JPH04276057A - Manufacture of high si-containing high tensile strength galvannealed steel sheet having good plating adhesion - Google Patents
Manufacture of high si-containing high tensile strength galvannealed steel sheet having good plating adhesionInfo
- Publication number
- JPH04276057A JPH04276057A JP6235691A JP6235691A JPH04276057A JP H04276057 A JPH04276057 A JP H04276057A JP 6235691 A JP6235691 A JP 6235691A JP 6235691 A JP6235691 A JP 6235691A JP H04276057 A JPH04276057 A JP H04276057A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plating
- tensile strength
- plating adhesion
- contg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000007747 plating Methods 0.000 title claims abstract description 39
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 27
- 239000010959 steel Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005275 alloying Methods 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 238000005246 galvanizing Methods 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 22
- 239000011572 manganese Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、めっき密着性の良好な
高Ｓｉ含有高張力合金化溶融亜鉛めっき鋼板の製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-Si-containing, high-strength alloyed hot-dip galvanized steel sheet with good coating adhesion.
【０００２】0002
【従来技術】近年、排気ガス規制の観点から自動車の車
体重量の軽量化が積極的に行なわれている。車体軽量化
の有効な手段の一つとして外板の板厚を薄くするという
方法があるが、安全性確保のため板厚を薄くするために
はその分、板の強度を向上させる必要がある。高Ｓｉ含
有高張力鋼板を外板として使用した場合、溶融めっき処
理に於て、めっき性不良が問題となる。めっき性改善の
ための従来技術として、特開昭５５−１２２８６５号公
報によれば無酸化炉において鋼表面に酸化膜の厚みが４
００〜１００００Åになるように酸化した後、水素を含
む雰囲気中で焼鈍し、めっきする方法が知られている。
この方法によれば鉄の酸化膜によりＳｉの表面濃化を抑
制し、めっき密着性を阻害するシリコン酸化物の生成を
抑制できるので、めっき密着性を向上させることができ
る。しかし、 従来技術に於いては鉄の酸化膜の還元時
間の調節が実際上不可能であり、還元時間が長すぎれば
Ｓｉの表面濃化を引き起こし、短かすぎれば鋼表面に鉄
の酸化膜が残存するので、結局完全にめっき性不良の解
消にはならないという問題がある。2. Description of the Related Art In recent years, efforts have been made to reduce the weight of automobiles from the viewpoint of exhaust gas regulations. One effective way to reduce the weight of a car body is to reduce the thickness of the outer panels, but in order to ensure safety, it is necessary to increase the strength of the panels accordingly. . When a high-Si-containing high-strength steel plate is used as an outer plate, poor plating properties become a problem in hot-dip plating. As a conventional technique for improving plating properties, according to Japanese Patent Application Laid-Open No. 55-122865, the thickness of an oxide film on the steel surface was increased to 4.
A known method is to oxidize the film to a thickness of 00 to 10,000 Å, then annealing it in an atmosphere containing hydrogen, and plating. According to this method, the surface concentration of Si can be suppressed by the iron oxide film, and the generation of silicon oxide that inhibits plating adhesion can be suppressed, so that the plating adhesion can be improved. However, in the conventional technology, it is practically impossible to adjust the reduction time of the iron oxide film; if the reduction time is too long, Si will concentrate on the surface, and if it is too short, the iron oxide film will form on the steel surface. remains, so there is a problem that the poor plating quality cannot be completely resolved after all.
【０００３】0003
【発明が解決しようとする課題】高張力鋼板のめっき処
理について鋭意研究を重ねた結果、以下のような知見を
得た。従来技術は酸化鉄の還元時間を予測し、還元が終
了した直後に鋼板をめっき浴に浸せきさせる。これは鉄
の酸化膜厚がどんなに薄くなっても、鉄の酸化物が鋼板
表面に存在している限りＳｉの表面濃化は抑制されると
いう仮定に基づいている。しかし、実際には鉄の酸化膜
は鋼板表面に於て不均一に分布しており、酸化膜が薄く
なると完全に無くなる前にＳｉの表面濃化も徐々に始ま
るので完全なめっき不良解消ができないという問題点を
持っている。燃焼空気比０．９〜１．２の直火炉にて酸
化後、水素を含む還元炉で酸化膜が５００Å以下になる
程度に還元した後、 該鋼板をＭｎを０．０１〜２％、
Ａｌを０．０１〜２％、残部Ｚｎよりなる亜鉛めっき浴
を用いて溶融めっき処理をすることにより残りの酸化膜
の還元を浴中のＭｎ、Ａｌでおこなう。本発明方法では
めっき浴に板が浸せきするまで鋼板表面に鉄の数百Åの
酸化膜が存在しているため、Ｓｉの表面濃化は完全に抑
制でき、非常に良好なめっき密着性を有する鋼板を得る
ことができる。自動車鋼板に使用されることの多い溶融
めっき鋼板においてめっき密着性は直接耐食性にも影響
するため非常に重要な性質である。以上の知見に基づい
て本発明をなすに至った。[Problems to be Solved by the Invention] As a result of extensive research into plating treatments for high-strength steel sheets, the following findings were obtained. The conventional technique predicts the reduction time of iron oxide and immerses the steel plate in the plating bath immediately after the reduction is completed. This is based on the assumption that no matter how thin the iron oxide film becomes, as long as iron oxide exists on the surface of the steel sheet, surface concentration of Si will be suppressed. However, in reality, the iron oxide film is unevenly distributed on the surface of the steel sheet, and when the oxide film becomes thin, Si gradually begins to concentrate on the surface before it completely disappears, making it impossible to completely eliminate plating defects. There is a problem with this. After oxidizing in a direct-fired furnace with a combustion air ratio of 0.9 to 1.2, the steel plate is reduced to an oxide film of 500 Å or less in a reduction furnace containing hydrogen, and then the steel plate is treated with Mn of 0.01 to 2%.
The remaining oxide film is reduced by the Mn and Al in the bath by hot dipping using a galvanizing bath containing 0.01 to 2% Al and the balance Zn. In the method of the present invention, an oxide film of several hundred angstroms of iron exists on the surface of the steel sheet until it is immersed in the plating bath, so surface concentration of Si can be completely suppressed, resulting in very good plating adhesion. You can get steel plates. Plating adhesion is a very important property in hot-dip galvanized steel sheets, which are often used for automobile steel sheets, because it directly affects corrosion resistance. The present invention has been accomplished based on the above findings.
【０００４】0004
【課題を解決するための手段】本発明の要旨は、Ｓｉを
０．２％以上の範囲で含有する鋼板を燃焼空気比０．９
〜１．２の直火炉にて酸化後、水素を含む還元炉で還元
した後、該鋼板をＭｎを０．０１〜２％、Ａｌを０．０
１〜２％、残部Ｚｎよりなる亜鉛めっき浴を用いて溶融
めっき処理を行ない、更に加熱合金化処理することを特
徴とするめっき密着性の良好な高Ｓｉ含有高張力合金化
溶融亜鉛めっき鋼板の製造方法である。[Means for Solving the Problems] The gist of the present invention is to provide a steel plate containing Si in a range of 0.2% or more with a combustion air ratio of 0.9%.
~1.2 After oxidation in a direct-fired furnace and reduced in a hydrogen-containing reduction furnace, the steel plate was reduced to 0.01 to 2% Mn and 0.0% Al.
A high-Si-containing, high-tensile-alloyed hot-dip galvanized steel sheet with good plating adhesion, characterized in that it is hot-dipped using a galvanizing bath consisting of 1 to 2% Zn and the balance is Zn, and is further heat-alloyed. This is the manufacturing method.
【０００５】[0005]
【作用】以下に本発明を詳細に説明する。本発明法はＳ
ｉの表面濃化を抑制するため直火炉に於て鉄の酸化膜を
生成させ、還元炉で酸化膜が５００Å以下になる程度に
還元をし、めっき浴中に於いて浴中のアルミニウムとマ
ンガンにより、残りの酸化膜を還元させる。この方法の
利点は、鋼板がめっき浴に浸せきするまで鋼板表面に鉄
の酸化膜が存在しているため、Ｓｉの表面濃化を完全に
抑制した状態でめっき処理ができるため、めっき密着性
が非常に優れた鋼板を得ることができる点にある。 但
し、直火炉または無酸化炉の燃焼空気比はＳｉを抑制す
るために十分な鉄の酸化膜を生成するには０．９以上必
要であり、１．２を越えると、生成する鉄の酸化膜厚が
厚すぎて還元しきれなくなるため０．９〜１．２の範囲
で酸化するべきである。更に該鋼板を加熱合金化する。
本発明方法ではＳｉの表面濃化を完全に抑制しているた
め加熱合金化処理ができるが、従来法に於て加熱合金化
をするとめっき不良部分が広がって、逆に耐食性が非常
に悪くなってしまう。このときの加熱温度は３００℃〜
９００℃の範囲が好ましい。浴中のＭｎ、Ａｌは共に、
鉄の酸化膜を還元するために０．０１％以上必要であり
、２％を越えると加熱合金化の時の合金化速度を落とす
ので０．０１〜２％の範囲であるべきである。[Operation] The present invention will be explained in detail below. The method of the present invention is S
In order to suppress the surface concentration of iron, an oxide film of iron is generated in a direct-fired furnace, and the oxide film is reduced to less than 500 Å in a reduction furnace, and the aluminum and manganese in the plating bath are removed. The remaining oxide film is reduced. The advantage of this method is that since an iron oxide film exists on the surface of the steel plate until the steel plate is immersed in the plating bath, plating can be performed with the surface concentration of Si completely suppressed, resulting in improved plating adhesion. The advantage is that it is possible to obtain extremely high-quality steel sheets. However, the combustion air ratio in a direct-fired furnace or non-oxidizing furnace must be 0.9 or more to generate a sufficient iron oxide film to suppress Si, and if it exceeds 1.2, the oxidation of the iron produced Since the film thickness is too thick and cannot be completely reduced, oxidation should be performed within the range of 0.9 to 1.2. Furthermore, the steel plate is heated and alloyed. The method of the present invention completely suppresses the surface enrichment of Si, so it can be heated and alloyed. However, when heat-alloyed using the conventional method, the defective plating area spreads, and the corrosion resistance deteriorates considerably. I end up. The heating temperature at this time is 300℃~
A range of 900°C is preferred. Both Mn and Al in the bath are
0.01% or more is necessary to reduce the iron oxide film, and if it exceeds 2%, the alloying rate during heating alloying will be reduced, so it should be in the range of 0.01 to 2%.
【０００６】[0006]
【実施例】実施例は表１に示す。試験方法は次の通り（
１）めっき密着性試験
めっき密着性は６０°Ｖ曲げによるパウダリング試験に
よって評価した。
◎：剥離量 ０ｍｍ
○：剥離量 ０ｍｍ超、１ｍｍ以下
△：剥離量 １ｍｍ超 ３ｍｍ以下×：剥離量
３ｍｍ超
（２）耐食性試験
ＪＩＳ Ｚ ２３７１による塩水噴霧試験を２００
０時間連続して行い、板厚減少量の比較調査。
◎：板厚減少量が極小
○：板厚減少量が小
△：板厚減少量が大
（３）めっき濡れ性試験
めっき濡れ性は実ラインにおけるめっき性不良の発生の
程度により評価した。
○：めっき不良無し
△：ピンホール状のめっき不良
×：直径１ｍｍ以上のめっき不良
表１に於ける１〜５は鋼板中Ｓｉ濃度を０．１〜０．５
％まで変化させたもの、６〜１０は無酸化炉中板温を３
００〜８００℃に変化させたもの、１１〜１２は無酸化
炉中空気比を０．９５〜１．２に変化させたもの、１３
〜１７は還元炉板温を３００〜８００℃に変化させたも
の、１８〜２１は還元時間を１０秒〜２分に変化させた
もの、２２〜２５は還元炉の水素濃度を２０〜８０％に
変化させたもの、２６〜３０は加熱合金化炉の板温を３
００〜７００℃に変化させたもの、３１〜３６は加熱合
金化炉の昇温速度５〜６０℃／秒、３７〜４１は浴中ア
ルミニウム濃度、４２〜５０は浴中マンガン濃度を変化
させたもの。５１はＨＯＴ材を使用したもの、５２〜５
４は比較例である。５２は浴中にＭｎが含まれていない
ため、５３は浴中にＡｌが含まれていないため、５４は
燃焼空気比が低いためにめっき密着性、耐食性、めっき
濡れ性を低下させている。[Examples] Examples are shown in Table 1. The test method is as follows (
1) Plating adhesion test Plating adhesion was evaluated by a powdering test using 60° V bending. ◎: Peeling amount 0 mm ○: Peeling amount more than 0 mm, 1 mm or less △: Peeling amount more than 1 mm, 3 mm or less ×: Peeling amount
More than 3mm (2) Corrosion resistance test Salt water spray test according to JIS Z 2371 200
Comparative investigation of the amount of plate thickness reduction conducted continuously for 0 hours. ◎: The amount of decrease in plate thickness is minimal.○: The amount of decrease in plate thickness is small.△: The amount of decrease in plate thickness is large. (3) Plating wettability test Plating wettability was evaluated based on the degree of occurrence of poor plating properties in the actual line. ○: No plating defects △: Pinhole-like plating defects ×: Plating defects with a diameter of 1 mm or more 1 to 5 in Table 1 indicate the Si concentration in the steel sheet from 0.1 to 0.5.
%, 6 to 10 is a non-oxidizing furnace middle plate temperature of 3
00 to 800°C, 11 to 12 are non-oxidizing furnace air ratios changed to 0.95 to 1.2, 13
- 17 are those in which the reduction furnace plate temperature was changed from 300 to 800°C, 18 to 21 are those in which the reduction time is changed to 10 seconds to 2 minutes, and 22 to 25 are those in which the hydrogen concentration in the reduction furnace is changed to 20 to 80%. For 26 to 30, the plate temperature in the heating alloying furnace was changed to 3.
00 to 700°C, 31 to 36, the heating rate of the heating alloying furnace was 5 to 60°C/sec, 37 to 41, the aluminum concentration in the bath, and 42 to 50, the manganese concentration in the bath. thing. 51 uses HOT material, 52-5
4 is a comparative example. No. 52 does not contain Mn in the bath, No. 53 does not contain Al in the bath, and No. 54 has a low combustion air ratio, resulting in poor plating adhesion, corrosion resistance, and plating wettability.
【０００７】[0007]
【表１Ａ】[Table 1A]
【０００８】[0008]
【表１Ｂ】[Table 1B]
【０００９】[0009]
【発明の効果】本発明法に従うとつぎの効果がある。鉄
の酸化膜が残った状態でめっき浴に浸せきするためＳｉ
の表面濃化を完全に抑制した状態でめっき処理ができる
ため、めっき密着性が良好な高Ｓｉ含有高張力合金化溶
融亜鉛めっき鋼板を得ることができる。[Effects of the Invention] The method of the present invention has the following effects. Si is immersed in a plating bath with the iron oxide film remaining.
Since the plating treatment can be carried out in a state where the surface concentration of .
Claims (1)
鋼板を燃焼空気比０．９〜１．２の直火炉にて酸化後、
水素を含む還元炉で還元した後、該鋼板をＭｎを０．０
１〜２％、Ａｌを０．０１〜２％、残部Ｚｎよりなる亜
鉛めっき浴を用いて溶融めっき処理を行ない、更に加熱
合金化処理することを特徴とするめっき密着性の良好な
高Ｓｉ含有高張力合金化溶融亜鉛めっき鋼板の製造方法
。Claim 1: After oxidizing a steel plate containing Si in a range of 0.2% or more in a direct fire furnace with a combustion air ratio of 0.9 to 1.2,
After reducing the steel plate in a reduction furnace containing hydrogen, the Mn content of the steel plate was reduced to 0.0.
High Si content with good plating adhesion, characterized by performing hot-dip plating using a galvanizing bath consisting of 1% to 2% Al, 0.01 to 2% Al, and the balance Zn, and further heat alloying treatment. A method for manufacturing high tensile strength alloyed hot-dip galvanized steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6235691A JPH04276057A (en) | 1991-03-05 | 1991-03-05 | Manufacture of high si-containing high tensile strength galvannealed steel sheet having good plating adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6235691A JPH04276057A (en) | 1991-03-05 | 1991-03-05 | Manufacture of high si-containing high tensile strength galvannealed steel sheet having good plating adhesion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04276057A true JPH04276057A (en) | 1992-10-01 |
Family
ID=13197754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6235691A Withdrawn JPH04276057A (en) | 1991-03-05 | 1991-03-05 | Manufacture of high si-containing high tensile strength galvannealed steel sheet having good plating adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04276057A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0681096A (en) * | 1992-09-01 | 1994-03-22 | Nippon Steel Corp | Production of si-containing high strength galvannealed steel sheet good in plating adhesion |
| JPH06192854A (en) * | 1992-12-28 | 1994-07-12 | Nippon Steel Corp | Si-containing galvannealed steel sheet |
| US5447802A (en) * | 1992-03-30 | 1995-09-05 | Kawasaki Steel Corporation | Surface treated steel strip with minimal plating defects and method for making |
| EP1205571A1 (en) * | 2000-11-08 | 2002-05-15 | Kawasaki Steel Corporation | High tensile steel sheet having a plating layer comprising zinc |
| US7601433B2 (en) * | 2004-12-28 | 2009-10-13 | Sakuratech Co., Ltd. | Highly corrosion-resistant/highly workable plated steel wire, plating bath composition, method for producing the plated steel wire and wire netting product |
| JP2010121212A (en) * | 2009-12-22 | 2010-06-03 | Jfe Steel Corp | Method for producing cold-rolled steel sheet |
| WO2011025042A1 (en) | 2009-08-31 | 2011-03-03 | 新日本製鐵株式会社 | High-strength hot-dip galvanized steel sheet and process for producing same |
| JP2014505168A (en) * | 2010-12-28 | 2014-02-27 | ポスコ | Hot-dip plated steel sheet with excellent plating adhesion and method for producing the same |
| WO2014037627A1 (en) * | 2012-09-06 | 2014-03-13 | Arcelormittal Investigación Y Desarrollo Sl | Process for manufacturing press-hardened coated steel parts and precoated sheets allowing these parts to be manufactured |
| WO2014102901A1 (en) | 2012-12-25 | 2014-07-03 | 新日鐵住金株式会社 | Alloyed hot-dip galvanized steel plate and manufacturing method therefor |
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-
1991
- 1991-03-05 JP JP6235691A patent/JPH04276057A/en not_active Withdrawn
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| US10704132B2 (en) | 2016-02-25 | 2020-07-07 | Nippon Steel Corporation | High-strength hot-dip galvanized steel sheet excellent in impact peeling resistance and worked portion corrosion resistance |
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