JP2011219783A - High-strength hot-dip galvanized steel plate and method for manufacturing the same - Google Patents
High-strength hot-dip galvanized steel plate and method for manufacturing the same Download PDFInfo
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Abstract
Description
本発明は、ＳｉおよびＭｎを含有する高強度鋼板を母材とする加工性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法に関するものである。 The present invention relates to a high-strength hot-dip galvanized steel sheet excellent in workability using a high-strength steel sheet containing Si and Mn as a base material and a method for producing the same.
近年、自動車、家電、建材等の分野において、素材鋼板に防錆性を付与した表面処理鋼板、中でも溶融亜鉛めっき鋼板、合金化溶融亜鉛めっき鋼板が広範に使用されている。また、自動車の燃費向上および自動車の衝突安全性向上の観点から、車体材料の高強度化によって薄肉化を図り、車体そのものを軽量化しかつ高強度化する要望が高まっている。そのために高強度鋼板の自動車への適用が促進されている。 In recent years, in the fields of automobiles, home appliances, building materials and the like, surface-treated steel sheets imparted with rust resistance to raw steel sheets, particularly hot-dip galvanized steel sheets and galvannealed steel sheets have been widely used. In addition, from the viewpoint of improving the fuel efficiency of automobiles and improving the collision safety of automobiles, there is an increasing demand for reducing the thickness of the vehicle body by increasing the strength of the vehicle body material and reducing the weight of the vehicle body. Therefore, application of high-strength steel sheets to automobiles is being promoted.
一般的に、溶融亜鉛めっき鋼板は、スラブを熱間圧延や冷間圧延した薄鋼板を母材として用い、母材鋼板を連続式溶融亜鉛めっきライン（以下、ＣＧＬと称す）の焼鈍炉にて再結晶焼鈍および溶融亜鉛めっき処理を行い製造される。合金化溶融亜鉛めっき鋼板の場合は、溶融亜鉛めっき処理の後、さらに合金化処理を行い製造される。 In general, a hot dip galvanized steel sheet uses a thin steel sheet obtained by hot rolling or cold rolling a slab as a base material, and the base steel sheet is used in an annealing furnace of a continuous hot dip galvanizing line (hereinafter referred to as CGL). Manufactured by recrystallization annealing and hot dip galvanizing. In the case of an alloyed hot-dip galvanized steel sheet, it is manufactured after further hot-dip galvanizing treatment.
ここで、ＣＧＬの焼鈍炉の加熱炉タイプとしては、ＤＦＦ型（直火型）、ＮＯＦ型（無酸化型）、オールラジアントチューブ型等があるが、近年では、操業のし易さやピックアップが発生しにくい等により低コストで高品質なめっき鋼板を製造できるなどの理由からオールラジアントチューブ型の加熱炉を備えるＣＧＬの建設が増加している。しかしながら、ＤＦＦ型（直火型）、ＮＯＦ型（無酸化型）と異なり、オールラジアントチューブ型の加熱炉は焼鈍直前に酸化工程がないため、Ｓｉ、Ｍｎ等の易酸化性元素を含有する鋼板についてはめっき性確保の点で不利である。 Here, there are DFF type (direct flame type), NOF type (non-oxidation type), all radiant tube type, etc. as the heating furnace type of CGL annealing furnace. The construction of CGLs equipped with an all-radiant tube type heating furnace is increasing for the reason that it is possible to produce high-quality plated steel sheets at low cost due to difficulty in carrying out the process. However, unlike the DFF type (direct flame type) and NOF type (non-oxidation type), the all-radiant tube type heating furnace does not have an oxidation step immediately before annealing, so a steel plate containing an easily oxidizable element such as Si or Mn. Is disadvantageous in terms of securing plating properties.
Ｓｉ、Ｍｎを多量に含む高強度鋼板を母材とした溶融めっき鋼板の製造方法として、特許文献１および特許文献２には、還元炉における加熱温度を水蒸気分圧で表される式で規定し露点を上げることで、地鉄表層を内部酸化させる技術が開示されている。しかしながら、露点を制御するエリアが炉内全体を前提としたものであるため、露点の制御が困難であり安定操業が困難である。また、不安定な露点制御のもとでの合金化溶融亜鉛めっき鋼板の製造は、下地鋼板に形成される内部酸化物の分布状態にバラツキが認められ、鋼板の長手方向や幅方向でめっき濡れ性ムラや合金化ムラなどの欠陥が発生する懸念がある。 As a method for producing a hot-dip galvanized steel sheet using a high-strength steel sheet containing a large amount of Si and Mn as a base material, Patent Document 1 and Patent Document 2 define a heating temperature in a reduction furnace by an expression expressed by a partial pressure of water vapor. A technique for internally oxidizing the surface layer of the railway by increasing the dew point is disclosed. However, since the area for controlling the dew point is premised on the entire inside of the furnace, it is difficult to control the dew point, and stable operation is difficult. In addition, in the manufacture of galvannealed steel sheets under unstable dew point control, variations in the distribution of internal oxides formed on the base steel sheet were observed, and wetting in the longitudinal and width directions of the steel sheet was observed. There is a concern that defects such as unevenness in properties and unevenness in alloying may occur.
また特許文献３には、酸化性ガスであるＨ２ＯやＯ２だけでなく、ＣＯ２濃度も同時に規定することで、めっき直前の地鉄表層を内部酸化させ外部酸化を抑制してめっき外観を改善する技術が開示されている。しかしながら、特許文献３のようにＳｉを特に多量に含有する場合には、内部酸化物の存在により加工時に割れが発生しやすくなり、耐めっき剥離性が劣化する。また、耐食性の劣化も認められる。さらにＣＯ２は炉内汚染や鋼板表面への浸炭などが起こり機械特性が変化するなどの問題が懸念される。 In Patent Document 3, not only the oxidizing gases H 2 O and O 2, but also the CO 2 concentration is defined at the same time, so that the surface layer immediately before plating is internally oxidized to suppress external oxidation and the appearance of plating. A technique for improving the above is disclosed. However, in the case where Si is contained in a particularly large amount as in Patent Document 3, cracks are likely to occur during processing due to the presence of the internal oxide, and the plating peel resistance deteriorates. Moreover, deterioration of corrosion resistance is also recognized. Furthermore, there is a concern that CO 2 may cause problems such as in-furnace contamination and carburizing on the steel sheet surface, resulting in changes in mechanical properties.
さらに、最近では、加工の厳しい箇所への高強度溶融亜鉛めっき鋼板、高強度合金化溶融亜鉛めっき鋼板の適用が進んでおり、高加工時の耐めっき剥離特性が重要視されるようになっている。具体的にはめっき鋼板に９０°超えの曲げ加工を行い、より鋭角に曲げた時や、衝撃が加わり鋼板が加工を受けた場合の、加工部のめっき剥離の抑制が要求される。 Furthermore, recently, the application of high-strength hot-dip galvanized steel sheets and high-strength alloyed hot-dip galvanized steel sheets to places where machining is severe has progressed, and the anti-plating resistance characteristics at the time of high processing have become important. Yes. Specifically, when the plated steel sheet is bent over 90 ° and bent at a more acute angle, or when the steel sheet is subjected to processing due to an impact, suppression of plating peeling at the processed portion is required.
このような特性を満たすためには、鋼中に多量にＳｉを添加し所望の鋼板組織を確保するだけでなく、高加工時の割れなどの起点になる可能性があるめっき層直下の地鉄表層の
組織、構造のより高度な制御が求められる。しかしながら従来技術ではそのような制御は困難であり、焼鈍炉にオールラジアントチューブ型の加熱炉を備えるＣＧＬでＳｉ含有高強度鋼板を母材として高加工時の耐めっき剥離特性に優れた溶融亜鉛めっき鋼板を製造することができなかった。
In order to satisfy such characteristics, not only does a large amount of Si be added to the steel to ensure the desired steel sheet structure, but also the iron core directly under the plating layer, which may be the starting point of cracking during high processing. More advanced control of the structure and structure of the surface layer is required. However, such control is difficult with the prior art, and hot dip galvanization with excellent anti-plating properties at the time of high processing using Si-containing high-strength steel sheet as a base material in CGL with an all-radiant tube type heating furnace in the annealing furnace. A steel plate could not be produced.
本発明は、かかる事情に鑑みてなされたものであって、Ｓｉ、Ｍｎを含有する鋼板を母材とし、めっき外観および高加工時の耐めっき剥離性に優れる高強度溶融亜鉛めっき鋼板およびその製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and uses a steel sheet containing Si and Mn as a base material, and is a high-strength hot-dip galvanized steel sheet excellent in plating appearance and plating peeling resistance during high processing and its manufacture It aims to provide a method.
従来は、単に焼鈍炉内の水蒸気分圧を上昇させることで露点を上げて過剰に鋼板の内部を酸化させていたため、上述したように、加工時に割れが発生しやすくなり、耐めっき剥離性が劣化していた。また、内部酸化と同時に鋼中易酸化性元素の表面拡散及び表面酸化（以降、表面濃化と称す）も起こるため、内部酸化が十分に起こるまでの比較的低温域においては表面濃化を抑制しきれず、不めっき等の表面欠陥を完全に防止するには至っていなかった。そこで、本発明者らは、従来の考えにとらわれない新たな方法で課題を解決する方法を検討した。その結果、内部酸化が十分に起こらない一方で表面濃化が起こる、比較的低い温度域で水素濃度を制御し、限定温度域で雰囲気露点を制御することで、選択的表面酸化を抑制し表面濃化を抑制することができることを知見した。具体的には、加熱過程における加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域において、水素濃度を２０ｖｏｌ%以上に制御し、かつ、加熱炉内温度：Ａ℃超えＢ℃以下
（Ｂ：８００≦Ｂ≦９００）の限定された温度域において、雰囲気の露点を−５℃以上となるように制御して溶融亜鉛めっき処理を行う。このような処理を行うことによって、選択的表面酸化を抑制し、表面濃化を抑制することができ、めっき外観および高加工時の耐めっき剥離性に優れる高強度溶融亜鉛めっき鋼板が得られることになる。なお、めっき外観に優れるとは、不めっきや合金化ムラが認められない外観を有することを言う。
そして、以上の方法により得られる高強度溶融亜鉛めっき鋼板は、めっき層直下の鋼板表層部において、下地鋼板表面から１００μｍ以内の鋼板表層部にＦｅ、Ｓｉ、Ｍｎ、Ａｌ、Ｐ、さらには、Ｂ、Ｎｂ、Ｔｉ、Ｃｒ、Ｍｏ、Ｃｕ、Ｎｉの中から選ばれる少なくとも１種以上の酸化物を片面あたり０．０１０〜０．５０ｇ/m２形成し、めっき層直下から１０μｍまでの領域において、粒界から１μｍ以内の地鉄粒内に結晶性Ｓｉ、Ｍｎ系複合酸化物が析出している組織、構造となる。これによって地鉄表層における曲げ加工時の応力緩和や割れ防止が実現でき、めっき外観および高加工時の耐めっき剥離性に優れることになる。なお、前記結晶性Ｓｉ、Ｍｎ系複合酸化物とは、結晶性Ｓｉ系酸化物および／または結晶性Ｍｎ系酸化物であり、結晶性Ｓｉ系酸化物にはＭｎをＳｉ含有量（質量％）未満含有する場合を含み、結晶性Ｍｎ系酸化物にはＳｉをＭｎ含有量（質量％）未満含有する場合を含む。また、ＦｅがＳｉおよび／またはＭｎの含有率（質量％）よりも多い場合でも、酸素を除く成分の含有率（質量％）としてＳｉまたはＭｎがＦｅに次いで多い場合には、それぞれ結晶性Ｓｉ系酸化物、結晶性Ｍｎ系酸化物とみなす。また、以下において、前記結晶性Ｓｉ、Ｍｎ系複合酸化物を、略して、結晶性Ｓｉ、Ｍｎ系酸化物と記載することもある。
In the past, simply increasing the partial pressure of water vapor in the annealing furnace raised the dew point and excessively oxidized the interior of the steel sheet. It was deteriorated. In addition, surface diffusion and surface oxidation (hereinafter referred to as surface concentration) of easily oxidizable elements in steel occur simultaneously with internal oxidation, so surface concentration is suppressed in a relatively low temperature range until internal oxidation occurs sufficiently. It has not been able to completely prevent surface defects such as non-plating. Therefore, the present inventors have studied a method for solving the problem by a new method not confined to the conventional idea. As a result, surface oxidation occurs while internal oxidation does not occur sufficiently. Controlling the hydrogen concentration in a relatively low temperature range and controlling the atmospheric dew point in a limited temperature range suppresses selective surface oxidation. It has been found that concentration can be suppressed. Specifically, in the temperature range of the heating furnace in the heating process: 600 ° C. to A ° C. (A: 650 ≦ A ≦ 780), the hydrogen concentration is controlled to 20 vol% or more, and the heating furnace temperature: In a limited temperature range of A ° C. and B ° C. or less (B: 800 ≦ B ≦ 900), the hot dip galvanizing treatment is performed by controlling the dew point of the atmosphere to be −5 ° C. or higher. By performing such treatment, selective surface oxidation can be suppressed, surface enrichment can be suppressed, and a high-strength hot-dip galvanized steel sheet excellent in plating appearance and plating peeling resistance during high processing can be obtained. become. In addition, having excellent plating appearance means having an appearance in which non-plating and alloying unevenness are not recognized.
And the high-strength hot-dip galvanized steel sheet obtained by the above method has Fe, Si, Mn, Al, P, and B in the steel sheet surface layer part within 100 μm from the surface of the base steel sheet in the steel sheet surface layer part directly under the plating layer. , Nb, Ti, Cr, Mo, Cu, Ni at least one oxide selected from 0.010 to 0.50 g / m 2 per side is formed, and in a region from immediately below the plating layer to 10 μm, It becomes a structure and structure in which crystalline Si and Mn-based composite oxide are precipitated in the ground iron grains within 1 μm from the grain boundary. As a result, stress relaxation and prevention of cracking at the time of bending processing on the surface layer of the ground iron can be realized, and the plating appearance and plating peeling resistance at the time of high processing will be excellent. The crystalline Si and Mn-based composite oxide is a crystalline Si-based oxide and / or a crystalline Mn-based oxide, and the crystalline Si-based oxide contains Mn in an Si content (% by mass). The crystalline Mn-based oxide includes a case where Si is contained less than the Mn content (mass%). Further, even when Fe is larger than the content (mass%) of Si and / or Mn, when Si or Mn is the second largest after Fe as the content (mass%) of the component excluding oxygen, each of crystalline Si It is regarded as a system oxide or a crystalline Mn-based oxide. In the following description, the crystalline Si and Mn-based composite oxide may be abbreviated as crystalline Si and Mn-based oxide.
本発明は上記知見に基づくものであり、特徴は以下の通りである。
［１］質量％で、Ｃ：０．０１〜０．１８％、Ｓｉ：０．０２〜２．０％、Ｍｎ：１．０〜３．０％、Ａｌ：０．００１〜１．０％、Ｐ：０．００５〜０．０６０％、Ｓ≦０．０１％を含有し、残部がＦｅおよび不可避的不純物からなる鋼板の表面に、片面あたりのめっき付着量が２０〜１２０ｇ／ｍ２の亜鉛めっき層を有する高強度溶融亜鉛めっき鋼板を製造する方法であって、鋼板に連続式溶融亜鉛めっき設備において焼鈍および溶融亜鉛めっき処理を施すに際し、加熱過程では、加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域を水素濃度：２０ｖｏｌ%以上で、加熱炉内温度：Ａ℃超えＢ℃以下（Ｂ：８００≦Ｂ≦９００）の温度域を雰囲気の露点：−５℃以上で行うことを特徴とする高強度溶融亜鉛めっき鋼板の製造方法。
［２］前記［１］において、前記鋼板は、成分組成として、質量％で、さらに、Ｂ：０．００１〜０．００５％、Ｎｂ：０．００５〜０．０５％、Ｔｉ：０．００５〜０．０５％、Ｃｒ：０．００１〜１．０％、Ｍｏ：０．０５〜１．０％、Ｃｕ：０．０５〜１．０％、Ｎｉ：０．０５〜１．０％の中から選ばれる１種以上の元素を含有することを特徴とする高強度溶融亜鉛めっき鋼板の製造方法。
［３］前記［１］または［２］において、溶融亜鉛めっき処理後、さらに、４５０℃以上６００℃以下の温度に鋼板を加熱して合金化処理を施し、亜鉛めっき層のＦｅ含有量を７〜１５質量％の範囲にすることを特徴とする高強度溶融亜鉛めっき鋼板の製造方法。
［４］前記［１］〜［３］に記載のいずれかの製造方法により製造され、亜鉛めっき層直下、下地鋼板表面から１００μm以内の鋼板表層部にＦｅ、Ｓｉ、Ｍｎ、Ａｌ、Ｐ、Ｂ、
Ｎｂ、Ｔｉ、Ｃｒ、Ｍｏ、Ｃｕ、Ｎｉの中から選ばれる少なくとも１種以上の酸化物を、片面あたり０．０１０〜０．５０ｇ／ｍ２形成し、更に、めっき層直下の下地鋼板表面から１０μm以内の領域において、下地鋼板結晶粒界から１μm以内の粒内に結晶性Ｓｉ、Ｍｎ系酸化物が存在していることを特徴とする高強度溶融亜鉛めっき鋼板。
The present invention is based on the above findings, and features are as follows.
[1] By mass%, C: 0.01 to 0.18%, Si: 0.02 to 2.0%, Mn: 1.0 to 3.0%, Al: 0.001 to 1.0% , P: 0.005 to 0.060%, S ≦ 0.01%, with the balance being Fe and unavoidable impurities on the surface of the steel sheet, the plating adhesion amount per side is 20 to 120 g / m 2 A method for producing a high-strength hot-dip galvanized steel sheet having a galvanized layer, and when the steel sheet is subjected to annealing and hot-dip galvanizing treatment in a continuous hot-dip galvanizing facility, the heating furnace temperature: 600 ° C. or higher A temperature range of A ° C. or lower (A: 650 ≦ A ≦ 780) in a hydrogen concentration: 20 vol% or higher, furnace temperature: A ° C. and B ° C. or lower (B: 800 ≦ B ≦ 900) Dew point: High-strength hot-dip zinc alloy, which is performed at -5 ° C or higher Method of manufacturing a steel plate.
[2] In the above [1], the steel sheet is in mass% as a component composition, and further B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005. -0.05%, Cr: 0.001-1.0%, Mo: 0.05-1.0%, Cu: 0.05-1.0%, Ni: 0.05-1.0% A method for producing a high-strength hot-dip galvanized steel sheet, comprising one or more elements selected from the inside.
[3] In the above [1] or [2], after the hot dip galvanizing treatment, the steel plate is further heated to a temperature of 450 ° C. or higher and 600 ° C. or lower to perform alloying treatment, and the Fe content of the galvanized layer is set to 7 A method for producing a high-strength hot-dip galvanized steel sheet, characterized by being in the range of ˜15 mass%.
[4] Fe, Si, Mn, Al, P, B, which is produced by any one of the production methods described in [1] to [3] above the surface layer portion of the steel plate within 100 μm from the surface of the underlying steel plate immediately below the galvanized layer. ,
At least one oxide selected from Nb, Ti, Cr, Mo, Cu, and Ni is formed at 0.010 to 0.50 g / m 2 per side, and further, from the surface of the underlying steel plate directly under the plating layer A high-strength hot-dip galvanized steel sheet characterized in that in a region within 10 μm, crystalline Si and Mn-based oxides are present in grains within 1 μm from the grain boundary of the underlying steel sheet.
なお、本発明において、高強度とは、引張強度ＴＳが３４０ＭＰa以上である。また、
本発明の高強度溶融亜鉛めっき鋼板は、溶融亜鉛めっき処理後合金化処理を施さないめっき鋼板（以下、ＧＩと称することもある）、合金化処理を施すめっき鋼板（以下、ＧＡと称することもある）のいずれも含むものである。
In the present invention, the high strength means that the tensile strength TS is 340 MPa or more. Also,
The high-strength hot-dip galvanized steel sheet of the present invention includes a plated steel sheet (hereinafter also referred to as GI) that is not subjected to an alloying treatment after the hot dip galvanizing process, and a plated steel sheet (hereinafter referred to as GA) that is subjected to an alloying process. Any).
本発明によれば、めっき外観および高加工時の耐めっき剥離性に優れる高強度溶融亜鉛めっき鋼板が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the high intensity | strength hot-dip galvanized steel plate which is excellent in a plating external appearance and the plating peeling resistance at the time of high processing is obtained.
以下、本発明について具体的に説明する。なお、以下の説明において、鋼成分組成の各元素の含有量、めっき層成分組成の各元素の含有量の単位はいずれも「質量％」であり、以下、特に断らない限り単に「％」で示す。 Hereinafter, the present invention will be specifically described. In the following description, the content of each element of the steel component composition and the unit of the content of each element of the plating layer component composition are all “mass%”, and hereinafter, simply “%” unless otherwise specified. Show.
先ず、本発明で最も重要な要件である、めっき層直下の下地鋼板表面の構造を決定する焼鈍雰囲気条件について説明する。 First, an annealing atmosphere condition that determines the structure of the surface of the underlying steel sheet immediately below the plating layer, which is the most important requirement in the present invention, will be described.
焼鈍炉内の加熱過程で、加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域において、水素濃度を２０ｖｏｌ%以上に制御して溶融亜鉛めっき処理を行うことで、鋼板表面の酸素ポテンシャルが低下し、選択的表面酸化（表面濃化）を抑制することが可能となる。 In the heating process in the annealing furnace, the hot dip galvanizing treatment is performed by controlling the hydrogen concentration to 20 vol% or more in the temperature range of the heating furnace temperature: 600 ° C. to A ° C. (A: 650 ≦ A ≦ 780). Thus, the oxygen potential on the surface of the steel sheet is lowered, and selective surface oxidation (surface concentration) can be suppressed.
水素濃度の上限は特に設けないが、７５ｖｏｌ％超えではコストアップし、かつ効果が飽和する。よって、コストの点から水素濃度は７５ｖｏｌ％以下が好ましい。 The upper limit of the hydrogen concentration is not particularly set, but if it exceeds 75 vol%, the cost increases and the effect is saturated. Therefore, the hydrogen concentration is preferably 75 vol% or less from the viewpoint of cost.
６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）とする理由は以下の通りである。６００℃未満の温度域では、低温のため表面拡散する易酸化性元素の量が少ない。また、表面濃化がもともと少ない温度域であり、溶融亜鉛と鋼板との濡れ性が阻害されることがない。よって、６００℃以上とする。また、上限温度をＡ℃とした理由は、後述するように、Ａ℃を超える温度域では、雰囲気露点を−５℃以上とすることにより、内部酸化が促進され、表面濃化が殆ど起こらなくなるためである。 The reason why the temperature is 600 ° C. or more and A ° C. or less (A: 650 ≦ A ≦ 780) is as follows. In the temperature range below 600 ° C., the amount of the easily oxidizable element that diffuses on the surface is small due to the low temperature. Moreover, the temperature concentration is originally low in the temperature range, and the wettability between the molten zinc and the steel sheet is not hindered. Therefore, it shall be 600 degreeC or more. The reason why the upper limit temperature is set to A ° C is that, as will be described later, in a temperature range exceeding A ° C, by setting the atmospheric dew point to -5 ° C or more, internal oxidation is promoted and surface concentration hardly occurs. Because.
焼鈍炉内の加熱過程で、加熱炉内温度：Ａ℃超えＢ℃以下（Ａ：６５０≦Ａ≦７８０、Ｂ：８００≦Ｂ≦９００）の限定された温度域において、雰囲気の露点を−５℃以上となるように制御して溶融亜鉛めっき処理することで、鋼板表層１０μm以内の内部に易酸化
性元素（Ｓｉ、Ｍｎなど）の酸化物（以下、内部酸化と称する）を適量に存在させ、焼鈍後の溶融亜鉛めっきと鋼板の濡れ性を劣化させる鋼中Ｓｉ、Ｍｎ等の鋼板表層における選択的表面酸化（以後、表面濃化と称する）を抑制することが可能となる。
In the heating process in the annealing furnace, the dew point of the atmosphere is −5 in the limited temperature range of the heating furnace temperature: A ° C. to B ° C. (A: 650 ≦ A ≦ 780, B: 800 ≦ B ≦ 900). By carrying out hot dip galvanizing treatment at a temperature of not lower than ° C., an appropriate amount of oxides of oxidizable elements (Si, Mn, etc.) (hereinafter referred to as internal oxidation) are present in the steel sheet surface layer within 10 μm. It is possible to suppress selective surface oxidation (hereinafter referred to as surface concentration) in the steel sheet surface layer such as Si and Mn in the steel, which deteriorates the wettability of the hot dip galvanizing and the steel sheet after annealing.
下限温度Ａを６５０≦Ａ≦７８０とする理由は以下の通りである。６５０℃よりも低い温度域では、露点を−５℃以上に制御しても、内部酸化が殆ど形成しない。６５０℃以上で内部酸化が起こり始める。また、露点制御せず７８０℃を超える温度まで昇温した場合、表面濃化が多いため、酸素の内方拡散が阻害され、内部酸化が起こりにくくなる。従って、少なくとも７８０℃以下の温度域から−５℃以上の露点に制御しなければならない。以上から、Ａの許容範囲は６５０≦Ａ≦７８０であり、上述した理由により、この範囲内においてＡはなるべく低い値であることが望ましい。 The reason why the lower limit temperature A is set to 650 ≦ A ≦ 780 is as follows. In the temperature range lower than 650 ° C., even if the dew point is controlled to be −5 ° C. or higher, almost no internal oxidation is formed. Internal oxidation begins to occur above 650 ° C. Further, when the temperature is raised to a temperature exceeding 780 ° C. without controlling the dew point, since the surface concentration is large, the inward diffusion of oxygen is inhibited and internal oxidation is less likely to occur. Therefore, the dew point must be controlled to at least −5 ° C. from a temperature range of 780 ° C. or less. From the above, the allowable range of A is 650 ≦ A ≦ 780, and for the reason described above, it is desirable that A be as low as possible within this range.
上限温度Ｂを８００≦Ｂ≦９００とする理由は以下の通りである。表面濃化を抑制するメカニズムは、以下の通りである。内部酸化を形成することにより、鋼板表層１０μm以
内の内部の易酸化性元素（Ｓｉ、Ｍｎなど）の固溶量を減少させた領域（以下、欠乏層と称する）を形成させ、鋼中からの易酸化性元素の表面拡散を抑制する。この内部酸化を形成し、表面濃化を抑制するために十分な欠乏層を形成させるためには、Ｂを８００≦Ｂ≦９００とする必要がある。８００℃を下回った場合、十分に内部酸化が形成されない。また、９００℃超えは内部酸化の形成量が過剰となり、加工時に割れが発生しやすくなり、耐めっき剥離性が劣化する。
Ａ℃超えＢ℃以下の温度域における露点を−５℃以上とする理由は以下の通りである。露点を上昇させることにより、Ｈ２Ｏの分解から生じるＯ２ポテンシャルを上昇させ、内部酸化を促進することが可能である。−５℃を下回る温度域では、内部酸化の形成量が少ない。また、露点の上限については特に定めないが、９０℃を超えてくるとＦｅの酸化量が多くなり、焼鈍炉壁やロールの劣化が懸念されるため、９０℃以下が望ましい。
The reason why the upper limit temperature B is set to 800 ≦ B ≦ 900 is as follows. The mechanism for suppressing surface concentration is as follows. By forming internal oxidation, a region (hereinafter referred to as a deficient layer) in which the solid solution amount of an easily oxidizable element (Si, Mn, etc.) within 10 μm of the steel sheet surface layer is reduced is formed. Suppresses surface diffusion of easily oxidizable elements. In order to form this internal oxidation and to form a deficient layer sufficient to suppress surface concentration, B needs to satisfy 800 ≦ B ≦ 900. When the temperature is lower than 800 ° C., sufficient internal oxidation is not formed. On the other hand, if the temperature exceeds 900 ° C., the amount of internal oxidation formed becomes excessive, cracks are likely to occur during processing, and the plating peel resistance deteriorates.
The reason why the dew point in the temperature range from A ° C. to B ° C. is −5 ° C. or higher is as follows. By increasing the dew point, it is possible to increase the O 2 potential resulting from the decomposition of H 2 O and promote internal oxidation. In the temperature range below -5 ° C, the amount of internal oxidation formed is small. The upper limit of the dew point is not particularly defined, but if it exceeds 90 ° C, the amount of Fe oxidation increases, and there is concern about deterioration of the annealing furnace wall and roll.
次いで、本発明の対象とする高強度溶融亜鉛めっき鋼板の鋼成分組成について説明する。
Ｃ：０．０１〜０．１８％
Ｃは、鋼組織としてマルテンサイトなどを形成させることで加工性を向上させる。そのためには０．０１％以上必要である。一方、０．１８％を超えると溶接性が劣化する。したがって、Ｃ量は０．０１％以上０．１８％以下とする。
Next, the steel component composition of the high-strength hot-dip galvanized steel sheet that is the subject of the present invention will be described.
C: 0.01 to 0.18%
C improves workability by forming martensite or the like as a steel structure. For that purpose, 0.01% or more is necessary. On the other hand, if it exceeds 0.18%, the weldability deteriorates. Therefore, the C content is 0.01% or more and 0.18% or less.
Ｓｉ：０．０２〜２．０％
Ｓｉは鋼を強化して良好な材質を得るのに有効な元素であり、本発明の目的とする強度を得るためには０．０２％以上が必要である。Ｓｉが０．０２％未満では本発明の適用範囲とする強度が得られず、高加工時の耐めっき剥離性についても特に問題とならない。一方、２．０％を超えると高加工時の耐めっき剥離性の改善が困難となってくる。したがって、Ｓｉ量は０．０２％以上２．０％以下とする。
Si: 0.02 to 2.0%
Si is an element effective for strengthening steel to obtain a good material, and 0.02% or more is necessary to obtain the intended strength of the present invention. If Si is less than 0.02%, the strength within the scope of application of the present invention cannot be obtained, and there is no particular problem with respect to resistance to plating peeling during high processing. On the other hand, if it exceeds 2.0%, it becomes difficult to improve the plating peel resistance at the time of high processing. Therefore, the Si content is 0.02% or more and 2.0% or less.
Ｍｎ：１．０〜３．０％
Ｍｎは鋼の高強度化に有効な元素である。機械特性や強度を確保するためは１．０％以上含有させることが必要である。一方、３．０％を超えると溶接性やめっき密着性の確保、強度と延性のバランスの確保が困難になる。したがって、Ｍｎ量は１．０％以上３．０％以下とする。
Mn: 1.0-3.0%
Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 1.0% or more. On the other hand, if it exceeds 3.0%, it becomes difficult to ensure weldability and plating adhesion, and to ensure a balance between strength and ductility. Therefore, the Mn content is 1.0% or more and 3.0% or less.
Ａｌ：０．００１〜１．０％
ＡｌはＳｉ、Ｍｎに比べ熱力学的に酸化し易い元素であるため、Ｓｉ、Ｍｎと複合酸化物を形成する。Ａｌが含有されない場合に比べ、Ａｌを含有することで地鉄表層直下におけるＳｉ、Ｍｎの内部酸化を促進する効果を有する。この効果は０．００１％以上で得られる。一方、１．０％を超えるとコストアップになる。したがって、Ａｌ量は０．００１％以上１．０％以下とする。
Al: 0.001 to 1.0%
Since Al is an element that is more easily thermodynamically oxidized than Si and Mn, it forms a complex oxide with Si and Mn. Compared with the case where Al is not contained, the inclusion of Al has an effect of promoting the internal oxidation of Si and Mn immediately below the surface layer of the ground iron. This effect is obtained at 0.001% or more. On the other hand, if it exceeds 1.0%, the cost increases. Therefore, the Al content is 0.001% or more and 1.0% or less.
Ｐ：０．００５〜０．０６０％以下
Ｐは不可避的に含有される元素のひとつであり、０．００５％未満にするためには、コストの増大が懸念されるため、０．００５％以上とする。一方、Ｐが０．０６０％を超えて含有されると溶接性が劣化する。さらに、表面品質が劣化する。また、合金化処理を施さない時にはめっき密着性が劣化し、合金化処理時には合金化処理温度を上昇しないと所望の合金化度とすることができない。また所望の合金化度とするために合金化処理温度を上昇させると延性が劣化すると同時に合金化めっき皮膜の密着性が劣化するため、所望の合金化度と、良好な延性、合金化めっき皮膜を両立させることができない。したがって、Ｐ量は０．００５％以上０．０６０％以下とする。
P: 0.005 to 0.060% or less P is one of the elements inevitably contained, and in order to make it less than 0.005%, there is a concern about an increase in cost, so 0.005% or more And On the other hand, if P exceeds 0.060%, weldability deteriorates. Furthermore, the surface quality deteriorates. Further, when the alloying treatment is not performed, the plating adhesion is deteriorated, and when the alloying treatment is performed, the alloying treatment temperature cannot be increased unless the alloying treatment temperature is increased. Also, if the alloying temperature is raised to achieve the desired degree of alloying, the ductility deteriorates and at the same time the adhesion of the alloyed plating film deteriorates, so the desired degree of alloying, good ductility, and alloyed plating film Cannot be achieved. Therefore, the P content is 0.005% or more and 0.060% or less.
Ｓ≦０．０１％
Ｓは不可避的に含有される元素のひとつである。下限は規定しないが、多量に含有されると溶接性が劣化するため０．０１％以下とする。
S ≦ 0.01%
S is one of the elements inevitably contained. The lower limit is not specified, but if it is contained in a large amount, the weldability deteriorates, so the content is made 0.01% or less.
なお、強度と延性のバランスを制御するため、Ｂ：０．００１〜０．００５％、Ｎｂ：０．００５〜０．０５％、Ｔｉ：０．００５〜０．０５％、Ｃｒ：０．００１〜１．０％、Ｍｏ：０．０５〜１．０％、Ｃｕ：０．０５〜１．０％、Ｎｉ：０．０５〜１．０％の中から選ばれる１種以上の元素を必要に応じて添加してもよい。また、これらの元素のうち、Ｃｒ、Ｍｏ、Ｎｂ、Ｃｕ、Ｎｉは単独または２種以上の複合添加で焼鈍雰囲気がＨ２Ｏを比較的多量に含むような湿潤雰囲気である場合に、Ｓｉの内部酸化を促進し、表面濃化を抑制する効果を有するため、機械的特性改善のためではなく、良好なめっき密着性を得るために添加してもよい。
これらの元素を添加する場合における適正添加量の限定理由は以下の通りである。
In order to control the balance between strength and ductility, B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005 to 0.05%, Cr: 0.001 One or more elements selected from -1.0%, Mo: 0.05-1.0%, Cu: 0.05-1.0%, Ni: 0.05-1.0% are required. It may be added depending on. Of these elements, Cr, Mo, Nb, Cu, and Ni are used alone or in combination of two or more, and when the annealing atmosphere is a humid atmosphere containing a relatively large amount of H 2 O, Since it has an effect of promoting internal oxidation and suppressing surface concentration, it may be added not for improving mechanical properties but for obtaining good plating adhesion.
The reason for limiting the appropriate addition amount in the case of adding these elements is as follows.
Ｂ：０．００１〜０．００５％
Ｂは０．００１％未満では焼き入れ促進効果が得られにくい。一方、０．００５％超えではめっき密着性が劣化する。よって、含有する場合、Ｂ量は０．００１％以上０．００５％以下とする。
B: 0.001 to 0.005%
When B is less than 0.001%, it is difficult to obtain an effect of promoting quenching. On the other hand, if it exceeds 0.005%, the plating adhesion deteriorates. Therefore, when it contains, B amount shall be 0.001% or more and 0.005% or less.
Ｎｂ：０．００５〜０．０５％
Ｎｂは０．００５％未満では強度調整の効果やＭｏとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、０．０５％超えではコストアップを招く。よって、含有する場合、Ｎｂ量は０．００５％以上０．０５％以下とする。
Nb: 0.005 to 0.05%
If Nb is less than 0.005%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Mo. On the other hand, if it exceeds 0.05%, the cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.05% or less.
Ｔｉ：０．００５〜０．０５％
Ｔｉは０．００５％未満では強度調整の効果が得られにくい。一方、０．０５％超えではめっき密着性の劣化を招く。よって、含有する場合、Ｔｉ量は０．００５％以上０．０５％以下とする。
Ti: 0.005 to 0.05%
If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, the plating adhesion deteriorates. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.05% or less.
Ｃｒ：０．００１〜１．０％
Ｃｒは０．００１％未満では焼き入れ性や焼鈍雰囲気がＨ２Ｏを比較的多量に含むような湿潤雰囲気である場合の内部酸化促進効果が得られにくい。一方、１．０％超えではＣｒが表面濃化するため、めっき密着性や溶接性が劣化する。よって、含有する場合、Ｃｒ量は０．００１％以上１．０％以下とする。
Cr: 0.001 to 1.0%
When Cr is less than 0.001%, it is difficult to obtain the effect of promoting internal oxidation when the hardenability and the annealing atmosphere are humid atmospheres containing a relatively large amount of H 2 O. On the other hand, if it exceeds 1.0%, the surface of Cr is concentrated, so that the plating adhesion and weldability deteriorate. Therefore, when it contains, Cr amount shall be 0.001% or more and 1.0% or less.
Ｍｏ：０．０５〜１．０％
Ｍｏは０．０５％未満では強度調整の効果やＮｂ、またはＮｉやＣｕとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、１．０％超えではコストアップを招く。よって、含有する場合、Ｍｏ量は０．０５％以上１．０％以下とする。
Mo: 0.05-1.0%
If Mo is less than 0.05%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Nb, Ni or Cu. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Mo content is 0.05% or more and 1.0% or less.
Ｃｕ：０．０５〜１．０％
Ｃｕは０．０５％未満では残留γ相形成促進効果やＮｉやＭｏとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、１．０％超えではコストアップを招く。よって、含有する場合、Ｃｕ量は０．０５％以上１．０％以下とする。
Cu: 0.05 to 1.0%
If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual γ phase and the effect of improving the plating adhesion when combined with Ni or Mo. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.0% or less.
Ｎｉ：０．０５〜１．０％
Ｎｉは０．０５％未満では残留γ相形成促進効果やＣｕとＭｏとの複合添加時におけるめっき密着性改善効果が得られにくい。一方、１．０％超えではコストアップを招く。よって、含有する場合、Ｎｉ量は０．０５％以上１．０％以下とする。
Ni: 0.05-1.0%
When Ni is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual γ phase and the effect of improving the plating adhesion upon the combined addition of Cu and Mo. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when it contains, Ni amount shall be 0.05% or more and 1.0% or less.
上記以外の残部はＦｅおよび不可避的不純物である。 The balance other than the above is Fe and inevitable impurities.
次に、本発明の高強度溶融亜鉛めっき鋼板の製造方法とその限定理由について説明する。 Next, the manufacturing method of the high-strength hot-dip galvanized steel sheet of the present invention and the reason for limitation will be described.
上記化学成分を有する鋼を熱間圧延した後、冷間圧延し鋼板とし、次いで、連続式溶融亜鉛めっき設備において焼鈍および溶融亜鉛めっき処理を行う。なお、この時、本発明においては、焼鈍時の加熱過程では、加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域を水素濃度：２０ｖｏｌ%以上で、加熱炉内温度：Ａ℃超えＢ℃以
下（Ｂ：８００≦Ｂ≦９００）の温度域を雰囲気の露点：−５℃以上で行うこととする。これは本発明において、最も重要な要件である。このように焼鈍、溶融亜鉛めっき処理工程において露点、すなわち雰囲気中酸素分圧を制御することで、酸素ポテンシャルを高め易酸化性元素であるＳｉやＭｎ等がめっき直前に予め内部酸化し地鉄表層部におけるＳｉ、Ｍｎの活量が低下する。そして、これらの元素の外部酸化が抑制され、結果的にめっき性及び耐めっき剥離性が改善することになる。
The steel having the above chemical components is hot-rolled and then cold-rolled to obtain a steel plate, and then subjected to annealing and hot-dip galvanizing treatment in a continuous hot-dip galvanizing facility. At this time, in the present invention, in the heating process at the time of annealing, a heating furnace temperature: 600 ° C. or more and A ° C. or less (A: 650 ≦ A ≦ 780) is heated at a hydrogen concentration of 20 vol% or more. Furnace temperature: A temperature range exceeding A ° C. and B ° C. or less (B: 800 ≦ B ≦ 900) is performed at a dew point of the atmosphere: −5 ° C. or more. This is the most important requirement in the present invention. In this way, by controlling the dew point, that is, the oxygen partial pressure in the atmosphere, in the annealing and hot dip galvanizing processes, the oxygen potential is increased, and oxidizable elements such as Si and Mn are internally oxidized in advance immediately before plating. The activity of Si and Mn in the part decreases. And the external oxidation of these elements is suppressed, and as a result, plating property and plating peeling resistance are improved.
熱間圧延
通常、行われる条件にて行うことができる。
Hot rolling Usually, it can be performed on the conditions performed.
酸洗
熱間圧延後は酸洗処理を行うのが好ましい。酸洗工程で表面に生成した黒皮スケールを除去し、しかる後冷間圧延する。なお、酸洗条件は特に限定しない。
It is preferable to perform a pickling treatment after hot pickling. The black scale formed on the surface in the pickling process is removed, and then cold-rolled. The pickling conditions are not particularly limited.
冷間圧延
４０％以上８０％以下の圧下率で行うことが好ましい。圧下率が４０％未満では再結晶温度が低温化するため、機械特性が劣化しやすい。一方、圧下率が８０％超えでは高強度鋼板であるため、圧延コストがアップするだけでなく、焼鈍時の表面濃化が増加するため、めっき特性が劣化する。
Cold rolling is preferably performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, when the rolling reduction exceeds 80%, the steel sheet is a high-strength steel plate, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the plating characteristics are deteriorated.
冷間圧延した鋼板に対して、焼鈍した後溶融亜鉛めっき処理を施す。
焼鈍炉では、前段の加熱帯で鋼板を所定温度まで加熱する加熱工程を行い、後段の均熱帯で所定温度に所定時間保持する均熱工程を行う。
上述したように、加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域において、水素濃度が２０ｖｏｌ%以上となるように制御し、かつ、加熱炉内温度：
Ａ℃超えＢ℃以下（Ｂ：８００≦Ｂ≦９００）の温度域において、雰囲気の露点が−５℃以上となるように制御して溶融亜鉛めっき処理を行う。Ａ℃超えＢ℃以下の領域以外の焼鈍炉内雰囲気の露点は特に限定されない。好ましくは−４０℃超〜−１０の範囲が望ましい。
なお、６００℃を下回る温度域、及びＡ℃超え（Ａ：６５０≦Ａ≦７８０）の温度域においては、水素濃度が１ｖｏｌ％未満では還元による活性化効果が得られず耐めっき剥離性が劣化する。上限は特に規定しないが、２０ｖｏｌ％未満が好ましい。なお、焼鈍炉内の気体成分は、水素以外には窒素と不可避不純物気体からなる。本発明効果を損するものでなければ他の気体成分を含有してもよい。
溶融亜鉛めっき処理は、常法で行うことができる。
The cold-rolled steel sheet is annealed and then hot dip galvanized.
In the annealing furnace, a heating process is performed in which the steel sheet is heated to a predetermined temperature in a preceding heating zone, and a soaking process is performed in which the temperature is maintained at a predetermined temperature for a predetermined time in a subsequent soaking zone.
As described above, in the heating furnace temperature: 600 ° C. or more and A ° C. or less (A: 650 ≦ A ≦ 780), the hydrogen concentration is controlled to be 20 vol% or more, and the heating furnace temperature:
In the temperature range of A ° C. to B ° C. (B: 800 ≦ B ≦ 900), the hot dip galvanizing treatment is performed while controlling the dew point of the atmosphere to be −5 ° C. or higher. The dew point of the atmosphere in the annealing furnace other than the region of A ° C. and B ° C. is not particularly limited. The range of more than −40 ° C. to −10 is desirable.
In the temperature range below 600 ° C. and the temperature range exceeding A ° C. (A: 650 ≦ A ≦ 780), if the hydrogen concentration is less than 1 vol%, the activation effect due to reduction cannot be obtained and the plating peel resistance is deteriorated. To do. The upper limit is not particularly defined, but is preferably less than 20 vol%. In addition, the gas component in an annealing furnace consists of nitrogen and an unavoidable impurity gas other than hydrogen. Other gas components may be included as long as the effects of the present invention are not impaired.
The hot dip galvanizing treatment can be performed by a conventional method.
また、同一焼鈍条件で比較した場合、Ｓｉ、Ｍｎの表面濃化量は、鋼中Ｓｉ、Ｍｎ量に比例して大きくなる。また、同一鋼種の場合、比較的高い酸素ポテンシャル雰囲気では、鋼中Ｓｉ、Ｍｎが内部酸化に移行するため、雰囲気中酸素ポテンシャルの増加に伴い、表面濃化量も少なくなる。そのため、鋼中Ｓｉ、Ｍｎ量が多い場合、露点を上昇させることにより、雰囲気中酸素ポテンシャルを増加させる必要がある。 Further, when compared under the same annealing conditions, the surface enrichment amount of Si and Mn increases in proportion to the amount of Si and Mn in the steel. In the case of the same steel type, in a relatively high oxygen potential atmosphere, since Si and Mn in the steel move to internal oxidation, the amount of surface enrichment decreases as the oxygen potential in the atmosphere increases. Therefore, when the amount of Si and Mn in steel is large, it is necessary to increase the oxygen potential in the atmosphere by increasing the dew point.
次いで、必要に応じて合金化処理を行う。
溶融亜鉛めっき処理に引き続き合金化処理を行うときは、溶融亜鉛めっき処理をしたのち、４５０℃以上６００℃以下に鋼板を加熱して合金化処理を施し、めっき層のＦｅ含有量が７〜１５質量％になるよう行うのが好ましい。７質量％未満では合金化ムラが発生したりフレーキング性が劣化する。一方、１５質量％超えは耐めっき剥離性が劣化する。
Next, an alloying treatment is performed as necessary.
When the alloying treatment is performed subsequent to the hot dip galvanizing treatment, the hot dip galvanizing treatment is performed, and then the steel plate is heated to 450 ° C. or more and 600 ° C. or less to perform the alloying treatment, and the Fe content of the plating layer is 7 to 15 It is preferable to carry out so that it may become mass%. If it is less than 7% by mass, uneven alloying occurs or flaking properties deteriorate. On the other hand, if it exceeds 15% by mass, the plating peel resistance deteriorates.
以上により、本発明の高強度溶融亜鉛めっき鋼板が得られる。本発明の高強度溶融亜鉛めっき鋼板は、鋼板の表面に、片面あたりのめっき付着量が２０〜１２０ｇ／ｍ２の亜鉛めっき層を有する。２０ｇ／ｍ２未満では耐食性の確保が困難になる。一方、１２０ｇ／ｍ２を超えると耐めっき剥離性が劣化する。
そして、以下のように、めっき層直下の下地鋼板表面の構造に特徴を有することになる。亜鉛めっき層の直下の、下地鋼板表面から１００μｍ以内の鋼板表層部には、Ｆｅ、Ｓｉ、Ｍｎ、Ａｌ、Ｐ、さらには、Ｂ、Ｎｂ、Ｔｉ、Ｃr、Ｍｏ、Ｃu、Ｎｉの中から選ばれる１種以上の酸化物が合計で片面あたり０．０１０〜０．５０ｇ/m２形成される。また、めっき層直下の、下地鋼板表面から１０μｍまでの領域においては、粒界から１μｍ以内の地鉄粒内に結晶性Ｓｉ、Ｍｎ系複合酸化物が存在する。
鋼中にＳｉ及び多量のＭｎが添加された溶融亜鉛めっき鋼板において、高加工時の耐めっき剥離性を満足させるためには高加工時の割れなどの起点になる可能性があるめっき層直下の地鉄表層の組織、構造をより高度に制御する必要がある。そこで、本発明では、まず、めっき性を確保するために焼鈍工程において酸素ポテンシャルを高めるため、露点制御を上述のように制御した。その結果、酸素ポテンシャルを高めることで易酸化性元素であるＳｉやＭｎ等がめっき直前に予め内部酸化し地鉄表層部におけるＳｉ、Ｍｎの活量が低下する。そして、これらの元素の外部酸化が抑制され、結果的にめっき性及び耐めっき剥離性が改善する。さらに、この改善効果は、亜鉛めっき層の直下の、下地鋼板表面から１００μｍ以内の鋼板表層部にＦｅ、Ｓｉ、Ｍｎ、Ａｌ、Ｐ、さらには、Ｂ、Ｎｂ、Ｔｉ、Ｃr、Ｍｏ、Ｃu、Ｎｉの中から選ばれる少なくとも１種以上の酸化物を片面あたり０．０１０ｇ/m２以上存在させることになる。一方、０．５０ｇ/m２を超えて存在させてもこの効果は飽和するため、上限は０．５０ｇ/m２とする。
As described above, the high-strength hot-dip galvanized steel sheet of the present invention is obtained. The high-strength hot-dip galvanized steel sheet of the present invention has a galvanized layer having a plating adhesion amount of 20 to 120 g / m 2 on one surface of the steel sheet. If it is less than 20 g / m 2 , it becomes difficult to ensure corrosion resistance. On the other hand, when it exceeds 120 g / m 2 , the plating peel resistance deteriorates.
And it has the characteristic in the structure of the base steel plate surface just under a plating layer as follows. For the surface layer of the steel plate within 100 μm from the surface of the underlying steel plate immediately below the galvanized layer, choose from Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, Ni One or more oxides are formed in a total of 0.010 to 0.50 g / m 2 per side. Further, in the region immediately below the plating layer and from the surface of the underlying steel plate to 10 μm, crystalline Si and Mn-based composite oxide exist in the ground iron grains within 1 μm from the grain boundary.
In hot-dip galvanized steel sheets with Si and a large amount of Mn added to the steel, in order to satisfy the anti-plating resistance at the time of high processing, it is directly under the plating layer that may be the starting point of cracking at the time of high processing. It is necessary to control the structure and structure of the surface layer of the railway. Therefore, in the present invention, first, the dew point control is controlled as described above in order to increase the oxygen potential in the annealing process in order to ensure the plating property. As a result, by increasing the oxygen potential, easily oxidizable elements such as Si and Mn are internally oxidized in advance immediately before plating, and the activity of Si and Mn in the surface iron surface layer portion is reduced. And the external oxidation of these elements is suppressed, and as a result, plating property and plating peeling resistance are improved. Further, this improvement effect is obtained by applying Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, and a steel plate surface layer portion within 100 μm from the surface of the base steel plate directly below the galvanized layer. At least one oxide selected from Ni is present in an amount of 0.010 g / m 2 or more per side. On the other hand, since this effect is saturated even if it exceeds 0.50 g / m 2 , the upper limit is set to 0.50 g / m 2 .
また、内部酸化物が粒界にのみ存在し、粒内に存在しない場合、鋼中易酸化性元素の粒界拡散は抑制できるが、粒内拡散は十分に抑制できない場合がある。したがって、本発明では、上述したように、加熱過程では、加熱炉内温度：６００℃以上Ａ℃以下（Ａ：６５０≦Ａ≦７８０）の温度域を水素濃度：２０ｖｏｌ%以上で、加熱炉内温度：Ａ℃超えＢ
℃以下（Ｂ：８００≦Ｂ≦９００）の温度域を雰囲気の露点：−５℃以上で行うことで、粒界のみならず粒内でも内部酸化させる。具体的には、めっき層直下から１０μｍまでの領域において、粒界から１μｍ以内の地鉄粒内に結晶性Ｓｉ、Ｍｎ系複合酸化物を存在させることになる。地鉄粒内に酸化物が存在することで、酸化物近傍の地鉄粒内の固溶Ｓｉ、Ｍｎの量が減少する。その結果、Ｓｉ、Ｍｎの粒内拡散による表面への濃化を抑制することができる。
Moreover, when an internal oxide exists only in a grain boundary and does not exist in a grain, the grain boundary diffusion of an easily oxidizable element in steel can be suppressed, but the intragranular diffusion may not be sufficiently suppressed. Therefore, in the present invention, as described above, in the heating process, in the heating process, a temperature range of 600 ° C. or more and A ° C. or less (A: 650 ≦ A ≦ 780) is set to a hydrogen concentration of 20 vol% or more, and in the heating furnace. Temperature: A ° C over B
By performing a temperature range of ≦ C ° C. (B: 800 ≦ B ≦ 900) at the dew point of the atmosphere: −5 ° C. or more, internal oxidation is performed not only at the grain boundary but also within the grain. Specifically, in a region from immediately below the plating layer to 10 μm, crystalline Si and Mn-based composite oxide are present in the ground iron grains within 1 μm from the grain boundary. The presence of oxide in the ground iron grains reduces the amount of solid solution Si and Mn in the ground iron grains near the oxide. As a result, concentration on the surface due to intragranular diffusion of Si and Mn can be suppressed.
なお、本発明の製造方法で得られる高強度溶融亜鉛めっき鋼板のめっき層直下の下地鋼板表面の構造は、上記の通りであるが、例えば、めっき層直下（めっき／地鉄界面）から１００μｍを超えた領域で前記酸化物が成長していても問題はない。また、めっき層直下の、下地鋼板表面から１０μｍを超えた領域おいて、粒界から１μｍ以上の地鉄粒内に結晶性Ｓｉ、Ｍｎ系複合酸化物を存在させても問題はない。 In addition, although the structure of the base steel plate surface directly under the plating layer of the high-strength hot-dip galvanized steel plate obtained by the manufacturing method of the present invention is as described above, for example, 100 μm from directly under the plating layer (plating / base metal interface) There is no problem even if the oxide grows in a region beyond the above. In addition, there is no problem even if crystalline Si and Mn-based composite oxide are present in the ground iron grains having a size of 1 μm or more from the grain boundary in a region exceeding 10 μm from the surface of the underlying steel plate immediately below the plating layer.
さらに、上記に加え、本発明では、耐めっき剥離性を向上させるために、Ｓｉ、Ｍｎ系複合酸化物が成長する地鉄組織は軟質で加工性に富むフェライト相が好ましい。 Furthermore, in addition to the above, in the present invention, in order to improve the plating peel resistance, the base iron structure on which the Si and Mn-based composite oxide grows is preferably a soft and rich workability ferrite phase.
以下、本発明を、実施例に基いて具体的に説明する。 Hereinafter, the present invention will be specifically described based on examples.
表１に示す鋼組成からなる熱延鋼板を酸洗し、黒皮スケール除去した後、表２に示す条件にて冷間圧延し、厚さ１．０ｍｍの冷延鋼板を得た。 The hot-rolled steel sheet having the steel composition shown in Table 1 was pickled and the black scale removed, and then cold-rolled under the conditions shown in Table 2 to obtain a cold-rolled steel sheet having a thickness of 1.0 mm.
次いで、上記で得た冷延鋼板を、焼鈍炉にオールラジアントチューブ型の加熱炉を備えるＣＧＬに装入した。ＣＧＬでは、表２に示す通り、加熱炉内の所定の温度域の露点を制御して通板し、加熱帯で加熱し、均熱帯で均熱保持し、焼鈍したのち、４６０℃のＡｌ含有Ｚｎ浴にて溶融亜鉛めっき処理を施した。上記で露点を制御した領域以外の焼鈍炉内雰囲気の露点は−３５℃を基本とした。同じく、上記で水素濃度を制御した領域以外の水素
濃度は１０ｖｏｌ％を基本とした。なお、雰囲気の気体成分は窒素と水素および不可避不純物気体からなり、露点が−５℃以上となる領域の露点の制御については、窒素雰囲気中に設置した水タンクを加熱して加湿した窒素ガスが流れる配管を予め別途設置し、加湿した窒素ガス中に水素ガスを導入して混合し、これを炉内に導入することで雰囲気の露点を制御した。雰囲気の水素％の制御は、窒素ガス中へ導入する水素ガス量をガスバルブで調整することで行った。
Next, the cold-rolled steel sheet obtained above was charged into a CGL equipped with an all-radiant tube type heating furnace in an annealing furnace. In CGL, as shown in Table 2, the dew point in a predetermined temperature range in the heating furnace is controlled to pass through, heated in a heating zone, soaked in a soaking zone, annealed, and then contained at 460 ° C. Hot dip galvanizing treatment was performed in a Zn bath. The dew point of the atmosphere in the annealing furnace other than the region where the dew point was controlled was basically -35 ° C. Similarly, the hydrogen concentration outside the region where the hydrogen concentration was controlled was basically 10 vol%. Note that the atmospheric gas components are nitrogen, hydrogen, and inevitable impurity gases. The dew point in the region where the dew point is −5 ° C. or higher is controlled by heating and humidifying a nitrogen tank in a nitrogen atmosphere. A flowing pipe was separately installed in advance, hydrogen gas was introduced into and mixed with humidified nitrogen gas, and this was introduced into the furnace to control the dew point of the atmosphere. Control of the hydrogen% of the atmosphere was performed by adjusting the amount of hydrogen gas introduced into the nitrogen gas with a gas valve.
６００℃を下回る温度域、及びＡ℃超え（Ａ：６５０≦Ａ≦７８０）の温度域においては、水素濃度を１０ｖｏｌ％とした。
また、ＧＡは０．１４％Ａｌ含有Ｚｎ浴を、ＧＩは０．１８％Ａｌ含有Ｚｎ浴を用いた。付着量はガスワイピングにより４０ｇ／ｍ２、７０ｇ／ｍ２または１４０ｇ／ｍ２（片面あたり付着量）に調節し、ＧＡは合金化処理した。
In the temperature range below 600 ° C. and the temperature range exceeding A ° C. (A: 650 ≦ A ≦ 780), the hydrogen concentration was set to 10 vol%.
In addition, GA used a 0.14% Al-containing Zn bath, and GI used a 0.18% Al-containing Zn bath. The adhesion amount was adjusted to 40 g / m 2 , 70 g / m 2 or 140 g / m 2 (adhesion amount per side) by gas wiping, and GA was alloyed.
以上により得られた溶融亜鉛めっき鋼板（ＧＡおよびＧＩ）に対して、外観性（めっき外観）、高加工時の耐めっき剥離性、加工性を調査した。また、めっき層直下の１００μｍまでの地鉄鋼板表層部に存在する酸化物の量（内部酸化量）、および、めっき層直下１０μｍまでの地鉄鋼板表層に存在するＳｉ、Ｍｎ系複合酸化物の形態と成長箇所、粒界から１μｍ以内の位置におけるめっき層直下の粒内析出物を測定した。測定方法および評価基準を下記に示す。 The hot-dip galvanized steel sheets (GA and GI) obtained as described above were examined for appearance (plating appearance), plating peel resistance during high working, and workability. In addition, the amount of oxide (internal oxidation amount) present in the surface layer of the steel sheet up to 100 μm immediately below the plating layer, and the Si and Mn-based composite oxides present in the surface layer of the steel sheet up to 10 μm directly below the plating layer Intragranular precipitates immediately below the plating layer at a position within 1 μm from the morphology, growth location, and grain boundary were measured. The measurement method and evaluation criteria are shown below.
＜外観性＞
外観性は、不めっきや合金化ムラなどの外観不良が無い場合は外観良好（記号○）、ある場合は外観不良（記号×）と判定した。
<Appearance>
Appearance was judged as good appearance (symbol ◯) when there was no appearance defect such as non-plating or alloying unevenness, and when it was present, it was judged as poor appearance (symbol x).
＜耐めっき剥離性＞
高加工時の耐めっき剥離性は、ＧＡでは、９０°を超えて鋭角に曲げたときの曲げ加工部のめっき剥離の抑制が要求される。本実施例では１２０°曲げした加工部にセロハンテープを押し付けて剥離物をセロハンテープに転移させ、セロハンテープ上の剥離物量をＺｎカウント数として蛍光Ｘ線法で求めた。なお、この時のマスク径は３０ｍｍ、蛍光Ｘ線の加速電圧は５０ｋＶ、加速電流は５０ｍＡ、測定時間は２０秒である。下記の基準に照らして、ランク１、２のものを耐めっき剥離性が良好（記号○）、３以上のものを耐めっき剥離性が不良（記号×）と評価した。
蛍光Ｘ線Ｚｎカウント数 ランク
０−５００未満：１（良）
５００以上−１０００未満：２
１０００以上−２０００未満：３
２０００以上−３０００未満：４
３０００以上：５（劣）
ＧＩでは、衝撃試験時の耐めっき剥離性が要求される。ボールインパクト試験を行い、加工部をテープ剥離し、めっき層の剥離有無を目視判定した。ボールインパクト条件は、ボール重量１０００ｇ、落下高さ１００ｃｍである。
○：めっき層の剥離無し
×：めっき層が剥離
<Plating resistance>
With regard to the resistance to plating peeling at the time of high processing, in GA, it is required to suppress plating peeling at the bent portion when bent at an acute angle exceeding 90 °. In this example, the cellophane tape was pressed against the processed portion bent by 120 ° to transfer the peeled material to the cellophane tape, and the amount of the peeled material on the cellophane tape was determined by the fluorescent X-ray method as the Zn count number. At this time, the mask diameter is 30 mm, the fluorescent X-ray acceleration voltage is 50 kV, the acceleration current is 50 mA, and the measurement time is 20 seconds. In light of the following criteria, those with ranks 1 and 2 were evaluated to have good plating peel resistance (symbol ◯), and those with three or more were evaluated to have poor plating peel resistance (symbol x).
Fluorescent X-ray Zn count number Rank 0 to less than 500: 1 (good)
500 or more and less than 1000: 2
1000 or more and less than −2000: 3
2000 or more and less than −3000: 4
3000 or more: 5 (poor)
In GI, resistance to plating peeling during an impact test is required. A ball impact test was performed, the processed part was peeled off with tape, and the presence or absence of peeling of the plating layer was visually determined. Ball impact conditions are a ball weight of 1000 g and a drop height of 100 cm.
○: Plating layer is not peeled ×: Plating layer is peeled
＜加工性＞
加工性は、ＪＩＳ５号片を作成し引っ張り強度（ＴＳ／ＭＰａ）と伸び（Ｅｌ％）を測定し、ＴＳが６５０ＭＰａ未満の場合は、ＴＳ×Ｅｌ≧２２０００のものを良好、ＴＳ×Ｅｌ＜２２０００のものを不良とした。ＴＳが６５０ＭＰａ以上９００ＭＰａ未満の場合は、ＴＳ×Ｅｌ≧２００００のものを良好、ＴＳ×Ｅｌ＜２００００のものを不良とした。ＴＳが９００ＭＰａ以上の場合は、ＴＳ×Ｅｌ≧１８０００のものを良好、ＴＳ×Ｅｌ＜１８０００のものを不良とした。
<Processability>
As for workability, tensile strength (TS / MPa) and elongation (El%) are measured by preparing a JIS No. 5 piece. When TS is less than 650 MPa, TS × El ≧ 22000 is good, TS × El <22000 The thing was considered bad. When TS was 650 MPa or more and less than 900 MPa, TS × El ≧ 20000 was judged good, and TS × El <20000 was judged poor. When TS was 900 MPa or more, TS × El ≧ 18000 was judged good, and TS × El <18000 was judged poor.
＜めっき層直下１００μmまでの領域における内部酸化量＞
内部酸化量は、「インパルス炉溶融−赤外線吸収法」により測定した。ただし、素材（すなわち焼鈍を施す前の高強度鋼板）に含まれる酸素量を差し引く必要があるので、本発明では、連続焼鈍後の高強度鋼板の両面の表層部を１００μｍ以上研磨して鋼中酸素濃度を測定し、その測定値を素材に含まれる酸素量ＯＨとし、また、連続焼鈍後の高強度鋼板の板厚方向全体での鋼中酸素濃度を測定して、その測定値を内部酸化後の酸素量ＯＩとした。このようにして得られた高強度鋼板の内部酸化後の酸素量ＯＩと、素材に含まれる酸素量ＯＨとを用いて、ＯＩとＯＨの差（＝ＯＩ−ＯＨ）を算出し、さらに片面単位面積（すなわち１m２）当たりの量に換算した値（ｇ／ｍ２）を内部酸化量とした。
<Internal oxidation amount in the region of 100 μm directly under the plating layer>
The amount of internal oxidation was measured by “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 μm or more in the steel. Measure the oxygen concentration, set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally. The subsequent oxygen amount OI was used. The difference between OI and OH (= OI-OH) is calculated using the oxygen amount OI after internal oxidation of the high-strength steel plate thus obtained and the oxygen amount OH contained in the material, and further, single-sided unit area (i.e. 1 m 2) value converted into the amount per (g / m 2) as an internal oxide amount.
＜めっき層直下１０μｍまでの領域の鋼板表層部に存在するＳｉ、Ｍｎ系複合酸化物の成長箇所、粒界から１μｍ以内の位置におけるめっき層直下の粒内析出物＞
めっき層を溶解除去後、その断面をＳＥＭで観察し、粒内析出物の電子線回折で非晶質、結晶性の別を調査し、ＥＤＸ、ＥＥＬＳで組成を決定した。粒内析出物が結晶性で、Ｓｉ、Ｍｎが主成分である場合にＳｉ、Ｍｎ系複合酸化物であると判定した。視野倍率は５０００〜２００００倍で、各々５箇所調査した。５箇所の内、１箇所以上にＳｉ、Ｍｎ系複合酸化物が観察された場合、Ｓｉ、Ｍｎ系複合酸化物が析出していると判断した。内部酸化の成長箇所がフェライトであるか否かは、断面ＳＥＭで第２相の有無を調査し、第２相が認められないときはフェライトと判定した。また、めっき層直下から１０μｍまでの領域において、粒界から１μｍ以内の地鉄粒内のＳｉ、Ｍｎ系複合酸化物は、断面を抽出レプリカ法で析出酸化物を抽出し上記と同様の手法で決定した。
<In-granular precipitates immediately below the plating layer at a position within 1 μm from the growth location of Si and Mn-based composite oxide existing in the steel sheet surface layer in the region up to 10 μm immediately below the plating layer>
After the plating layer was dissolved and removed, the cross section was observed with an SEM, the amorphous and crystalline properties were investigated by electron diffraction of the intragranular precipitate, and the composition was determined by EDX and EELS. When the intragranular precipitate was crystalline and Si and Mn were the main components, it was determined to be a Si and Mn-based composite oxide. The field of view magnification was 5000 to 20000 times, and 5 locations were investigated. When Si and Mn-based composite oxide were observed at one or more of the five locations, it was determined that Si and Mn-based composite oxide were precipitated. Whether or not the growth site of internal oxidation is ferrite was determined by examining the presence or absence of the second phase with a cross-sectional SEM, and when the second phase was not observed, it was determined as ferrite. Also, in the region from just below the plating layer to 10 μm, the Si and Mn complex oxides in the ground iron grains within 1 μm from the grain boundary are extracted in the same manner as above by extracting the precipitated oxide by the extraction replica method. Were determined.
以上により得られた結果を製造条件と併せて表２に示す。 The results obtained as described above are shown in Table 2 together with the production conditions.
表２から明らかなように、本発明法で製造されたＧＩ、ＧＡ（本発明例）は、Ｓｉ、Ｍｎ等の易酸化性元素を多量に含有する高強度鋼板であるにもかかわらず加工性および高加工時の耐めっき剥離性に優れ、めっき外観も良好である。
一方、比較例では、めっき外観、加工性、高加工時の耐めっき剥離性のいずれか一つ以上が劣る。
As is apparent from Table 2, GI and GA (examples of the present invention) produced by the method of the present invention are workability despite being high-strength steel sheets containing a large amount of oxidizable elements such as Si and Mn. In addition, it has excellent anti-plating resistance during high processing and a good plating appearance.
On the other hand, in the comparative example, any one or more of plating appearance, workability, and resistance to plating peeling during high processing is inferior.
表３に示す鋼組成からなる熱延鋼板を酸洗し、黒皮スケール除去した後、表４に示す条件にて冷間圧延し、厚さ１．０ｍｍの冷延鋼板を得た。 The hot-rolled steel sheet having the steel composition shown in Table 3 was pickled and the black scale was removed, and then cold-rolled under the conditions shown in Table 4 to obtain a cold-rolled steel sheet having a thickness of 1.0 mm.
次いで、上記で得た冷延鋼板を、焼鈍炉にオールラジアントチューブ型の加熱炉を備えるＣＧＬに装入した。ＣＧＬでは、表４に示す通り、加熱炉内の所定の温度域の露点を制御して通板し、加熱帯で加熱し、均熱帯で均熱保持し、焼鈍したのち、４６０℃のＡｌ含有Ｚｎ浴にて溶融亜鉛めっき処理を施した。上記で露点を制御した領域以外の焼鈍炉内雰囲気の露点は−３５℃を基本とした。同じく、上記で水素濃度を制御した領域以外の水素
濃度は１０ｖｏｌ％を基本とした。
Next, the cold-rolled steel sheet obtained above was charged into a CGL equipped with an all-radiant tube type heating furnace in an annealing furnace. In CGL, as shown in Table 4, the dew point in a predetermined temperature range in the heating furnace is controlled to pass through, heated in a heating zone, soaked in the soaking zone, and annealed, and then contains Al at 460 ° C. Hot dip galvanizing treatment was performed in a Zn bath. The dew point of the atmosphere in the annealing furnace other than the region where the dew point was controlled was basically -35 ° C. Similarly, the hydrogen concentration outside the region where the hydrogen concentration was controlled was basically 10 vol%.
なお、雰囲気の気体成分は窒素と水素および不可避不純物気体からなり、露点が−５℃以上となる領域の露点の制御については、窒素雰囲気中に設置した水タンクを加熱して加湿した窒素ガスが流れる配管を予め別途設置し、加湿した窒素ガス中に水素ガスを導入して混合し、これを炉内に導入することで雰囲気の露点を制御した。雰囲気の水素％の制御は、窒素ガス中へ導入する水素ガス量をガスバルブで調整することで行った。 Note that the atmospheric gas components are nitrogen, hydrogen, and inevitable impurity gases. The dew point in the region where the dew point is −5 ° C. or higher is controlled by heating and humidifying a nitrogen tank in a nitrogen atmosphere. A flowing pipe was separately installed in advance, hydrogen gas was introduced into and mixed with humidified nitrogen gas, and this was introduced into the furnace to control the dew point of the atmosphere. Control of the hydrogen% of the atmosphere was performed by adjusting the amount of hydrogen gas introduced into the nitrogen gas with a gas valve.
また、ＧＡは０．１４％Ａｌ含有Ｚｎ浴を、ＧＩは０．１８％Ａｌ含有Ｚｎ浴を用いた。付着量はガスワイピングにより４０ｇ／ｍ２、７０ｇ／ｍ２または１４０ｇ／ｍ２（片面あたり付着量）に調節し、ＧＡは合金化処理した。 In addition, GA used a 0.14% Al-containing Zn bath, and GI used a 0.18% Al-containing Zn bath. The adhesion amount was adjusted to 40 g / m 2 , 70 g / m 2 or 140 g / m 2 (adhesion amount per side) by gas wiping, and GA was alloyed.
以上により得られた溶融亜鉛めっき鋼板（ＧＡおよびＧＩ）に対して、外観性（めっき外観）、高加工時の耐めっき剥離性、加工性を調査した。また、めっき層直下の１００μｍまでの地鉄鋼板表層部に存在する酸化物の量（内部酸化量）、および、めっき層直下１０μｍまでの地鉄鋼板表層に存在するＳｉ、Ｍｎ系複合酸化物の形態と成長箇所、粒界から１μｍ以内の位置におけるめっき層直下の粒内析出物を測定した。測定方法および評価基準を下記に示す。 The hot-dip galvanized steel sheets (GA and GI) obtained as described above were examined for appearance (plating appearance), plating peel resistance during high working, and workability. In addition, the amount of oxide (internal oxidation amount) present in the surface layer of the steel sheet up to 100 μm immediately below the plating layer, and the Si and Mn-based composite oxides present in the surface layer of the steel sheet up to 10 μm directly below the plating layer Intragranular precipitates immediately below the plating layer at a position within 1 μm from the morphology, growth location, and grain boundary were measured. The measurement method and evaluation criteria are shown below.
＜外観性＞
外観性は、不めっきや合金化ムラなどの外観不良が無い場合は外観良好（記号○）、ある場合は外観不良（記号×）と判定した。
<Appearance>
Appearance was judged as good appearance (symbol ◯) when there was no appearance defect such as non-plating or alloying unevenness, and when it was present, it was judged as poor appearance (symbol x).
＜耐めっき剥離性＞
高加工時の耐めっき剥離性は、ＧＡでは、９０°を超えて鋭角に曲げたときの曲げ加工部のめっき剥離の抑制が要求される。本実施例では１２０°曲げした加工部にセロハンテープを押し付けて剥離物をセロハンテープに転移させ、セロハンテープ上の剥離物量をＺｎカウント数として蛍光Ｘ線法で求めた。なお、この時のマスク径は３０ｍｍ、蛍光Ｘ線の加速電圧は５０ｋＶ、加速電流は５０ｍＡ、測定時間は２０秒である。◎、○は高加工時のめっき剥離性にまったく問題のない性能である。△は加工度によっては実用できる場合がある性能であり、×、××は通常の使用には適さない性能である。
蛍光Ｘ線Ｚｎカウント数 ランク
０−５００未満：◎
５００以上−１０００未満：○
１０００以上−２０００未満：△
２０００以上−３０００未満：×
３０００以上：××（劣）
ＧＩでは、衝撃試験時の耐めっき剥離性が要求される。ボールインパクト試験を行い、加工部をテープ剥離し、めっき層の剥離有無を目視判定した。ボールインパクト条件は、ボール重量１０００ｇ、落下高さ１００ｃｍである。
○：めっき層の剥離無し
×：めっき層が剥離
<Plating resistance>
With regard to the resistance to plating peeling at the time of high processing, in GA, it is required to suppress plating peeling at the bent portion when bent at an acute angle exceeding 90 °. In this example, the cellophane tape was pressed against the processed portion bent by 120 ° to transfer the peeled material to the cellophane tape, and the amount of the peeled material on the cellophane tape was determined by the fluorescent X-ray method as the Zn count number. At this time, the mask diameter is 30 mm, the fluorescent X-ray acceleration voltage is 50 kV, the acceleration current is 50 mA, and the measurement time is 20 seconds. ◎ and ○ are performances that have no problem with the plating peelability during high processing. Δ is a performance that may be practically used depending on the degree of processing, and x and xx are performances that are not suitable for normal use.
Fluorescent X-ray Zn count number Rank 0 to less than 500: ◎
500 or more and less than -1000: ○
1000 or more and less than −2000: Δ
2000 or more and less than 3000: x
3000 or more: xx (poor)
In GI, resistance to plating peeling during an impact test is required. A ball impact test was performed, the processed part was peeled off with tape, and the presence or absence of peeling of the plating layer was visually determined. Ball impact conditions are a ball weight of 1000 g and a drop height of 100 cm.
○: Plating layer is not peeled ×: Plating layer is peeled
＜加工性＞
加工性は、ＪＩＳ５号片を作成し引っ張り強度（ＴＳ／ＭＰａ）と伸び（Ｅｌ％）を測定し、ＴＳが６５０ＭＰａ未満の場合は、ＴＳ×Ｅｌ≧２２０００のものを良好、ＴＳ×Ｅｌ＜２２０００のものを不良とした。ＴＳが６５０ＭＰａ以上９００ＭＰａ未満の場合は、ＴＳ×Ｅｌ≧２００００のものを良好、ＴＳ×Ｅｌ＜２００００のものを不良とした。ＴＳが９００ＭＰａ以上の場合は、ＴＳ×Ｅｌ≧１８０００のものを良好、ＴＳ×Ｅｌ＜１８０００のものを不良とした。
<Processability>
As for workability, tensile strength (TS / MPa) and elongation (El%) are measured by preparing a JIS No. 5 piece. When TS is less than 650 MPa, TS × El ≧ 22000 is good, TS × El <22000 The thing was considered bad. When TS was 650 MPa or more and less than 900 MPa, TS × El ≧ 20000 was judged good, and TS × El <20000 was judged poor. When TS was 900 MPa or more, TS × El ≧ 18000 was judged good, and TS × El <18000 was judged poor.
＜めっき層直下１００μmまでの領域における内部酸化量＞
内部酸化量は、「インパルス炉溶融−赤外線吸収法」により測定した。ただし、素材（すなわち焼鈍を施す前の高強度鋼板）に含まれる酸素量を差し引く必要があるので、本発明では、連続焼鈍後の高強度鋼板の両面の表層部を１００μｍ以上研磨して鋼中酸素濃度を測定し、その測定値を素材に含まれる酸素量ＯＨとし、また、連続焼鈍後の高強度鋼板の板厚方向全体での鋼中酸素濃度を測定して、その測定値を内部酸化後の酸素量ＯＩとした。このようにして得られた高強度鋼板の内部酸化後の酸素量ＯＩと、素材に含まれる酸素量ＯＨとを用いて、ＯＩとＯＨの差（＝ＯＩ−ＯＨ）を算出し、さらに片面単位面積（すなわち１m２）当たりの量に換算した値（ｇ／ｍ２）を内部酸化量とした。
<Internal oxidation amount in the region of 100 μm directly under the plating layer>
The amount of internal oxidation was measured by “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 μm or more in the steel. Measure the oxygen concentration, set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally. The subsequent oxygen amount OI was used. The difference between OI and OH (= OI-OH) is calculated using the oxygen amount OI after internal oxidation of the high-strength steel plate thus obtained and the oxygen amount OH contained in the material, and further, single-sided unit area (i.e. 1 m 2) value converted into the amount per (g / m 2) as an internal oxide amount.
＜めっき層直下１０μｍまでの領域の鋼板表層部に存在するＳｉ、Ｍｎ系複合酸化物の成長箇所、粒界から１μｍ以内の位置におけるめっき層直下の粒内析出物＞
めっき層を溶解除去後、その断面をＳＥＭで観察し、粒内析出物の電子線回折で非晶質、結晶性の別を調査し、ＥＤＸ、ＥＥＬＳで組成を決定した。粒内析出物が結晶性で、Ｓｉ、Ｍｎが主成分である場合にＳｉ、Ｍｎ系複合酸化物であると判定した。視野倍率は５０００〜２００００倍で、各々５箇所調査した。５箇所の内、１箇所以上にＳｉ、Ｍｎ系複合酸化物が観察された場合、Ｓｉ、Ｍｎ系複合酸化物が析出していると判断した。内部酸化の成長箇所がフェライトであるか否かは、断面ＳＥＭで第２相の有無を調査し、第２相が認められないときはフェライトと判定した。また、めっき層直下から１０μｍまでの領域において、粒界から１μｍ以内の地鉄粒内のＳｉ、Ｍｎ系複合酸化物は、断面を抽出レプリカ法で析出酸化物を抽出し上記と同様の手法で決定した。
<In-granular precipitates immediately below the plating layer at a position within 1 μm from the growth location of Si and Mn-based composite oxide existing in the steel sheet surface layer in the region up to 10 μm immediately below the plating layer>
After the plating layer was dissolved and removed, the cross section was observed with an SEM, the amorphous and crystalline properties were investigated by electron diffraction of the intragranular precipitate, and the composition was determined by EDX and EELS. When the intragranular precipitate was crystalline and Si and Mn were the main components, it was determined to be a Si and Mn-based composite oxide. The field of view magnification was 5000 to 20000 times, and 5 locations were investigated. When Si and Mn-based composite oxide were observed at one or more of the five locations, it was determined that Si and Mn-based composite oxide were precipitated. Whether or not the growth site of internal oxidation is ferrite was determined by examining the presence or absence of the second phase with a cross-sectional SEM, and when the second phase was not observed, it was determined as ferrite. Also, in the region from just below the plating layer to 10 μm, the Si and Mn complex oxides in the ground iron grains within 1 μm from the grain boundary are extracted in the same manner as above by extracting the precipitated oxide by the extraction replica method. Were determined.
以上により得られた結果を製造条件と併せて表４に示す。 The results obtained above are shown in Table 4 together with the production conditions.
表４から明らかなように、本発明法で製造されたＧＩ、ＧＡ（本発明例）は、Ｓｉ、Ｍｎ等の易酸化性元素を多量に含有する高強度鋼板であるにもかかわらず加工性および高加工時の耐めっき剥離性に優れ、めっき外観も良好である。
一方、比較例では、めっき外観、加工性、高加工時の耐めっき剥離性のいずれか一つ以上が劣る。
As is clear from Table 4, GI and GA (invention examples) produced by the method of the present invention are high-strength steel sheets containing a large amount of easily oxidizable elements such as Si and Mn. In addition, it has excellent anti-plating resistance during high processing and a good plating appearance.
On the other hand, in the comparative example, any one or more of plating appearance, workability, and resistance to plating peeling during high processing is inferior.
本発明の高強度溶融亜鉛めっき鋼板は、めっき外観、加工性および高加工時の耐めっき剥離性に優れ、自動車の車体そのものを軽量化かつ高強度化するための表面処理鋼板として利用することができる。また、自動車以外にも、素材鋼板に防錆性を付与した表面処理鋼板として、家電、建材の分野等、広範な分野で適用できる。 The high-strength hot-dip galvanized steel sheet of the present invention is excellent in plating appearance, workability and anti-plating resistance during high processing, and can be used as a surface-treated steel sheet for reducing the weight and strength of an automobile body. it can. In addition to automobiles, the steel sheet can be applied in a wide range of fields such as home appliances and building materials as a surface-treated steel sheet provided with rust prevention properties.
Claims (4)
鋼板表面から１００μm以内の鋼板表層部にＦｅ、Ｓｉ、Ｍｎ、Ａｌ、Ｐ、Ｂ、Ｎｂ、Ｔ
ｉ、Ｃｒ、Ｍｏ、Ｃｕ、Ｎｉの中から選ばれる少なくとも１種以上の酸化物を、片面あたり０．０１０〜０．５０ｇ／ｍ2形成し、更に、めっき層直下の下地鋼板表面から１０μm以内の領域において、下地鋼板結晶粒界から１μm以内の粒内に結晶性Ｓｉ、Ｍｎ系酸化
物が存在していることを特徴とする高強度溶融亜鉛めっき鋼板。 It is manufactured by the manufacturing method according to any one of claims 1 to 3, and Fe, Si, Mn, Al, P, B, Nb, T is formed on a steel plate surface layer portion within 100 μm from the surface of the underlying steel plate immediately below the galvanized layer.
At least one oxide selected from i, Cr, Mo, Cu, and Ni is formed at 0.010 to 0.50 g / m 2 per side, and within 10 μm from the surface of the underlying steel plate immediately below the plating layer A high-strength hot-dip galvanized steel sheet characterized by the presence of crystalline Si and Mn-based oxide in grains within 1 μm from the grain boundary of the base steel sheet.
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| JP2013142198A (en) * | 2012-01-13 | 2013-07-22 | Nippon Steel & Sumitomo Metal Corp | Method for producing hot-dip galvanized steel sheet having excellent plating wettability and pickup resistance |
| JP2014015675A (en) * | 2012-06-15 | 2014-01-30 | Jfe Steel Corp | Method of producing high strength hot-dip galvanized steel sheet, and high strength hot-dip galvanized steel sheet |
| JP2014095143A (en) * | 2012-10-11 | 2014-05-22 | Jfe Steel Corp | Method of producing high-strength galvanized steel sheet and high-strength galvanized steel sheet |
| JP2014095142A (en) * | 2012-10-11 | 2014-05-22 | Jfe Steel Corp | Method for producing high strength hot dip galvanized steel sheet, and high strength hot dip galvanized steel sheet |
| JP2014169487A (en) * | 2013-03-05 | 2014-09-18 | Jfe Steel Corp | Method of producing high strength hot-dip galvanized steel sheet and high strength hot-dip galvanized steel sheet |
| WO2014157155A1 (en) * | 2013-03-27 | 2014-10-02 | 日新製鋼株式会社 | Hot-dip galvanized steel plate with excellent coating adhesion and process for producing same |
| WO2015133061A1 (en) * | 2014-03-05 | 2015-09-11 | Ｊｆｅスチール株式会社 | Cold-rolled steel sheet, method for producing same, high-strength hot-dipped galvanized steel sheet, and high-strength alloyed hot-dipped galvanized steel sheet |
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| JP2013142198A (en) * | 2012-01-13 | 2013-07-22 | Nippon Steel & Sumitomo Metal Corp | Method for producing hot-dip galvanized steel sheet having excellent plating wettability and pickup resistance |
| JP2014015675A (en) * | 2012-06-15 | 2014-01-30 | Jfe Steel Corp | Method of producing high strength hot-dip galvanized steel sheet, and high strength hot-dip galvanized steel sheet |
| JP2014095143A (en) * | 2012-10-11 | 2014-05-22 | Jfe Steel Corp | Method of producing high-strength galvanized steel sheet and high-strength galvanized steel sheet |
| JP2014095142A (en) * | 2012-10-11 | 2014-05-22 | Jfe Steel Corp | Method for producing high strength hot dip galvanized steel sheet, and high strength hot dip galvanized steel sheet |
| JP2014169487A (en) * | 2013-03-05 | 2014-09-18 | Jfe Steel Corp | Method of producing high strength hot-dip galvanized steel sheet and high strength hot-dip galvanized steel sheet |
| WO2014157155A1 (en) * | 2013-03-27 | 2014-10-02 | 日新製鋼株式会社 | Hot-dip galvanized steel plate with excellent coating adhesion and process for producing same |
| JP2014208902A (en) * | 2013-03-27 | 2014-11-06 | 日新製鋼株式会社 | Galvanized steel sheet excellent in plating adhesion, and manufacturing method thereof |
| JP2016006230A (en) * | 2013-03-27 | 2016-01-14 | 日新製鋼株式会社 | Hot-dip galvanized steel plate excellent in plating adhesion |
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| WO2015133061A1 (en) * | 2014-03-05 | 2015-09-11 | Ｊｆｅスチール株式会社 | Cold-rolled steel sheet, method for producing same, high-strength hot-dipped galvanized steel sheet, and high-strength alloyed hot-dipped galvanized steel sheet |
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