含有する鋼板に対し、平均粒径が30〜300μmの固体粒子を投射することにより高張力鋼板の耐かじり性と化成処理性を改善するという手段が開示されている。また、特許文献2には、冷延鋼板の表面にメチルブタン類などの特定の硫黄含有化合物を硫黄分といて0.01〜500mg/m2を吸着せしめることによりりん酸塩処理性を向上せしめるという発明が開示されている。特許文献3には、金属酸化物もしくは金属を鋼板表面に付着させることによりりん酸塩処理性を向上させるという発明が開示されている。さらに、特許文献4には、質量%で、Alを0.1%以上3%未満を含有する鋼の表層部にAlN析出層を有せしめることによって化成処理性を含む表面処理性を向上せしめるという発明が開示されている。
In order to solve such a problem,
しかしながら、特許文献1に開示された発明は、Siを含有し、鋼板表面がSi系酸化物により不活性化されている場合の化成処理性の改善手段としては有効であるが、他の合金元素、たとえばCrにより化成処理性が阻害されている場合には効果がない。一方、特許文献2及び3に開示の発明では特殊な薬剤を使用することが要求され、また、電解槽などの設備を設ける必要があり、コスト高を招くおそれがある。特許文献4に開示の発明は、Alを含有する鋼にのみしか適用できず、しかもAlNの析出処理のために特殊な熱処理を施す必要があり、特許文献2に開示の発明と同様、コスト高を招くおそれがある。
However, the invention disclosed in
本発明は、上記従来技術に係る問題を解決することを目的とし、すべての鋼種に適用することができ、また、低コストで実施することができる化成処理性改善手段を提案することを目的としている。 The present invention aims to solve the problems related to the above prior art, and can be applied to all steel types, and also aims to propose a chemical conversion treatment improving means that can be carried out at a low cost. Yes.
本発明に係る化成処理用鋼板は、表層部の転位密度が2×1013/m2以上となっているものである。上記転位密度は、5×1013/m2以上、5×1015/m2以下であることが望ましい。 The steel sheet for chemical conversion treatment according to the present invention has a dislocation density of 2 × 10 13 / m 2 or more in the surface layer portion. The dislocation density is desirably 5 × 10 13 / m 2 or more and 5 × 10 15 / m 2 or less.
上記発明に係る化成処理用鋼板は、質量比で、C:0.001〜0.20%、Si:0.02〜2.00%、Mn:0.15〜2.00%、P:0.020%以下、S:0.010%以下、Al:0.050%以下、残部不可避不純物を除きFeからなる冷延鋼板であることとすることができる。上記冷延鋼板は、さらに、Mo:0.05〜0.30%、Ni:0.05〜0.50%、Cu:0.05〜0.50%、Cr:0.05〜0.50%、Ti:0.01〜0.20%、Nb:0.01〜0.05%及びB:0.0002〜0.001%から選んだ1種又は2種以上の元素を含有することができる。 The steel sheet for chemical conversion treatment according to the above invention is, by mass ratio, C: 0.001 to 0.20%, Si: 0.02 to 2.00%, Mn: 0.15 to 2.00%, P: 0. 0.020% or less, S: 0.010% or less, Al: 0.050% or less, and a cold-rolled steel sheet made of Fe except for the remaining inevitable impurities. The cold-rolled steel sheet further includes Mo: 0.05 to 0.30%, Ni: 0.05 to 0.50%, Cu: 0.05 to 0.50%, Cr: 0.05 to 0.50. %, Ti: 0.01 to 0.20%, Nb: 0.01 to 0.05%, and B: 0.0002 to 0.001%. it can.
本発明において、化成処理用鋼板を、質量比で、C:0.01〜0.10%、Si:0.01〜2.00%、Mn:0.15〜2.00%、P:0.020%以下、S:0.010%以下、Al:0.050%以下、残部不可避不純物を除きFeからなる熱延鋼板とすることができる。また、この熱延鋼板を、さらに、Cr:0.05〜1.00を含有するものとすることができる。 In the present invention, the steel sheet for chemical conversion treatment is, by mass ratio, C: 0.01 to 0.10%, Si: 0.01 to 2.00%, Mn: 0.15 to 2.00%, P: 0. 0.020% or less, S: 0.010% or less, Al: 0.050% or less, and a hot-rolled steel sheet made of Fe except for the remaining inevitable impurities. Moreover, this hot-rolled steel sheet can further contain Cr: 0.05 to 1.00.
本発明に係る化成処理鋼板は、前記冷延鋼板に対し、焼鈍・酸洗後又はさらに調質圧延後、表層部の転位密度が2×1013/m2以上となるように転位導入操作を行うこと又は前記熱延鋼板に対し、焼鈍・酸洗後、表層部の転位密度が2×1013/m2以上となるように転位導入操作を行うことによって製造することができる。 In the chemical conversion treated steel sheet according to the present invention, the dislocation introduction operation is performed on the cold-rolled steel sheet so that the dislocation density of the surface layer portion is 2 × 10 13 / m 2 or more after annealing / pickling or further temper rolling. It can manufacture by performing dislocation introduction operation so that the dislocation density of a surface layer part may become 2 * 10 < 13 > / m < 2 > or more after annealing or pickling.
本発明により、鋼種に無関係に化成処理性の優れた鋼板を提供することができ、自動車、電機、缶材料等の塗装工程を効率化することができる。また、その製造コストを、従来の提案に比べて低減することができる。 According to the present invention, it is possible to provide a steel plate having excellent chemical conversion properties regardless of the steel type, and to improve the efficiency of the coating process for automobiles, electric machines, can materials, and the like. Moreover, the manufacturing cost can be reduced compared with the conventional proposal.
本発明に係る化成処理鋼板の原板は、冷延鋼板及び熱延鋼板のいずれでもよい。また、これら冷延鋼板又は熱延鋼板に組成、あるいは組織、特性上の制限を特に設ける必要はない。鋼板の用途に応じて強度、加工性などに応じて組成、組織を選定すればよい。 The raw sheet of the chemical conversion treated steel sheet according to the present invention may be either a cold rolled steel sheet or a hot rolled steel sheet. Moreover, it is not necessary to provide restrictions on the composition, structure, or characteristics of these cold-rolled steel sheets or hot-rolled steel sheets. What is necessary is just to select a composition and a structure | tissue according to intensity | strength, workability, etc. according to the use of a steel plate.
冷延鋼板の場合、質量比で、C:0.001〜0.20%、Si:0.02〜2.00%、Mn:0.15〜2.00%、P:0.020%以下、S:0.010%以下、Al:0.050%以下、残部不可避不純物を除きFeからなる冷延鋼板を典型的に選択することができ、これに、強度、加工性の向上を目的として、さらに、Mo:0.05〜0.30%、Ni:0.05〜0.50%、Cu:0.05〜0.50%、Cr:0.05〜0.50%、Ti:0.03〜0.20%、Nb:0.01〜0.05%及びB:0.0002〜0.001%から選んだ1種又は2種以上の元素を含有させることができる。 In the case of a cold-rolled steel sheet, by mass ratio, C: 0.001 to 0.20%, Si: 0.02 to 2.00%, Mn: 0.15 to 2.00%, P: 0.020% or less , S: 0.010% or less, Al: 0.050% or less, except for the remaining inevitable impurities, a cold-rolled steel sheet made of Fe can be typically selected, and for the purpose of improving strength and workability Furthermore, Mo: 0.05 to 0.30%, Ni: 0.05 to 0.50%, Cu: 0.05 to 0.50%, Cr: 0.05 to 0.50%, Ti: 0 One or two or more elements selected from 0.03 to 0.20%, Nb: 0.01 to 0.05% and B: 0.0002 to 0.001% can be contained.
熱延鋼板の場合は、質量比で、C:0.01〜0.10%、Si:0.01〜2.00%、Mn:0.15〜2.00%、P:0.020%以下、S:0.010%以下、Al:0.050%以下、残部不可避不純物を除きFeからなる低炭素・低合金鋼とするのがよく、これにCr:0.05〜1.00を含有させることもできる。 In the case of a hot-rolled steel sheet, by mass ratio, C: 0.01 to 0.10%, Si: 0.01 to 2.00%, Mn: 0.15 to 2.00%, P: 0.020% Hereinafter, S: 0.010% or less, Al: 0.050% or less, except for the remaining inevitable impurities, it is good to be a low carbon, low alloy steel made of Fe, Cr: 0.05-1.00 is added to this It can also be contained.
本発明では、上記いずれの鋼種においても、鋼板表層部の転位密度が2×1013/m2以上とすることが重要である。後述するように、転位密度が2×1013/m2以上となるときに化成処理を行ったとき、化成処理鋼板表面に「すけ」などの欠陥が認められなくなる。 In the present invention, in any of the above steel types, it is important that the dislocation density of the steel sheet surface layer portion is 2 × 10 13 / m 2 or more. As will be described later, when the chemical conversion treatment is performed when the dislocation density is 2 × 10 13 / m 2 or more, defects such as “suke” are not recognized on the chemical conversion treated steel sheet surface.
ここに鋼板表層部の転位密度とは、化成処理に供される直前の鋼板表層部に存在する転位密度をいい、その測定のための試料の調整方法及び転位密度の決定方法は下記のとおりである。
(1)測定試料の調整:鋼板1/4の位置から試料を切り出して脱脂して
(2)転位密度の決定方法:上記のようにして調整された試料についてX線回折装置によって鋼板表面の歪を測定した。測定にはX線回折装置を用い、CoKα線を用いて鋼板表面層のα鉄の(110)面、(211)面、及び(220)面の回折強度を測定し、その測定チャートから各結晶面の反射強度のピーク値の半価幅を求め、下記式(1)及び式(2)により鋼板表面に付与された局所ひずみεを決定する。
βcosθ/λ=0.9/D+2ε’sinθ/λ・・・・・・(1)
ここで、
β:ピーク値の半価幅(ただし、式(2)により補正した値を用いる)
θ:回折角
λ:Cokα線の波長(0.1791nm)
D:結晶子サイズ(転位セル、結晶粒の大きさ)
ε’:局所ひずみ
β2=βm 2−β0 2・・・・・・(2)
ここで、
βm:転位密度を測定する試料のピークの半価幅
β0:ひずみのない試料のピークの半価幅
である。
sinθ/λに対してβcosθ/λをプロットして傾きと切片からbとε’とが求まる。求められた局所歪ε’から下記(3)式により転位密度ρを決定する。
ρ=14.4ε’2/b2・・・・・・(3)
ここで、
b:バーガースベクトル(8.25nm)
Here, the dislocation density of the steel sheet surface layer part means the dislocation density existing in the steel sheet surface layer part immediately before being subjected to the chemical conversion treatment, and the adjustment method of the sample for the measurement and the determination method of the dislocation density are as follows. is there.
(1) Measurement sample adjustment: A sample was cut out from the position of the
βcos θ / λ = 0.9 / D + 2ε'sin θ / λ (1)
here,
β: half width of peak value (however, the value corrected by equation (2) is used)
θ: diffraction angle λ: wavelength of Cokα ray (0.1791 nm)
D: Crystallite size (dislocation cell, crystal grain size)
ε ′: local strain β 2 = β m 2 −β 0 2 (2)
here,
β m : half width of peak of sample for measuring dislocation density β 0 : half width of peak of sample without strain.
By plotting β cos θ / λ against sin θ / λ, b and ε ′ are obtained from the slope and intercept. The dislocation density ρ is determined from the obtained local strain ε ′ by the following equation (3).
ρ = 14.4ε ′ 2 / b 2 (3)
here,
b: Burgers vector (8.25 nm)
図1は、表1に示す組成を有する冷延鋼板及び表2に示す組成を有する熱延鋼板に対して表3に示す条件で処理して、鋼板表面に転位を導入し、化成処理を行ったときの転位密度と化成処理被膜の状態(「すけ」あり又は「すけ」なしの発生状態)の関係を示すグラフである。なお、冷延鋼板は、表1に示す組成を有するスラブを熱間圧延した後、酸洗後、最終厚さに冷間圧延し、さらに焼鈍、酸洗し、0.3%の調質圧延を施したものであり、熱延鋼板は、表2に示す組成を有するスラブを最終厚さまで熱間圧延した後、酸洗したものである。 FIG. 1 shows a cold-rolled steel sheet having the composition shown in Table 1 and a hot-rolled steel sheet having the composition shown in Table 2 under the conditions shown in Table 3, introducing dislocations on the steel sheet surface, and performing chemical conversion treatment. 5 is a graph showing the relationship between the dislocation density and the state of the chemical conversion coating (occurrence state with or without “suke”). The cold-rolled steel sheet is obtained by hot rolling a slab having the composition shown in Table 1, pickling, cold rolling to a final thickness, further annealing and pickling, and 0.3% temper rolling. The hot-rolled steel sheet is obtained by hot rolling a slab having the composition shown in Table 2 to the final thickness and then pickling.
鋼板表面への転位の導入は、上記により得られた冷延鋼板又は熱延鋼板にショットブラスト処理又は高強度ブラシによるひずみ付与処理によって行った。これらひずみ付与処理の具体的内容は、表3及び表4に記したとおりである。 Introduction of dislocations on the steel sheet surface was performed on the cold-rolled steel sheet or hot-rolled steel sheet obtained as described above by shot blasting or strain imparting with a high-strength brush. Specific contents of these strain imparting processes are as described in Tables 3 and 4.
なお、化成処理は、表面調整液として日本ペイント製サーフファイン5N−10、化成処理液として日本ペイント製サーフダインSD2500を用い、液温43℃で行った。 The chemical conversion treatment was performed at a liquid temperature of 43 ° C. using Nippon Paint Surf Fine 5N-10 as the surface conditioning liquid and Nippon Paint Surf Dyne SD2500 as the chemical conversion liquid.
図1から分かるとおり、鋼板表層部の転位密度が2×1013/m2以上となるとき、鋼種の如何にかかわらず、化成処理した鋼板に「すけ」が認められなくなる。「すけ」が認められるようになる。なお、りん酸亜鉛の結晶サイズが微細化し、緻密な結晶を生成させるためには、鋼板表層部の転位密度が5×1013/m2以上とするのがよいが、転位密度が5×1015/m2を超えると鋼板の成形性が低下するため、上限を5×1015/m2とするのがよい。ここに、「すけ」とはりん酸亜鉛結晶の析出していない部分であり、その有無はSEMにて350倍の写真を3視野撮影し、目視により判定したものである。 As can be seen from FIG. 1, when the dislocation density of the surface layer portion of the steel sheet is 2 × 10 13 / m 2 or more, “suke” is not recognized in the chemically treated steel sheet regardless of the steel type. “Suke” is recognized. In order to reduce the crystal size of zinc phosphate and generate dense crystals, the dislocation density of the steel sheet surface layer portion is preferably 5 × 10 13 / m 2 or more, but the dislocation density is 5 × 10 5. If it exceeds 15 / m 2 , the formability of the steel sheet decreases, so the upper limit is preferably 5 × 10 15 / m 2 . Here, “suke” is a portion where no zinc phosphate crystals are deposited, and the presence or absence is determined by visual observation of three 350 × photographs taken with a SEM and visually.
Claims (8)
The hot rolled steel sheet having the composition according to claim 5 or 6 is characterized in that after annealing and pickling, a dislocation introduction operation is performed so that a dislocation density of a surface layer portion is 2 × 10 13 / m 2 or more. The manufacturing method of the steel plate for chemical conversion treatment.
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WO2016157761A1 (en) * | 2015-03-27 | 2016-10-06 | Jfeスチール株式会社 | Steel sheet for can and method for producing same |
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JP2000087175A (en) * | 1998-07-16 | 2000-03-28 | Nippon Steel Corp | High strength steel sheet excellent in formability after welding and hardly causing softening in weld heat- affected zone |
JP2000248334A (en) * | 1999-03-03 | 2000-09-12 | Kawasaki Steel Corp | Cold rolled steel plate excellent in workability, hot dip plated steel plate and their production |
JP2000297348A (en) * | 1999-04-15 | 2000-10-24 | Nippon Steel Corp | Nigh strength cold rolled steel sheet excellent in fatigue characteristic of base material, excellent in formability after welding and hard to be softened in welding heat affected zone and high strength surface treated steel sheet |
JP2003073775A (en) * | 2001-06-19 | 2003-03-12 | Kawasaki Steel Corp | High-tension hot rolled steel sheet superior in shape freezability and durable fatigue characteristic after forming, and manufacturing method therefor |
JP2003231941A (en) * | 2002-02-08 | 2003-08-19 | Nippon Steel Corp | HOT-ROLLED STEEL SHEET SUPERIOR IN FORMABILITY AFTER WELDING, WITH HIGH STRENGTH HAVING TENSILE STRENGTH OF 780 MPa OR HIGHER, OF MAKING HEAT AFFECTED ZONE HARDLY BE SOFTENED, COLD-ROLLED STEEL SHEET WITH HIGH STRENGTH, AND SURFACE-TREATED STEEL SHEET WITH HIGH STRENGTH |
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WO2016157760A1 (en) * | 2015-03-27 | 2016-10-06 | Jfeスチール株式会社 | Steel sheet for can and method for producing same |
WO2016157761A1 (en) * | 2015-03-27 | 2016-10-06 | Jfeスチール株式会社 | Steel sheet for can and method for producing same |
JPWO2016157761A1 (en) * | 2015-03-27 | 2017-07-06 | Jfeスチール株式会社 | Steel plate for can and manufacturing method thereof |
JPWO2016157760A1 (en) * | 2015-03-27 | 2017-07-06 | Jfeスチール株式会社 | Steel plate for can and manufacturing method thereof |
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