JP2001234318A - Steel sheet having hot dip aluminized coating excellent in workability, heat resistance and oxidation resistance and its producing method - Google Patents
Steel sheet having hot dip aluminized coating excellent in workability, heat resistance and oxidation resistance and its producing methodInfo
- Publication number
- JP2001234318A JP2001234318A JP2000043732A JP2000043732A JP2001234318A JP 2001234318 A JP2001234318 A JP 2001234318A JP 2000043732 A JP2000043732 A JP 2000043732A JP 2000043732 A JP2000043732 A JP 2000043732A JP 2001234318 A JP2001234318 A JP 2001234318A
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- JP
- Japan
- Prior art keywords
- hot
- alloy layer
- layer
- steel sheet
- dip
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、加工性，耐熱性，耐酸
化性に優れた溶融アルミめっき系鋼板及びその製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-dip aluminized steel sheet having excellent workability, heat resistance and oxidation resistance, and a method for producing the same.
【０００２】[0002]
【従来の技術】溶融アルミめっき系鋼板は、溶融亜鉛め
っき鋼板や溶融Ｚｎ−Ａｌ合金めっき鋼板に比較して耐
食性，耐熱性，耐酸化性に優れているため、自動車の排
気系部材，熱機器等の広範な分野で使用されている。こ
の溶融アルミめっき系鋼板は、連続式溶融めっきライン
でめっき原板をガス還元焼鈍した後、溶融アルミめっき
浴に浸漬することにより製造されている。溶融アルミめ
っき浴には、通常、溶融アルミめっき層と下地鋼との合
金化を抑制し、加工性，耐熱性，耐酸化性を向上させる
ため７〜１２質量％のＳｉが添加されている。Ｓｉ濃度
７〜１２質量％の溶融アルミめっき浴を用いて溶融めっ
きすると、溶融アルミめっき層１と下地鋼２との反応に
よって層厚３μｍ程度のＦｅ−Ａｌ−Ｓｉ合金層３が界
面に生成する（図１）。溶融アルミめっき層１は、溶融
アルミめっき浴と同様に７〜１２質量％のＳｉを含んで
いる。Ｆｅ−Ａｌ−Ｓｉ合金層３は、ほぼＦｅ：３２質
量％，Ａｌ：５９質量％，Ｓｉ：９質量％の組成にな
る。2. Description of the Related Art Hot-dip aluminized steel sheets have better corrosion resistance, heat resistance and oxidation resistance than hot-dip galvanized steel sheets and hot-dip Zn-Al alloy coated steel sheets. And so on. This hot-dip aluminum-plated steel sheet is manufactured by immersing it in a hot-dip aluminum plating bath after subjecting a raw plate to gas reduction annealing in a continuous hot-dip plating line. Usually, 7 to 12% by mass of Si is added to the hot-dip aluminum plating bath in order to suppress alloying between the hot-dip aluminum plating layer and the base steel and to improve workability, heat resistance and oxidation resistance. When hot-dip plating is performed using a hot-dip aluminum plating bath having an Si concentration of 7 to 12% by mass, a reaction between the hot-dip aluminum plating layer 1 and the base steel 2 forms an Fe—Al—Si alloy layer 3 having a thickness of about 3 μm at the interface. (FIG. 1). The hot-dip aluminum plating layer 1 contains 7 to 12% by mass of Si as in the hot-dip aluminum plating bath. The Fe—Al—Si alloy layer 3 has a composition of approximately 32% by mass of Fe, 59% by mass of Al, and 9% by mass of Si.
【０００３】[0003]
【発明が解決しようとする課題】Ｆｅ−Ａｌ−Ｓｉ合金
層３は，硬質で靭性に劣るため、厚く成長すると加工時
に溶融アルミめっき層１及びＦｅ−Ａｌ−Ｓｉ合金層３
を貫通するクラックを発生させる原因になる。クラック
の発生によって下地鋼２が露出すると、耐食性，耐熱
性，耐酸化性が低下する。なかでも、深絞り等の高度加
工が予定される溶融アルミめっき系鋼のめっき原板とし
て使用される極低炭素Ｔｉ添加鋼やＴｉ-Ｎｂ添加鋼で
は、清浄度が高く合金化速度が大きいため、Ｆｅ−Ａｌ
−Ｓｉ合金層３が成長しやすい。その結果、加工度が大
きな部位に使用すると、溶融アルミめっき層１に発生し
たクラックに起因して耐食性，耐熱性，耐酸化性の低下
が顕在化する。The Fe--Al--Si alloy layer 3 is hard and inferior in toughness.
Causes cracks to penetrate through. When the base steel 2 is exposed due to the occurrence of cracks, the corrosion resistance, heat resistance, and oxidation resistance decrease. Above all, ultra-low carbon Ti-added steel and Ti-Nb-added steel used as plating base plates for hot-dip aluminized steel, which is scheduled for advanced processing such as deep drawing, have high cleanliness and high alloying speed, Fe-Al
-Si alloy layer 3 grows easily. As a result, when used in a part with a high degree of processing, the corrosion resistance, heat resistance, and oxidation resistance are reduced due to cracks generated in the hot-dip aluminum plating layer 1.
【０００４】また、Ｓｉによる合金成長抑制効果は、６
００℃を超える加熱温度では著しく低下する。溶融アル
ミめっき系鋼板が６００℃を超える温度に長時間加熱さ
れると、溶融アルミめっき層１と下地鋼２との合金化反
応が促進されＦｅ−Ａｌ−Ｓｉ合金層３が成長すると共
に、Ｆｅ−Ａｌ−Ｓｉ合金層３の下層にＦｅ−Ａｌ合金
層が生成・成長する。溶融アルミめっき系鋼板製部材の
使用形態にもよるが、合金成長が溶融アルミめっき層１
の表層にまで達するＦｅの拡散が進行すると、耐熱性低
下だけでなく耐酸化性も低下し、溶融アルミめっき系鋼
板本来の特性が損なわれる。そのため、高温での耐熱性
や耐酸化性が要求される用途ではステンレス鋼が使用さ
れている。しかし、ステンレス鋼は、溶融アルミめっき
系鋼板に比較して高価であるため、価格面からの制約が
加わる。[0004] The effect of Si to suppress alloy growth is 6%.
At a heating temperature exceeding 00 ° C., the temperature significantly decreases. When the hot-dip aluminized steel sheet is heated to a temperature exceeding 600 ° C. for a long time, the alloying reaction between the hot-dip aluminized layer 1 and the base steel 2 is promoted, and the Fe—Al—Si alloy layer 3 grows, and -An Fe-Al alloy layer is generated and grown below the Al-Si alloy layer 3. Depending on the type of use of the hot-dip aluminized steel sheet member, the alloy growth is
When the diffusion of Fe reaching the surface layer of the steel sheet progresses, not only the heat resistance but also the oxidation resistance is lowered, and the original properties of the hot-dip aluminized steel sheet are impaired. Therefore, stainless steel is used in applications that require heat resistance and oxidation resistance at high temperatures. However, stainless steel is more expensive than a hot-dip aluminized steel sheet, which imposes restrictions on price.
【０００５】[0005]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、溶融アルミめっ
き層と下地鋼との界面にＭｏを含む合金層（以下、Ｆｅ
−Ａｌ−Ｓｉ−Ｍｏ合金層という）を形成することによ
り、Ｆｅ−Ａｌ合金層は勿論，Ｆｅ−Ａｌ−Ｓｉ合金層
の生成を抑制し、加工性，耐熱性，耐酸化性に優れた溶
融アルミめっき系鋼板を得ることを目的とする。SUMMARY OF THE INVENTION The present invention has been devised to solve such a problem. An alloy layer containing Mo (hereinafter referred to as Fe) is provided at an interface between a hot-dip aluminum plating layer and a base steel.
-Al-Si-Mo alloy layer), the formation of the Fe-Al-Si alloy layer as well as the Fe-Al alloy layer is suppressed, and the molten metal is excellent in workability, heat resistance, and oxidation resistance. The purpose is to obtain an aluminum-plated steel sheet.
【０００６】本発明の溶融アルミめっき系鋼板は、その
目的を達成するため、下地鋼の上にＦｅ−Ａｌ−Ｓｉ−
Ｍｏ合金層を介して溶融アルミめっき層が形成されてい
ることを特徴とする。下地鋼とＦｅ−Ａｌ−Ｓｉ−Ｍｏ
合金層と界面にＦｅ−Ｍｏ合金層を設けてもよい。この
溶融アルミめっき系鋼板は、めっき原板の片面又は両面
にＦｅ−Ｍｏプレめっきを施した後、めっき原板をＳｉ
含有溶融アルミめっき浴に浸漬して溶融アルミめっき層
を形成することにより製造される。[0006] In order to achieve the object, the hot-dip aluminized steel sheet according to the present invention comprises Fe-Al-Si-
It is characterized in that a hot-dip aluminum plating layer is formed via a Mo alloy layer. Base steel and Fe-Al-Si-Mo
An Fe-Mo alloy layer may be provided at the interface with the alloy layer. This hot-dip aluminized steel sheet is prepared by applying Fe-Mo pre-plating to one or both sides of a plating base sheet, and then converting the plating base sheet to Si.
It is manufactured by immersing in a hot-dip aluminum plating bath to form a hot-dip aluminum plating layer.
【０００７】[0007]
【作用】本発明者等は、溶融アルミめっき系鋼板の溶融
アルミめっき層１と下地鋼２との間に生成・成長するＦ
ｅ−Ａｌ−Ｓｉ合金層３に及ぼす各種元素の影響を調査
した。その結果、めっき原板にＦｅ−Ｍｏプレめっきを
施すことがＦｅ−Ａｌ−Ｓｉ合金層３の抑制に有効であ
ることを見出した。めっき原板に施されたＦｅ−Ｍｏプ
レめっき層は、Ｓｉ含有溶融アルミめっき浴にめっき原
板を浸漬して溶融めっきすると、一部又は全部が溶融ア
ルミめっき浴と反応し、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層
４が溶融アルミめっき層１と下地鋼２との界面に生成す
る。Ｆｅ−Ｍｏプレめっき層の全部が溶融アルミめっき
浴と反応する場合、従来のＦｅ−Ａｌ−Ｓｉ合金層３に
Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４が置き換わる（図
２）。Ｆｅ−Ｍｏプレめっき層の一部が溶融アルミめっ
き浴と反応する場合、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４
の下にＦｅ−Ｍｏ合金層５が残存する（図３）。The present inventors have developed and grown F between the hot-dip aluminized steel sheet and the base steel 2 of the hot-dip aluminized steel sheet.
The effects of various elements on the e-Al-Si alloy layer 3 were investigated. As a result, it has been found that applying Fe-Mo pre-plating to the original plating plate is effective for suppressing the Fe-Al-Si alloy layer 3. When the Fe-Mo pre-plated layer applied to the plating base plate is dipped and dipped in the Si-containing hot dipping aluminum plating bath, a part or all of the Fe-Mo pre-plated layer reacts with the hot dipping aluminum plating bath, and the Fe-Al-Si- Mo alloy layer 4 is formed at the interface between hot-dip aluminum plating layer 1 and base steel 2. When all of the Fe-Mo pre-plated layers react with the hot-dip aluminum plating bath, the Fe-Al-Si-Mo alloy layer 4 replaces the conventional Fe-Al-Si alloy layer 3 (Fig. 2). When a part of the Fe-Mo pre-plating layer reacts with the hot-dip aluminum plating bath, the Fe-Al-Si-Mo alloy layer 4
The Fe—Mo alloy layer 5 remains under the layer (FIG. 3).
【０００８】Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ
−Ｍｏ合金層５は、溶融アルミめっき層１と下地鋼２と
の拡散反応を抑制するバリアとして働く。そのため、溶
融アルミめっき時にＦｅ−Ａｌ−Ｓｉ合金層３の成長が
抑制され、溶融アルミめっき系鋼板の加工性が向上す
る。なお、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ−
Ｍｏ合金層５は、好ましくは０．５μｍ以下の層厚にす
るとき、加工性に悪影響を及ぼすことはない。高温雰囲
気に曝される部材に溶融アルミめっき系鋼板を使用する
用途でも、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ−
Ｍｏ合金層５によってＦｅ−Ａｌ−Ｓｉ合金層３の成長
が抑制され、溶融アルミめっき系鋼板本来の優れた耐食
性，耐熱性，耐酸化性が維持される。[0008] Fe-Al-Si-Mo alloy layer 4 and Fe
The -Mo alloy layer 5 functions as a barrier that suppresses a diffusion reaction between the hot-dip aluminum plating layer 1 and the base steel 2. Therefore, the growth of the Fe—Al—Si alloy layer 3 during hot-dip aluminum plating is suppressed, and workability of the hot-dip aluminum-plated steel sheet is improved. The Fe—Al—Si—Mo alloy layer 4 and the Fe—Al—Si—Mo alloy layer 4
When the Mo alloy layer 5 preferably has a thickness of 0.5 μm or less, it does not adversely affect the workability. Even in applications where a hot-dip aluminized steel sheet is used for a member exposed to a high-temperature atmosphere, the Fe—Al—Si—Mo alloy layer 4 and the Fe—Al—Si—Mo alloy layer 4
The growth of the Fe-Al-Si alloy layer 3 is suppressed by the Mo alloy layer 5, and the excellent corrosion resistance, heat resistance and oxidation resistance inherent in the hot-dip aluminized steel sheet are maintained.
【０００９】[0009]
【実施の形態】本発明で使用されるめっき原板は、組
成，種類等の鋼種に制約を受けるものではなく、用途に
応じて種種の鋼材が選択される。なかでも、溶融アルミ
めっき層１との間に合金化反応が生じやすい極低炭素Ｔ
ｉ添加鋼，Ｔｉ-Ｎｂ添加鋼等の高清浄度鋼では、Ｆｅ
−Ａｌ−Ｓｉ−Ｍｏ合金層４による効果が顕著となる。
めっき原板は、電解脱脂で表面が清浄化された後、Ｆｅ
−Ｍｏプレめっきされる。Ｆｅ−Ｍｏプレめっき層は、
必ずしもめっき原板の両面に施す必要はない。たとえ
ば、溶融アルミめっき系鋼板の片面のみに加工性，耐熱
性，耐酸化性が要求される用途では、めっき原板の片面
のみにＦｅ−Ｍｏプレめっき層を形成する。溶融アルミ
めっき系鋼板の両面に加工性，耐熱性，耐酸化性が要求
される用途では、めっき原板の両面にＦｅ−Ｍｏプレめ
っき層を形成する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The plating base plate used in the present invention is not limited by the type of steel such as composition and type, and various types of steel materials are selected according to the application. Above all, extremely low carbon T in which alloying reaction easily occurs with the hot-dip aluminum plating layer 1
In high cleanliness steels such as i-added steel and Ti-Nb added steel, Fe
-The effect of the Al-Si-Mo alloy layer 4 becomes remarkable.
After the surface of the original plate is cleaned by electrolytic degreasing,
-Mo pre-plated. The Fe-Mo pre-plating layer is
It is not always necessary to apply it to both sides of the original plate. For example, in applications where workability, heat resistance, and oxidation resistance are required only on one side of a hot-dip aluminum-plated steel sheet, an Fe-Mo pre-plated layer is formed only on one side of an original plating plate. In applications where workability, heat resistance, and oxidation resistance are required on both sides of a hot-dip aluminum-plated steel sheet, an Fe-Mo pre-plated layer is formed on both sides of the original plate.
【００１０】Ｆｅ−Ｍｏプレめっき層は電気めっき，蒸
着めっき，溶融めっき等で形成できるが、特殊な設備を
必要とせず安価にＦｅ−Ｍｏプレめっき層が形成できる
電気めっきが好ましい。電気めっきによるとき、形成さ
れるＦｅ−Ｍｏプレめっき層の組成や層厚が電気めっき
浴の浴組成，電解条件等によって容易に調整される。こ
の点でも，電気めっきが有利である。Ｆｅ−Ｍｏプレめ
っき層は、既存の電気めっきラインで形成することもで
きるが、電気めっき設備を入側に付設した連続式溶融め
っきラインを使用するとき、Ｆｅ−Ｍｏプレめっき及び
溶融アルミめっきを連続化できるため生産性，製造コス
トの面でも有利になる。電気めっきでは、Ｍｏは、単独
で析出することなく、Ｆｅ族元素との誘起共析で析出す
る。電気めっき浴としては、具体的にはピロリン酸塩浴
等のアルカリ浴やクエン酸浴等の酸性浴がある。The Fe-Mo pre-plated layer can be formed by electroplating, vapor deposition plating, hot-dip plating, etc., but electroplating which can form the Fe-Mo pre-plated layer at low cost without requiring special equipment is preferred. In the case of electroplating, the composition and thickness of the Fe-Mo pre-plated layer to be formed can be easily adjusted by the bath composition of the electroplating bath, electrolysis conditions and the like. Also in this respect, electroplating is advantageous. The Fe-Mo pre-plating layer can be formed by an existing electroplating line. However, when using a continuous hot-dip plating line provided with an electroplating facility on the entrance side, the Fe-Mo pre-plating and hot-dip aluminum plating can be performed. Because it can be continuous, it is advantageous in terms of productivity and manufacturing cost. In electroplating, Mo does not precipitate alone, but precipitates by induced eutectoid with Fe group elements. Specific examples of the electroplating bath include an alkaline bath such as a pyrophosphate bath and an acidic bath such as a citric acid bath.
【００１１】Ｆｅ−Ｍｏプレめっき層は、具体的にはＭ
ｏ濃度２０〜６０質量％，層厚０．１〜３μｍが好まし
い。２０質量％以上のＭｏ及び０．１μｍ以上の層厚で
Ｆｅ−Ｍｏプレめっき層を形成するとき、溶融アルミめ
っき層１と下地鋼２との反応抑制に顕著なバリア作用を
呈するＦｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４が形成される。
しかし、６０質量％を超えるＭｏ濃度や３μｍを超える
層厚は、製造コストを上昇させる原因となる。Ｆｅ−Ｍ
ｏプレめっき層のＭｏ濃度は、溶融アルミめっき条件，
溶融アルミめっき浴のＳｉ濃度等に応じて２０〜６０質
量％の範囲で好適に定められる。The Fe—Mo pre-plated layer is specifically made of M
The o concentration is preferably 20 to 60% by mass, and the layer thickness is preferably 0.1 to 3 μm. When forming the Fe-Mo pre-plated layer with Mo of 20% by mass or more and a layer thickness of 0.1 µm or more, Fe-Al- which exhibits a remarkable barrier effect on suppressing the reaction between the hot-dip aluminum layer 1 and the base steel 2 is provided. The Si—Mo alloy layer 4 is formed.
However, a Mo concentration exceeding 60% by mass or a layer thickness exceeding 3 μm causes an increase in manufacturing cost. Fe-M
oMo concentration of pre-plated layer depends on hot-dip aluminum plating conditions,
It is suitably determined in the range of 20 to 60% by mass according to the Si concentration of the hot-dip aluminum plating bath.
【００１２】Ｆｅ−Ｍｏプレめっき層が形成されためっ
き原板は、連続式溶融めっきラインのガス還元焼鈍炉に
導入され、Ｈ2−Ｎ2混合ガス雰囲気中で還元焼鈍され
る。還元焼鈍条件は、特に制約されるものではなく、溶
融アルミめっき系鋼板に要求される機械的性質に応じて
加熱温度，時間等が設定される。還元焼鈍されためっき
原板は、溶融アルミめっき浴に導入され、溶融アルミめ
っきされる。溶融アルミめっき浴には、Ｆｅ−Ａｌ−Ｓ
ｉ合金層３の成長を抑制するＳｉが添加されている。溶
融アルミめっき浴に添加されたＳｉは、７質量％以上の
濃度でＦｅ−Ａｌ−Ｓｉ合金層３に対する成長抑制効果
が顕著になる。しかし、１２質量％を超えるＳｉ濃度で
は、溶融アルミめっき浴の融点が高くなるため溶融アル
ミめっき浴を高温保持するためのエネルギーコストが上
昇すると共に、めっきポット，シンクロール等のめっき
設備の侵食が激しくなる。[0012] Plating original plate Fe-Mo preplating layer is formed is introduced into the gas reduction annealing furnace of a continuous hot-dip plating line, it is reduced annealed in H 2 -N 2 mixed gas atmosphere. The conditions of the reduction annealing are not particularly limited, and the heating temperature, time and the like are set according to the mechanical properties required for the hot-dip aluminized steel sheet. The reduction-annealed plating base plate is introduced into a hot-dip aluminum plating bath and hot-dip aluminized. Fe-Al-S
Si for suppressing the growth of the i-alloy layer 3 is added. Si added to the hot-dip aluminum plating bath has a remarkable effect of suppressing the growth of the Fe-Al-Si alloy layer 3 at a concentration of 7% by mass or more. However, when the Si concentration exceeds 12% by mass, the melting point of the hot-dip aluminum plating bath increases, so that the energy cost for maintaining the hot-dip aluminum bath at a high temperature increases, and the erosion of the plating equipment such as a plating pot and a sink roll occurs. It becomes intense.
【００１３】溶融アルミめっき時、溶融アルミめっき浴
の浴温及びインレット温度を共に６５０〜６７０℃の温
度域に維持することが好ましい。浴温及びインレット温
度が６５０℃未満では不めっきが発生しやすく、６７０
℃を超えるとＦｅ−Ａｌ−Ｓｉ合金層３が成長しやすく
なる。溶融アルミめっき浴からめっき原板を引き上げ、
付着量を調整する。冷却後に溶融アルミめっき系鋼板の
断面を観察すると、Ｆｅ−Ｍｏプレめっき層と溶融アル
ミめっき層１及び下地鋼２との反応生成物であるＦｅ−
Ａｌ−Ｓｉ−Ｍｏ合金層４が溶融アルミめっき層１と下
地鋼２との界面に観察される。It is preferable that the bath temperature and the inlet temperature of the hot-dip aluminum plating bath are both maintained in a temperature range of 650 to 670 ° C. during hot-dip aluminum plating. If the bath temperature and the inlet temperature are lower than 650 ° C., unplating is likely to occur, and 670
If the temperature exceeds ℃, the Fe—Al—Si alloy layer 3 tends to grow. Lift the plating base plate from the hot-dip aluminum plating bath,
Adjust the amount of adhesion. Observation of the cross section of the hot-dip aluminized steel sheet after cooling reveals that the reaction product of the Fe-Mo pre-plated layer and the hot-dip aluminized layer 1 and the base steel 2 is Fe-
An Al—Si—Mo alloy layer 4 is observed at the interface between the hot-dip aluminum plating layer 1 and the base steel 2.
【００１４】Ｆｅ−Ｍｏプレめっき層が全て反応した場
合、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４の単相（図２）に
なる。たとえば、層厚０．１〜０．３μｍでＦｅ−Ｍｏ
プレめっき層を設けたものでは、Ｆｅ−Ｍｏプレめっき
層の全量が溶融アルミめっき層１，下地鋼２と反応し、
Ｍｏ濃度１０〜３０質量％，層厚０．２〜０．５μｍの
Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４が形成される。Ｆｅ−
Ｍｏプレめっき層の一部が反応した場合、Ｆｅ−Ａｌ−
Ｓｉ−Ｍｏ合金層４及びＦｅ−Ｍｏ合金層５の複層（図
３）となる。たとえば、層厚０．４〜３μｍでＦｅ−Ｍ
ｏプレめっき層を設けたものでは、Ｆｅ−Ａｌ−Ｓｉ−
Ｍｏ合金層４の一部が溶融アルミめっき層１と反応し、
Ｍｏ濃度１０〜３０質量％，層厚０．２〜０．５μｍの
Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４が形成され、層厚０．
１〜２．７μｍのＦｅ−Ｍｏ合金層５がＦｅ−Ａｌ−Ｓ
ｉ−Ｍｏ合金層４の下に残存する。Ｆｅ−Ａｌ−Ｓｉ−
Ｍｏ合金層４単層型（図２）及びＦｅ−Ｍｏ合金層５が
残存する複層型（図３）の何れにするかは、溶融アルミ
めっき系鋼板の用途に応じて適宜定められる。たとえ
ば、高度の耐熱性，耐酸化性が要求される用途では、比
較的厚いＦｅ−Ｍｏプレめっき層を設けることによりＦ
ｅ−Ｍｏ合金層５を残存させた複層型が好ましい。When all of the Fe—Mo pre-plated layers react, the Fe—Al—Si—Mo alloy layer 4 becomes a single phase (FIG. 2). For example, when the layer thickness is 0.1 to 0.3 μm,
In the case where the pre-plating layer is provided, the entire amount of the Fe-Mo pre-plating layer reacts with the hot-dip aluminum plating layer 1 and the base steel 2,
The Fe—Al—Si—Mo alloy layer 4 having a Mo concentration of 10 to 30% by mass and a layer thickness of 0.2 to 0.5 μm is formed. Fe-
When a part of the Mo pre-plated layer reacts, Fe-Al-
It becomes a multilayer (FIG. 3) of the Si—Mo alloy layer 4 and the Fe—Mo alloy layer 5. For example, with a layer thickness of 0.4 to 3 μm, Fe-M
o In the case where the pre-plated layer is provided, Fe-Al-Si-
Part of the Mo alloy layer 4 reacts with the hot-dip aluminum plating layer 1,
An Fe—Al—Si—Mo alloy layer 4 having a Mo concentration of 10 to 30% by mass and a layer thickness of 0.2 to 0.5 μm is formed.
The Fe—Mo alloy layer 5 of 1 to 2.7 μm is made of Fe—Al—S
It remains under the i-Mo alloy layer 4. Fe-Al-Si-
Whether to use the Mo alloy layer 4 single layer type (FIG. 2) or the multi-layer type in which the Fe—Mo alloy layer 5 remains (FIG. 3) is appropriately determined according to the use of the hot-dip aluminized steel sheet. For example, in applications where high heat resistance and oxidation resistance are required, the provision of a relatively thick Fe-Mo pre-plating layer allows
The multilayer structure in which the e-Mo alloy layer 5 is left is preferable.
【００１５】[0015]
【実施例】めっき原板として、板厚０．７ｍｍ，板幅１
０００ｍｍの極低炭素Ｔｉ添加鋼帯（Ｃ：０．００３質
量％，Ｓｉ：０．０２質量％，Ｍｎ：０．１４質量％，
Ａｌ：０．０２質量％，Ｔｉ：０．０７質量％）を使用
し、入側に電気めっき装置を付設した連続式溶融めっき
ラインで溶融アルミめっき系鋼板を製造した。製造条件
は、次の通りである。 ラインスピード：７０ｍ／分 Ｆｅ−Ｍｏプレめっき：表１の条件でＦｅ−Ｍｏプレめ
っき層を電気めっきによりめっき原板の両面に形成し
た。Ｆｅ−Ｍｏプレめっき層の層厚は、通電時間によっ
て０．１〜３μｍの範囲に調整した。[Embodiment] As plating base plate, plate thickness 0.7 mm, plate width 1
000 mm ultra-low carbon Ti-added steel strip (C: 0.003% by mass, Si: 0.02% by mass, Mn: 0.14% by mass,
(Al: 0.02% by mass, Ti: 0.07% by mass), and a hot-dip aluminized steel sheet was manufactured in a continuous hot-dip plating line provided with an electroplating apparatus on the inlet side. The manufacturing conditions are as follows. Line speed: 70 m / min Fe-Mo pre-plating: Fe-Mo pre-plating layers were formed on both surfaces of the original plating plate by electroplating under the conditions shown in Table 1. The thickness of the Fe—Mo pre-plated layer was adjusted to a range of 0.1 to 3 μm depending on the energization time.
【００１６】 [0016]
【００１７】還元焼鈍：Ｆｅ−Ｍｏプレめっきしためっ
き原板を還元焼鈍炉に導入し、露点−４０℃の５０体積
％Ｈ2−Ｎ2雰囲気中で８００℃に４０秒間加熱した。 溶融アルミめっき：還元焼鈍されためっき原板をインレ
ット温度６７０℃で浴温６６０℃，Ｓｉ濃度７〜１２質
量％の溶融アルミめっき浴に３秒間浸漬し、溶融アルミ
めっき浴から引き上げた後、めっき付着量を片面当り４
５ｇ／ｍ2に調整した。Reduction Annealing: The Fe-Mo preplated original plate was introduced into a reduction annealing furnace and heated to 800 ° C. for 40 seconds in a 50% by volume H 2 —N 2 atmosphere with a dew point of −40 ° C. Hot-dip aluminum plating: The reduction-annealed original plate is immersed in a hot-dip aluminum plating bath with an inlet temperature of 670 ° C. and a bath temperature of 660 ° C. and a Si concentration of 7 to 12% by mass for 3 seconds. 4 per side
It was adjusted to 5 g / m 2 .
【００１８】製造された溶融アルミめっき系鋼板から試
験片を切り出し、走査型電子顕微鏡を用いて断面組織を
観察し、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ−Ｍ
ｏ合金層５の層厚を測定すると共に、各層を組成分析し
た。また、次の各試験で加工性，耐熱性，耐酸化性も調
査した。比較のため、Ｆｅ−Ｍｏプレめっきを施さずに
同じ条件下で溶融アルミめっきした従来の溶融アルミめ
っき系鋼板についても、同じ試験で断面組織を観察する
と共に加工性，耐熱性，耐酸化性を調査した。 〔断面組織観察〕幅１０ｍｍ，長さ２０ｍｍの試験片の
断面を鏡面研磨した後、３質量％硝酸アルコール液でエ
ッチングし、ランダムに選んだ視野を倍率１０4倍で撮
影し、Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ−Ｍｏ
合金層５の層厚を測定した。また、走査型電子顕微鏡に
付設されているエネルギー分散型Ｘ線マイクロアナライ
ザでＦｅ−Ａｌ−Ｓｉ−Ｍｏ合金層４及びＦｅ−Ｍｏ合
金層５の組成をスポット分析した。A test piece was cut out from the manufactured hot-dip aluminized steel sheet, and the cross-sectional structure was observed using a scanning electron microscope, and the Fe-Al-Si-Mo alloy layer 4 and the Fe-M
The thickness of the o-alloy layer 5 was measured and the composition of each layer was analyzed. In addition, workability, heat resistance, and oxidation resistance were also investigated in the following tests. For comparison, the cross-sectional structure of the conventional hot-dip aluminized steel sheet that was hot-dip aluminized under the same conditions without applying the Fe-Mo pre-plating was observed in the same test, and the workability, heat resistance, and oxidation resistance were observed. investigated. [Cross-sectional structure observation] The cross section of a test piece having a width of 10 mm and a length of 20 mm was mirror-polished, etched with a 3% by mass nitric acid alcohol solution, and a randomly selected visual field was photographed at a magnification of 10 4 times. Si-Mo alloy layer 4 and Fe-Mo
The thickness of the alloy layer 5 was measured. The composition of the Fe—Al—Si—Mo alloy layer 4 and the composition of the Fe—Mo alloy layer 5 were spot analyzed by an energy dispersive X-ray microanalyzer attached to a scanning electron microscope.
【００１９】〔加工性試験〕幅２０ｍｍ，長さ５０ｍｍ
の試験片を１８０度密着曲げ試験し、走査型電子顕微鏡
を用いて曲げ部の外側を５００倍の倍率で観察し、クラ
ックの発生状況を調査した。クラックの発生状況から加
工性を判定し、クラックが観察されなかったものを○，
中程度のクラックが発生したものを△，クラックが著し
く発生しているものを×として加工性を３段階評価し
た。 〔耐熱性試験〕幅５０ｍｍ，長さ５０ｍｍの試験片を大
気雰囲気中で６００℃に５分間加熱した後、走査型電子
顕微鏡を用いて倍率５００倍で断面組織を観察し、Ｆｅ
−Ａｌ−Ｓｉ合金層及びＦｅ−Ａｌ合金層の生成有無を
調査した。Ｆｅ−Ａｌ−Ｓｉ合金層及びＦｅ−Ａｌ合金
層が検出できなかったものを○，観察されたものを×と
して耐熱性を評価した。 〔耐酸化性試験〕幅３５ｍｍ，長さ６０ｍｍの試験片を
大気雰囲気中で６００℃に１０００時間加熱し、試験片
の酸化増量を測定した。この耐酸化性試験では、切断端
面の酸化に起因する酸化増量の増加分は補正しなかっ
た。[Workability test] width 20 mm, length 50 mm
Was subjected to a 180 ° close contact bending test, and the outside of the bent portion was observed at a magnification of 500 times using a scanning electron microscope to investigate the occurrence of cracks. The workability was determined from the occurrence of cracks.
Workability was evaluated on a three-point scale, with Δ indicating that a moderate crack was generated and X indicating that a significant crack was generated. [Heat resistance test] A test piece having a width of 50 mm and a length of 50 mm was heated at 600 ° C. for 5 minutes in an air atmosphere, and the cross-sectional structure was observed at a magnification of 500 times using a scanning electron microscope.
The presence or absence of the formation of the -Al-Si alloy layer and the Fe-Al alloy layer was investigated. The heat resistance was evaluated as ○ when no Fe-Al-Si alloy layer or Fe-Al alloy layer could be detected, and as x when observed. [Oxidation Resistance Test] A test piece having a width of 35 mm and a length of 60 mm was heated at 600 ° C. for 1,000 hours in an air atmosphere, and the oxidation increase of the test piece was measured. In the oxidation resistance test, the amount of increase in the amount of oxidation caused by oxidation of the cut end face was not corrected.
【００２０】以上の調査結果を、Ｆｅ−Ａｌ−Ｓｉ−Ｍ
ｏ合金層４及びＦｅ−Ｍｏ合金層５の有無と併せて表２
に示す。表２から明らかなように、Ｆｅ−Ａｌ−Ｓｉ−
Ｍｏ合金層４及びＦｅ−Ｍｏ合金層５を介在させた試験
番号１〜１８（本発明例）では、何れも優れた加工性及
び耐熱性を示した。酸化増量も比較例の半分程度，或い
はそれ以下であり、耐酸化性に優れていることが判る。
これに対し、Ｆｅ−Ｍｏプレめっきを施さずに溶融アル
ミめっきした試験番号１９（比較例）では、層厚約３．
５ｍｍとＦｅ−Ａｌ−Ｓｉ合金層３が厚く成長してお
り、曲げ加工試験でクラックが著しく発生した。また、
耐熱性及び耐酸化性も不良であった。The above investigation results show that Fe-Al-Si-M
Table 2 together with the presence or absence of the o-alloy layer 4 and the Fe-Mo alloy layer 5
Shown in As is clear from Table 2, Fe-Al-Si-
In Test Nos. 1 to 18 (Examples of the present invention) in which the Mo alloy layer 4 and the Fe-Mo alloy layer 5 were interposed, all exhibited excellent workability and heat resistance. The increase in oxidation is about half or less than that of the comparative example, and it is understood that the oxidation resistance is excellent.
On the other hand, in Test No. 19 (Comparative Example) in which hot-dip aluminum plating was performed without performing Fe-Mo pre-plating, the layer thickness was about 3.
The Fe—Al—Si alloy layer 3 was 5 mm thick and grew thick, and cracks were remarkably generated in the bending test. Also,
Heat resistance and oxidation resistance were also poor.
【００２１】 [0021]
【００２２】[0022]
【発明の効果】以上に説明したように、本発明の溶融ア
ルミめっき系鋼板は、溶融アルミめっき層／下地鋼の界
面にＦｅ−Ａｌ−Ｓｉ−Ｍｏ合金層，或いは更にＦｅ−
Ｍｏ合金層を介在させている。Ｆｅ−Ａｌ−Ｓｉ−Ｍｏ
合金層及びＦｅ−Ｍｏ合金層は、溶融アルミめっき時及
び使用状態での高温雰囲気に溶融アルミめっき系鋼板が
長時間曝されたとき、Ｆｅ−Ａｌ−Ｓｉ合金層の生成・
成長を抑制するバリアとして働く。そのため、製造され
た溶融アルミめっき系鋼板は加工性が良好で、また当該
溶融アルミめっき系鋼板から作られた部材は耐熱性，耐
酸化性に優れた製品となる。As described above, the hot-dip aluminized steel sheet of the present invention has a Fe-Al-Si-Mo alloy layer or an Fe-Al-Si-Mo alloy layer at the interface between the hot-dip aluminized layer and the underlying steel.
The Mo alloy layer is interposed. Fe-Al-Si-Mo
The alloy layer and the Fe-Mo alloy layer form the Fe-Al-Si alloy layer when the hot-dip aluminized steel sheet is exposed to a high-temperature atmosphere for a long time during hot-dip aluminum plating and in use.
Acts as a barrier to growth. Therefore, the manufactured hot-dip aluminized steel sheet has good workability, and a member made from the hot-dip aluminized steel sheet is a product having excellent heat resistance and oxidation resistance.
【図１】 Ｆｅ−Ａｌ−Ｓｉ合金層が生成成長した従来
の溶融アルミめっき系鋼板を示す断面図FIG. 1 is a cross-sectional view showing a conventional hot-dip aluminized steel sheet on which an Fe—Al—Si alloy layer has been formed and grown.
【図２】 本発明に従って溶融アルミめっき層／下地鋼
の界面にＦｅ−Ａｌ−Ｓｉ−Ｍｏ合金層を介在させた溶
融アルミめっき系鋼板FIG. 2 is a hot-dip aluminized steel sheet having an Fe-Al-Si-Mo alloy layer interposed at the interface between the hot-dip aluminized layer and the base steel according to the present invention.
【図３】 本発明に従って溶融アルミめっき層／下地鋼
の界面にＦｅ−Ａｌ−Ｓｉ−Ｍｏ合金層及びＦｅ−Ｍｏ
合金層を介在させた溶融アルミめっき系鋼板FIG. 3 shows a Fe—Al—Si—Mo alloy layer and an Fe—Mo layer at the interface between a hot-dip aluminum coating layer and a base steel according to the present invention.
Hot-dip aluminized steel sheet with an alloy layer interposed
フロントページの続き Ｆターム(参考） 4K027 AA02 AA22 AB02 AB04 AB08 AB26 AB28 AB48 AC15 AD01 AE03 4K044 AA02 AB02 BA06 BA10 BB03 BC02 BC05 BC11 CA11 CA18Continued on the front page F term (reference) 4K027 AA02 AA22 AB02 AB04 AB08 AB26 AB28 AB48 AC15 AD01 AE03 4K044 AA02 AB02 BA06 BA10 BB03 BC02 BC05 BC11 CA11 CA18
Claims (3)
金層を介して溶融アルミめっき層が形成されていること
を特徴とする加工性，耐熱性，耐酸化性に優れた溶融ア
ルミめっき系鋼板。1. A molten aluminum having excellent workability, heat resistance and oxidation resistance, characterized in that a molten aluminum plating layer is formed on a base steel via an Fe-Al-Si-Mo alloy layer. Plating steel sheet.
との界面にＦｅ−Ｍｏ合金層がある請求項１記載の溶融
アルミめっき系鋼板。2. The hot-dip aluminized steel sheet according to claim 1, wherein an Fe—Mo alloy layer is provided at an interface between the Fe—Al—Si—Mo alloy layer and the base steel.
プレめっきを施した後、めっき原板をＳｉ含有溶融アル
ミめっき浴に浸漬して溶融アルミめっき層を形成するこ
とを特徴とする加工性，耐熱性，耐酸化性に優れた溶融
アルミめっき系鋼板の製造方法。3. An Fe-Mo coating on one or both sides of a plating base sheet.
After pre-plating, a hot-dip aluminized steel sheet with excellent workability, heat resistance, and oxidation resistance is characterized by forming a hot-dip aluminized layer by immersing the base plate in a hot-dip aluminum-containing bath. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000043732A JP4453853B2 (en) | 2000-02-22 | 2000-02-22 | Manufacturing method of hot-dip aluminized steel sheet with excellent workability, heat resistance and oxidation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000043732A JP4453853B2 (en) | 2000-02-22 | 2000-02-22 | Manufacturing method of hot-dip aluminized steel sheet with excellent workability, heat resistance and oxidation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001234318A true JP2001234318A (en) | 2001-08-31 |
| JP4453853B2 JP4453853B2 (en) | 2010-04-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166913A (en) * | 2018-11-30 | 2021-07-23 | Posco公司 | Aluminum-iron alloy plated steel sheet for hot forming excellent in corrosion resistance and heat resistance, hot press formed member, and method for producing same |
-
2000
- 2000-02-22 JP JP2000043732A patent/JP4453853B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166913A (en) * | 2018-11-30 | 2021-07-23 | Posco公司 | Aluminum-iron alloy plated steel sheet for hot forming excellent in corrosion resistance and heat resistance, hot press formed member, and method for producing same |
| CN113166913B (en) * | 2018-11-30 | 2023-12-29 | 浦项股份有限公司 | Aluminum-iron alloy plated steel sheet for hot forming excellent in corrosion resistance and heat resistance, hot press formed part, and method for producing same |
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